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Material for coating and product coated with the material |
The invention relates to an iron based material for coating of surfaces which comprises a binding phase in the form of a corrosion dense alloy which contains at least 50% Fe, 12-30% Cr, maximally 5% Mn, 0-40% Ni, preferably 6-20% Ni and 0-7% Mo and 0-1% N and 6-20% Si, all stated as weight percent, which addition of Si lowers the liquidus temperature, that is the temperature at which the binding phase is completely melted. The invention also aims at products of metal coated with the iron based material mentioned above. |
1-6. (canceled) 7. An iron based material for coating surfaces, comprising a binding phase in the form of a corrosion dense alloy which contains at least 50% Fe, 12-30% Cr, maximally 5% Mn, 0-40% Ni, 0-7% Mo and 0-1% N and 6-20% Si, all stated as weight percent, which Si-addition lowers the liquidus temperature, that is the temperature at which the binding phase is completely melted, to a value below 1250° C., preferably below 1200° C. 8. An iron based material as defined by claim 7, wherein said 0-40% Ni is 6-20% Ni. 9. An iron based material according to claim 7, wherein the material comprises hard particles based on one or a mixture of two or more of oxides, nitrides, carbides and borides. 10. An iron based material as defined by claim 7, wherein one or a mixture of two or more of oxygen, carbon, nitrogen, and boron are added to the materials in such amounts that formation of one or a mixture of two or more of oxides, nitrides and carbides is formed. 11. An iron based material according to claim 7, wherein the binding phase apart from Si also contains one or a mixture of two or more of B, P, Hf, C, which elements also lower the liquidus temperature, at which the amount of B is 0-1,5%, while the amount of P is 0-15% and the amount of Hf is 0-15% and the amount of C 0-2%. 12. An iron based material according to claim 7, wherein the amount of Si in the binding phase is 7-16%. 13. An iron based material according to claim 12, wherein said 7-16% Si in the binding phase is 8-12%. 14. An iron based material according to claim 7, wherein the binding phase is produced by gas at least one of water atomisation of a melt, melt spinning of a melt, which melts have a composition as stated above, and by crushing an ingot with the composition as stated above. |
<SOH> BACKGROUND OF THE INVENTION <EOH>It is known earlier to make surfaces more wear resistant and corrosion resistant by coating them with an abrasion resistant material. Such hard metal coatings usually consist of Ni- and Co-alloys, which form a softer binding phase and in addition contain hard particles such as oxides, carbides, borides and nitrides. The hard particles may either be mixed with the binding phase or oxygen, carbon, nitrogen and/or boron are added in such amounts that these form oxides, carbides, nitrides and/or borides. The abrasion resistant material is usually applied to the surface that should be treated in the form of a powder. The powder is applied to the surface and the binding phase is melted. Alternatively the material may already be melted when it is applied to the surface. Coating material with a binding phase consisting of a Ni- or a Co-alloy may cause problems in that the coated surface in many instances is more noble than the parent metal which may give rise to galvanic corrosion. These coating materials are also relatively expensive. Today there are also coatings of stainless steel for certain applications. The surfaces which shall be protected are coated with stainless steel, either by thermal spraying or by welding the stainless steel. There are certain drawbacks. If the stairdess steel is added by thermal spraying there is no tight layer. If the stainless steel is welded, the material which is to be coated melts. |
<SOH> SUMMARY OF THE INVENTION <EOH>The present invention relates to a new material for coating surfaces, which material is proportionately inexpensive but offers the same possibility to obtain a tight layer which is well attached to the surface of the object which is coated as Ni- or Co-alloys. The coating material is based on a corrosion dense material (stainless steel). According to the invention the material comprises a binding phase of a corrosion dense alloy which contains at least 50% Fe, 12-30% Cr, maximally 5% Mn, 040% Ni, preferably 6-20% Ni, 0-7% Mo and 0-1% N and 6-20% Si, all stated as weight percent. The addition of Si lowers the liquidus temperature, that is the temperature at which the binding phase is melted completely to a value below 1250° C., preferably below 1200° C. The coating material contains apart from iron and chromium, manganese and silicon in the amount given above. The coating material may contain hard particles based on oxides, nitrides, carbides and/or mixtures of these. Alternatively one may add oxygen, carbon, nitrogen and/or boron in such amounts that these elements form oxides, carbides, nitrides and/or borides. The expression “iron based material” refers henceforth to the binding phase including the hard particles. By coating a surface with an iron based material according to the invention one may obtain a corrosion dense surface layer on a surface that is not in itself corrosion resistant. One may also obtain a wear resistant surface on an object manufactured from a less wear resistant material. By a local coating of the iron based material one may, if so is desired, obtain a coating in certain points. detailed-description description="Detailed Description" end="lead"? |
Methods and compositions for controlling pests |
The present invention is directed to pest-controlling compositions comprising as active ingredients one or more β-diones, particularly β-diketones and β-triketones, and to the use of these compositions inter alia for preventing, eradicating, destroying, repelling or mitigating harmful, annoying or undesired pests including insects, arachnids, helminths, molluscs, protozoa and viruses. The present invention is further directed to processes of preparing β-diones by de novo synthesis or from natural sources such as volatile oil-bearing plants from families including Alliaceae, Apiaceae, Asteraceae, Cannabinaceae, Lamiaceae, Pteridaceae, Myrtaceae, Myoporaceae, Proteaceae, Rutaceae and Zingiberaceae. |
1.-24. (canceled) 25. A method for controlling harmful, annoying or undesired pests, other than plants, microbes, helminths and nematodes, said method comprising exposing said pests to a pest-controlling effective amount of a composition comprising a β-dione compound represented by the general formula (I) wherein A is (C═O)R1, (C═S)R1, OR2, SR2, (CR3NR4R5), C(R3)2OR2, NR4R5, (C═N—R4)R1, N═O, N(═O)2, NR4OR2 or SO4R2; R1 is selected from H, C1-C10 alkyl, C2-C10 arylalkyl, C3-C6 cycloalkyl, C2-C10 alkenyl, C2-C10 heteroarylalkyl, C1-C10 haloalkyl, C1-C10 dihaloalkyl, C2-C1, trihaloalkyl, C2-C10 haloalkoxy, C1-C10 hydroxyalkyl, C1-C10 thioalkyl and C1-C10 nitroalkyl, OR2, SR2, (CR3NR4R5), NR4R5, (C═N—R4)R, N═O, N(═O)2, NR4OR7 or SO4R7; R2 is selected from H, C1-C10 alkyl, C2-C10 arylalkyl, C3-C6 cycloalkyl, C2-C10 alkenyl, C2-C10 heteroarylalkyl, C2-C10 haloalkyl, C2-C10 dihaloalkyl, C2-C10 trihaloalkyl, (CR3NR4R5), NR4R5, (C═N—R4)R&, N═O, N(═O)2 or NR4OR7; R3 is selected from H, C1-C10 alkyl, C2-C10 arylalkyl, C3-C6 cycloalkyl, C2-C10 alkenyl, C2-C10 heteroarylalkyl, C2-C10 haloalkyl, C2-C10 dihaloalkyl, C2-C10 trihaloalkyl, C2-C10 haloalkoxy, OR7, SR7, (CR8NR4R5), NR4R5, (C═N—R4)R6, N═O, N(═O)2, NR4OR7 or SO4R7; R4 and R5 are independently selected from H, C1-C10 alkyl, C2-C10 arylalkyl, C3-C6 cycloalkyl, C2-C10 alkenyl, C2-C10 heteroarylalkyl, C2-C10 haloalkyl, C2-C10 dihaloalkyl, C2-C10 trihaloalkyl, OR7 or SR7; R6 is selected from H, C1-C10 alkyl, C2-C10 arylalkyl, C3-C6 cycloalkyl, C2-C10 alkenyl, C2-C10 heteroarylalkyl, C2-C10 haloalkyl, C2-C10 dihaloalkyl, C2-C10 trihaloalkyl, C2-C10 haloalkoxy, OR7, SR7, (CR8NR9R10), NR9R10 or NR9OR7; R7 is selected from H, C1-C10 alkyl, C2-C10 arylalkyl, C3-C6 cycloalkyl, C2-C10 alkenyl, C2-C10 heteroarylalkyl, C2-C10 haloalkyl, C2-C10 dihaloalkyl, C2-C10 trihaloalkyl; R8 is selected from H, C1C10 alkyl, C2-C10 arylalkyl, C3-C6 cycloalkyl, C2-C10 alkenyl, C2-C10 heteroarylalkyl, C2-C10 haloalkyl, C2-C10 dihaloalkyl, C2-C10 trihaloalkyl, OR11, SR11 or NR9R10; R9 and R10 are independently selected from H, C1-C10 alkyl, C2-C10 arylalkyl, C3-C6 cycloalkyl, C2-C10 alkenyl, C2-C10 heteroarylalkyl, C2-C10 haloalkyl, C2-C10 dihaloalkyl, C2-C10 trihaloalkyl, OR12 or SR12; R11 is selected from H, C1-C10 alkyl, C2-C10 arylalkyl, C3-C6 cycloalkyl, C2-C10 alkenyl, C2-C10 heteroarylalkyl, C2-C10 haloalkyl, C2-C10 dihaloalkyl, C2-C10 trihaloalkyl; R12 is selected from H, C1-C10 alkyl, C2-C10 arylalkyl, C3-C6 cycloalkyl, C2-C10 alkenyl, C2-C10 heteroarylalkyl, C2-C10 haloalkyl, C2-C10 dihaloalkyl, C2-C10 trihaloalkyl; B is H, C1-C10 alkyl, C2-C10 alkenyl, aryl or heteroaryl; X and Y are independently selected from oxygen, sulfur, —N—R4; and Q completes a 5-8-member saturated or unsaturated carbocyclic or heterocyclic ring. 26. The method of claim 25, wherein the compound is represented by the general formula (III) wherein X, Y and Z are each independently selected from oxygen, sulfur, —N—R4 or one of C═X, C═Y or C=Z is CH2; A is (C═O)R1, (C═S)R1, OR2, SR2, (CR3NR4R5), C(R3)2OR2, NR4R5, (C═N—R4)R1, N═O, N(═O)2, NR4OR2 or SO4R2; B is H, C1-C10 alkyl, C2-C10 alkenyl, aryl or heteroaryl; C, D, E and F are each independently selected from H, C1-C10 alkyl, C3-C6 cycloalkyl, C2-C10 alkenyl, C2-C10 haloalkyl, C2-C10 dihaloalkyl, C2-C10 trihaloalkyl, OR2, SR2, (CR3NR4R5), NR4R5, (C═N—R4)R1, N═O, N(═O)2, NR4OR2, SO4R2, C2-C10 1-arylalkyl, C2-C10 2-arylalkyl or (C═X)R1; and R1 is selected from H, C1-C10 alkyl, C2-C10 arylalkyl, C3-C6 cycloalkyl, C2-C10 alkenyl, C2-C10 heteroarylalkyl, C1-C10 haloalkyl, C1-C10 dihaloalkyl, C2-C10 trihaloalkyl, C2-C10 haloalkoxy, C1-C10 hydroxyalkyl, C1-C10 thioalkyl and C1-C10 nitroalkyl, OR2, SR2 (CR3NR4R5), NR4R5, (C═N—R4)R6, N═O, N(═O)2, NR4OR7 or SO4R7; R2 is selected from H, C1-C10 alkyl, C2-C10 arylalkyl, C3-C6 cycloalkyl, C2-C10 alkenyl, C2-C10 heteroarylalkyl, C2-C10 haloalkyl, C2-C10 dihaloalkyl, C2-C10 trihaloalkyl, (CR3NR4R5), NR4R5, (C═N—R4)R6, N═O, N(═O)2 or NR4OR7; R3 is selected from H, C1-C10 alkyl, C2-C10 arylalkyl, C3-C6 cycloalkyl, C2-C10 alkenyl, C2-C10 heteroarylalkyl, C2-C10 haloalkyl, C2-C10 dihaloalkyl, C2-C10 trihaloalkyl, C2-C10 haloalkoxy, OR7, SR7, (CR8NR4R5), NR4R5, (C═N—R1)R6, N═O, N(═O)2, NR4OR7 or SO4R7; R4 and R5 are independently selected from H, C1-C10 alkyl, C2-C10 arylalkyl, C3-C6 cycloalkyl, C2-C10 alkenyl, C2-C10 heteroarylalkyl, C2-C10 haloalkyl, C2-C10 dihaloalkyl, C2-C10 trihaloalkyl, OR7 or SR7. 27. The method of claim 26, wherein the compound is selected from flavesone (1-isobutyroyl-3,3,5,5-tetramethylcyclohexan-2,4,6-trione), isoleptospermone (1-isovaleroyl-3,3,5,5-tetramethylcyclohexan-2,4,6-trione), leptospermone (1-valeroyl-3,3,5,5-tetramethylcyclohexan-2,4,6-trione), papuanone (1-pentoyl-3,3,5,5-tetramethylcyclohexan-2,4,6-trione), grandiflorone (1-(2-phenylethyl)-3,3,5,5-tetramethylcyclohexan-2,4,6-trione) and jensenone (1-valeroyl-3,5-dicarbonylcyclohexan-2,4,6-trione), including analogues and derivatives thereof. 28. The method of claim 26, wherein the compound has a structural formula selected from: 29. The method of claim 26, wherein the compound has a structural formula selected from: 30. The method of claim 26, wherein the compound has a structural formula selected from: 31. The method of claim 26, wherein the compound has a structural formula selected from: 32. The method of claim 25, wherein the compound is represented by the general formula (IV) wherein X and Y are each independently selected from oxygen, sulfur —N—R4 or one of C═X or C═Y is CH2; A is (C═O)R1, (C═S)R1, OR2, SR2, (CR3NR4R), C(R3)2OR2, NR4R5, (C═N—R4)R1, N═O, N(═O)2, NR4OR2 or SO4R2; B is H, C1-C10 alkyl, C2-C10 alkenyl, aryl or heteroaryl; C, D, E and F are each independently selected from H, C1-C10 alkyl, C2-C10 arylalkyl, C3-C6 cycloalkyl, C2-C10 alkenyl, C2-C10 heteroarylalkyl, C2-C10 haloalkyl, C2-C10 dihaloalkyl, C2-C10 trihaloalkyl, C2-C10 haloalkoxy, OR2, SR2, (CR3NR4R5), NR4R5, (C═N—R4)R1, N═O, N(═O)2, NR4OR2, SO4R2; and R1 is selected from H, C1-C10 alkyl, C2-C10 arylalkyl, C3-C6 cycloalkyl, C2-C10 alkenyl, C2-C10 heteroarylalkyl, C1-C10 haloalkyl, C1-C10 dihaloalkyl, C2-C10 trihaloalkyl, C2-C10 haloalkoxy, C1-C10 hydroxyalkyl, C1-C10 thioalkyl and C1-C10 nitroalkyl, OR2, SR2, (CR3NR4R5), NR4R5, (C═N—R4)R6, N═O, N(═O)2, NR4OR7 or SO4R7; R2 is selected from H, C1-C10 alkyl, C2-C10 cloalkyl, C2-C10 alkenyl, C2-C10 heteroarylalkyl, C1-C10 haloalkyl, C1-C10 dihaloalkyl, C2-C10 trihaloalkyl, (CR3NR4R5), NR4R5, (C═N—R4)R6, N═O, N(═O)2 or NR4OR7; R3 is selected from H, C1-C10 alkyl, C2-C10 arylalkyl, C3-C6 cycloalkyl, C2-C10 alkenyl, C2-C10, heteroarylalkyl, C2-C10 haloalkyl, C2-C10 dihaloalkyl, C2-C10 trihaloalkyl, C2-C10 haloalkoxy, OR7, SR7, (CR8NR4R5), NR4R5, (C═N—R4)R6, N═O, N(═O)2, NR4OR7 or SO4R7; R1 and R5 are independently selected from H, C1-C10 alkyl, C2-C10 arylalkyl, C3-C6 cycloalkyl, C2-C10 alkenyl, C2-C10 heteroarylalkyl, C2-C10 haloalkyl, C2-C10 dihaloalkyl, C2-C10 trihaloalkyl, OR7 or SR7. 33. The method of claim 32, wherein the compound is selected from tasmanone (1-isobutroyl-4-methoxy-3,5,5-trimethylcyclohex-3-en-2,6-dione), agglomerone (1-isobutroyl-4-methoxy-5,5-dimethylcyclohex-3-en-2,6-dione), lateriticone (1-valeroyl-4-methoxy-3,5,5-trimethylcyclohex-3-en-2,6-dione), isolateriticone (1-isovaleroyl-4-methoxy-3,5,5-trimethylcyclohex-3-en-2,6-dione and platyphyllol (6,6-dimethyl-2-acetyl-5-methoxycyclohex-4-ene-1,3-dione), including analogues and derivatives thereof. 34. The method of claim 32, wherein the compound has a structural formula selected from: 35. The method of claim 25, wherein the compound is represented by the general formula (V) wherein X and Y are independently selected from oxygen, sulfur or —N—R4; and A is (C═O)R1, (C═S)R1, OR2, SR2, (CR3NR4R5), C(R3)2OR2, NR4R5, (C═N—R4)R1, N═O, N(═O)2, NR4OR2 or SO4R2; B is H, C1-C10 alkyl C2-C10 alkenyl, aryl or heteroaryl; C, D, E, F, G and H are each independently selected from H, C1-C10 alkyl, C2-C10 arylalkyl, C3-C6 cycloalkyl, C2-C10 alkenyl, C2-C10 heteroarylalkyl, C2-C10 haloalkyl, C2-C10 dihaloalkyl, C2-C10 trihaloalkyl, C2-C10 haloalkoxy, OR2, SR2, (CR3NR4R5), NR4R5, (C═N—R4)R1, N═O, N(═O)2, NR4OR2 or SO4R2; and R1 is selected from H, C1-C10 alkyl, C2-C10 arylalkyl, C3-C6 cycloalkyl, C2-C10 alkenyl, C2-C10 heteroarylalkyl, C1-C10 haloalkyl, C1-C10 dihaloalkyl, C2-C10 trihaloalkyl, C2-C10 haloalkoxy, C1-C10 hydroxyalkyl, C1-C10 thioalkyl and C1-C10 nitroalkyl, OR2, SR2, (CR3NR4R5), NR4R5, (C═N—R4)R6, N═O, N(═O)2, NR4OR7 or SO4R7; R2 is selected from H, C1-C10 alkyl, C2-C10 arylalkyl, C3-C6 cycloalkyl, C2-C10 alkenyl, C2-C10 heteroarylalkyl, C2-C10 haloalkyl, C2-C10 dihaloalkyl, C2-C10 trihaloalkyl, (CR3NR4R5), NR4R5, (C═N—R4)R6, N═O, N(═O)2 or NR4OR7; R3 is selected from H, C1-C10 alkyl C2-C10 arylalkyl, C3-C6 cycloalkyl, C2-C10 alkenyl, C2-C10 heteroarylalkyl, C2-C10 haloalkyl, C2-C10 dihaloalkyl, C2-C10 trihaloalkyl, C2-C10 haloalkoxy, OR7, SR7, (CR8NR4R5), NR4R5, (C═N—R4)R6, N═O, N(═O)2, NR4OR7 or SO4R7; R4 and R5 are independently selected from H, C1-C10 alkyl, C2-C10 arylalkyl, C3-C6 cycloalkyl, C2-C10 alkenyl, C2-C10 heteroarylalkyl, C2-C10 haloalkyl, C2-C10 dihaloalkyl, C2-C10 trihaloalkyl, OR7 or SR7. 36. The method of claim 35, wherein the compound is selected from are angustione (1-acetyl-3,5,5-trimethylcyclohex-2,6-dione), dehydroangustione (1-acetyl-3,5,5-trimethylcyclohex-3-en-2,6-dione) and xanthostemone (1-isobutroyl-5,5-dimethylcyclohex-3-en-2,6-dione), including their analogues and derivatives. 37. The method of claim 35, wherein the compound has a structural formula selected from: 38. The method of claim 35, wherein the compound has a structural formula selected from: 39. The method of claim 35, wherein the compound has a structural formula selected from: 40. The method of claim 25, wherein the compound is obtainable from a volatile oil-bearing organism. 41. The method of claim 40, wherein the compound is present in an essential oil derived from said volatile oil-bearing organism. 42. The method of claim 40, wherein the volatile oil-bearing organism is selected from volatile oil-bearing plants. 43. The method of claim 40, wherein the volatile oil-bearing organism is selected from plants from the families Alliaceae, Apiaceae, Asteraceae, Cannabinaceae, Lamiaceae, Pteridaceae, Myrtaceae, Myoporaceae, Proteaceae, Rutaceae and Zingiberaceae. 44. The method of claim 40, wherein the volatile oil-bearing organism is selected from genera of the Myrtaceae family. 45. The method of claim 40, wherein the volatile oil-bearing organism belongs to a genus selected from Angophora, Austromyrtus, Backhousia, Baeckea, Callistemon, Corymbia, Darwinia, Eucalyptus, Kunzea, Leptospermum, Melaleuca, Syzygium and Xanthostemon 46. The method of claim 25, wherein the pest that is controlled is selected from insects, arachnids, helminths, molluscs, protozoa and viruses. 47. The method of claim 25, wherein the pest that is controlled is selected from insects, arachnids, helminths and molluscs. 48. The method of claim 25, wherein the compound is used in the form of, a pest-controlling composition which comprises from about 0.00005% to about 90% by weight of said compound. 49.-73. (canceled) 74. A method for controlling harmful, annoying or undesired pests, other than plants and microbes, said method comprising exposing said pests to a pest-controlling effective amount of a composition comprising a β-dione compound represented by the general formula (I) wherein A is (C═O)R1, (C═S)R1, OR2, SR2, (CR3NR4R5), C(R3)2OR2, NR4R5, (C═N—R4)R1, N═O, N(═O)2, NR4OR2 or SO4R2; R1 is selected from H, C1-C10 alkyl, C2-C10 arylalkyl, C3-C6 cycloalkyl, C2-C10 alkenyl, C2-C10 heteroarylalkyl, C1-C10 haloalkyl, C1-C10 dihaloalkyl, C2-C10 trihaloalkyl, C2-C10 haloalkoxy, C1-C10 hydroxyalkyl, C1-C10 thioalkyl and C1-C10 nitroalkyl, OR2, SR2, (CR3NR4R5), NR4R5, (C═N—R4)R, N═O, N(═O)2, NR4OR7 or SO4R7; R2 is selected from H, C1-C10 alkyl, C2-C10 arylalkyl, C3-C6 cycloalkyl, C2-C10 alkenyl, C2-C10 heteroarylalkyl, C2-C10 haloalkyl, C2-C10 dihaloalkyl, C2-C10 trihaloalkyl, (CR3NR4R5), NR4R5, (C═N—R4)R6, N═O, N(═O)2 or NR4OR7; R3 is selected from H, C1-C10 alkyl, C2-C10 arylalkyl, C3-C6 cycloalkyl, C2-C10 alkenyl, C2-C10 heteroarylalkyl, C2-C10 haloalkyl, C2-C10 dihaloalkyl, C2-C10 trihaloalkyl, C2-C10 haloalkoxy, OR7, SR7, (CR8NR4R5), NR4R5, (C═N—R4)R6, N═O, N(═O)2, NR4OR7 or SO4R7; R4 and R5 are independently selected from H, C1-C10 alkyl, C2-C10 arylalkyl, C3-C6 cycloalkyl, C2-C10 alkenyl, C2-C10 heteroarylalkyl, C2-C10 haloalkyl, C2-C10 dihaloalkyl, C2-C10 trihaloalkyl, OR7 or SR7; R6 is selected from H, C1-C10 alkyl, C2-C10 arylalkyl, C3-C6 cycloalkyl, C2-C10 alkenyl, C2-C10 heteroarylalkyl, C2-C10 haloalkyl, C2-C10 dihaloalkyl, C2-C10 trihaloalkyl, C2-C10 haloalkoxy, OR7, SR7, (CR8NR9R10), NR9R10 or NR9OR7; R7 is selected from H, C1C10 alkyl, C2-C10 arylalkyl, C3-C6 cycloalkyl, C2-C10 alkenyl, C2-C10 heteroarylalkyl, C2-C10 haloalkyl, C2-C10 dihaloalkyl, C2-C10 trihaloalkyl; R8 is selected from H, C1-C10 alkyl, C2-C10 arylalkyl, C3-C6 cycloalkyl, C2-C10 alkenyl, C2-C10 heteroarylalkyl, C2-C10 haloalkyl, C2-C10 dihaloalkyl, C2-C10 trihaloalkyl, OR11, SR11 or NR9R10; R9 and R10 are independently selected from H, C1-C10 alkyl, C2-C10 arylalkyl, C3-C6 cycloalkyl, C2-C10 alkenyl, C2-C10 heteroarylalkyl, C2-C10 haloalkyl, C2-C10 dihaloalkyl, C2-C10 trihaloalkyl, OR12 or SR12; R11 is selected from H, C1-C10 alkyl, C2-C10 arylalkyl, C3-C6 cycloalkyl, C2-C10 alkenyl, C2-C10 heteroarylalkyl, C2-C10 haloalkyl, C2-C10 dihaloalkyl, C2-C10 trihaloalkyl; R12 is selected from H, C1-C10 alkyl, C2-C10 arylalkyl, C3-C6 cycloalkyl, C2-C10 alkenyl, C2-C10 heteroarylalkyl, C2-C10 haloalkyl, C2-C10 dihaloalkyl, C2-C10 trihaloalkyl; B is H, C1-C10 alkyl, C2-C10 alkenyl, aryl or heteroaryl; X and Y are independently selected from oxygen, sulfur, —N—R4; and Q completes a 5-8-member saturated or unsaturated carbocyclic or heterocyclic ring, with the proviso that when B═H1, C1-C10, alkyl or aryl, A is not CR3NR4R5 or C(R3)2OR2. 75. The method of claim 74, wherein the compound is represented by the general formula (III) wherein X, Y and Z are each independently selected from oxygen, sulfur, —N—R4 or one of C═X, C═Y or C=Z is CH2; A is (C═O)R1, (C═S)R1, OR2, SR2, (CR3NR4R5), C(R3)2OR2, NR4R5, (C═N—R4)R1, N═O, N(═O)2, NR4OR2 or SO4R2; B is H, C1-C10 alkyl, C2-C10 alkenyl, aryl or heteroaryl; C, D, E and F are each independently selected from H, C1-C10 alkyl, C3-C6 cycloalkyl, C2-C10 alkenyl, C2-C10 haloalkyl, C2-C10 dihaloalkyl, C2-C10 trihaloalkyl, OR2, SR2, (CR3NR4R5), NR4R5, (C═N—R4)R1, N═O, N(═O)2, NR4OR2, SO4R2, C2-C10 1-arylalkyl, C2-C10 2-arylalkyl or (C═X)R1; and R1 is selected from H, C1-C10 alkyl, C2-C10 arylalkyl, C3-C6 cycloalkyl, C2-C10 alkenyl, C2-C10 heteroarylalkyl, C1-C10 haloalkyl, C1-C10 dihaloalkyl, C2-C10 trihaloalkyl, C2-C10 haloalkoxy, C1-C10 hydroxyalkyl, C1-C10 thioalkyl and C1-C10 nitroalkyl, OR2, SR2, (CR3NR4R5), NR4R5, (C═N—R4)R6, N═O, N(═O)2, NR4OR7 or SO4R7; R2 is selected from H, C1-C10 alkyl, C2-C10 arylalkyl, C3-C6 cycloalky, C2-C10 alkenyl, C2-C10 heteroarylalkyl, C2-C10 haloalkyl, C2-C10 dihaloalkyl, C2-C10 trihaloalkyl, (CR3NR4R5), NR4R5, (C═N—R1)R6, N═O, N(═O)2 or NR4OR7; R3 is selected from H, C1-C10 alkyl, C2-C10 arylalkyl, C3-C6 cycloalkyl, C2-C10 alkenyl, C2-C10 heteroarylalkyl, C2-C10 haloalkyl, C2-C10 dihaloalkyl, C2-C10 trihaloalkyl, C2-C10 haloalkoxy, OR7, SR7, (CR8NR4R5), NR4R5, (C═N—R4)R6, N═O, N(═O)2, NR4OR7 or SO4R7; R4 and R5 are independently selected from H, C1-C10 alkyl, C2-C10 arylalkyl, C3-C6 cycloalkyl, C2-C10 alkenyl, C2-C10 heteroarylalkyl, C2-C10 haloalkyl, C2-C10 dihaloalkyl, C2-C10 trihaloalkyl, OR7 or SR7, with the proviso that when B═H1, C1-C10, alkyl or aryl, A is not CR3NR4R5 or C(R3)2OR2. 76. The method of claim 75, wherein the compound is selected from flavesone (1-isobutyroyl-3,3,5,5-tetramethylcyclohexan-2,4,6-trione), isoleptospermone (1-isovaleroyl-3,3,5,5-tetramethylcyclohexan-2,4,6-trione), leptospermone (1-valeroyl-3,3,5,5-tetramethylcyclohexan-2,4,6-trione), papuanone (1-pentoyl-3,3,5,5-tetramethylcyclohexan-2,4,6-trione), grandiflorone (1-(2-phenylethyl)-3,3,5,5-tetramethylcyclohexan-2,4,6-trione) and jensenone (1-valeroyl-3,5-dicarbonylcyclohexan-2,4,6-trione), including analogues and derivatives thereof. 77. The method of claim 75, wherein the compound has a structural formula selected from: 78. The method of claim 75, wherein the compound has a structural formula selected from: 79. The method of claim 75, wherein the compound has a structural formula selected from: 80. The method of claim 75, wherein the compound has a structural formula selected from: 81. The method of claim 74, wherein the compound is represented by the general formula (IV) wherein X and Y are each independently selected from oxygen, sulfur —N—R4 or one of C═X or C═Y is CH2; A is (C═O)R1, (C═S)R1, OR2, SR2, (CR3NR4R5), C(R3)2OR2, NR4R5, (C═N—R4)R1, N═O, N(═O)2, NR4OR2 or SO4R2; B is H, C1-C10 alkyl, C2-C10 alkenyl, aryl or heteroaryl; C, D, E and F are each independently selected from H, C1-C10 alkyl, C2-C10 arylalkyl, C3-C6 cycloalkyl, C2-C10 alkenyl, C2-C10 heteroarylalkyl, C2-C10 haloalkyl, C2-C10 dihaloalkyl, C2-C10 trihaloalkyl, C2-C10 haloalkoxy, OR2, SR2, (CR3NR4R5), NR4R5, (C═N—R4)R1, N═O, N(═O)2, NR4OR2, SO4R2; and R1 is selected from H, C1-C10 alkyl C2-C10 arylalkyl, C3-C6 cycloalkyl, C2-C10 alkenyl. C2-C10 heteroarylalkyl, C1-C10 haloalkyl, C1-C10 dihaloalkyl, C2-C10 trihaloalkyl, C2-C10 haloalkoxy. C1-C10 hydroxyalkyl, C1-C10 thioalkyl and C1-C10 nitroalkyl, OR2, SR2, (CR3NR4R5), NR4R5, (C═N—R4)R6, N═O, N(═O)2, NR4OR7 or SO4R7; R2 is selected from H, C1-C10 alkyl, C2-C10 arylalkyl, C3-C6 cycloalkyl, C2-C10 alkenyl, C2-C10 heteroarylalkyl, C2-C10 haloalkyl, C2-C10 dihaloalkyl, C2-C10 trihaloalkyl, (CR3NR4R5), NR4R5, (C═N—R4)R6, N═O, N(═O2) or NR4OR7; R3 is selected from H, C1-C10 alkyl, C2-C10 arylalkyl C3-C6 cycloalkyl, C2-C10 alkenyl, C2-C10 heteroarylalkyl, C2-C10 haloalkyl, C2-C10 dihaloalkyl, C2-C10 trihaloalkyl, C2-C10 haloalkoxy, OR7, SR7, (CR8NR4R5), NR4R5, (C═N—R4)R6, N═O, N(═O)2, NR4OR7 or SO4R7; R4 and R5 are independently selected from H, C1-C10 alkyl C2-C10 arylalkyl, C3-C6 cycloalkyl, C2-C10 alkenyl, C2-C10 heteroarylalkyl, C2-C10 haloalkyl, C2-C10 dihaloalkyl, C2-C10 trihaloalkyl, OR7 or SR7, with the proviso that when B═H1, C1-C10, alkyl or aryl, A is not CR3NR4R5 or C(R3)2OR2. 82. The method of claim 81, wherein the compound is selected from tasmanone (1-isobutroyl-4-methoxy-3,5,5-trimethylcyclohex-3-en-2,6-dione), agglomerone (1-isobutroyl-4-methoxy-5,5-dimethylcyclohex-3-en-2,6-dione), lateriticone (1-valeroyl-4-methoxy-3,5,5-trimethylcyclohex-3-en-2,6-dione), isolateriticone (1-isovaleroyl-4-methoxy-3,5,5-trimethylcyclohex-3-en-2,6-dione and platyphyllol (6,6-dimethyl-2-acetyl-5-methoxycyclohex-4-ene-1,3-dione), including analogues and derivatives thereof. 83. The method of claim 81, wherein the compound has a structural formula selected from: 84. The method of claim 74, wherein the compound is represented by the general formula (V) wherein X and Y are independently selected from oxygen, sulfur or —N—R4; and A is (C═O)R1, (C═S)R1, OR2, SR2, (CR3NR4R5), C(R3)2OR2, NR4R5, (C═N—R4)R1, N═O, N(═O)2, NR4OR2 or SO4R2; B is H, C1-C10 alkyl, C2-C10 alkenyl, aryl or heteroaryl; C, D, E, F, G and H are each independently selected from H, C1-C10 alkyl, C2-C10 arylalkyl, C3-C6 cycloalkyl, C2-C10 alkenyl, C2-C10 heteroarylalkyl, C2-C10 haloalkyl, C2-C10 dihaloalkyl, C2-C10 trihaloalkyl, C2-C10 haloalkoxy, OR2, SR2, (CR3NR4R5), NR4R5, (C═N—R4)R1, N═O, N(═O)2, NR4OR2 or SO4R2; and R1 is selected from H, C1-C10 alkyl, C2-C10 arylalkyl, C3-C6 cycloalkyl, C2-C10 alkenyl, C2-C10 heteroarylalkyl, C1-C10 haloalkyl, C1-C10 dihaloalkyl, C2-C10 trihaloalkyl, C2-C10 haloalkoxy, C1-C10 hydroxyalkyl, C1-C10 thioalkyl and C1-C10 nitroalkyl, OR2, SR2, (CR3NR4R5), NR4R5, (C═N—R4)R6, N═O, N(═O)2 or NR4OR7 or SO4R7; R2 is selected from H, C1-C10 alkyl, C2-C10 arylalkyl, C3-C6 cycloalkyl, C2-C10 alkenyl, C2-C10 heteroarylalkyl, c2-C10 haloalkyl, C2-C10 dihaloalkyl, C2-C10 trihaloalkyl, (CR3NR4R5), NR4R5, (C═N—R4)R6, N═O, N(═O)2 or NR4OR7; R3 is selected from H, C1-C10 alkyl, C2-C10 arylalkyl, c3-C6 cycloalkyl, C2-C10 alkenyl, C2-C10 heteroarylalkyl, C2-C10 haloalkyl, C2-C10 dihaloalkyl, C2-C10 trihaloalkyl, C2-C10 haloalkoxy, OR7, SR7, (CR8NR4R5), NR4R5, (C═N—R4)R6, N═O, N(═O)2, NR4OR7 or SO4R7; R4 and R5 are independently selected from H, C1-C10 alkyl, C2-C10 arylalkyl, C3-C6 cycloalkyl, C2-C10 alkenyl, C2-C10 heteroarylalkyl, C2-C10 haloalkyl, C2-C10 dihaloalkyl, C2-C10 trihaloalkyl, OR7 or SR7, with the proviso that when B═H1, C1-C10, alkyl or aryl, A is not CR3NR4R5 or C(R3)2OR2. 85. The method of claim 84, wherein the compound is selected from are angustione (1-acetyl-3,5,5-trimethylcyclohex-2,6-dione), dehydroangustione (1-acetyl-3,5,5-trimethylcyclohex-3-en-2,6-dione) and xanthostemone (1-isobutroyl-5,5-dimethylcyclohex-3-en-2,6-dione), including their analogues and derivatives. 86. The method of claim 35, wherein the compound has a structural formula selected from: 87. The method of claim 84, wherein the compound has a structural formula selected from: 88. The method of claim 84, wherein the compound has a structural formula selected from: 89. The method of claim 74, wherein the compound is obtainable from a volatile oil-bearing organism. 90. The method of claim 89, wherein the compound is present in an essential oil derived from said volatile oil-bearing organism. 91. The method of claim 89, wherein the volatile oil-bearing organism is selected from volatile oil-bearing plants. 92. The method of claim 89, wherein the volatile oil-bearing organism is selected from plants from the families Alliaceae, Apiaceae, Asteraceae, Cannabinaceae, Lamiaceae, Pteridaceae, Myrtaceae, Myoporaceae, Proteaceae, Rutaceae and Zingiberaceae. 93. The method of claim 89, wherein the volatile oil-bearing organism is selected from genera of the Myrtaceae family. 94. The method of claim 89, wherein the volatile oil-bearing organism belongs to a genus selected from Angophora, Austromyrtus, Backhousia, Baeckea, Callistemon, Corymbia, Darwinia, Eucalyptus, Kunzea, Leptospermum, Melaleuca, Syzygium and Xanthostemon 95. The method of claim 74, wherein the pest that is controlled is selected from insects, arachnids, helminths, molluscs, protozoa and viruses. 96. The method of claim 74, wherein the pest that is controlled is selected from insects, arachnids, helminths and molluscs. 97. The method of claim 74, wherein the compound is used in the form of a pest-controlling composition which comprises from about 0.00005% to about 90% by weight of said compound. 98. The method of claim 25, wherein Q completes the 5-8-member saturated or unsaturated carbocyclic or heterocyclic ring in which one or more members comprise —C(═X)—; and wherein Q is substituted with one or more substituents selected from C1-C10 alkyl, C3-C6 cycloalkyl, C2-C10 alkenyl, C2-C10 haloalkyl, C2-C10 dihaloalkyl, C2-C10 trihaloalkyl, C2-C10 haloalkoxy, OR2, SR2, (CR3NR4R5), NR4R5, (C═N—R4)R1, N═O, N(═O)2, NR4OR2, SO4R2, C2-C10 1-arylalkyl, C2-C10 2-arylalkyl or (C═X)R1. 99. The method of claim 74, wherein Q completes the 5-8-member saturated or unsaturated carbocyclic or heterocyclic ring in which one or more members comprise —C(═X)—; and wherein Q is substituted with one or more substituents selected from C1-C10 alkyl, C3-C6 cycloalkyl, C2-C10 alkenyl, C2-C10 haloalkyl, C2-C10 dihaloalkyl, C2-C10 trihaloalkyl, C2-C10 haloalkoxy, OR2, SR2, (CR3NR4R5), NR4R5, (C═N—R4)R1, N═O, N(═O)2, NR4OR2, SO4R2, C2-C10 1-arylalkyl, C2-C10 2-arylalkyl or (C═X)R1. |
<SOH> BACKGROUND OF THE INVENTION <EOH>Triketones have been used for many years as herbicides for the control of undesired vegetation. Herbicidal triketones have been described, for example, in EP-A-338992, EP-A-336898, U.S. Pat. No. 4,869,748, EP-A-186118, EP-A-186119, EP-A-186120, U.S. Pat. No. 4,202,840, U.S. Pat. No. 4,695,673, U.S. Pat. No. 4,780,127, U.S. Pat. No. 4,921,526, U.S. Pat. No. 5,006,150, U.S. Pat. No. 5,545,607, U.S. Pat. No. 5,925,795, U.S. Pat. No. 5,990,046, U.S. Pat. No. 6,218,579, EP-A-249150, EP-A-137963, EP-A-394889, EP-A-506907 or EP-B-135191. Examples of herbicidal triketones are inter alia Sulcotrione (MIKADO®) whose chemical designation is 2-(2-chloro-4-methanesulfonylbenzoyl)-1,3-cyclohexandione, 2-(4-methylsulfonyloxy-2-nitrobenzoyl)-4,4,6,6-tetramethyl-1,3-cyclohexane dione; 3-(4-methylsulfonyloxy-2-nitrobenzoyl)-bicyclo-[3,2,1]octane-2,4-dione; 3-(4-methylsulfonyl-2-nitrobenzoyl)-bicyclo-[3,2,1]octane-2,4-dione; 4-(4-chloro-2-nitrobenzoyl)-2,6,6-trimethyl-2H-1,2-oxazine-3,5(4H, 6H)-dione; 3-(4-methylthio-2-nitrobenzoyl)-bicyclo[3,2,1]octane-2,4-dione; 4-(2-nitro-4-trifluoromethoxybenzoyl)-2,6,6-trimethyl-2H-1,2-oxazine-3,5(4H, 6H)-dione. |
<SOH> SUMMARY OF THE INVENTION <EOH>The instant invention is predicated in part on the discovery that β-diones, particularly β-diketones and β-triketones, such as those obtainable from volatile oil-bearing plants including plants from the families Alliaceae, Apiaceae, Asteraceae, Cannabinaceae, Lamiaceae, Pteridaceae, Myrtaceae, Myoporaceae, Proteaceae, Rutaceae and Zingiberaceae, exhibit significant pesticidal, especially insecticidal, arachnicidal, helminthicidal and/or molluscicidal activity. This discovery has been reduced to practice in novel pest-controlling compositions and methods for their preparation and use, as described hereinafter. |
Production of pure molybdenum oxide from low grade molybdenite concentrates |
High purity ammonium dimolybdate or molybdenum oxide is produced by the pressure oxidation of low grade molybdenite concentrates or molybdenum intermediates. The process entails nearly complete oxidation of the sulfide minerals while optimizing the process chemistry and autoclave conditions to solubilize as little of the molybdenum values as possible. The autoclave discharge 12 is then subjected to a leaching step, either an alkaline leach 50, 400 or ammonium leach 250 process, before or after a liquid/solid separation step 20, 220, 410. The solution is then subjected to (a) filtration 60, 410, solvent extraction 70, 440, crystallization 90, 450, and calcination 120, 480 or (b) filtration 260, 280, crystallization 290, and calcination 320 to produce a product suitable for chemical-grade molybdenum oxide 125, 325, 485. |
1-54. (canceled) 55. A method of producing high purity ammonium dimolybdate from low grade molybdenite concentrates comprising: a) forming an aqueous slurry of said low grade molybdenite concentrates; b) oxidizing said slurry in an atmosphere containing free oxygen at a pressure of at least about 50 p.s.i. and at a temperature of at least about 200° C. and thereafter producing a first discharge with greater than about 99% of the molybdenum in said low grade molybdenite concentrates oxidized and greater than about 80% of molybdenum values insoluble; c) filtering said first discharge to produce a first liquid filtrate containing soluble molybdenum values and a first solid filter cake containing the insoluble molybdenum values; d) leaching said first solid filter cake with an alkaline solution to produce a second discharge wherein greater than about 98% of the insoluble molybdenum values are solubilized; e) filtering said second discharge to produce a second liquid filtrate and a second solid filter cake; f) recovering the molybdenum values from said second liquid filtrate by solvent extraction with an organic solvent to produce a first liquor by (1) contacting said second liquid filtrate with said organic solvent to form a two-phase mixture and simultaneously reducing the pH level in said two-phase mixture such that the molybdenum values in said second liquid filtrate are extracted into said organic solvent; and (2) stripping said organic solvent with aqueous ammonia to recover the molybdenum values; g) crystallizing said first liquor containing the extracted molybdenum values to produce crystals and a second liquor; and h) recovering said high purity ammonium dimolybdate from said crystals. 56. The method of claim 55, wherein the organic solvent contains a secondary amine. 57. The method of claim 56, wherein the organic solvent contains ditridecyl amine. 58. The method of claim 55, wherein the reduced pH level in said two-phase mixture ranges from about 4.0 to about 4.5. 59. The method of claim 55, wherein the reducing is accomplished by adding hydrated sulfuric acid to said two-phase mixture. 60. The method of claim 55, wherein ammonium hydroxide is used during the stripping to recover the molybdenum values. 61. The method of claim 55, wherein the pH level during the stripping is maintained at about 9.0. 62. A method of producing high purity ammonium dimolybdate from low grade molybdenite concentrates comprising: a) forming an aqueous slurry of said low grade molybdenite concentrates; b) oxidizing said slurry in an atmosphere containing free oxygen at an pressure of at least about 50 p.s.i. and at a temperature of at least about 200° C. and thereafter producing a first discharge with greater than about 99% of the molybdenum in said low grade molybdenite concentrates oxidized and greater than about 80% of molybdenum values insoluble; c) separating and filtering said first discharge to produce a first liquid filtrate containing soluble molybdenum values and a first solid filter cake containing the insoluble molybdenum values; d) leaching said first solid filter cake with an ammoniacal solution to produce a second discharge wherein greater than about 98% of the insoluble molybdenum values are solubilized; e) filtering said second discharge to produce a second liquid filtrate and a second solid filter cake; f) aging said second liquid filtrate; g) crystallizing said second liquid filtrate to produce crystals and a first liquor; and h) recovering said high purity ammonium dimolybdate from said crystals; wherein the method further comprises subjecting said first liquid filtrate produced in step (c) to a solvent extraction process to recover molybdenum values, said solvent extraction process comprising contacting said first liquid filtrate with an organic solvent to form a two-phase mixture and simultaneously reducing the pH level in said two-phase mixture such that the molybdenum values in said first liquid filtrate are extracted into said organic solvent, and stripping said organic solvent to produce a second liquor containing the recovered molybdenum values. 63. The method of claim 62, wherein the organic solvent contains a secondary amine. 64. The method of claim 63, wherein the organic solvent contains ditridecyl amine. 65. The method of claim 62, wherein the reduced pH level in said two-phase mixture ranges from about 4.0 to about 4.5. 66. The method of claim 62, wherein the reducing is accomplished by adding hydrated sulfuric acid to said two-phase mixture. 67. The method of claim 62, wherein sulfuric acid is used during the stripping to recover the molybdenum values. 68. The method of claim 62, wherein the pH level during the stripping is maintained at about less than 3.0. 69. The method of claim 62, further comprising recycling a portion of said second liquor back to the aqueous slurry in step (a). 70. The method of claim 62, further comprising subjecting said second liquor to a cementation process to recover copper values, said cementation process comprising adding iron to said second liquor and mixing to produce a first solution, filtering said first solution to produce a third liquid filtrate and a third solid filter cake, and then recovering said copper values from said third solid filter cake. 71. A method of producing high purity ammonium dimolybdate from low grade molybdenite concentrates comprising: a) forming an aqueous slurry of said low grade molybdenite concentrates; b) oxidizing said slurry in an atmosphere containing free oxygen at an pressure of at least about 50 p.s.i. and at a temperature of at least about 200° C. and thereafter producing a first discharge with greater than about 99% of the molybdenum in said low grade molybdenite concentrates oxidized and greater than about 80% of molybdenum values insoluble; c) separating and filtering said first discharge to produce a first liquid filtrate containing soluble molybdenum values and a first solid filter cake containing the insoluble molybdenum values; d) leaching said first solid filter cake with an ammoniacal solution to produce a second discharge wherein greater than about 98% of the insoluble molybdenum values are solubilized; e) filtering said second discharge to produce a second liquid filtrate and a second solid filter cake; f) aging said second liquid filtrate and adding a reagent selected from the group consisting of iron molybdate, ammonium sulfide, sulfide compounds, and ferric sulfate to said second liquid filtrate; g) crystallizing said second liquid filtrate to produce crystals and a first liquor; and h) recovering said high purity ammonium dimolybdate from said crystals. 72. A method of producing high purity ammonium dimolybdate from low grade molybdenite concentrates comprising: a) forming an aqueous slurry of said low grade molybdenite concentrates; b) oxidizing said slurry in an atmosphere containing free oxygen at an pressure of at least about 50 p.s.i. and at a temperature of at least about 200° C. and thereafter producing a first discharge with greater than about 99% of the molybdenum in said low grade molybdenite concentrates oxidized and greater than about 80% of molybdenum values insoluble; c) leaching said first discharge with an alkaline solution to produce a second discharge wherein greater than about 98% of the insoluble molybdenum values are solubilized; d) separating and filtering said second discharge to produce a liquid filtrate containing soluble molybdenum values and a solid filter cake containing the insoluble molybdenum values; e) recovering the molybdenum values from said liquid filtrate by solvent extraction with an organic solvent to produce a first liquor by (1) contacting said liquid filtrate with said organic solvent to form a two-phase mixture and simultaneously reducing the pH level in said two-phase mixture such that the molybdenum values in said liquid filtrate are extracted into said organic solvent; and (2) stripping said organic solvent to recover the molybdenum values; f) crystallizing said first liquor containing the extracted molybdenum values to produce crystals and a second liquor; and g) recovering said high purity ammonium dimolybdate from said crystals. 73. The method of claim 72, wherein the organic solvent contains a secondary amine. 74. The method of claim 73, wherein the organic solvent contains ditridecyl amine. 75. The method of claim 72, wherein the reduced pH level in said two-phase mixture ranges from about 4.0 to about 4.5. 76. The method of claim 72, wherein the reducing is accomplished by adding hydrated sulfuric acid to said two-phase mixture. 77. The method of claim 72, wherein ammonium hydroxide is used during the stripping to recover the molybdenum values. 78. The method of claim 72, wherein the pH level during the stripping is maintained at about 9.0. |
<SOH> BACKGROUND OF THE INVENTION <EOH>Extraction of molybdenum from molybdenite-containing materials by an aqueous process has been the subject of study for over 50 years. In 1952, E. S. Usataya 1 reported on the oxidation of molybdenite in water solutions. He found that in neutral, acidic, or weakly alkaline solutions the decomposition products precipitate on the molybdenite surface and protect the molybdenite from further oxidation. He found that strong bases and strong oxidizing agents impede the formation of the protective layers. Increasing temperature accelerated the oxidation rate in alkaline solutions, but up to 60° C. had no effect in acidic solutions. 1 Usataya, E. S., “Oxidation of molybdenite in water solutions,” Zapiski Vsesoyuz Mineral Obshschestva, v 81, 298-303 (1952). A Japanese patent 2 was issued for oxygen pressure oxidation (POX) of molybdenite in 1962. The example in this patent leached a 55.5% Mo, 36.4% S, and 4.4% Cu concentrate at 9% solids at 200° C. and 200 atmospheres oxygen. The molybdic acid precipitate that formed during leaching was dissolved using ammonia for recovery of an ammonium molybdate. 2 Sada, Koji, “Extraction of molybdenum,” Japanese patent 15.207('62), assigned to Awamura Mining Co., Ltd. In another process disclosure 3 , alkali hydroxide and alternatively ammonium hydroxide was added continuously to the aqueous solution to neutralize the acid as it formed and maintain the pH at 7-12. Other authors 4 postulated the formation of a molybdenum-iron heteropoly complex that decomposes as the acid concentration increases. It also may be a ferrous complex that decomposes as the soluble iron is oxidized to ferric. 3 Hallada, Calvin J., et al., “Conversion of molybdenum disulfide to molybdenum oxide,” German patent 2,045,308 (1971). 4 Mel'nikov, B. S. and Shapiro, K. A., “Water-autoclave decomposition of molybdenite raw material,” Protsessy Poluch. Rafinirovaniya Tugoplavkikh Met. (1975) 113-120, 253-260. Early applications of molybdenum solvent extraction utilized tertiary amine to extract the molybdenum solubilized by sodium hydroxide leaching of roasted molybdenite calcines. Secondary amines and quaternary ammonium compounds extract anionic molybdenum using a similar chemistry. Amines also were used for extraction of molybdenum from molybdenite roaster scrubber solutions. Molybdenum is an impurity in many uranium ores. When uranium ores are acid leached, some molybdenum reports to the acid leach solution. The tertiary amines readily available during the 1950's and early 1960's tended to have an amine-molybdenum complex with poor solubility in aliphatic diluents (kerosene). Several Russian researchers worked with acid leaching of oxide ores. In many cases the acidity was sufficient for most of the molybdenum to be in a cationic form. Therefore, the cation exchanger (di, 2, ethylhexyl phosphoric acid (DEHPA)) received much study regarding the recovery of molybdenum from complex acid solutions. Karpacheva et al. 5 determined that in acid solutions the molybdenum was not present as the simple molybdenyl cation but, the molybdenum was present as polymeric cations. The co-extraction of iron is a major problem when using DEHPA. The authors noted that in a nitric acid system, the acid concentration needs to equal or exceed 3 molar to prevent significant iron extraction. Other authors 6 reported on the benefit of modifiers in reducing the iron coextraction, e.g. tributyl phosphate, dibutyl butyl phosphonate. 5 Karpacheva, S. M. et al., “Extraction of molybdenum and iron (III) by di-2-ethylhexyl hydrogen phosphate,” Russian Journal of Inorganic Chemistry, V 12, 7, p 1014-1016 (1967). 6 Chiola, Vincent, “Separation of molybdenum values from tungsten values by solvent extraction,” U.S. Pat. No. 3,607,008 (1971). Palant et al. 7 made a detailed study of the extraction of molybdenum by DEHPA. The solutions studies were prepared by dissolving MoO 3 in sulfuric acid, hydrochloric acid, or nitric acid solutions. Palant, A. A. et. al. “Extraction of molybdenum (VI) with bis(2-ethylhexyl) hydrogen phosphate from an acidic medium,” Inst. Metall. im. Baikova, Moskow, USSR, Report deposited (1979) pp. 1-19. Amine exchange has also received much study during the past 40 to 50 years. The difficulties presented by the poor solubility of the amine-molybdenum complex were addressed by using aromatic diluents. MacInnis et al. 8 used tri-n-capryl amine (Alamine 336) with the aromatic diluent #28 9 . The authors discuss amine extraction of a complex sulfate-bearing anion. At pH values of 3 and higher, they determined that the ion exchange type mechanism shown in Equation I below predominates. 8 MacInnis, M. B., Kim, T. K., and Laferty, J. M., “The use of solvent extraction for the production and recovery of high-purity ammonium paramolybdate from normal alkali molybdate solution,” First Intl Conf on Chemistry and Uses for Molybdenum, p. 56-58 (1973). 9 Aromatic diluent #28 is a solvent from 1960 available from Missouri Solvents & Chemicals. The solvent had a boiling range of 165 to 193° C., a flash point of 122° F., a Kauri butanol value of 73, and was 74% aromatics. in-line-formulae description="In-line Formulae" end="lead"? 2MoS 2 +6H 2 O+9O 2 →2H 2 MoO 4 ↓+4H 2 SO 4 (I) in-line-formulae description="In-line Formulae" end="tail"? At pH values below 3, they postulate that the following occurs along with Equation I. in-line-formulae description="In-line Formulae" end="lead"? n (R 3 NH.HSO 4 )+(Mo x O y H z ) n .(SO 4 ) m →(R 3 NH) n .(Mo x O y H z ) n .(HSO4) n .(SO 4 ) m (II) in-line-formulae description="In-line Formulae" end="tail"? Equation II infers that (Mo x O y H z ) n .(SO 4 ) m is not ionized and Maclnnis postulates some cation transfer. This postulation is based on the fact that 35 S tagged sulfur was found to transfer both from the organic to the aqueous phase and from the aqueous to the organic phase. Litz found in 1970, that tris, tridecyl amine could be used successfully for molybdenum solvent extraction with an aliphatic diluent. There still was potential for formation of insoluble molybdenum-amine complexes, but the molybdenum-tris tridecyl amine complex's solubility in the diluent was much higher than with other tertiary amines. Tris tridecyl amine in an aliphatic diluent was used in a number of pilot circuits for molybdenum solvent extraction from roaster scrubber solutions and to recover byproduct from uranium leach solutions, but it may never have been used in a commercial circuit. The transfer of sulfate from strongly acid solutions is a problem with using amines. Also, the amines are relatively nonselective and will transfer silicon, phosphorus, and arsenic probably as heteropoly compounds. The coextraction of silicon and subsequent solids precipitation during stripping has been a major problem during other studies. The silicon problem was addressed by filtration of the first stripping stage mixture prior to advancing to the settler. Sulfate transfer was high because the solvent could not be fully loaded with molybdenum, i.e., to avoid diluent-insoluble molybdenum-amine complexes, the sulfate transfer was large. Efficient recovery of chemical-grade ammonium dimolybdate (ADM) requires high purity feed solutions containing 200 to 230 g Mo per liter. Impurities in the solution must be removed to avoid inclusion in the ADM. Impurities, that form hydroxides or sulfides, can be removed by additions or pH-control. Other impurities will build up and unless the mother liquor is bled from the crystallization will report to the ADM. Typical molybdenum solvent extraction systems acidulate the feed solution, if necessary, prior to contact with the extractant in the mixer. Generally this means that the extractant is converted to the bisulfate form by acid in the feed solution and then the desired anion exchanges with the bisulfate. When molybdenum is acidulated there is potential for localized high acid concentrations that can form sulfate-bearing molybdenum species. It is an object of the present invention to provide an integrated process for producing high purity ammonium dimolybdate or molybdenum oxide through a process that includes the pressure oxidation of low grade molybdenite concentrates or molybdenum intermediates. It is a further object of the present invention to provide an improved molybdenum pressure oxidation process which produces a high purity product at reduced capital and operating costs. It is a further object of the present invention to provide an improved solvent extraction method which rejects sulfate and metallic impurities by extracting the molybdenum in an ionic form that contains no sulfate. |
<SOH> SUMMARY OF THE INVENTION <EOH>The objects set forth above as well as further and other objects and advantages of the present invention are achieved by the present invention now described in summary fashion and with further examples below in preferred embodiments of the practice of the invention. The present invention provides a process of producing a high purity ammonium dimolybdate or molybdenum oxide through the pressure oxidation of low grade molybdenite concentrates or molybdenum intermediates. The process entails oxidizing the molybdenite concentrates or intermediates in an autoclave operating at greater than 50 p.s.i. oxygen overpressure, preferably between 80-120 p.s.i., at a temperature greater than 200° C., preferably between 210-220° C. to effect almost complete oxidation of the concentrate while optimizing the process chemistry and autoclave conditions to solubilize as little of the molybdenum values as possible. A method of maximizing the insoluble molybdenum values is disclosed in U.S Patent Application entitled “Autoclave Control Mechanisms for Pressure Oxidation of Molybdenite” which is incorporated by reference herein (and a copy of which is provided at Appendix A hereto). The resulting autoclave discharge has greater than 99% of the molybdenum concentrates oxidized and greater than 80% of the molybdenum values insoluble. The autoclave discharge is then subjected to an alkaline leaching of the POX residue using sodium carbonate and sodium hydroxide. More than 99% of the molybdenum dissolves. The molybdenum in this alkaline solution is recovered readily using a secondary amine solvent, di,tridecyl amine (DTDA). The molybdenum is loaded into the organic phase at 4.0 to 4.5 pH. The molybdenum-loaded organic is stripped with ammonium hydroxide to produce solutions suitable for recovery of chemical-grade ADM and ultimately chemical-grade molybdenum oxide. Alternatively, the autoclave discharge may be subjected to an ammoniacal leaching of the POX residue. More than 99% of the molybdenum dissolves. Most of the cosolubilized impurities are precipitated from the ammoniacal leach solution. The solution is evaporated to crystallize chemical grade ADM. An additional route is provided when the leach solution contains more sulfate than is desirable for crystallization of chemical-grade ADM, producing a product suitable for technical grade ADM and ultimately technical grade molybdenum oxide. Alternatively, the POX residue may be subjected to an alkaline leach with sodium carbonate and sodium hydroxide before a liquid-solid separation step such that all of the molybdenum is soluble and the copper and iron transfer to the solids. More than 98% of the molybdenum is transferred to the filtrate from this neutralization. The molybdenum is readily recoverable using the DTDA solvent extraction process. The ammoniacal strip solutions from the DTDA extraction are suitable for recovery of chemical-grade ADM and ultimately chemical-grade molybdenum oxide. Cementation by scrap iron can be used to readily recover the copper either from the raffinate produced from molybdenum solvent extraction of the POX leach solution or directly from the POX leach solution. Gold and silver values transfer to the final leached solid residue produced by each embodiment and are recyclable to a copper smelter. Most of the rhenium, arsenic, and phosphorus are dissolved regardless of the leaching conditions. Other objects, features and advantages of the invention will be apparent from the following description of preferred embodiments thereof, including illustrative non-limiting examples of the practice of the process. |
Liquid usage monitoring |
A method and apparatus for monitoring usage of liquids of high value or sensitive nature which are applied in repeated small controlled volumes are provided by monitoring and recording parameters including the number of applications, purging, priming and cleaning steps and the usage of liquid supply and circulation pumps. The monitored parameters present a record of the total liquid usage. The recorded usage of the liquid pumps can be cross-checked with the volumes indicated by the other parameters so as to highlight any disagreement between the respective indications of total liquid volumes employed, thereby alerting the user to possible operating problems and permitting prompt remedial action to be taken. |
1. A method of monitoring the usage of a liquid applied in repeated small controlled volumes from an application apparatus which provides for purging, priming and cleaning steps, which apparatus includes at least one liquid pump (17) for supply or circulation of liquid, said method comprising the steps of: monitoring one or more parameters of liquid usage; recording the one or more parameters of liquid usage in a transmittable form; wherein the one or more parameters of liquid usage include the periods of usage of each liquid pump (17). 2. A method as claimed in claim 1, in which the one or more parameters of liquid usage further include the number of on and off operations of switches and control valves (13) in the apparatus. 3. A method as claimed in claim 1, in which the one or more parameters of liquid usage further include (i) the number of applications, and (ii) the number of purging, priming and cleaning steps. 4. A method as claimed in claim 1, in which the one or more parameters of liquid usage further include the rate of liquid transfer through at least one flow meter (12, 31). 5. A method as claimed in claim 1, further comprising the step of: cross-checking a total volume of liquid employed, which is determined from the periods of usage of each liquid pump (17) and a liquid handling capacity of each pump (17) with an estimated usage of liquid determined by adding (i) the product of multiplying the number of applications by a typical liquid volume used in each individual application and (ii) the product of multiplying the number of purging, priming and cleaning steps by a volume routinely consumed in these steps. 6. A method as claimed in claim 1, in which the liquid is supplied from a replaceable container holding a defined initial liquid volume. 7. A method as claimed in claim 6, in which the container is returned to an approved supplier for refilling. 8. A method as claimed in claim 7, in which the container is sealed after approved refilling to prevent tampering with its contents. 9. A method as claimed in claim 6, in which the container forms an integral part of the apparatus employing the liquid. 10. A method as claimed in claim 1, in which the volumes and/or associated actions of the respective elements are monitored and controlled by at least one microprocessor. 11. A method as claimed in claim 10, in which a microprocessor is housed within the application apparatus. 12. A method as claimed in claim 11, in which one microprocessor forms part of the apparatus as such and another microprocessor is located remotely. 13. A method as claimed in claim 12, in which the microprocessors are configured to receive data electronically by one or more of a direct wiring connection, dedicated telephone line, radio link or internet link. 14. A method as claimed in claim 10, in which a microprocessor is configured to transmit warning signals. 15. A method as claimed in claim 10, in which a serial number is recorded on one or more liquid containers of the application apparatus in such a way that the serial number(s) can also be transmitted to the microprocessor. 16. A method as claimed in claim 15, in which the microprocessor is programmed so as to permit operation of the apparatus only if it recognizes one or more liquid containers as having an approved serial number. 17. A method as claimed in claim 10, in which the microprocessor is programmed to demand a password before opening up the apparatus to a replacement container. 18. A method as claimed in claim 10, in which the microprocessor is programmed to alert an operator to the approach of an expiration date of the liquid. 19. A method as claimed in claim 10, in which the microprocessor is programmed to stop supply of the liquid at the expiration date of the liquid. 20. A method as claimed in claim 1, in which a homing device associated with one or more liquid containers transmits a signal to indicate its whereabouts. 21. Apparatus for monitoring the usage of a liquid applied in repeated small controlled volumes, said apparatus including: one or more liquid pumps (17) for supply or circulation of liquid; and at least one microprocessor (50) to monitor and record in a transmittable form one or more parameters of liquid usage, wherein the one or more parameters of liquid usage include the periods of usage of each liquid pump (17). 22. Apparatus as claimed in claim 21, in which the one or more parameters of liquid usage further include (i) the number of on and off operations of switches and control valves (13) in the apparatus, (ii) the number of applications, (iii) the number of purging, priming and cleaning steps, (iv) the rate of liquid transfer through at least one flow meter (12, 31). 23. Apparatus as claimed in claim 21, wherein the apparatus is capable of cross-checking a total volume of liquid employed, which is determined from the periods of usage of each liquid pump (17) and a liquid handling capacity of each pump (17) with an estimated usage of liquid determined by adding (i) the product of multiplying the number of applications by a typical liquid volume used in each individual application and (ii) the product of multiplying the number of purging, priming and cleaning steps by a volume routinely consumed in these steps. 24. Apparatus as claimed in claim 21, in which one microprocessor forms part of the apparatus and another microprocessor is located remotely. 25. Apparatus as claimed in claim 21, which includes a replaceable container holding a defined initial liquid volume. 26. Apparatus as claimed in claim 21, which includes a homing device which transmits a signal to indicate its whereabouts. 27. An inkjet printer including an apparatus as claimed in claim 21. |
<SOH> BACKGROUND OF THE INVENTION <EOH>There is a wide variety of processes and procedures in which the level of usage of a liquid material needs to be monitored. In its simplest form the need is to ensure the presence of sufficient liquid to perform the required duty, for example in a storage vessel such as a vehicle fuel tank. In such applications a float or other liquid level indicator monitors the liquid volume, albeit without great precision, and may trigger a signal to indicate when the volume falls to a low level. Somewhat more precise monitoring has been provided by flow meters, for example including a rotor or turbine in a liquid conduit, which can be linked directly or indirectly to signalling and control elements. The number of rotations are counted and used to generate a signal indicating the volume flow. Such rotary meters have been well developed in the field of fuel pumps, especially for vehicle filling stations, and provide a sufficiently precise measurement for supply of relatively high liquid volumes. Various features have been adopted for the electrical control circuits of such pumps. For example U.S. Pat. No. 3,990,607 relates to a relay-controlled circuit of a gasoline pump in which momentary closure of a key-operated switch is required before normal operation of the pump can be reinstated after a dispensing operation. For certain liquids a higher level of monitoring precision is required than for such commodities as gasoline. These liquids include pharmaceuticals, certain chemical treatment agents, radioactive or toxic materials, and special purpose materials, for example special purpose printing inks as may be used in inkjet printers. In general such materials are applied in dosed quantities, i.e. a small controlled volume is applied repeatedly from a source container which is refilled or replaced as the liquid is consumed. In the field of inkjet printing it is customary to monitor the remaining volumes of ink in supply cartridges so as to warn the user of when to fit a replacement cartridge. In its simplest form the monitoring is provided by a small inspection window in the cartridge. More sophisticated monitoring has been proposed in certain instances. U.S. Pat. No. 6,045,206 discloses a method of operating an inkjet printer comprising the steps of using a maintenance algorithm to control timing of a maintenance action, keeping a historical log of an operating characteristic of the printer over a period of time, and changing the maintenance algorithm for subsequent use by the printer based upon the historical log. A complete record of the usage of liquid materials requires not just an awareness of operating characteristics and of volumes directly applied, but also any wastage resulting from such steps as priming, purging and cleaning the apparatus used in the application. |
<SOH> SUMMARY OF THE INVENTION <EOH>According to the invention there is provided a method of monitoring the usage of a liquid applied in repeated small controlled volumes from application apparatus which provides for purging, priming and cleaning steps, which apparatus includes one or more liquid pumps for supply or circulation of liquid and in which method parameters of usage are monitored and recorded in transmittable form, the monitored parameters including the number of applications, the number of purging, priming and cleaning steps and the periods of usage of each liquid pump. The invention further provides apparatus for monitoring the usage of a liquid applied in repeated small controlled volumes, which apparatus provides for purging, priming and cleaning steps and includes one or more liquid pumps for supply or circulation of liquid, in which parameters of usage are monitored and recorded in transmittable form, the monitored parameters including the number of applications, the number of purging, priming and cleaning steps and the periods of usage of each liquid pump. The objective is to ensure that the monitored parameters represent a substantially complete record of the liquid usage. Given that the typical liquid volume used in each individual application is known, recordal of the number of applications shows the volumes directly used in the application. The volumes used indirectly, and which may be regarded as waste, are shown by the total of any volumes used in purging, priming and cleaning the apparatus. These waste volumes can either be measured directly, for example by measuring an increase in weight of an absorbent material used in cleaning the apparatus, or indirectly by counting the number of purging, priming and cleaning steps and multiplying these by the volumes routinely consumed in these steps. A particular advantage of the invention is that recordal of the usage of liquid pumps, whose liquid handling capacity can also be determined, provides an indication of total volumes employed, which can be cross-checked with the volumes indicated by the other parameters. Any disagreement between the respective indications of total liquid volumes employed alerts the user to possible operating problems, for example errors or malfunctioning of the apparatus, and permits prompt remedial action to be taken. In order to increase the level of precision of the usage monitoring, or to provide additional cross-checks on the level of usage, it may also be desirable to monitor other parameters, including for example the number of on and off operations of switches and control valves in the apparatus. The volumes and/or associated actions of the respective elements are preferably monitored and controlled by one or more microprocessors, for example a programmable logic controller. The microprocessors can be housed within or alongside the application apparatus, but can be located remote from it. In one convenient arrangement one microprocessor forms part of the apparatus as such and another microprocessor is located remotely. A remote location is beneficial in permitting a reduction in on-site inspection time by local personnel and in permitting several application stations to be monitored and controlled from a single point. The microprocessors can be configured to receive data electronically by such transmission routes as a direct wiring connection, dedicated telephone line, radio link or internet link. |
Novel azole or triazole derivatives, method for preparing same and use thereof as fungicides |
The invention concerns novel azole or triazole derivatives of formula (I), wherein X, Ar1, Ar2, Ar3, A, B, and R1 are as defined herein, their preparation method and their use as fungicides. |
1-15. (canceled) 16. A compound of the formula (I): wherein X is nitrogen or CH; Ar1 is a carbocyclic or heterocyclic aryl, non-substituted or substituted by one or more R2, R3 or R4; Ar2is phenylene or naphthalene, non-substituted or substituted by one or more R5, R6 or R7; Ar3 is a carbocyclic or heterocyclic aryl, non-substituted or substituted by one or more R8, R9 or R10; A is (C1-C4)-alkylene or C(O); B is (C1-C4)-alkylene-CH═CH— or (C1-C4)-alkylene-cyclopropylene, said cyclopropylene or —CH═CH— is optionally substituted by R2 or R3; R1 is hydrogen, —SO3H or (C1-C6)-alkyl, non-substituted or substituted by R2; and wherein R2, R3, R4, R5, R6, R7, R8, R9 or R10, are the same or different and are independently selected from the group consisting of: fluorine, chlorine, bromine, cyano, mono- bi- or trihalogeno(C1-C8)alkyl, mono- bi- or trihalogeno(C1-C8)-alkyloxy, hydroxy, nitro, carboxyl, formyl, —SO3H, —OSO3H, (R11O)2P(O)—, (R11O)2P(O)—O—, amino, (C1-C8)-alkylamino, di((C1-C8)alkyl)amino, (C5-C14)-aryl-(C1-C6)-alkylenamino or (C5-C14)-arylamino, (C1-C8)-alkyl, (C5-C14)-aryl, a heterocycle optionally substituted by oxo, (C5-C14)-aryl-(C1-C6)alkyl, amino-(C1-C6)-alkyl, (C1-C8)-alkylamino-(C1-C6)-alkyl, di-((C1-C8)alkyl)amino-(C1-C6)-alkyl, hydroxy-(C1-C6)alkyl, (C1-C6)-alkyloxy-(C1-C6)-alkyl, (C1-C8)-alkyloxy optionally interrupted by one or more oxygen atoms, (C5-C14)-aryl-(C1-C6)-alkylenoxy, (C5-C14)-aryloxy, hydroxy-(C1-C6)alkylenoxy, (C1-C6)-alkyloxy-(C1-C6)alkylenoxy, amino-(C1-C6)-alkylenoxy, (C1-C6)-alkylamino-(C1-C6)-alkylenoxy, di((C1-C8)-alkyl)amino-(C1-C6)-alkylenoxy, methylenedioxy, (C1-C6)-alkyloxycarbonyl, (C1-C6)-alkylcarbonyl, (C5-C14)aryl-(C1-C6)-alkylenecarbonyl, (C5-C14)-arylcarbonyl, (C1-C6)-alkylaminocarbonyl, (C1-C6)alkanoylamino, (C1-C6)-alkylsulfonylamino, (C5-C14)-arylsulfonylamino, (C5-C14)-aryl-(C1-C6)-alkylenesulfonylamino, (C1-C6)-alkylaminosulfonyl, (C5-C14)-aryl-(C1-C6)-alkylenaminosulfonyl, (C1-C6)-alkylsulfonyl, (C5-C14)-aryl-(C1-C8)-alkylenesulfonyl or (C5-C14)-aryl-sulfonyl, said alkyl, aryl or heterocycle are optionally substituted; and wherein R11 is hydrogen, (C1-C10)-alkyl, (C6-C14)-aryl or (C6-C14)-aryl-(C1-C6)-alkyl, or an enantiomer, a stereoisomer, a tautomer or a mixture thereof, or a physiologically acceptable salt, a solvate or a derivative thereof, or a prodrug thereof. 17. The compound of formula (I) as defined in claim 16, wherein A is —CH2—, B is —CH2—CH═CH— or —CH2-cyclopropyl- and Ar1 is phenyl and Ar2 is phenylene or a physiologically acceptable salt thereof. 18. The compound of formula (I) as defined in claim 16 having the structure (IA): wherein, B, X, Ar3, R5 and R1 are as defined in claim 1 and R2 and R3 are the same or different and are independently selected from the group consisting of: fluorine, chlorine, bromine or a physiologically acceptable salt thereof. 19. The compound of formula (I) as defined in claim 16, wherein R2 and R3 are chlorine, X is CH or N and Ar3 is phenyl, non-substituted or substituted by R8 as defined in claim 1, or a physiologically acceptable salt thereof. 20. The compound of formula (I) as defined in claim 16, wherein R1 is hydrogen, methyl or ethyl and wherein methyl or ethyl is optionally substituted by F, OH, NH2, (C1-C6)-alkyloxy, (C1-C6)-alkylamino, di-(C1-C6)-alkylamino, pyrrolidino or 2-oxo-pyrrolidino, or a physiologically acceptable salt thereof. 21. The compound of formula (I) as defined in claim 16, wherein Ar3 is phenyl, non substituted or substituted by R8 representing —Cl, —F, CN, —CF3, —OCF3, —OH, —NH2, (C1-C6)-alkyloxy, (C1-C6)-alkylamino, or di-(C1-C6)-alkylamino or a heterocycle chosen from: physiologically acceptable salt thereof. 22. The compound of formula (I) as defined in claim 16, selected from the group consisting of: cis-4-[[2-(2,4-dichlorophenyl)-2-(1H-imidazol-1-ylmethyl)-1,3-dioxolan-4-yl]methoxy]-N-methyl-N-(3-phenyl-2(E)-propenyl)-benzenemethanamine; 4-[[2-(2,4-dichlorophenyl)-2-(1H-imidazol-1-ylmethyl)-1,3-dioxolan-4-yl]methoxy]-N-methyl-N- [3-(4-chloro-phenyl-2(E)-propenyl]-1-benzenemethanamine; cis-4-[3-[[[4-[[2-(2,4-dichlorophenyl)-2-(1H-imidazol-1-ylmethyl)-1,3-dioxan-4-yl]methoxy]phenyl]methyl]-methylamino]-1(E)-propenyl]-phenol; cis-4-[[2-(2,4-dichlorophenyl)-2-(1H-imidazol-1-ylmethyl)-1,3-dioxolan-4-yl]methoxy]-N-(3-phenyl-2(E)-propenyl)-benzenemethanamine; cis-4-[3-[[[4-[[2-(2,4-dichlorophenyl)-2-(1H-imidazol-1-ylmethyl)-1,3-dioxan-4-yl]methoxy]phenyl]methyl]-methylamino]-1(E)-propenyl]-phenol phosphate and trifluoroacetate; 4-[[2-(2,4-dichlorophenyl)-2-(1H-imidazol-1-ylmethyl)-1,3-dioxolan-4-yl]methoxy]-N-methyl-N-(3-phenyl-2(E)-propenyl)-1-naphthalenemethanamine; cis-4-[[2-(2,4-dichlorophenyl)-2-(1H-imidazol-1-ylmethyl)-1,3-dioxolan-4-yl]methoxy]-N-(3-phenyl-2(E)-propenyl)-4-chloro-benzenemethanamine; cis-N-(2-aminoethyl)-4-[[2-(2,4-dichlorophenyl)-2-(1H-imidazol-1-ylmethyl)-1,3-dioxolan-4-yl]methoxy]-N-(3-phenyl-2(E)-propenyl)-benzenemethanamine trifluoroacetate; cis-N-(2-aminoethyl)-N-[3-(4-chlorophenyl)-2(E)-propenyl]-4-[[2-(2,4-dichlorophenyl)-2-(1H-imidazol-1-ylmethyl)-1,3-dioxolan-4-yl]methoxy]-benzenemethanamine; and cis-2-[[[4-[[2-(2,4-dichlorophenyl)-2-(1H-imidazol-1-ylmethyl)-1,3-dioxolan-4-yl]methoxy]phenyl]methyl](3-phenyl-2(E)-propenyl)amino]-ethanol. 23. A process for the preparation of a compound of formula (I) according to claim 16 comprising: reacting a compound of formula (II): wherein Y is a leaving group and X and Ar1 are as defined in claim 16, in the presence of a base, with a compound of formula (III): HO-Ar2-A-N(R1)-B-Ar3 (III), wherein Ar2, A, R1, B and Ar3 are as defined in claim 16, to obtain the corresponding compound of formula (I). 24. A process for the preparation of a compound of formula (I) according to claim 16 comprising: reacting a compound of formula (II′): wherein Y is a leaving group and X, R2 and R3 are as defined in claim 16, with a compound of formula (III′): HO—C6H4—CHO, (III′) in the presence of a base, the phenylene of (III′) is optionally substituted by R5 to obtain a compound of formula (IIa): reacting compound of formula (IIa) with R1—NH2; reducing the resulting product in the presence of a reducing agent such as NaBH3CN, to obtain the amine of formula (IIb): reacting the compound of formula (IIb) either with a derivative of formula: OHC—CH═CH—C6H4—R8 or OHC-(cyclopropyl)-C6H4—R8 followed by a reduction reaction in the presence of a reducing agent such as NaBH3CN or pyridine.BH3; or reacting compound of formula (lIb) with a compound of formula: AcO—CH2—CH═CH—C6H4—R8 in the presence of a palladium derivative to obtain the following compound of formulae (IAA) or (IAB): wherein X, R1, R2, R3, R5 and R8 are as defined in claim 16. 25. A process for the preparation of compound of formula (I) according to claim 16 comprising: reacting a compound of formula (IIa): with an amine of formula R′1—(CH2)2—NH2, wherein R′1 is F, OH, amine or a suitably protected alkylamine, pyrrolidino or 2-oxo-pyrrolidino or a dialkylamine, to obtain a compound of formula (IIc) in the presence of a reducing agent such as NaBH3CN; reacting compound of formula (IIc) with a conjugated aldehyde of formula OHC—CH═CH—C6H4—R8 to obtain a compound of formula (IAB): wherein X, R2, R3, R5 and R8 are as defined in claim 16. 26. A method for the treatment of a fungal disease comprising administering to a patient in need of such treatment a therapeutically effective amount of a compound of the formula (I): wherein X is nitrogen or CH; Ar1 is a carbocyclic or heterocyclic aryl, non-substituted or substituted by one or more R2, R3 or R4; Ar2 is phenylene or naphthalene, non-substituted or substituted by one or more R5, R6 or R7; Ar3 is a carbocyclic or heterocyclic aryl, non-substituted or substituted by one or more R8, R9 or R10; A is (C1-C4)-alkylene or C(O); B is (C1-C4)-alkylene-CH═CH— or (C1-C4)-alkylene-cyclopropylene, said cyclopropylene or —CH═CH— is optionally substituted by R2 or R3; R1 is hydrogen, —SO3H or (C1-C6)-alkyl, non-substituted or substituted by R2; and wherein R2, R3, R4, R5, R6, R7, R8, R9 or R10, are the same or different and are independently selected from the group consisting of: fluorine, chlorine, bromine, cyano, mono- bi- or trihalogeno(C1-C8)alkyl, mono- bi- or trihalogeno(C1-C8)-alkyloxy, hydroxy, nitro, carboxyl, formyl, —SO3H, —OSO3H, (R11O)2P(O)—, (R11O)2P(O)—O—, amino, (C1-C8)-alkylamino, di((C1-C8)alkyl)amino, (C5-C14)-aryl-(C1-C6)-alkylenamino or (C5-C14)-arylamino, (C1-C8)-alkyl, (C5-C14)-aryl, a heterocycle optionally substituted by oxo, (C5-C14)-aryl-(C1-C6)alkyl, amino-(C1-C6)-alkyl, (C1-C8)-alkylamino-(C1-C6)-alkyl, di-((C1-C8)alkyl)amino-(C1-C6)-alkyl, hydroxy-(C1-C6)alkyl, (C1-C6)-alkyloxy-(C1-C6)-alkyl, (C1-C8)-alkyloxy optionally interrupted by one or more oxygen atoms, (C5-C14)-aryl-(C1-C6)-alkylenoxy, (C5-C14)-aryloxy, hydroxy-(C1-C6)alkylenoxy, (C1-C6)-alkyloxy-(C1-C6)alkylenoxy, amino-(C1-C6)-alkylenoxy, (C1-C6)-alkylamino-(C1-C6)-alkylenoxy, di((C1-C8)-alkyl)amino-(C1-C6)-alkylenoxy, methylenedioxy, (C1-C6)-alkyloxycarbonyl, (C1-C6)-alkylcarbonyl, (C5-C14)aryl-(C1-C6)-alkylenecarbonyl, (C5-C14)-arylcarbonyl, (C1-C6)-alkylaminocarbonyl, (C1-C6)alkanoylamino, (C1-C6)-alkylsulfonylamino, (C5-C14)-arylsulfonylamino, (C5-C14)-aryl-(C1-C6)-alkylenesulfonylamino, (C1-C6)-alkylaminosulfonyl, (C5-C14)-aryl-(C1-C6)-alkylenaminosulfonyl, (C1-C6)-alkylsulfonyl, (C5-C14)-aryl-(C1-C8)-alkylenesulfonyl or (C5-C14)-aryl-sulfonyl, said alkyl, aryl or heterocycle are optionally substituted; and wherein R11 is hydrogen, (C1-C10)-alkyl, (C6-C14)-aryl or (C6-C14)-aryl-(C1-C6)-alkyl, or an enantiomer, a stereoisomer, a tautomer or a mixture thereof, or a physiologically acceptable salt, a solvate or a derivative thereof, or a prodrug thereof, optionally in combination with a pharmaceutically acceptable carrier. 27. The method as defined in claim 26 wherein said fungal disease is caused by Candida albicans, Candida glabrata, krusei, tropicalis, pseudotropicalis, parapsilosis, Aspergillus, Aspergillus flavus, Aspergillus niger, Cryptococcus neoformans, Microsporum canis, Trichophyton rubrun or Trichophyton mentagrophyte. 28. The method as defined in claim 26 wherein said fungal disease is selected from the group consisting of candidoses, cryptococcoses, bronchopulmonary and pulmonary aspergilloses and invasive aspergilloses in immunodeficient individuals. 29. The method as defined in claim 28 wherein said candidoses is selected from the group consisting of digestive, urinary, vaginal and cutaneous candidoses. 30. The method as defined in claim 28 wherein said cryptococcoses is selected from the group consisting of neuromeningeal, pulmonary and cutaneous cryptococcoses. 31. The method as defined in claim 26 wherein said compound of formula (I) is having A is —CH2—, B is —CH2—CH═CH— or —CH2-cyclopropyl- and Ar1 is phenyl and Ar2 is phenylene or a physiologically acceptable salt thereof. 32. The method as defined in claim 26 wherein said compound of formula (I) is having the structure (IA): wherein, B, X, Ar3, R5 and R1 are as defined in claim 26 and R2 and R3 are the same or different and are independently selected from the group consisting of: fluorine, chlorine, bromine or a physiologically acceptable salt thereof. 33. The method as defined in claim 26, wherein said compound of formula (I) is having R2 and R3 are chlorine, X is CH or N and Ar3 is phenyl, non-substituted or substituted by R8 as defined in claim 26, or a physiologically acceptable salt thereof. 34. The method as defined in claim 26, wherein said compound of formula (I) is having R1 is hydrogen, methyl or ethyl and wherein methyl or ethyl is optionally substituted by F, OH, NH2, (C1-C6)-alkyloxy, (C1-C6)-alkylamino, di-(C1-C6)-alkylamino, pyrrolidino or 2-oxo-pyrrolidino, or a physiologically acceptable salt thereof. 35. The method as defined in claim 26, wherein said compound of formula (I) is having Ar3 is phenyl, non substituted or substituted by R8 representing —Cl, —F, CN, —CF3, —OCF3, —OH, —NH2, (C1-C6)-alkyloxy, (C1-C6)-alkylamino, or di-(C1-C6)-alkylamino radical or a heterocycle chosen from: or a physiologically acceptable salt thereof. 36. The method as defined in claim 26, wherein said compound of formula (I) is selected from the group consisting of: cis-4- [[2-(2,4-dichlorophenyl)-2-(1H-imidazol-1-ylmethyl)-1,3-dioxolan-4-yl]methoxy]-N-methyl-N-(3-phenyl-2(E)-propenyl)-benzenemethanamine; 4-[[2-(2,4-dichlorophenyl)-2-(1H-imidazol-1-ylmethyl)-1,3-dioxolan-4-yl]methoxy]-N-methyl-N-[3-(4-chloro-phenyl-2(E)-propenyl]-1-benzenemethanamine; cis-4-[3-[[[4-[[2-(2,4-dichlorophenyl)-2-(1H-imidazol-1-ylmethyl)-1,3-dioxan-4-yl]methoxy]phenyl]methyl]-methylamino]-1(E)-propenyl]-phenol; cis-4-[[2-(2,4-dichlorophenyl)-2-(1H-imidazol-1-ylmethyl)-1,3-dioxolan-4-yl]methoxy]-N-(3-phenyl-2(E)-propenyl)-benzenemethanamine; cis-4-[3-[[[4-[[2-(2,4-dichlorophenyl)-2-(1H-imidazol-1-ylmethyl)-1,3-dioxan-4-yl]methoxy]phenyl]methyl]-methylamino]-1(E)-propenyl]-phenol phosphate and trifluoroacetate; 4-[[2-(2,4-dichlorophenyl)-2-(1H-imidazol-1-ylmethyl)-1,3-dioxolan-4-yl]methoxy]-N-methyl-N-(3-phenyl-2(E)-propenyl)-1-naphthalenemethanamine; cis-4-[[2-(2,4-dichlorophenyl)-2-(1H-imidazol-1-ylmethyl)-1,3-dioxolan-4-yl]methoxy]-N-(3-phenyl-2(E)-propenyl)-4-chloro-benzenemethanamine; cis-N-(2-aminoethyl)-4-[[2-(2,4-dichlorophenyl)-2-(1H-imidazol-1-ylmethyl)-1,3-dioxolan-4-yl]methoxy]-N-(3-phenyl-2(E)-propenyl)-benzenemethanamine trifluoroacetate; cis-N-(2-aminoethyl)-N-[3-(4-chlorophenyl)-2(E)-propenyl]-4-[[2-(2,4-dichlorophenyl)-2-(1H-imidazol-1-ylmethyl)-1,3-dioxolan-4-yl]methoxy]-benzenemethanamine; and cis-2-[[[4-[[2-(2,4-dichlorophenyl)-2-(1H-imidazol-1-ylmethyl)-1,3-dioxolan-4-yl]methoxy]phenyl]methyl](3-phenyl-2(E)-propenyl)amino]-ethanol. 37. A pharmaceutical composition comprising at least one compound of formula (I) as defined in claim 16 or an enantiomer, a stereoisomer, a tautomer or a mixture thereof, or a physiologically acceptable salt, a solvate or a derivative thereof, or a prodrug thereof in combination with one or more pharmaceutically acceptable carriers. 38. A compound of formula: wherein X is nitrogen or CH; D is —CHO, —CH2NH—R1 or —CH2NH(CH2)2R′1; R1 is hydrogen, —SO3H or (C1-C6)-alkyl, non-substituted or substituted by R2; R′1 is F, OH, amine or a suitably protected alkylamine, pyrrolidino or 2-oxo-pyrrolidino or a dialkylamine; R2, R3 or R5 are the same or different and are independently selected from the group consisting of: fluorine, chlorine, bromine, cyano, mono- bi- or trihalogeno(C1-C8)alkyl, mono- bi- or trihalogeno(C1-C8)-alkyloxy, hydroxy, nitro, carboxyl, formyl, —SO3H, —OSO3H, (R11O)2P(O)—, (R11O)2P(O)—O—, amino, (C1-C8)-alkylamino, di((C1-C8)alkyl)amino, (C5-C14)-aryl-(C1-C6)-alkylenamino or (C5-C14)-arylamino, (C1-C8)-alkyl, (C5-C14)-aryl, a heterocycle optionally substituted by oxo, (C5-C14)-aryl-(C1-C6)alkyl, amino-(C1-C6)-alkyl, (C1-C8)-alkylamino-(C1-C6)-alkyl, di-((C1-C8)alkyl)amino-(C1-C6)-alkyl, hydroxy-(C1-C6)alkyl, (C1-C6)-alkyloxy-(C1-C6)-alkyl, (C1-C8)-alkyloxy optionally interrupted by one or more oxygen atoms, (C5-C14)-aryl-(C1-C6)-alkylenoxy, (C5-C14)-aryloxy, hydroxy-(C1-C6)alkylenoxy, (C1-C6)-alkyloxy-(C1-C6)alkylenoxy, amino-(C1-C6)-alkylenoxy, (C1-C6)-alkylamino-(C1-C6)-alkylenoxy, di((C1-C8)-alkyl)amino-(C1-C6)-alkylenoxy, methylenedioxy, (C1-C6)-alkyloxycarbonyl, (C1-C6)-alkylcarbonyl, (C5-C14)aryl-(C1-C6)-alkylenecarbonyl, (C5-C14)-aryl-carbonyl, (C1-C6)-alkylaminocarbonyl, (C1-C6)alkanoylamino, (C1-C6)-alkylsulfonylamino, (C5-C14)-arylsulfonylamino, (C5-C14)-aryl-(C1-C6)-alkylenesulfonylamino, (C1-C6)-alkylaminosulfonyl, (C5-C14)-aryl-(C1-C6)-alkylenaminosulfonyl, (C1-C6)-alkylsulfonyl, (C5-C4)-aryl-(C1-C8)-alkylenesulfonyl or (C5-C14)-arylsulfonyl, said alkyl, aryl or heterocycle are optionally substituted; and wherein R11 is hydrogen, (C1-C10)-alkyl, (C6-C14)-aryl or (C6-C14)-aryl-(C1-C6)-alkyl, or an enantiomer, a stereoisomer, a tautomer or a mixture thereof, or a physiologically acceptable salt, a solvate or a derivative thereof, or a prodrug thereof. |
Method of manufacturing hot formed object, and device and method for continous high-frequency heating |
Raw materials are portioned in a plurality of molds, which are continuously moved and transferred to a heating area by a conveyer. The heating area is divided into a plurality of sub-areas, each of which has power source means and power feeding means. The raw materials are heated and molded by applying high frequency to the molds from the power feeding means. Even if the heating apparatus is large, it is possible to restrain or prevent concentration of high-frequency energy since the heating area is divided into sub-areas. |
1. A method for manufacturing heated and molded articles, comprising the steps of: feeding raw materials in electrically conductive molds; continuously transferring the molds along a moving passage; and dielectrically heating and molding the raw materials by continuously applying high-frequency alternating current to the moving molds with no contact in a heating area provided along the moving passage, the heating area being divided into sub-areas, each of which has at least power source means and power feeding means. 2. The method for manufacturing heated and molded articles according to claim 1, wherein the high-frequency alternating current is applied to the molds by rail-shaped power feeding means continuously disposed along the moving passage in the sub-areas, and each of the molds is equipped with power receiving means for receiving the high-frequency alternating current with no contact from the rail-shaped power feeding means. 3. The method for manufacturing heated and molded articles, according to claim 2, wherein the power receiving means is shaped like a plate, the rail-shaped power feeding means has a surface opposite to the power receiving means, and high-frequency alternating current is applied with no contact by placing the plate-shaped power receiving means opposite to the surface. 4. The method for manufacturing heated and molded articles according to claim 3, wherein the rail-shaped power feeding means or power receiving means is constructed so that an area where the rail-shaped power feeding means and the power receiving means oppose each other is changed along the moving passage of the molds to change a level of high-frequency alternating current applied to the molds through the power receiving means. 5. The method for manufacturing heated and molded articles according to claim 4, wherein the rail-shaped power feeding means is constructed so that the area is changed along the moving passage. 6. The method for manufacturing heated and molded articles according to claim 3, wherein the rail-shaped power feeding means is constructed so that a distance between the rail-shaped power feeding means and the power receiving means is changed along the moving passage of the molds to change a level of high-frequency alternating current applied to the molds through the power receiving means. 7. The method for manufacturing heated and molded articles according to claim 1, wherein a length of each of the sub-areas is determined so that a rate of variation of the continuously moving molds to be heated in the entire sub-area is less than 0.5. 8. The method for manufacturing heated and molded articles according to claim 7, wherein the length is determined so that the rate of variation is less than 0.1 in case that one of the sub-areas corresponds to either an initial stage or a last stage of heating the raw materials. 9. The method for manufacturing heated and molded articles according to claim 1, wherein each of the molds comprises a plurality of mold halves which can be divided into a feeder electrode block receiving power supply from the power feeding means and a grounding electrode block grounded to the earth, and each of the blocks is insulated from each other. 10. The method for manufacturing heated and molded articles according to claim 9, wherein each of the molds is a united mold integrating a plurality of molds. 11. The method for manufacturing heated and molded articles according to claim 1, wherein both dielectric heating by applying high-frequency alternating current and external heating by external heating means are used at least in part of the heating area. 12. The method for manufacturing heated and molded articles according to claim 1, wherein the heating area further includes an application suspension zone where no high-frequency alternating current is applied. 13. The method for manufacturing heated and molded articles according to claim 12, wherein the application suspension zone included in the heating area is provided-in an area corresponding to at least either an initial stage or a last stage of heating the raw materials. 14. The method for manufacturing heated and molded articles according to claim 1, wherein conditions of applying high-frequency alternating current to the molds in each of the sub-areas are differently specified. 15. The method for manufacturing heated and molded articles according to claim 14, wherein the conditions include at least one of the conditions; an output of high-frequency alternating current in each of the sub-areas, an output of high-frequency alternating current applied to each of the molds, and a length of each of the sub-areas. 16. The method for manufacturing heated and molded articles according to claim 14, wherein the conditions are specified depending on properties of the raw materials which changes by applying high-frequency alternating current. 17. The method for manufacturing heated and molded articles according to claim 1, wherein a starchy and watery mixture including at least starch and water and having fluidity or plasticity is used as the raw materials, and baked and molded articles are made as heated and molded articles. 18. The method for manufacturing heated and molded articles according to claim 17, wherein flour is used as starch in the starchy and watery mixture, and the baked and molded articles are molded and baked confectioneries mainly containing flour. 19. The method for manufacturing heated and molded articles according to claim 1, wherein a conveyer rotatably stretched by axes is used as moving means. 20. A continuous high-frequency heating apparatus comprising: a heating unit where the objects to be heated is placed between a pair of electrodes, moving means continuously transferring heating units along a moving passage, power feeding means provided along the moving passage, wherein the objects to be heated are dielectrically heated by continuously applying high-frequency alternating current to the moving heating units from the power feeding means, and further comprising a plurality of power feeding means, each of which has power source means, and making a heating area by continuously disposing the power feeding means. 21. The continuous high-frequency heating apparatus according to claim 20, wherein the power feeding means apply high-frequency alternating current to the heating units with no contact. 22. The continuous high-frequency heating apparatus according to claim 21, wherein the power feeding means is shaped like a rail continuously disposed along the heating area of the moving passage, and the heating units are equipped with power receiving means to receive alternating current from the rail-shaped power feeding means with no contact. 23. The continuous high-frequency heating apparatus according to claim 22, wherein the power receiving means is shaped like a plate, the rail-shaped power feeding means has a surface opposite to the power receiving means, and high-frequency alternating current is applied with no contact by placing the plate-shaped power receiving means opposite to the surface. 24. The continuous high-frequency heating apparatus according to claim 23, wherein the rail-shaped power feeding means or the power receiving means is constructed so that an area between the opposite surfaces is changed along the moving passage of the heating units to change a level of high-frequency alternating current applied to the heating units through the power receiving means. 25. The continuous high-frequency heating apparatus according to claim 24, wherein the rail-shaped power feeding means is constructed so that the area between the opposite surfaces is changed along the moving passage. 26. The continuous high-frequency heating apparatus according to claim 23, wherein the rail-shaped power feeding means is constructed so that the opposite distance is changed along the moving passage of the heating units to change a level of the high-frequency alternating current applied to the heating units through the power receiving means. 27. The continuous high-frequency heating apparatus according to claim 20, wherein a length of the power feeding means is determined so that a rate of variation of the continuously moving heating units heated by the entire power feeding means is less than 0.5. 28. The continuous high-frequency heating apparatus according to claim 27, wherein the length of the power feeding means is further determined so that the rate of variation of the continuously moving heating units may be less than 0.1 in case that the power feeding means are disposed in the heating area corresponding to at least either an initial heating stage or a last heating stage in the heating area. 29. The continuous high-frequency heating apparatus according to claim 22, wherein a pair of electrodes have the power receiving means, consisting of a power feeder electrode receiving power supply from the power feeding means and a grounding electrode grounded to the earth insulated from each other. 30. The continuous high-frequency heating apparatus according to claim 20, wherein the heating area includes an application suspension zone where no high-frequency alternating current is applied. 31. The continuous high-frequency heating apparatus according to claim 30, wherein the application suspension zone included in the heating area is provided corresponding to at least either an initial heating stage or a last heating stage in the heating area. 32. The continuous high-frequency heating apparatus according to claim 20, wherein a conveyer rotatably stretched by axes is used as the moving means. 33. A continuous high-frequency heating apparatus comprising: heating units where the objects to be heated are placed between a pair of electrodes, moving means continuously transferring the heating units along a moving passage, power feeding means disposed corresponding to a heating area provided along the moving passage, wherein the objects to be heated are dielectrically heated by continuously applying high-frequency alternating current to the moving heating units from the power feeding means with no contact, and further comprising spark-detecting means to anticipate a spark between the electrodes, the spark-detecting means include a spark-sensing part disposed near the heating area along the moving direction of the heating units so as to contact on either of the electrodes in the moving heating units, and a high-frequency filter for the spark-sensing part individually provided for the spark-sensing parts disposed corresponding to a position where a potential difference is generated between adjacent heating units, out of the spark-sensing parts. 34. The continuous high-frequency heating apparatus according to claim 33, wherein the position includes an inlet located in the most precedent area looking from the moving direction of the heating units in the heating area and an outlet located in the most subsequent area looking from the moving direction of the heating units in the heating area. 35. The continuous high-frequency heating apparatus according to claim 33, wherein the position further includes a part where a property for high frequency alternating current of the objects to be heated changes significantly with the progress of heating by applying high-frequency alternating current. 36. The continuous high-frequency heating apparatus according to claim 33, wherein the high-frequency filters are individually provided for all the spark-sensing parts. 37. The continuous high-frequency heating apparatus according to claim 33, wherein the spark-sensing parts are divided into groups based on the positions, each of the groups has the spark-detecting means. 38. The continuous high-frequency heating apparatus according to claim 33, wherein the spark-detecting means further includes a direct current power source section to apply direct current between a pair of electrodes, wherein the spark-detecting means checks for electrification by a resistance value between the electrodes to which direct current is applied and anticipate a spark by checking for electrification. 39. The continuous high-frequency heating apparatus according to claim 33, wherein the electrodes are electrically conductive molds and the objects to be heated are raw materials. 40. The continuous high-frequency heating apparatus according to claim 39, wherein a starchy and watery mixture containing at least starch and water and having fluidity or plasticity is used as the raw materials, and baked and molded articles are molded by dielectrically heating the raw materials. 41. The continuous high-frequency heating apparatus according to claim 40, wherein flour is used as starch for the starchy and watery mixture, and the baked and molded articles are molded and baked confectioneries mainly containing flour. 42. The continuous high-frequency heating apparatus according to claim 33, wherein the power feeding means is shaped like a rail continuously disposed along the heating area of the moving passage, and the electrodes include the power feeder electrode receiving power supply from the power feeding means and the grounding electrode grounded to the earth, and the power feeder electrode is provided for the power receiving means for the power feeder electrode to receive alternating current with no contact from the rail-shaped power feeding means. 43. A continuous high-frequency heating apparatus: wherein heating units where objects to be heated are placed between a pair of electrodes are- continuously transferred along a moving passage and dielectrically heated by continuously applying high-frequency alternating current to moving heating units with no contact from a heating area provided along the moving passage, and a spark between the electrodes is anticipated by spark-sensing parts disposed near the heating area along the moving direction of the heating units to contact on either of the electrodes in the moving heating units, and spark-detecting means including a high-frequency filter individually provided for the spark-sensing parts disposed corresponding to a position where a potential difference is generated between adjacent heating units, out of the spark-sensing parts. |
<SOH> BACKGROUND ART <EOH>A high-frequency heating method has been known as an art capable of effectively performing heat treatment on an object to be heated. More particularly, a high-frequency heating method is, in general, a method to dielectrically heat the object by applying high-frequency alternating current (hereinafter referred to as high frequency) to a pair of opposite electrodes which the object is placed between. This art has an advantage not only that the object can be uniformly heated, but also that it is easier to control heating, by using dielectric heating. Generally, in the heating technique using high frequency, the position of the heating electrodes is almost fixed. When the objects to be heated are transferred to the heating electrodes and stopped therein, high frequency is applied for heating. For example, this high-frequency heating technique is used for manufacturing plywood or veneer, disclosed in (A) “Patent No. Hei 11-42755 (publication dated Feb. 16, 1999)” of the Japanese unexamined patent application publication. The above art (A) uses an apparatus equipped with two high-frequency heating parts; a first high-frequency heating part performing high-frequency heating, where a plate-type material to be heated is placed between a pair of plate-type opposite electrodes (heating electrodes or electrodes), and a second high-frequency heating part performing high-frequency heating where a material to be heated is placed between an upper latticed electrode and a lower latticed electrode, consisting of bar-type electrodes placed in parallel facing to a surface of the plate-type material to be heated. For example, an adhesive is applied to a surface on a core material consisting of a wood frame and a metal frame, and another surface material is attached to the core material to make materials to be heated. The materials are transferred to the first high-frequency heating part by a conveyer in order to be applied to high frequency heating, and then transferred to the second high-frequency heating part in order to be applied to high frequency heating again. Thus, in this art, high-frequency heating is performed on the material to be heated by combination of different heating electrodes, not only by high-frequency heating. Even if a core material included in the material to be heated, consists of several kinds of materials having a different electrical property, it is possible to effectively attach a surface material to the core material by performing a combination of high-frequency heating parts with a different heating property. The high-frequency heating part in the above art (A), will be particularly explained below. A pair of electrodes is used in combination both on the first high-frequency heating part and on the second high-frequency heating part. One electrode is a feeder electrode block connected to a power source section, and the other electrode is a grounding electrode block connected to the earth. Each of the blocks may consist of an electrode or electrodes. When high frequency is applied, the objects to be heated are placed between the blocks being insulated from each other. Accordingly, high frequency applied between the blocks can heat the objects. If there is any electrification between the feeder electrode and the grounding electrode to be insulated from each other, a spark is generated between the electrodes, which cause problems of damage to the electrodes or a scorch on the objects to be heated. Usually, a spark-detecting circuit anticipates a spark between the electrodes. More specifically, the spark-detecting circuit detects a spark by applying direct current between the electrodes and measuring a resistance value therein to check for any electrification. For example, as shown in FIG. 51 , five heating units 10 consisting of the electrodes 11 and 12 with the objects 14 to be heated in between, are fixed in a heating zone to apply high frequency from the power source section 2 . The spark-detecting circuit 51 is connected to the feeder electrode block and the grounding electrode block in the heating units 10 in order to anticipate a spark. To prevent high frequency from flowing into the spark-detecting circuit 51 , a high-frequency filter 52 is provided. The above heating condition is shown as a parallel circuit of a condenser in FIG. 52 . More specifically, the part corresponding to each of the heating units 10 constitutes a condenser. Each condenser is in parallel on the circuit. While the electrode 12 (feeder electrode) constituting the condenser (heating unit 10 ) is connected to the power source section 2 , the other electrode 13 (grounding electrode) is grounded to the earth. In addition, the spark-detecting circuit 51 is connected to the electrodes 12 and 13 . The high-frequency filter 52 and a direct current power source section 54 are provided between the electrode 12 (feeder electrode) and the spark-detecting circuit 51 . In the above structure, the spark-detecting circuit 51 checks for electrification by applying direct current between the electrodes 12 and 13 insulated from each other, that is, in the heating units 10 . Since any electrification is more likely to generate a spark, the spark-detecting circuit 51 anticipates a spark, sends out a kind of control signal, and stops applying high frequency from the power source section 2 . By the way, an art for manufacturing molded articles by using molds such as metal molds, portioning raw materials for molding (raw materials) in the molds and heating (hereinafter referred to as a method for heating molds), has been widely used. The above method for heating molds has been widely used also for manufacturing molded and baked confectioneries including edible containers such as cones, Monaka, and wafers, etc. In a technical field of manufacturing the molded and baked confectioneries, various kinds of starch is a main ingredient. A mixture of water and starch, for example, viscose dough or slurry dough, is used. A technical field of molding the watery mixture primarily containing starch through the method for heating molds, is applied not only to make the molded and baked confectioneries, but also to make biodegradable molded articles. In this specification, the articles attained by heating and molding the watery mixture primarily containing starch, for example, molded and baked confectioneries and biodegradable molded articles, are referred to as baked and molded articles. In the above method for heating molds, an external heating method that metal molds are simply heated and raw materials are heated and molded through thermal conduction, was conventionally utilized. However, the conventional external heating method needs a long molding time with less production efficiency. It also causes uneven baking and thereby uneven molded articles due to unequal temperature inside or between molds. Thus, in recent years the above-mentioned high-frequency heating method has been widely used as the method for heating molds. In general, the high-frequency heating method is a method to dielectrically heat raw materials by applying high frequency to molds (equivalent to heating electrodes), which has advantages of uniformly heating and molding raw materials and easy heating control. The above-mentioned method to temporarily suspend the objects to be heated for application of high frequency is effective for objects of relatively large size and relatively high unit cost, such as plywood or veneer, as the above-mentioned art (A). However, this method is ineffective for objects of relatively small size and relatively low unit cost, as the above molded articles. To solve the above problems, the applicants previously proposed an art using a continuous manufacturing process that many molds are continuously transferred and heated in order to improve production efficiency in production of biodegradable molded articles by high-frequency heating, disclosed in (B) “Patent No. Hei 10-230527 (publication dated Sep. 2, 1998)” of the Japanese unexamined patent application publication. In the production of baked and molded articles including baked and molded confectioneries, the continuous manufacturing process that many metal molds are continuously transferred and heated, is generally used to improve production efficiency. According to the above art (B), in the continuous manufacturing process, no contact on method is adopted that high frequency is applied to heating electrodes (i.e. generically called heating units including metal molds or molds) without direct contact on thereof. For example, as shown in FIG. 24 , in the manufacturing apparatus disclosed in the above unexamined patent application publication, the metal molds 7 are moved to the direction of the arrow shown in the figure by a conveyer 6 (moving means or conveyer means) disposed in no-end plate-type layout. In a heating zone B (heating area) performing dielectric heating, a power feeding section 3 (power feeding means) is placed along the conveyer 6 . Also, a power receiving section (power receiving means) matching to the power feeding section 3 with no contact is provided on the metal molds 7 (not shown in FIG. 24 ). The power feeding section 3 and the power receiving section constitute a high-frequency power feeding and receiving section. When the metal molds 7 wherein the raw materials are fed are transferred by the conveyer 6 and reach the heating zone B, high frequency is applied to the metal molds 7 from the power feeding section 3 with no contact, and the raw materials inside the metal molds 7 (raw materials for molding) are dielectrically heated. In result, the raw materials can be heated effectively and steadily, and the molded articles can be made with excellent moldability and physical property. Namely, in the above art (B), it is possible to apply high frequency to the continuously moving metal molds 7 from the power feeding section 3 provided in the heating zone B. Thus, when applying high frequency, it is possible to dielectrically heat the raw materials inside the metal molds 7 without suspending the application. In result, the manufacturing process can be easily controlled and production efficiency of the biodegradable molded articles is also improved. Especially, in the continuous manufacturing process according to the above art (B), a “no contact on” method is used that high frequency is applied to heat the metal molds 7 , i.e., the heating electrodes, without direct contact on with the power feeding section 3 , giving an advantage that generation of a spark can be restrained between the power feeding section 3 and the metal molds 7 in the heating zone. Thus, it is possible not only to heat all of the objects to be heated uniformly through high-frequency heating, transferring and continuously heating the objects by the moving means, but also to reduce a heating time for some kinds of objects. Whereas in the art (B), for example, making a large-scale manufacturing equipment for improving production efficiency practically causes problems of generation of a spark, dielectric breakdown and an arc, as mentioned below. First, in the art (B), when high frequency is applied to the entire heating zone B, localization of high frequency is found on part of the heating zone B. Therefore, if a manufacturing apparatus becomes larger, concentration of high-frequency energy is generated due to the localization of high frequency, thereby giving problems such as overheating of the raw materials wherein high frequency is localized, a spark or dielectric breakdown between the metal molds 7 (electrodes) in the localized area, as well as generation of a spark at the power feeding and receiving section even with no contact. In other words, in the large-scale manufacturing apparatus, the apparatus becomes very large on a whole. Moreover, for the purpose of improving production efficiency, not only in the large-scale apparatus, but also in many apparatuses, a united metal mold is used which consists of many metal molds 7 , for example, placed in parallel and transferred by the conveyer 6 . Thus, the number of metal molds 7 transferred to the heating zone B significantly increases accordingly. Therefore, if the manufacturing apparatus becomes larger, the number of raw materials in the metal molds 7 significantly increases. In the heating zone B, a larger output of high frequency must be applied in proportion to the number of raw materials. More particularly, for example, in a small manufacturing apparatus, as shown in FIG. 24 , twenty-two metal molds 7 are mounted on an outer periphery of the conveyer 6 , and eleven metal molds 7 may be heated in the heating zone B. If a high-frequency output applied from the power source section 2 is set at 9 kW, the high-frequency output applied to each of the metal molds 7 is about 0.8 kW. In this case, since the high-frequency output is not so large in the entire heating zone B, large high-frequency energy does not concentrate even if high frequency is localized on a certain position in the heating zone B. Accordingly, overheating or a spark is not generated, and there is little influence on the production of the molded articles. In other words, the art disclosed in the above Japanese unexamined patent application publication is a very preferable art for a small-scale manufacturing apparatus. On the other hand, in a large-scale manufacturing apparatus, a high-frequency output in the entire heating zone becomes very large, and high-frequency energy increasingly concentrates on part of the heating zone. In result, concentration of high-frequency energy, which is not almost found in a small-scale manufacturing apparatus, causes overheating, a spark or dielectric breakdown. It is thus difficult to use the art disclosed in the above-mentioned unexamined patent application publication for a large-scale manufacturing apparatus. More particularly, as shown in FIG. 25 , thirty-six united metal molds 5 are mounted on an outer periphery of the conveyer 6 and twenty-five united metal molds 5 may be heated in the heating zone B. If the united metal mold 5 is, for example, a unit consisting of five metal molds 7 , an output from the power source section 2 should be set at 100 kW to apply about 0.8 kW high frequency to each of the metal molds 7 , as the above small manufacturing apparatus. In the above example, it is simply calculated that high-frequency energy up to more than 10 times as that of the small manufacturing apparatus may be concentrated. In addition, in the large-scale manufacturing apparatus, a length of the power feeding section 3 located in the heating zone B is longer than that for a small-scale manufacturing apparatus. For example, a length of the power feeding section 3 equals to eleven metal molds 7 in FIG. 24 , while it equals to twenty-five metal molds 7 (united metal molds 5 ) in FIG. 25 . Depending on a shape of the power feeding section 3 , a high-frequency potential is more likely to be localized, thereby practically making it difficult to provide the power feeding section 3 longer than a specific length. Namely, high-frequency energy more than what can be simply calculated from the length (width) of the heating zone B or the number of united metal molds 5 is more likely to concentrate. To prevent the concentration of high-frequency energy, it is necessary to limit a length of the power feeding section 3 , that is, a length of the heating zone B, and thereby significantly reducing efficiency of heating and molding. Next, utilization of the above spark-detecting circuit 51 in the above art (B) gives problems that an arc is generated at part of the feeder electrode of the heating units 10 at the moment of contacting or leaving a contactor terminal to apply direct current to the heating units 10 . More specifically, when the spark-detecting circuit 51 is used for a continuous heating process, as shown in FIG. 53 , a plurality of spark-sensing parts (contactor terminals) 53 is disposed along the moving passage of the heating units 10 . The spark-sensing parts 53 are brought to contact on an optional position on the feeder electrode of the heating units 10 (power receiving section 4 in FIG. 53 ) from the power receiving section 4 to anticipate a spark with the spark-detecting circuit 51 . The power feeding section 3 and the power receiving section 4 constitute the power feeding and receiving section 11 . For convenience, the position where the spark-sensing part 53 contacts, that is, the optional position on the feeder electrode of the heating units 10 including the power receiving section 4 is named a contact position of the spark-sensing part. A circuit diagram of the above structure is basically the same as that of the fixed circuit diagram ( FIG. 52 ) as shown in FIG. 54 , while in the above continuous heating process, the power feeding section 3 and power receiving section 4 , that is, the power feeding and receiving section 11 makes a condenser, since high frequency is applied with no contact. The heating units 10 move to the direction of the arrow for both in FIG. 53 and FIG. 54 . In the structure of the continuous heating process, the heating units 10 continuously transferred along the moving passage, and in the heating zone, the spark-sensing parts 53 are disposed so that the heating units 10 may contact on at least more than one of the spark-sensing parts 53 , wherever the heating units 10 are positioned. Thus, it is possible to continuously anticipate a spark on each of the heating units 10 in the heating zone also in the continuous heating process. In the structure of the spark-detecting circuit 51 , taking notice of the spark-sensing parts 53 , they do not always contact on with the power receiving section 4 , repeating contact and no contact condition with the movement of the heating units 10 . Furthermore, in the continuous heating process' there is a big potential difference between the adjacent heating units 10 and 10 (power receiving sections 4 and 4 ) when the heating units 10 enter or leave the heating zone or at an initial heating stage. In result, an arc is generated at the moment when the spark-sensing parts 53 contact on or leave the heating units 10 and 10 . For example, as shown in FIG. 53 , there is a big potential difference between the heating unit 10 - 1 just before entering into the heating zone (the left-most heating unit 10 in the figure) and the heating unit 10 - 2 just after high frequency starts to be applied from the power feeding section 3 (the heating unit 10 adjacent to the heating unit 10 - 1 ). Then, a potential of the spark-sensing part 53 a increases, before contacting the contact position of the spark-sensing part of the heating unit 10 - 1 having a lower potential, connected to the spark-sensing part 53 b contacting the contact position of the spark-sensing part of the heating unit 10 - 2 having a higher potential. Accordingly, an arc is generated between the spark-sensing part 53 a and the heating unit 10 - 1 at the moment when the spark-sensing part 53 a contacts the heating unit 10 - 1 . As described above, when an arc is generated between the heating unit 10 - 1 and the spark-sensing part 53 a, the spark-detecting circuit 51 malfunctions or the contact position of the spark-sensing part 53 a gets damages or imperfect contact, giving a problem that a resistance value thereat increases and a spark cannot be anticipated correctly. The present invention was made in consideration with the above problems. An objective of the present invention is to provide a method and an apparatus for continuous high-frequency heating, and a method for manufacturing heated and molded articles, accomplishing effective and safe heating which can effectively restrain or prevent concentration of high-frequency energy when in a large-scale equipment continuously moving objects to be heated, for example, raw materials fed in molds, are heated through high frequency heating. Another objective of the present invention is to further effectively perform continuous dielectric heating by using a new spark-detecting method to prevent an arc at a spark-sensing part and to monitor a spark exactly, when the spark-detecting method is used for the continuous high-frequency heating. |
<SOH> BRIEF DESCRIPTION OF DRAWINGS <EOH>FIG. 1 is a diagrammatic illustration showing an example of an outlined structure of a manufacturing apparatus used in a manufacturing method in accordance with an embodiment in the present invention. FIG. 2 is a circuit diagram showing an outlined structure of the manufacturing apparatus shown in FIG. 1 . FIGS. 3 ( a ) and ( b ) are perspective views showing an example of united metal molds used for the manufacturing apparatus shown in FIG. 1 . FIGS. 4 ( a ) and ( b ) are perspective views showing another example of united metal molds used for the manufacturing apparatus shown in FIG. 1 . FIG. 5 is a bird's-eye view showing an example of a configuration of cone cups as molded articles made by a manufacturing method in accordance with the present invention. FIG. 5 ( b ) is a cross sectional view as seen along the line D-D of FIG. 5 (a). FIG. 6 ( a ) is a bird's-eye view of an example of a configuration of a waffle cone as a molded article made by a manufacturing method in accordance with the present invention. FIG. 6 ( b ) is a cross sectional view as seen along the line E-E of FIG. 6 ( a ). FIG. 7 ( a ) is a bird's-eye view showing an example of a configuration of a tray as a molded article made by a manufacturing method in accordance with the present invention. FIG. 7 ( b ) is a cross sectional view as seen along the line F-F of FIG. 7 ( a ). FIGS. 8 ( a ) and ( b ) are diagrammatic illustrations showing an example of a layout of the conveyer included in the manufacturing apparatus shown in FIG. 1 . FIGS. 9 ( a ) and ( b ) are diagrammatic illustrations showing an example of a structure for a gas heating section as external heating means included in the manufacturing apparatus shown in FIG. 1 . FIGS. 10 ( a ), ( b ), and ( c ) are diagrammatic illustrations showing an example of a structure of a power feeding and receiving section included in the manufacturing apparatus shown in FIG. 1 . FIGS. 11 ( a ) and ( b ) are diagrammatic illustrations showing an example of a more specific structure of the power feeding and receiving section shown in FIG. 10 . FIG. 12 is a diagrammatic illustration showing another example of an outlined structure of the manufacturing apparatus shown in FIG. 1 . FIG. 13 is a diagrammatic illustration showing still another example of an outlined structure of the manufacturing apparatus shown in FIG. 1 . FIG. 14 is a diagrammatic illustration showing an example of an outlined structure of a manufacturing apparatus used in a manufacturing method in accordance with another embodiment in the present invention. FIG. 15 is a diagrammatic illustration showing another example of an outlined structure of the manufacturing apparatus shown in FIG. 14 . FIG. 16 is a diagrammatic illustration showing another example of an outlined structure of the manufacturing apparatus shown in FIG. 14 . FIG. 17 is a diagrammatic illustration showing an example of an outlined structure of a manufacturing apparatus used in a manufacturing method in accordance with still another embodiment in the present invention. FIG. 18 is a diagrammatic illustration showing another example of an outlined structure of the manufacturing apparatus shown in FIG. 17 . FIGS. 19 ( a ) and ( b ) are diagrammatic illustrations showing an example of a structure of the gas heating section as external heating means included in the manufacturing apparatus shown in FIG. 18 . FIGS. 20 ( a ) and ( b ) are diagrammatic illustrations showing an example of a disposition of a conveyer included in a manufacturing apparatus used in a manufacturing method in accordance with still another embodiment in the present invention. FIGS. 21 ( a ) and ( b ) are diagrammatic illustrations showing another example of a disposition of the conveyer included in the manufacturing apparatus used in the manufacturing method in accordance with still another embodiment in the present invention. FIGS. 22 ( a ) and ( b ) are diagrammatic illustrations showing still another example of a disposition of the conveyer included in the manufacturing apparatus used in the manufacturing method in accordance with still another embodiment in the present invention. FIGS. 23 ( a ) and ( b ) are diagrammatic illustrations showing still another example of the layout for the conveyer included in the manufacturing apparatus used in the manufacturing method in accordance with still another embodiment in the present invention. FIG. 24 is a diagrammatic illustration showing an example of an outlined structure of a conventional manufacturing apparatus. FIG. 25 is a diagrammatic illustration showing an example of an outlined structure in case that the conventional manufacturing apparatus is made larger. FIG. 26 is a diagrammatic illustration showing an example of an outlined structure of a manufacturing apparatus used in a manufacturing method in accordance with still another embodiment in the present invention. FIG. 27 is a diagrammatic illustration showing another example of an outlined structure of the manufacturing apparatus shown in FIG. 26 . FIGS. 28 ( a ) and ( b ) are diagrammatic illustrations showing a condition in case that plate-type power receiving sections are inserted in the neighborhood of an inlet at a rail-shaped power feeding section shown in FIG. 10 (a) to (c). FIGS. 29 ( a ) and ( b ) are diagrammatic illustrations showing a condition in case that plate-type power receiving sections are inserted in the neighborhood of an inlet at a rail-shaped power feeding section for a manufacturing apparatus used in a manufacturing method in accordance with still another embodiment in the present invention. FIGS. 30 ( a ) and ( b ) are diagrammatic illustrations showing another example of a condition in case that plate-type power receiving sections are inserted in the neighborhood of an outlet at a rail-shaped power feeding section for a manufacturing apparatus shown in FIGS. 29 ( a ) and ( b ). FIGS. 31 ( a ) and ( b ) are diagrammatic illustrations showing a condition in case that the plate-type power receiving sections are inserted in the neighborhood of an outlet at the rail-shaped power feeding section shown in FIG. 10 ( a ) to ( c ). FIGS. 32 ( a ) and ( b ) are diagrammatic illustrations showing a condition in case that plate-type power receiving sections are inserted in the neighborhood of an outlet at a rail-shaped power feeding section for a manufacturing apparatus used in a manufacturing method in accordance with still another embodiment in the present invention. FIGS. 33 ( a ) and ( b ) are diagrammatic illustrations showing another example of a condition in case that the plate-type power receiving sections are inserted in the neighborhood of an inlet at the rail-shaped power feeding section for the manufacturing apparatus shown in FIGS. 32 ( a ) and ( b ). FIG. 34 ( a ) is a diagrammatic illustration showing a change in the number of power receiving sections inserted into the rail-shaped power feeding section including R-member for a manufacturing apparatus used in a manufacturing method in accordance with still another embodiment in the present invention. FIG. 34 ( b ) is a graph showing a change in anode current accompanying a change in the number of the power receiving sections inserted. FIG. 35 ( a ) is a diagrammatic illustration showing a change in the number of power receiving sections inserted in a rail-shaped power feeding section including R-member for a manufacturing apparatus used in a manufacturing method in accordance with still another embodiment in the present invention. FIG. 35 ( b ) is a graph showing a change in anode current accompanying a change in the number of the power receiving sections inserted. FIG. 36 ( a ) is a diagrammatic illustration showing a change in the number of the power receiving sections inserted in the rail-shaped power feeding section consisting of straight-line members for the manufacturing apparatus used in the manufacturing method in accordance with still another embodiment in the present invention. FIG. 36 ( b ) is a graph showing a change in anode current accompanying a change in the number of the power receiving sections inserted. FIG. 37 is a diagrammatic illustration showing an example of an outlined structure for a heating apparatus in accordance with still another embodiment in the present invention. FIGS. 38 ( a ) and ( b ) are diagrammatic illustrations showing an example of a layout for the conveyer included in the heating apparatus shown in FIG. 37 . FIG. 39 is a diagrammatic illustration showing an example of an outlined structure of a heating apparatus in accordance with still another embodiment in the present invention. FIG. 40 is a diagrammatic illustration showing an example of an outlined structure of a heating apparatus in accordance with still another embodiment in the present invention. FIG. 41 is a diagrammatic illustration showing an example of an outlined structure of main parts for a heating apparatus in accordance with still another embodiment in the present invention. FIG. 42 is a circuit diagram showing an outlined structure of the entire heating apparatus shown in FIG. 41 . FIG. 43 is a diagrammatically sectional view showing an example of a metal mold and a power feeding and receiving section for the heating apparatus shown in FIG. 41 . FIG. 44 is a circuit diagram schematically corresponding to the main parts for the heating apparatus shown in FIG. 41 . FIG. 45 is a diagrammatic illustration showing another example of the main parts for the heating apparatus shown in FIG. 41 . FIG. 46 is a circuit diagram schematically corresponding to the main parts for the heating apparatus shown in FIG. 45 . FIG. 47 is a diagrammatic illustration showing an example of an outlined structure of main parts for a heating apparatus in accordance with still another embodiment in the present invention. FIG. 48 is a circuit diagram schematically corresponding to the main parts for the heating apparatus shown in FIG. 47 . FIG. 49 is a diagrammatic illustration showing another example of the main parts for the heating apparatus shown in FIG. 47 . FIG. 50 is a circuit diagram schematically corresponding to the main parts for the heating apparatus shown in FIG. 49 . FIG. 51 is an explanatory illustration showing an outlined structure of main parts for a conventional heating apparatus. FIG. 52 is a circuit diagram schematically corresponding to the main parts for the conventional heating apparatus shown in FIG. 51 . FIG. 53 is a diagrammatic illustration showing an outlined structure of the main parts in case that the conventional heating apparatus shown in FIG. 51 is used for a continuous heating apparatus. FIG. 54 is a circuit diagram schematically corresponding to the main parts for the heating apparatus shown in FIG. 53 . FIG. 55 ( a ) is an explanatory illustration showing an example of a condition whereat a potential difference is generated between the metal molds in the heating apparatus shown in FIG. 53 . FIG. 55 ( b ) is a graph showing a potential corresponding to the position of the metal molds in FIG. 55 ( a ). FIG. 56 is an explanatory illustration showing another example of a condition whereat a potential difference is generated between the metal molds in the heating apparatus shown in FIG. 53 . FIG. 56 ( b ) is a graph showing a potential corresponding to the position of the metal molds in FIG. 56 ( a ). detailed-description description="Detailed Description" end="lead"? |
Protein polymer having unfold activity on higher-order structure of protein |
The invention of this application provides a protein polymer of 8 to 15 proteins in association, each of the proteins having the amino acid sequence SQ ID NO. 1, where the protein polymer has an unfold activity on higher-order structure of protein and this protein polymer is useful for the development of therapeutic agents of various diseases due to the failure in the formation of higher-order structure of protein, and the like. |
1. A protein polymer of 8 to 15 proteins in association, each of the proteins having the amino acid sequence SQ ID NO.1, where the protein polymer has an unfold activity on higher-order structure of protein. 2. A protein polymer according to claim 1, where a protein of an amino acid sequence modified from the amino acid sequence SQ ID NO.1 via the deletion of one or more amino acid residues therein or the substitution of one or more amino acid residues therein with other amino acid residues or the addition of one or more amino acid residues thereto is associated together. |
<SOH> BACKGROUND ART <EOH>Amino acids synthesized in biological organisms can function as a protein, only when the polypeptide synthesized from amino acids can form the correct steric structure of the protein. Essentially, the correct formation of the steric structure is consistently rapidly and efficiently done intracellularly. Cells have a factor promoting the formation of higher-order structure, which is called molecular chaperone. Some disadvantage for cells may sometimes occur, such as the insufficiency of molecular chaperone formation or protein denaturation due to the formation of an erroneous sequence. It has been elucidated recently that various diseases emerge because the control system for higher-order structure of proteins do not work properly. For example, Alzheimer's disease is a neuropathic disease occurring because the component called amyloid has aggregated together intracellularly. Amyloid generally forms a helix steric structure. In case of the disease, however, the helix steric structure is transformed into a structure called cross β structure. Thus, amyloid adheres to each other and accumulates intracellularly, triggering brain nerve damages. Furthermore, neuropathic Huntington's disease occurs because elongated polyglutamic acid attached to the tail part of the protein, huntintin, due to genetic mutation, is involved in the adhesion of the protein to each other and thereby leading to the failure of cellular functions. Furthermore, it is suggested that the functional impairment of HSP (HSC) as one of molecular chaperones is the pathogenesis of Parkinson's disease, cystic fibrosis, and in some cases of spinocerebellar degeneration. It has been elucidated that a group of apparently different diseases such as these have the common molecular base, namely the failure in the formation of higher-order structure of protein as the underlining pathogenesis. No therapeutic method extremely effective for these diseases has existed yet. Because any component with an unfolding activity on higher-order structure without substrate specificity has not yet been found, protein aggregates, the direct cause of such disease, cannot be targeted and unfolded. On the other hand, cell should be so flexible that the structure of protein can be unfolded rapidly during dynamic movements such as cell migration, cell division. Furthermore, once formed protein aggregates with an erroneous higher-order structure are quickly unfolded, and transferred to a decomposition system. Although it has been recognized so far that such factor is essential, the factor has not yet been identified because of the difficulty in the purification thereof. So as to radically cure various diseases due to the failure in the formation of higher-order structure of protein, the aggregation of the diseased protein should essentially be untangled, as described above. It is indispensable therefore that “a factor unfolding higher-order structure of protein” should be identified, and isolated and purified. Additionally, it is expected that such factor can be used as a very useful material for research works in cell biology. The invention of the application has been achieved in such circumstance. It is an object of the invention to provide a new protein polymer showing a great activity for unfolding higher-order structure of protein. |
<SOH> BRIEF DESCRIPTION OF THE DRAWINGS <EOH>FIG. 1 is an electron microscopic photopicture depicting the structure of the YDL178W polymer of the invention. FIG. 2 shows the molecular weight of the YDL178W polymer of the invention as the results of the determination by size exclusion chromatography. FIG. 3 is an electron microscopic photopicture depicting the structure of rabbit skeletal muscle myosin. FIG. 4 is an electron microscopic photopicture depicting the structural change of myosin incubated with the YDL178W polymer of the invention. FIG. 5 shows the molecular weight of the protein YDL178-del with deficiency in the coil-forming part as the results of the determination by size exclusion chromatography. FIG. 6 shows the activity of the enzyme luciferase incubated with the YDL178W polymer of the invention or the protein monomer YDL178W-del. detailed-description description="Detailed Description" end="lead"? |
Enhanced production of recombinant proteins by transient transfection of suspension-growing mammalian cells |
Disclosed is a new process for the production of recombinant proteins, by transient transfection of suspension-grown human embryonic kidney cells (293 cell line and its genetic variants) with an expression vector, using polyethylenimine (PEI) as a transfection reagent. In a preferred embodiment, the process uses 293E cells expressing the Epstein-Barr virus (EBV) EBNA 1 protein, in combination with an oriP-based episomal expression vector having an improved cytomegalovirus expression cassette comprising the CMV5 promoter. The process combines in a single step the cell growth, transfection and protein expression, is carried out without changing the culture medium, and allows to achieve high expression levels in a short period of time. The process may be carried out in a serum-free, low-protein culture medium, is easily scalable, compatible with continuous production processes, and fully adapted to high-throughput production of milligram quantities of recombinant proteins. |
1-39. (canceled) 40. An expression vector for an enhanced expression of a recombinant protein in human cells which stably express EBNA1 protein or a fragment thereof, said vector comprising a first DNA sequence encoding the recombinant protein, said first DNA sequence being under control of a CMV5 promoter, said expression vector further comprising a second DNA sequence of the oriP sequence of Epstein-Barr virus (EBV) or a fragment thereof enhancing transcriptional activity of the promoter. 41. An expression vector according to claim 40, wherein the vector is a plasmid. 42. An expression vector according to claim 40, wherein the fragment of the EBV oriP sequence comprises at least one EBNA1 binding site (EBS). 43. An expression vector according to claim 40, wherein the fragment of the oriP sequence is selected from the group consisting of BstX I FR fragment, a BstX I EcoR I FR fragment, the FR domain, and fragments thereof. 44. A human kidney cell line designated 293SFE and deposited under IDAC Accession No. 020502. 45. A process for preparing transfected human kidney cells of the 293 cell line, which process comprises transfecting said human kidney cells with an expression vector according to claim 40. 46. A process according to claim 45, when carried out in the presence of polyethylenimine (PEI) as a transfection reagent. 47. A process according to claim 46, wherein the polyethylenimine is a linear polyethylenimine or a branched polyethylenimine. 48. A process according to claim 47, wherein the average molecular weight of the polyethylenimine is from about 10 to about 100 kDa. 49. A process according to claim 48, wherein the average molecular weight of the polyethylenimine is about 25 kDa. 50. A process for preparing a recombinant protein, which process comprises culturing transfected human kidney cells prepared by the process of claim 45 to yield said protein. 51. A process according to claim 50, wherein the cells are cultured in a serum-free culture medium. 52. A process according to claim 50, wherein the cells are cultured in a culture medium further comprising a serum or a subfraction thereof. 53. A process according to claim 50, wherein the cells are cultured in a culture medium further comprising a peptone. 54. A process according to claim 53, wherein the peptone is the gelatin peptone N3. 55. A process according to claim 50, wherein the process is carried out in a culture medium without changing the culture medium. 56. A process for preparing a recombinant protein, which process comprises transfecting human kidney cells of the 293 cell line with an expression vector according to claim 40 and then culturing said transfected human kidney cells to yield said protein. 57. A process for preparing a recombinant protein, which process comprises culturing human kidney cells designated 293SFE and deposited under IDAC Accession No. 020502 to yield said protein. |
<SOH> BACKGROUND OF THE INVENTION <EOH>Mammalian cells are an established expression system in the biotechnology industry for the production of recombinant proteins (r-proteins). In contrast to lower eukaryotes or prokaryotes, mammalian cells provide active r-proteins that possess relevant post-translational modifications. However, in order to obtain sufficient amount of protein for structure/activity analyses or high-throughput screenings, one needs to go through the long and tedious process of stable transfectoma isolation and characterization. As an alternative, the small-scale transient transfection of mammalian cells grown in monolayers can generate significant amount of r-proteins (Cullen B. R., Methods Enzymol., 152, 684-704 (1987); Blasey H. D. et al., Cytotechnology, 18, 183-192 (1996); Cachianes G. et al., Biotechniques, 15, 255-259 (1993)), but scalability of this process is limited by culture surface availability. The use of the well-established calcium phosphate precipitation technique or the recently described cationic polymer polyethylenimine (PEI) (Boussif O. et al., Proc, Natl. Acad. Sci. USA, 92, 7297-7301 (1995)) provides cost-effective ways of introducing plasmid DNA into mammalian cells. A major breakthrough has recently emerged for the fast production of milligram amounts of recombinant proteins when these gene transfer vehicles were shown to be effective for large-scale transient transfection of mammalian cells grown in suspension culture (Jordan M. et al., Cytotechnology, 26, 39-47 (1998); Schlaeger E-J. et al, Cytotechnology, 30, 71-83 (1999); Wurm F. et al., Curr. Opin. Biotechnol., 10, 156-159 (1999)). For an optimal large-scale transient transfection and r-protein expression in mammalian cells, four key aspects are to be taken into account, namely 1) the cell line, 2) the expression vector, 3) the transfection vehicle and 4) the culture medium. The human 293 cell line (a human embryonic kidney cell line containing the E1 region of human Ad5 adenovirus DNA) is widely used for r-protein production as it offers many advantages, such as high transfection yields with most common gene transfer vehicles, is easily grown in suspension culture, and can be adapted to serum-free media. Moreover, two genetic variants of the 293 cell line, the 293E and 293T cell lines, expressing the Epstein-Barr virus (EBV) Nuclear Antigen 1 (EBNA1) and the SV40 large-T antigen, respectively, allow episomal (extrachromosomal) amplification of plasmids containing the viral EBV (293E) or SV40 (293T) origins of replication. These cell lines are therefore expected to increase r-protein expression levels, by permitting more plasmid copies to persist in the transfected cells throughout the production phase (Van Craenenbroeck H. et al., Eur. J. Biochem., 267, 5665-5678 (2000)). The second important issue for high level r-protein expression is the use of vectors having promoters that are highly active in the host cell line, such as the human cytomegalovirus (CMV) promoter (Foecking M. K. et al, Gene, 45, 101-105 (1985)). This promoter is particularly powerful in 293 cells, where it has been shown to be strongly transactivated by the constitutively expressed adenovirus E1a protein (Gorman C. M. et al., Virology, 171, 377-385 (1989)). Moreover, a highly efficient expression cassette using this promoter has been recently described that provides adenovirus-mediated transgene expression levels reaching up to 20% of total cell proteins (TCP) (Massie B. et al., J. Virol., 72, 2289-2296 (1998); Massie B. et al., Cytotechnology, 28, 53-64 (1998)). The third aspect is related to gene transfer reagent efficacy. Even though many highly effective gene transfer reagents are commercially available, only few are cost-effective when considering operations at the multi-liters scale. For large-scale transient transfection applications, these reagents should also be simple to use, effective with suspension growing cells and have minimal cytotoxic effects. PEI satisfies most of these criteria, as it has high gene transfer activity in many cell lines while displaying low cytotoxicity (Boussif O., supra), is cost-effective, and efficiently transfects suspension growing 293 cells (Schlaeger E-J., supra). This polymer is available as both linear and branched isomers with a wide range of molecular weights and polydispersities, which physicochemical parameters are critical for efficient gene transfer activity (Godbey W. T. et al., J. Control Release, 60, 149-160 (1999). The last key aspect for efficient r-protein expression by transient transfection relates to the culture medium. Some gene transfer reagents work only in serum-free media whereas others are less sensitive to the presence of serum. Also, as the presence of cellular by-products in conditioned medium is associated with poor transfection yield, it is often necessary to perform a complete medium change prior to transfection. However, this step does not satisfy the need for a robust large-scale transient transfection process. Transient protein expression system are known in the prior art, for example the transient expression system disclosed in U.S. Pat. No. 5,024,939. However, these systems generally suffer from the above-discussed and other drawbacks and limitations and are not well suited to large-scale, high-throughput production of r-proteins. The present invention provides a transient expression system and process which is free of many such prior art limitations. |
<SOH> SUMMARY OF THE INVENTION <EOH>The invention provides a new process for the production of recombinant proteins, by transfection of suspension-growing eukaryotic cells with an expression vector comprising a first DNA sequence coding for the desired protein, said first DNA sequence being under control of a suitable promoter, and a second DNA sequence enhancing transcriptional activity of the promoter and increasing nuclear import of the expression vector. In a preferred embodiment, the second DNA sequence additionally supports an episomal replication of the vector in the transfected cells. The eukaryotic cells are preferably mammalian cells, more preferably the human embryonic kidney 293 cell line and its genetic variants, more preferably genetic variants stably expressing the EBNA1 protein or a fragment thereof. The expression vector is preferably a plasmid, comprising the first DNA sequence as a part of an expression cassette, the cassette further comprising the promoter, preferably a cytomegalovirus (CMV) promoter, most preferably the CMV5 promoter. The second DNA sequence is preferably of a viral origin, more preferably the oriP sequence of Epstein-Barr virus (EBV) or a fragment thereof. The transfection is preferably carried out using polyethylenimine (PEI) as a transfection reagent, more preferably using the 25 kDa linear isoform of PEI. The process combines in a single step the cell growth, transfection and protein expression, is carried out using suspension-growing cells without changing the culture medium, and allows to achieve high expression levels in a short period of time. The process may be carried out in a serum-free culture medium, is easily scalable, compatible with continuous production processes, and fully adapted to high-throughput production of milligram quantities of recombinant proteins. Thus, according to one aspect, the invention provides a process for the preparation of a recombinant protein, said process comprising the steps of: providing eukaryotic host cells suspension-growing in a culture medium; transfecting the host cells in the presence of a transfection reagent with an expression vector, said vector comprising a first DNA sequence encoding the recombinant protein, said first DNA sequence being under control of a promoter; culturing the transfected cells under conditions favoring expression of the recombinant protein, and harvesting the expressed protein. According to another aspect, the invention provides an expression vector for an enhanced expression of a recombinant protein in a mammalian cell, said vector comprising a first DNA sequence encoding the recombinant protein, said first DNA sequence being under control of a promoter, said expression vector further comprising a second DNA sequence enhancing the transcriptional activity of the promoter and increasing the nuclear import of the expression vector. According to still another aspect, the invention provides a human embryonic kidney cell line derived from the 293SF-3F6 cell line (ATCC Accession No. CRL-12585), said line constitutively expressing the EBNA1 protein or a fragment thereof. |
Secueity thread for the forgery-proof making of objects |
The invention relates to a security thread for the forgery-proof marking of objects, comprising at least one fibre (F) with nucleic acid molecules (N) bonded with the one end thereof to a fibre suface and the fibre (F). The other end of the nucleic acid molecule (N) is free such that complementary nucleic acid molecules (N′) may bind to the nucleic acid molecule (N). |
1. A security thread for the forgery-proof marking of objects having at least one fiber (F), where one end of one or more nucleic acid molecules (N) are linked to a fiber surface of the fibers (F), and where the other end of the nucleic acid molecules (N) is free, so that complementary nucleic acid molecules (N′) are able to undergo linkage to the nucleic acid molecules (N). 2. The security thread as claimed in claim 1, where the fiber (F) is formed from a natural polymer. 3. The security thread as claimed in claim 2, where the natural polymer is selected from the following group: cellulose, chitin, silk, wool, cotton, hemp, flax or derivatives of these polymers. 4. The security thread as claimed in claim 1, where the fiber (F) is formed from a synthetic polymer. 5. The security thread as claimed in claim 4, where the synthetic polymer is selected from the following group: polyamide, polyacrylonitrile, nylon, polypropylene, polyvinylidene fluoride, polycarbonate, polystyrene or derivatives of these polymers. 6. The security thread as claimed in claim 1, where the nucleic acid molecule (N) is linked via a covalent or noncovalent linkage to the fiber surface. 7. The security thread as claimed in claim 6, where the nucleic acid molecule (N) is linked via a biotin/streptavidin linkage, a carboxy, phosphate, amino, thiol, psoralen, cholesteryl or digoxigenine group to the fiber surface. 8. The security thread as claimed in claim 1, where the nucleic acid molecule (N) is linked via an intermediate layer to the fiber surface. 9. The security thread as claimed in claim 8, where the intermediate layer is a functionalized silane layer. 10. The security thread as claimed in claim 1, where different nucleic acid molecules (N, N1, N2) are linked to the fiber surface. 11. The security thread as claimed in claim 10, where the different nucleic acid molecules (N) are linked on defined zones of the fiber surface. 12. The security thread as claimed in claim 1, where the nucleic acid molecule (N) is produced by chemical synthesis directly on the fiber. 13. The security thread as claimed in claim 1, where the diameter of the fiber (F) is from 100 nm to 100 μm. 14. The security thread as claimed in claim 1, further comprising at least one second fiber. 15. The security thread as claimed in claim 14, where the second fiber consists of another material. 16. The security thread as claimed in claim 1, where the diameter of the security thread is from 1 μm to 1 mm. 17. A textile having at least one security thread (Fd) as claimed in claim 1. 18. A textile as claimed in claim 17, which comprises security threads (Fd) modified with different nucleic acid molecules. 19. The textile as claimed in claim 17, where nucleic acid-modified security threads (Fd) form a pattern which can be detected by means of the complementary nucleic acid molecules (N′). 20. A label where the label comprises at least one security thread (Fd) as claimed in claim 1. 21. The label as claimed in claim 20, where the security threads (Fd) are modified with different nucleic acid molecules. 22. The label as claimed in claim 21, where a nucleic acid microarrangement in the form of a matrix is formed from a plurality of security threads. 23. The label as claimed in claim 22, where the matrix is produced by techniques of textile processing of the security threads (Fd). 24. A forgery-proof marking, where at least one security thread (Fd) as claimed in claim 1 is applied to a basic article (2). 25. The forgery-proof marking as claimed in claim 24, where the basic article (2) is produced from a fabric, paper or flow agent which makes transport of liquid to the security thread (Fd) possible. 26. The forgery-proof marking as claimed in claim 25, where the basic article (2) has an absorbent pad (3). 27. The forgery-proof marking as claimed in claim 24, where a plurality of security threads (Fd) are arranged in parallel. 28. The forgery-proof marking as claimed in claim 24, where the covering (4) is applied to the basic article (2). 29. The forgery-proof marking as claimed in claim 28, where the covering (4) has a first orifice (4a) for application of detection liquid. 30. The forgery-proof marking as claimed in claim 29, where the covering (4) has a second orifice (4b) for observing the security thread (Fd). 31. A method for identifying a forgery proof marking on an object having the following steps: a) providing an object comprising at least one security thread (Fd) as claimed in claim 1, b) bringing the security thread (Fd) into contact with an indicator comprising the complementary nucleic acid molecules (N′) and c) detecting the specific linkage of the complementary nucleic acid molecules (N′) to the nucleic acid molecules (N) on the object. 32. (canceled) 33. The method as claimed in claim 31, where steps c and d are carried out in less than 5 minutes. 34. The method as claimed in claim 31, where only a solution or suspension is used for carrying out steps c and d. 35. The method as claimed in claim 31, where steps c and d are carried out without a washing step. 36. The method as claimed in claim 31, where detection is carried out by means of specific hybridization and by a change in optical properties brought about as a result of the hybridization. 37. (canceled) 38. The method as claimed in claim 31, where the detection is carried out by means of an enzymatic reaction and by a change in optical properties brought about as a result of the enzymatic reaction. 39. The method as claimed in claim 31, where the detection is carried out by means of laminar flow. 40. The method as claimed in claim 31, where the complementary nucleic acid molecules (N′) are linked to micro- or nanoparticles. 41. The method as claimed in claim 31, where a pattern formed by at least one security thread (Fd) is identified in the detection. 42. The method as claimed in claim 41, where the pattern is formed by a plurality of security threads (Fd) which are provided with different nucleic acid molecules (N, N1, N2). 43. The method as claimed in claim 41, where the pattern is formed by formed-loop knitting, weaving, drawn-loop knitting, crocheting, knotting, sewing or embroidery. 44. The security thread as claimed in claim 8, where the intermediate layer contains streptavidin. 45. The forgery proof marking as claimed in claim 28, where the covering (4) is plastic. 46. The method as claimed in claim 36, where the optical properties are fluorescence or a color reaction. 47. The method as claimed in claim 46, wherein the detection is carried out by means of a molecular beacon. 48. A method for the forgery proof marking of an object having the following steps: a) providing the object, and b) contacting the object with the security thread as claimed in claim 1. |
Hbm variants that modulate bone mass and lipid levels |
The present invention relates to methods and materials used to express an HBM-like polypeptide derived from HBM, LRP5 or LRP6 in animal cells and transgenic animals. The present invention also relates to transgenic animals expressing the HBM-like polypeptides. The invention provides nucleic acids, including coding sequences, oligonucleotide primers and probes, proteins, cloning vectors, expression vectors, transformed hosts, methods of developing pharmaceutical compositions, methods of identifying molecules involved in bone development, and methods of diagnosing and treating diseases involved in bone development and lipid modulation. In preferred embodiments, the present invention is directed to methods for treating, diagnosing and preventing osteoporosis. |
1. A nucleic acid comprising a mutation in LRP5 or LRP6 which results in a HBM-like phenotype when expressed in a cell, wherein said HBM-like phenotype results in bone mass modulation and/or lipid level modulation. 2. A LRP5 nucleic acid comprising at least one mutation of Tables 2 or 3 or which results in a mutation of one of the following G171V, A214V, A65V, M282V, G171K, G171F, G171I, G171Q, L200V, T201V, I202V, or S127V when expressed in a cell, and wherein expression of the nucleic acid in a subject results in bone mass modulation and/or lipid level modulation. 3. A LRP6 nucleic acid comprising at least one of Tables 2 or 3 or which results in a mutation of one of the following G171V, A214V, A65V, M282V, G171K, G171F, G171I, G171Q, L200V, T201V, I202V, or S127V when expressed in a cell, and wherein said mutation occurs in LRP6 in a position equivalent to LRP5 such that expression of the nucleic acid in a subject results in bone mass modulation and/or lipid level modulation. 4. A LRP5 nucleic acid encoding at least one amino acid mutation in propeller 1. 5. The LRP5 nucleic acid of claim 4, wherein said nucleic acid encodes for at least one mutation selected from the group consisting of: G171V, A214V, A65V, M282V, G171K, G171F, G171I, G171Q, L200V, T201V, I202V, and S127V. 6. A LRP6 nucleic acid encoding at least one amino acid mutation in propeller 1. 7. The LRP6 nucleic acid of claim 6, wherein said nucleic acid encodes for at least one mutation in an equivalent position of LRP6 selected from the group of LRP5 mutations consisting of: G171V, A214V, A65V, M282V, G171K, G171F, G171I, G171Q, L200V, T201V, I202V, and S127V. 8. The nucleic acid of claim 1, wherein the mutation is G171V, A214V, A65V, M282V, G171K, G171F, G171I or G171Q in LRP5 or in an equivalent domain in LRP6. 9. A polypeptide encoded by a nucleic acid of claim 1, wherein said polypeptide when expressed in a cell modulates Wnt signaling, Dkk activity, LRP5 activity and/or LRP6 activity. 10. The polypeptide of claim 9, wherein said polypeptide modulates bone mass and/or lipid levels when expressed in a subject. 11. A vector comprising a nucleic acid of claim 1. 12. A cell comprising the vector of claim 11. 13. The cell of claim 12, wherein said cell is a cancer cell, a liver cell or a bone cell. 14. A polypeptide or biologically active fragment thereof derived from LRP5 comprising at least one amino acid change of Table 2, G171V, A214V, A65V, M282V, G171K, G171F, G171I, G171Q, L200V, T201V, I202V, or S127V. 15. The polypeptide or biologically active fragment of claim 14, wherein said protein or biologically active fragment comprises at least one amino acid change of G171V, A214V, A65V, M282V, G171K, G171F, G171I, G171Q, L200V, T201V, I202V, or S127V.. 16. A polypeptide or biologically active fragment thereof derived from LRP6 comprising at least one amino acid change of Table 2, G171V, A214V, A65V, M282V, G171K, G171F, G171I, G171Q, L200V, T201V, I202V, or S127V when the amino acid change is expressed in an equivalent position in LRP6. 17. The polypeptide or biologically active fragment of claim 16, wherein said protein or biologically active fragment comprises at least one amino acid change of G171V, A214V, A65V, M282V, G171K, G171F, G171I, G171Q, L200V, T201V, I202V, or S127V. 18. A polypeptide or biologically active fragment which when expressed in a subject has a HBM-like phenotype comprising at least one amino acid mutation in propeller 1 with the proviso that if the mutation is G171V that a second mutation which maintains the HBM-like phenotype is also present. 19. The polypeptide or biologically active fragment of claim 18, wherein said polypeptide is derived from LRP5, LRP6 or HBM. 20. The polypeptide or biologically active fragment of claim 14, wherein the amino acid change is G171V, A214V, A65V, M282V, G171K, G171F, G171I or G171Q of LRP5 or an equivalent position in LRP6. 21. An antibody or immunogenic fragment thereof which binds to a polypeptide or antigenic fragment thereof of claim 14. 22. The antibody or immunogenic fragment thereof of claim 21, wherein the antibody is a monoclonal antibody, a chimeric antibody, a bispecific antibody, a humanized antibody, a primatized® antibody, a human antibody, or a labeled antibody. 23. An antibody which binds to a polypeptide comprising 208KLYWADAKLSFIHRAN223, 277ALYSPMDIQVLSQER291, 61GLEDAAAVDFQFSKGA73, 234EGSLTHPFALTLSG247, 249TLYWTDWQTRSIHACN264, 144VLFWQDLDQPRAI156, 194IYWPNGLTIDLEEQKLY210, 34LLLFANRRDVRLVD47, 75GAVYWTDVSEEAIKQ89, 121KLYWTDSETNRIEVA135 of LRP5 or an equivalent domain on LRP6 or variants thereof. 24. An antibody which binds to a polypeptide comprising 969LILPLHGLRNVKAIDYDPLDKFIYW993, 989KFIYWVDGRQNIKRAKDDGTQPFVL1013, 1009QPFVLTSLSQGQNPDRQPHDLSIDI1033, 1029LSIDIYSRTLFWTCEATNTINVHRL1053, 1049NVHRLSGEAMGVVLRGDRDKPRAIV1073, 1253CGEPPTCSPDQFAC1266, 1278WRCDGFPECDDQSDEEGC1295, 1316RCDGEADCQDRSDEADC1332, 1370CEITKPPSDDSPAH1383 of LRP5 or an equivalent domain on LRP6 or variants thereof, wherein said antibody modulates binding of LRP5, HBM, LRP6 or variants thereof to Dkk. 25. A method of diagnosing a HBM-like phenotype in a subject comprising (A) obtaining a biological sample from the subject; (B) exposing the sample to an antibody or an immunogenic fragment of claim 22; and (C) detecting whether the antibody bound a protein from the biological sample from the subject to determine whether the subject has a HBM-like phenotype. 26. A composition for modulating bone mass and/or lipid levels in a subject comprising a therapeutically effective amount of an antibody of claim 21 and a pharmaceutically acceptable carrier. 27. An antibody or an immunogenic fragment thereof of claim 21, wherein the antibody or immunogenic fragment thereof can (1) discriminate between LRP5 and an HBM-like protein, (2) discriminate between LRP6 and an HBM-like protein, or (3) discriminate between HBM and an HBM-like protein. 28. A transgenic animal having somatic and/or germ cells comprising a nucleic acid which comprises a promoter region that directs protein expression in animal and/or human cells operably linked to a nucleic acid of claim 2, and wherein said transgenic animal has at least three bone parameters modulated by the expression of said nucleic acid. 29. The transgenic animal of claim 28, wherein the promoter region is selected from the group consisting of CMV, RSV, SV40, and EF-1a, CMVβbActin, histone, type I collagen, TGFβ1, SX2, cfos/cjun, Cbfal, Fra/Jun, Dlx5, osteocalcin, osteopontin, bone sialoprotein, and collagenase promoter regions. 30. A transgenic animal having somatic and/or germ cells comprising a nucleic acid which comprises a sequence which encodes a polypeptide of claim 9, and wherein the nucleic acid further comprises an operably linked promoter region that directs protein expression in animal and/or human cells, and wherein the transgenic animal has at least three bone parameters modulated by the expression of said nucleic acid. 31. An animal embryo comprising a nucleic acid comprising a promoter region that directs protein expression in animal and/or human cells operably linked to a nucleic acid of claim 2. 32. An animal or human cell transfected with a nucleic acid which comprises a promoter region that directs protein expression in animal and/or human cells operably linked to a nucleic acid of claim 2. 33. The transgenic animal of claim 28, wherein a human HBM-like protein is expressed and passes the human HBM-like gene to its offspring. 34. A transgenic animal produced from the transgenic animal of claim 33 or its offspring. 35. An animal model for the study of bone density modulation and/or lipid level modulation comprising a first group of animals composed of the transgenic animal of claim 28 and a second group of control animals. 36. The animal model of claim 35, wherein the group of transgenic animals have cells which comprise a nucleic acid encoding human an HBM-like protein or biologically active polypeptide fragment thereof. 37. An animal model for the study of bone density modulation comprising a first group of animals composed of the transgenic animals of claim 30 and a second group of control animals. 38. A method of identifying agents which modulate the activity of an HBM-like nucleic acid comprising: (a) transfecting a cell with a vector of claim 11; (b) exposing the transfected cell of step (a) to a compound; and (c) determining whether the compound modulates the activity of the HBM-like nucleic acid. 39. A method of identifying agents which modulate the activity of an HBM-like protein comprising: (a) transfecting a cell with a vector of claim 11; (b) exposing the transfected cell of step (a) to a compound; and (c) determining whether the compound modulates the activity of the HBM-like protein. 40. The method of claim 39, wherein the compound is a hormone, a growth factor, a peptide, RNA, shRNA, siRNA, DNA, a mineral, a vitamin, a natural product, or a synthetic organic compound. 41. A method for identifying compounds which modulate the interaction of Dkk with the Wnt signaling pathway comprising: (a) transfecting cells with constructs containing a nucleic acid of claim 2; (b) assessing changes in expression of a reporter element linked to a Wnt-responsive promoter; and (c) identifying as a Dkk/Wnt interaction modulating compound any compound which alters reporter gene expression compared with cells transfected with a Dkk construct alone. 42. The method according to claim 41, wherein the cells are cancer cells, liver cells or bone cells. 43. The method according to claim 42, wherein the cells are U2-OS, HOB-03-CE6, or HEK293 cells. 44. The method according to claim 41, wherein the reporter element used is TCF-luciferase, tk-Renilla, or a combination thereof. 45. A method of diagnosing a subject as expressing a nucleic acid comprising a nucleotide change of Tables 2 or 3, the method comprising the steps of: (A) obtaining a biological sample from the subject; and (B) assaying for the presence of the nucleotide change which results in HBM phenotype. 46. A method for identifying agents which modulate LRP5, LRP6, or HBM comprising the steps of: (A) providing cells according to claim 32; (B) exposing the cells to a test compound; and (C) measuring the expression of LRP5, LRP6 or HBM respectively. 47. The method for identifying agents of claim 42, further comprising a step of determining whether the agent further modulates bone mass and/or lipid levels. 48. An agent identified by the method of claim 46. |
<SOH> BACKGROUND OF THE INVENTION <EOH>Two of the most common types of osteoporosis are postmenopausal and senile osteoporosis. Osteoporosis affects men as well as women, and, taken with other abnormalities of bone, presents an ever-increasing health risk for an aging population. The most common type of osteoporosis is that associated with menopause. Most women lose between 20-60% of the bone mass in the trabecular compartment of the bone within 3-6 years after the cessation of menses. This rapid loss is generally associated with an increase of bone resorption and formation. However, the resorptive cycle is more dominant and the result is a net loss of bone mass. Osteoporosis is a common and serious disease among postmenopausal women. There are an estimated 25 million women in the United States alone who are afflicted with this disease. The results of osteoporosis are both personally harmful, and also account for a large economic loss due to its chronicity and the need for extensive and long-term support (hospitalization and nursing home care) from the disease sequelae. This is especially true in more elderly patients. Additionally, while osteoporosis is generally not thought of as a life-threatening condition, a 20-30% mortality rate is related to hip fractures in elderly women. A large percentage of this mortality rate can be directly associated with postmenopausal osteoporosis. The costs alone associated with the treatment of osteoporotic fractures in the United States is $10 to $15 billion annually. Worldwide incidence of osteoporotic hip fractures is estimated to exceed 1.7 million cases. The most vulnerable tissue in the bone to the effects of postmenopausal osteoporosis is the trabecular bone. This tissue is often referred to as spongy bone and is particularly concentrated near the ends of the bone near the joints and in the vertebrae of the spine. The trabecular tissue is characterized by small structures which inter-connect with each other as well as the more solid and dense cortical tissue which makes up the outer surface and central shaft of the bone. This crisscross network of trabeculae gives lateral support to the outer cortical structure and is critical to the biomechanical strength of the overall structure. In postmenopausal osteoporosis, it is primarily the net resorption and loss of the trabeculae which lead to the failure and fracture of the bone. In light of the loss of the trabeculae in postmenopausal women, it is not surprising that the most common fractures are those associated with bones which are highly dependent on trabecular support, e.g., the vertebrae, the neck of the femur, and the forearm. Indeed, hip fracture, Colle's fractures, and vertebral crush fractures are indicative of postmenopausal osteoporosis. One of the earliest generally accepted methods for treatment of postmenopausal osteoporosis was estrogen replacement therapy. Although this therapy frequently is successful, patient compliance is low, primarily due to the undesirable side-effects of chronic estrogen treatment. Frequently cited side-effects of estrogen replacement therapy include reinitiation of menses, bloating, depression, and fear of breast or uterine cancer. In order to limit the known threat of uterine cancer in those women who have not undergone a hysterectomy, a protocol of estrogen and progestin cyclic therapy is often employed. This protocol is similar to that which is used in birth control regimens, and often is not tolerated by women because of the side-effects characteristic of progestin. More recently, certain antiestrogens, originally developed for the treatment of breast cancer, have been shown in experimental models of postmenopausal osteoporosis to be efficacious. Among these agents is raloxifene (See, U.S. Pat. No. 5,393,763, and Black et al, J. Clin. Invest., 93:63-69 (1994)). In addition, tamoxifene, a widely used clinical agent for the treatment of breast cancer, has been shown to increase bone mineral density in post menopausal women suffering from breast cancer (Love et al, N. Engl. J. Med., 326:852-856 (1992)). Another therapy for the treatment of postmenopausal osteoporosis is the use of calcitonin. Calcitonin is a naturally occurring peptide which inhibits bone resorption and has been approved for this use in many countries (Overgaard et al, Br. Med. J., 305:556-561 (1992)). The use of calcitonin has been somewhat limited, however. Its effects are very modest in increasing bone mineral density and the treatment is very expensive. Another therapy for the treatment of postmenopausal osteoporosis is the use of bis-phosphonates. These compounds were originally developed for use in Paget's disease and malignant hypercalcemia. They have been shown to inhibit bone resorption. Alendronate, one compound of this class, has been approved for the treatment of postmenopausal osteoporosis. These agents may be helpful in the treatment of osteoporosis, but these agents also have potential liabilities which include osteomalacia, extremely long half-life in bone (greater than 2 years), and possible “frozen bone syndrome,” e.g., the cessation of normal bone remodeling. Senile osteoporosis is similar to postmenopausal osteoporosis in that it is marked by the loss of bone mineral density and resulting increase in fracture rate, morbidity, and associated mortality. Generally, it occurs in later life, i.e., after 70 years of age. Historically, senile osteoporosis has been more common in females, but with the advent of a more elderly male population, this disease is becoming a major factor in the health of both sexes. It is not clear what, if any, role hormones such as testosterone or estrogen have in this disease, and its etiology remains obscure. Treatment of this disease has not been very satisfactory. Hormone therapy, estrogen in women and testosterone in men, has shown equivocal results; calcitonin and bis-phosphonates may be of some utility. The peak mass of the skeleton at maturity is largely under genetic control. Twin studies have shown that the variance in bone mass between adult monozygotic twins is smaller than between dizygotic twins (Slemenda et al, J. Bone Miner. Res., 6:561-567 (1991); Young et al, J. Bone Miner. Res., 6:561-567 (1995); Pocock et al, J. Clin. Invest., 80:706-710 (1987); Kelly et al, J. Bone Miner. Res., 8:11-17 (1993)), and it has been estimated that up to 60% or more of the variance in skeletal mass is inherited (Krall et al, J. Bone Miner. Res., 10:S367 (1993)). Peak skeletal mass is the most powerful determinant of bone mass in elderly years (Hui et al, Ann. Int. Med., 111:355-361 (1989)), even though the rate of age-related bone loss in adult and later life is also a strong determinant (Hui et al, Osteoporosis Int., 1:30-34 (1995)). Since bone mass is the principal measurable determinant of fracture risk, the inherited peak skeletal mass achieved at maturity is an important determinant of an individual's risk of fracture later in life. Thus, study of the genetic basis of bone mass is of considerable interest in the etiology of fractures due to osteoporosis. Recently, a strong interest in the genetic control of peak bone mass has developed in the field of osteoporosis. The interest has focused mainly on candidate genes with suitable polymorphisms to test for association with variation in bone mass within the normal range, or has focused on examination of genes and gene loci associated with low bone mass in the range found in patients with osteoporosis. The vitamin D receptor locus (VDR) (Morrison et al, Nature, 367:284-287 (1994)), PTH gene (Howard et al, J. Clin. Endocrinol. Metab., 80:2800-2805 (1995); Johnson et al, J. Bone Miner. Res., 8:11-17 (1995); Gong et al, J. Bone Miner. Res., 10:S462 (1995)) and the estrogen receptor gene (Hosoi et al, J. Bone Miner. Res., 10:S170 (1995); Morrison et al, Nature, 367:284-287 (1994)) have figured most prominently in this work. These studies are difficult because bone mass (the phenotype) is a continuous, quantitative, polygenic trait, and is confounded by environmental factors such as nutrition, co-morbid disease, age, physical activity, and other factors. Also, this type of study design requires large numbers of subjects. In particular, the results of VDR studies to date have been confusing and contradictory (Garnero et al, J. Bone Miner. Res., 10:1283-1288 (1995); Eisman et al, J. Bone. Miner. Res., 10:1289-1293 (1995); Peacock, J. Bone Miner. Res., 10:1294-1297 (1995)). Furthermore, the work thus far has not shed much light on the mechanism(s) whereby the genetic influences might exert their effect on bone mass. While it is well known that peak bone mass is largely determined by genetic rather than environmental factors, studies to determine the gene loci (and ultimately the genes) linked to variation in bone mass are difficult and expensive. Study designs which utilize the power of linkage analysis, e.g., sib-pair or extended family, are generally more informative than simple association studies, although the latter do have value. However, genetic linkage studies involving bone mass are hampered by two major problems. The first problem is the phenotype, as discussed briefly above. Bone mass is a continuous, quantitative trait, and establishing a discrete phenotype is difficult. Each anatomical site for measurement may be influenced by several genes, many of which may be different from site to site. The second problem is the age component of the phenotype. By the time an individual can be identified as having low bone mass, there is a high probability that their parents or other members of prior generations will be deceased and therefore unavailable for study, and younger generations may not have even reached peak bone mass, making their phenotyping uncertain for genetic analysis. Regardless, linkage analysis can be used to find the location of a gene causing a hereditary “disorder” and does not require any knowledge of the biochemical nature of the disorder, i.e., a mutated protein that is believed to cause the disorder does not need to be known. Traditional approaches depend on assumptions concerning the disease process that might implicate a known protein as a candidate to be evaluated. The genetic localization approach using linkage analysis can be used to first find the general chromosomal region in which the defective gene is located and then to gradually reduce the size of the region in order to determine the location of the specific mutated gene as precisely as possible. After the gene itself is discovered within the candidate region, the messenger RNA and the protein are identified and, along with the DNA, are checked for mutations. The genetic localization approach has practical implications since the location of the disease can be used for prenatal diagnosis even before the altered gene that causes the disease is found. Linkage analysis can enable families, even many of those that do not have a sick child, to know whether they are carriers of a disease gene and to evaluate the condition of an unborn child through molecular diagnosis. The transmission of a disease within families, then, can be used to find the defective gene. As used herein, reference to “high bone mass” (HBM) is analogous to reference to a disease state, although from a practical standpoint high bone mass can actually help a subject avoid the disease known as osteoporosis. Linkage analysis is possible because of the nature of inheritance of chromosomes from parents to offspring. During meiosis, the two parental homologues pair to guide their proper separation to daughter cells. While they are lined up and paired, the two homologues exchange pieces of the chromosomes, in an event called “crossing over” or “recombination.” The resulting chromosomes are chimeric, that is, they contain parts that originate from both parental homologues. The closer together two sequences are on the chromosome, the less likely that a recombination event will occur between them, and the more closely linked they are. In a linkage analysis experiment, two positions on the chromosomes are followed from one generation to the next to determine the frequency of recombination between them. In a study of an inherited disease, one of the chromosomal positions is marked by the disease gene or its normal counterpart, i.e., the inheritance of the chromosomal region can be determined by examining whether the individual displays symptoms of the disorder or not. The other position is marked by a DNA sequence that shows natural variation in the population such that the two homologues can be distinguished based on the copy of the “marker” sequence that they possess. In every family, the inheritance of the genetic marker sequence is compared to the inheritance of the disease state. If, within a family carrying an autosomal dominant disorder such as high bone mass, every affected individual carries the same form of the marker and all the unaffected individuals carry at least one different form of the marker, there is a great probability that the disease gene and the marker are located close to each other. In this way, chromosomes may be systematically checked with known markers and compared to the disease state. The data obtained from the different families is combined, and analyzed together by a computer using statistical methods. The result is information indicating the probability of linkage between the genetic marker and the disease allowing different distances between them. A positive result can mean that the disease is very close to the marker, while a negative result indicates that it is far away on that chromosome, or on an entirely different chromosome. Linkage analysis is performed by typing all members of the affected family at a given marker locus and evaluating the co-inheritance of a particular disease state with the marker probe, thereby determining how often the two of them are co-inherited. The recombination frequency can be used as a measure of the genetic distance between two gene loci. A recombination frequency of 1% is equivalent to 1 map unit, or 1 centiorgan (cM), which is roughly equivalent to 1,000 kb of DNA. This relationship holds up to frequencies of about 20% or 20 cM. The entire human genome is 3,300 cM long. In order to find an unknown disease gene within 5-10 cM of a marker locus, the whole human genome can be searched with roughly 330 informative marker loci spaced at approximately 10 cM intervals (Botstein et al., Am. J. Hum. Genet., 32:314-331 (1980)). The reliability of linkage results is established by using a number of statistical methods. The method most commonly used for the analysis of linkage in humans is the LOD score method (Morton, Prog. Clin. Biol. Res., 147:245-265 (1984), Morton et al., Am. J. Hum. Genet., 38:868-883 (1986)) which was incorporated into the computer program, LIPED, by Ott, Am. J. Hum. Genet., 28:528-529 (1976). LOD scores are the logarithm of the ratio of the likelihood that two loci are linked at a given distance to that they are not linked (>50 cM apart). The advantage of using logarithmic values is that they can be summed among families with the same disease. This becomes necessary given the relatively small size of human families. By convention, a total LOD score greater than +3.0 (that is, odds of linkage at the specified recombination frequency being 1000 times greater than odds of no linkage) is considered to be significant evidence for linkage at that particular recombination frequency. A total LOD score of less than −2.0 (that is, odds of no linkage being 100 times greater than odds of linkage at the specified frequency) is considered to be strong evidence that the two loci under consideration are not linked at that particular recombination frequency. Until recently, most linkage analyses have been performed on the basis of two-point data, which is the relationship between the disorder under consideration and a particular genetic marker. However, as a result of the rapid advances in mapping the human genome over the last few years, and concomitant improvements in computer methodology, it has become feasible to carry out linkage analyses using multi-point data. Multi-point analysis provide a simultaneous analysis of linkage between the disease and several linked genetic markers, when the recombination distance among the markers is known. Multi-point analysis is advantageous for two reasons. First, the informativeness of the pedigree is usually increased. Each pedigree has a certain amount of potential information, dependent on the number of parents heterozygous for the marker loci and the number of affected individuals in the family. However, few markers are sufficiently polymorphic as to be informative in all those individuals. If multiple markers are considered simultaneously, then the probability of an individual being heterozygous for at least one of the markers is greatly increased. Second, an indication of the position of the disease gene among the markers may be determined. This allows identification of flanking markers, and thus eventually allows isolation of a small region in which the disease gene resides. Lathrop et al., Proc. Natl. Acad. Sci. USA, 81:3443-3446 (1984) have written the most widely used computer package, LINKAGE, for multi-point analysis. There is a need in the art for identifying the gene associated with a high bone mass phenotype. There is also a need for tools for the study of the high bone mass gene and phenotype. More generally there is need for the development of diagnostic tools and treatments. The present invention is directed to these, as well as other, important ends. |
<SOH> SUMMARY OF THE INVENTION <EOH>It is an object of the invention to provide a nucleic acid comprising a mutation in LRP5 or LRP6 which results in a HBM phenotype when expressed in a cell, wherein said HBM phenotype results in bone mass modulation and/or lipid level modulation. Another embodiment contemplates that the mutation is located in propeller 1. In another embodiment, the nculeic acid encodes a mutation comprising at least one mutation of Tables 2 or 3 or which results in a mutation of one of the following G171V, A214V, A65V, M282V, G171K, G171F, G171I, G171Q, L200V, T201V, I202V, or S127V when expressed in a cell, and wherein expression of the nucleic acid in a subject results in bone mass modulation and/or lipid level modulation. In the instance of LRP6, the mutation is located in a position equivalent to LRP5 such that expression of the nucleic acid in a subject results in bone mass modulation and/or lipid level modulation. In another embodiment, the preferred mutation of LRP5 is G171V, A214V, A65V, M282V, G171K, G171F, G171I or G171Q or in an equivalent location if dealing with LRP6. Another embodiment contemplated herein is a polypeptide encoded by any of the above nucleic acids, wherein said polypeptide when expressed in a cell modulates Wnt signaling, LRP5 activity and/or LRP6 activity. The polypeptide can additionally or alternatively modulate bone mass and/or lipid levels when expressed in a subject. These polypeptides or biologically active fragments thereof may preferably contain any of the following mutations of Table 2, G171V, A214V, A65V, M282V, G171K, G171F, G171I, G171Q, L200V, T201V, I202V, or S127V in LRP5 or in a equivalent location in LRP6. The most preferred mutations are G171V, A214V, A65V, M282V, G171K, G171F, G171I or G171Q in LRP5 or an equivalent location in LRP6. Yet another embodiment contemplates antibodies an immunogenic fragments thereof which bind to these proteins. The contemplated antibodies include a monoclonal antibody, a chimeric antibody, a bispecific antibody, a humanized antibody, a primatized® antibody, a human antibody, or a labeled antibody. Preferably, some of the antibodies can discriminate between the wild type and variant forms of LRP5 and LRP6. Another embodiment contemplates antibodies which bind to polypeptides comprising: 208 KLYWADAKLSFIHRAN 233 , 277 ALYSPMDIQVLSQER 291 , 61 GLEDAAAVDFQFSKGA 73 , 234 EGSLTHPFALTLSG 247 , 249 TLYWTDWQTRSIHACN 264 , 144 VLFWQDLDQPRAI 156 , 194 IYWPNGLTIDLEEQKLY 210 , 34 LLLFANRRDVRLVD 47 , 75 GAVYWTDVSEEAIKQ 89 , 121 KLYWTDSETNRIEVA 135 of LRP5 or an equivalent domain on LRP6 or variants thereof. The above antibodies can also be used in a composition for modulating bone mass and/or lipid levels in a subject comprising a therapeutically effective amount of the antibody or immunogenic fragment and a pharmaceutically acceptable carrier. The invention further contemplates a method of diagnosing a HBM like phenotype in a subject comprising: (A) obtaining a biological sample from said subject; (B) exposing the sample to one of the described antibodies or immunogenic fragments; and (C) detecting whether the antibody bound a protein from the biological sample from said subject to determine whether the subject has a HBM-like phenotype. Another embodiment contemplates a transgenic animal having somatic and/or germ cells comprising a nucleic acid which comprises a promoter region that directs protein expression in animal and/or human cells operably linked to any of the herein described nucleic acids, and wherein said transgenic animal has at least three bone parameters modulated by the expression of said nucleic acid. The promoter region can be selected from the group consisting of CMV, RSV, SV40, and EF-1a, CMVβbActin, histone, type I collagen, TGFβ1, SX2, cfos/cjun, Cbfa1, Fra/Jun, Dlx5, osteocalcin, osteopontin, bone sialoprotein, and collagenase promoter regions. A further embodiment of the invention contemplates an animal model for the study of bone density modulation and/or lipid level modulation comprising a first group of animals composed of any of the described transgenic animals and a second group of control animals. Another embodiment provides for a method of identifying agents which modulate the activity of an HBM-like nucleic acid comprising: (A) transfecting a cell with a vector of claim 11 ; (B) exposing the transfected cell of step (A) to a compound; and (C) determining whether the compound modulates the activity of the HBM-like nucleic acid. Such agents can include a hormone, a growth factor, a peptide, RNA, siRNA, DNA, a mineral, a vitamin, a natural product, or a synthetic organic compound. Another aspect of the invention provides for a method for identifying compounds which modulate the interaction of Dkk with the Wnt signaling pathway comprising: (A) transfecting cells with constructs containing any of the described nucleic acids; (B) assessing changes in expression of a reporter element linked to a Wnt-responsive promoter; and (C) identifying as a Dkk/Wnt interaction modulating compound any compound which alters reporter gene expression compared with cells transfected with a Dkk construct alone. The cells are preferably cancer cells, liver cells or bone cells. The reporter element used is TCF-luciferase, tk-Renilla, or a combination thereof. Yet another embodiment includes a method of diagnosing a subject as expressing a nucleic acid comprising a nucleotide change of Tables 2 or 3 or any other mutations, the method comprising the steps of: (A) obtaining a biological sample from the subject; and (B) assaying for the presence of the nucleotide change which results in HBM phenotype. The invention also provides agents identified by the above methods which regulate Wnt activity, Dkk activity, bone mass and/or lipid levels. |
Surface-reformed exhaust gas guide assembly of vgs type turbo charger, and method surface-reforming component member thereof |
A novel exhaust gas guide assembly with an improved high-temperature sliding wear resistance, oxidation resistance, high-temperature strength or the like for a VGS turbocharger is provided. The invention is characterized in that a surface modification is applied to a component member of the exhaust gas guide assembly (A), such as adjustable blades (1), a turbine frame (2), a blade adjusting mechanism (3), or the like. |
1. An exhaust gas guide assembly (A), having a surface modification applied thereto, for a VGS turbocharger, comprising: adjustable blades (1) for suitably controlling the flow rate of exhaust gas (G) discharged from an engine to rotate an exhaust turbine wheel (T); a turbine frame (2) which rotatably supports the adjustable blades (1) at the outside of an outer periphery of the turbine wheel (T); and a blade adjusting mechanism (3) for suitably rotating the adjustable blades (1) to control the flow rate of the exhaust gas (G); wherein flow of the exhaust gas at a low flow rate is throttled by the adjustable blades (1) to increase the velocity of the exhaust gas so that a high output power is obtained at low rotational speeds, characterized in that: a member constituting the exhaust gas guide assembly (A) is provided on a surface thereof with a coating of carbide or nitride. 2. An exhaust gas guide assembly (A), having a surface modification applied thereto, for a VGS turbocharger, comprising: adjustable blades (1) for suitably controlling the flow rate of exhaust gas (G) discharged from an engine to rotate an exhaust turbine wheel (T); a turbine frame (2) which rotatably supports the adjustable blades (1) at the outside of an outer periphery of the turbine wheel (T); and a blade adjusting mechanism (3) for suitably rotating the adjustable blades (1) to control the flow rate of the exhaust gas (G); wherein flow of the exhaust gas at a low flow rate is throttled by the adjustable blades (1) to increase the velocity of the exhaust gas so that a high output power is obtained at low rotational speeds, characterized in that: a nickel-containing heat resisting member constituting the exhaust gas guide assembly (A) is provided on a surface thereof with a coating of carbide. 3. An exhaust gas guide assembly (A), having a surface modification applied thereto, for a VGS turbocharger as defined in claim 2, characterized in that: the coating provided on the nickel-containing heat resisting member constituting the exhaust gas guide assembly (A) comprises chromium carbide. 4. An exhaust gas guide assembly (A), having a surface modification applied thereto, for a VGS turbocharger, comprising: adjustable blades (1) for suitably controlling the flow rate of exhaust gas (G) discharged from an engine to rotate an exhaust turbine wheel (T); a turbine frame (2) which rotatably supports the adjustable blades (1) at the outside of an outer periphery of the turbine wheel (T); and a blade adjusting mechanism (3) for suitably rotating the adjustable blades (1) to control the flow rate of the exhaust gas (G); wherein flow of the exhaust gas at a low flow rate is throttled by the adjustable blades (1) to increase the velocity of the exhaust gas so that a high output power is obtained at low rotational speeds, characterized in that: a nickel-containing austenitic heat resisting member constituting the exhaust gas guide assembly (A) is provided on a surface thereof with a coating of carbide. 5. An exhaust gas guide assembly (A), having a surface modification applied thereto, for a VGS turbocharger as defined in claim 4, characterized in that: the coating provided on the nickel-containing austenitic heat resisting member constituting the exhaust gas guide assembly (A) comprises chromium carbide. 6. An exhaust gas guide assembly (A), having a surface modification applied thereto, for a VGS turbocharger, comprising: adjustable blades (1) for suitably controlling the flow rate of exhaust gas (G) discharged from an engine to rotate an exhaust turbine wheel (T); a turbine frame (2) which rotatably supports the adjustable blades (1) at the outside of an outer periphery of the turbine wheel (T); and a blade adjusting mechanism (3) for suitably rotating the adjustable blades (1) to control the flow rate of the exhaust gas (G); wherein flow of the exhaust gas at a low flow rate is throttled by the adjustable blades (1) to increase the velocity of the exhaust gas so that a high output power is obtained at low rotational speeds, characterized in that: a nickel-free heat resisting member constituting the exhaust gas guide assembly (A) is provided on a surface thereof with a coating of chromium carbide. 7. An exhaust gas guide assembly (A), having a surface modification applied thereto, for a VGS turbocharger as defined in claim 6, characterized in that: the coating provided on the nickel-free heat resisting member constituting the exhaust gas guide assembly (A) comprises Cr7C3 and/or Cr23C6. 8. An exhaust gas guide assembly (A), having a surface modification applied thereto, for a VGS turbocharger, comprising: adjustable blades (1) for suitably controlling the flow rate of exhaust gas (G) discharged from an engine to rotate an exhaust turbine wheel (T); a turbine frame (2) which rotatably supports the adjustable blades (1) at the outside of an outer periphery of the turbine wheel (T); and a blade adjusting mechanism (3) for suitably rotating the adjustable blades (1) to control the flow rate of the exhaust gas (G); wherein flow of the exhaust gas at a low flow rate is throttled by the adjustable blades (1) to increase the velocity of the exhaust gas so that a high output power is obtained at low rotational speeds, characterized in that: a ferritic SUS type heat resisting member constituting the exhaust gas guide assembly (A) is provided on a surface thereof with a coating of chromium carbide. 9. An exhaust gas guide assembly (A), having a surface modification applied thereto, for a VGS turbocharger as defined in claim 8, characterized in that: the coating provided on the ferritic SUS type heat resisting member constituting the exhaust gas guide assembly (A) comprises Cr7C3 and/or Cr23C6. 10. An exhaust gas guide assembly (A), having a surface modification applied thereto, for a VGS turbocharger, comprising: adjustable blades (1) for suitably controlling the flow rate of exhaust gas (G) discharged from an engine to rotate an exhaust turbine wheel (T); a turbine frame (2) which rotatably supports the adjustable blades (1) at the outside of an outer periphery of the turbine wheel (T); and a blade adjusting mechanism (3) for suitably rotating the adjustable blades (1) to control the flow rate of the exhaust gas (G); wherein flow of the exhaust gas at a low flow rate is throttled by the adjustable blades (1) to increase the velocity of the exhaust gas so that a high output power is obtained at low rotational speeds, characterized in that: a heat resisting member constituting a sliding portion of the exhaust gas guide assembly (A) is provided on a surface thereof with a coating of chromium carbide having a thickness of not less than 5 □m. 11. An exhaust gas guide assembly (A), having a surface modification applied thereto, for a VGS turbocharger as defined in claim 10, characterized in that: the heat resisting member constituting the sliding portion comprises a nickel-chromium heat resisting member. 12. An exhaust gas guide assembly (A), having a surface modification applied thereto, for a VGS turbocharger, comprising: adjustable blades (1) for suitably controlling the flow rate of exhaust gas (G) discharged from an engine to rotate an exhaust turbine wheel (T); a turbine frame (2) which rotatably supports the adjustable blades (1) at the outside of an outer periphery of the turbine wheel (T); and a blade adjusting mechanism (3) for suitably rotating the adjustable blades (1) to control the flow rate of the exhaust gas (G); wherein flow of the exhaust gas at a low flow rate is throttled by the adjustable blades (1) to increase the velocity of the exhaust gas so that a high output power is obtained at low rotational speeds, characterized in that: a heat resisting member constituting a sliding portion of the exhaust gas guide assembly (A) is provided on a surface thereof with a coating of chromium carbide substantially in a single phase. 13. An exhaust gas guide assembly (A), having a surface modification applied thereto, for a VGS turbocharger as defined in claim 12, characterized in that: the heat resisting member constituting the sliding portion comprises a nickel-chromium heat resisting member. 14. A method for applying a surface modification to a component member of an exhaust gas guide assembly (A) for a VGS turbocharger, wherein the exhaust gas guide assembly includes adjustable blades (1) for suitably controlling the flow rate of exhaust gas (G) discharged from an engine to rotate an exhaust turbine wheel (T); a turbine frame (2) which rotatably supports the adjustable blades (1) at the outside of an outer periphery of the turbine wheel (T); and a blade adjusting mechanism (3) for suitably rotating the adjustable blades (1) to control the flow rate of the exhaust gas (G); wherein flow of the exhaust gas at a low flow rate is throttled by the adjustable blades (1) to increase the velocity of the exhaust gas so that a high output power is obtained at low rotational speeds, and the component member of the exhaust gas guide assembly (A) is subjected to a surface treatment, characterized in that: the method comprises the steps of: removing a thin layer of oxide from a surface of a high-nickel and high-chromium heat resisting member constituting the exhaust gas guide assembly (A) in advance by a reducing gas under a reduced pressure; then performing a treatment with a carburizing gas having a weak inter-carbon polymerization; and subsequently, coating the surface of the high-nickel and high-chromium heat resisting member with chromium carbide, titanium carbide, niobium carbide, tungsten carbide or hafnium carbide. 15. A method for applying a surface mediation to a component member of an exhaust gas guide assembly (A) for a VGS turbocharger as defined in claim 14, characterized in that: the treatment with a carburizing gas is carried out by making the carburizing gas flow pulsedly. 16. An exhaust gas guide assembly (A), having a surface modification applied thereto, for a VGS turbocharger as defined in claim 14 or 15, characterized in that: the coating of chromium carbide provided on the component member of the exhaust gas guide assembly (A) comprises Cr7C3 and/or Cr23C6. 17. A method for applying a surface modification to a component member of an exhaust gas guide assembly (A) for a VGS turbocharger, wherein the exhaust gas guide assembly includes adjustable blades (1) for suitably controlling the flow rate of exhaust gas (G) discharged from an engine to rotate an exhaust turbine wheel (T); a turbine frame (2) which rotatably supports the adjustable blades (1) at the outside of an outer periphery of the turbine wheel (T); and a blade adjusting mechanism (3) for suitably rotating the adjustable blades (1) to control the flow rate of the exhaust gas (G); wherein flow of the exhaust gas at a low flow rate is throttled by the adjustable blades (1) to increase the velocity of the exhaust gas so that a high output power is obtained at low rotational speeds, and the component member of the exhaust gas guide assembly (A) is subjected to a surface treatment, characterized in that: the method comprises the steps of: ionizing carbon atoms under a reduced pressure in a plasma; carburizing a high-nickel and high-chromium heat resisting member constituting the exhaust gas guide assembly (A) with ionized carbon atoms to form an unequilibrium saturated solid-solution while the member is serving as an electrode; and subsequently, coating a surface of the high-nickel and high-chromium heat resisting member with chromium carbide, titanium carbide, niobium carbide, tungsten carbide or hafnium carbide. 18. An exhaust gas guide assembly (A), having a surface modification applied thereto, for a VGS turbocharger as defined in claim 17, characterized in that: the coating of chromium carbide provided on the member constituting the exhaust gas guide assembly (A) comprises Cr7C3 and/or Cr23C6. 19. An exhaust gas guide assembly (A), having a surface modification applied thereto, for a VGS turbocharger, comprising: adjustable blades (1) for suitably controlling the flow rate of exhaust gas (G) discharged from an engine to rotate an exhaust turbine wheel (T); a turbine frame (2) which rotatably supports the adjustable blades (1) at the outside of an outer periphery of the turbine wheel (T); and a blade adjusting mechanism (3) for suitably rotating the adjustable blades (1) to control the flow rate of the exhaust gas (G); wherein flow of the exhaust gas at a low flow rate is throttled by the adjustable blades (1) to increase the velocity of the exhaust gas so that a high output power is obtained at low rotational speeds, characterized in that: the assembly includes a constituent material which comprises a high-nickel and high-chromium heat resisting member having a surface coated with carbide according to the method of claim 14, 15 or 17. 20. An exhaust gas guide assembly (A), having a surface modification applied thereto, for a VGS turbocharger as defined in any one of claims 1 to 13 and 18, characterized in that: the surface is coated with chromium carbide by a TD salt bath method. 21. An exhaust gas guide assembly (A), having a surface modification applied thereto, for a VGS turbocharger as defined in any one of claims 1 to 13 and 18, characterized in that: the surface is coated with iron chromium nitride by gas soft nitriding. 22. An exhaust gas guide assembly (A), having a surface modification applied thereto, for a VGS turbocharger, comprising: adjustable blades (1) for suitably controlling the flow rate of exhaust gas (G) discharged from an engine to rotate an exhaust turbine wheel (T); a turbine frame (2) which rotatably supports the adjustable blades (1) at the outside of an outer periphery of the turbine wheel (T); and a blade adjusting mechanism (3) for suitably rotating the adjustable blades (1) to control the flow rate of the exhaust gas (G); wherein flow of the exhaust gas at a low flow rate is throttled by the adjustable blades (1) to increase the velocity of the exhaust gas so that a high output power is obtained at low rotational speeds, characterized in that: a non-high temperature member constituting the exhaust gas guide assembly (A) is provided on a surface thereof with a coating of Ti—Al—N. 23. An exhaust gas guide assembly (A), having a surface modification applied thereto, for a VGS turbocharger as defined in claim 22, characterized in that: the non-high temperature member resists temperatures of up to 800° C. 24. An exhaust gas guide assembly (A), having a surface modification applied thereto, for a VGS turbocharger as defined in claim 22 or 23, characterized in that: the coating provided on the non-high temperature member comprises Ti1-Al1-N1. 25. An exhaust gas guide assembly (A), having a surface modification applied thereto, for a VGS turbocharger as defined in claim 22 or 23, characterized in that: the coating provided on the non-high temperature member comprises Ti(x)-Al(y)-N(z), wherein x, y>z. 26. An exhaust gas guide assembly (A), having a surface modification applied thereto, for a VGS turbocharger as defined in claim 16, characterized in that: the surface is coated with chromium carbide by a TD salt bath method 27. An exhaust gas guide assembly (A), having a surface modification applied thereto, for a VGS turbocharger as defined in claim 19, characterized in that: the surface is coated with chromium carbide by a TD salt bath method 28. An exhaust gas guide assembly (A), having a surface modification applied thereto, for a VGS turbocharger as defined in claim 16, characterized in that: the surface is coated with iron chromium nitride by gas soft nitriding. 29. An exhaust gas guide assembly (A), having a surface modification applied thereto, for a VGS turbocharger as defined in claim 19, characterized in that: the surface is coated with iron chromium nitride by gas soft nitriding. |
<SOH> BACKGROUND ART <EOH>A turbocharger is known as a supercharger used as means for improving the power output and the performance of an automobile engine. The turbocharger is an apparatus in which a turbine is driven by the exhaust energy of the engine to rotate a compressor with the power of the turbine, whereby the engine is supercharged to have more air fed into it than fed into it by natural suction. The turbocharger, when the engine is running at a low rotational speed, can not avoid giving a slow-moving feeling caused by the reduced flow rate of the exhaust gas and continued until the exhaust turbine runs efficiently, and necessitating a subsequent time or a so-called turbo-lag before the turbine rapidly reaches the full-running state. Furthermore, in the case of a diesel engine which runs inherently at low rotational speeds, there is a disadvantage that it is difficult to produce an effect of the turbocharger. Therefore, a VGS turbocharger that works efficiently even when the engine is running at low rotational speeds has been developed. The turbocharger of this type is adapted to obtain a high power output when the engine is running at low rotational speeds by throttling flow of exhaust gas at a low flow rate with adjustable blades (vanes) to increase the velocity of the exhaust gas and increase work of an exhaust turbine. Especially, in a diesel engine in which the amount of NOx contained in its exhaust gas has become an issue in recent years, the VGS turbocharger is a useful turbocharger capable of improving the engine efficiency even when the engine is running at low rotational speeds. In the VGS turbocharger, an exhaust gas guide assembly is used in a high-temperature atmosphere of exhaust gas. Therefore, for the manufacture of the assembly, raw materials having a heat-resistance, for example, heat resisting materials such as SUS, SUH, SCH, NCF superalloys and the like according to the JIS used. However, since the assembly is used under very severe conditions, its life or durability has a certain limit. Therefore, further improvement of the durability of the assembly is desired. Among the components or portions of the exhaust gas guide assembly, a sliding portion especially needs to secure and maintain constant slidability in a high-temperature environment and it has been difficult to suppress its friction coefficient to a small value without generating any long-time metal adhesion, seizure or the like. An Ni—Cr-based heat resisting member is suitable for a constituent material for the sliding portion in terms of high-temperature strength thereof. However, it is difficult to use the member for the sliding portion because the member lacks high-temperature slidability due to the fact that the surface hardness of the member in a high-temperature environment is much lower than that in a room-temperature environment. The present invention has been made in view of such background and attempts to improve high-temperature wear property, oxidation resistance, high-temperature hardness or the like of a member constituting an exhaust gas guide assembly used for a long period of time under an exhaust gas atmosphere in heat cycles accompanied by high temperatures of 700° C. or above. |
<SOH> BRIEF DESCRIPTION OF DRAWINGS <EOH>FIG. 1 ( a ) is a perspective view showing a VGS turbocharger having a turbine frame integrated therein according to the present invention, and FIG. 1 ( b ) is an exploded perspective view showing an exhaust gas guide assembly according to the present invention; and FIG. 2 shows data of comparison of the durability between a non-coated product and a coated product according to the present invention. detailed-description description="Detailed Description" end="lead"? |
Method for the enzymatic production of a curing agent and its fluid state |
The invention relates to a method for the enzymatic production of a curing agent in its fluid state, e.g. liquid, comprising, in free phase, at least one oxygenated chemical species. Said method consists in bringing into contact at least one enzymatic catalysts agent, comprising at lease one peroxidase-type enzyme; an oxidasable substrate in aqueous phase that can be oxidized by the action of an oxygen donor, by catalysis by said enzymatic catalysis agent, generating said oxygenated chemical species in free phase; and said oxygen donor. The inventive method is characterized in that: e) an aqueous reaction bath is formed comprising, in addition to the oxidisable substrate and the oxygen donor, said enzymatic catalysis agent in divided solid phase, but in free phase, distributed is said bath, which may be set in motion; f) the aqueous reaction bath is separated into a fraction enriched with the enzymatic catalysis agent in divided solid phase and a fraction free from said catalysis agent, from which the curing agent is obtained. |
1. A process for enzymically producing a treatment agent in the fluid, for example liquid, state, comprising, in the free state, at least one oxygenated chemical species, by bringing into contact at least: one agent of enzymic catalysis, comprising at least one enzyme of the peroxidase type, and one substrate which can be oxidized in aqueous phase and which is capable of being oxidized by the action of an oxygen donor, by means of catalysis by said agent of enzymic catalysis, thereby generating said oxygenated chemical species in the free state, said donor, characterized in that: a) an aqueous reaction bath is formed, which bath comprises, in addition to the oxidizable substrate and the oxygen donor, said agent of enzymic catalysis in the solid and divided phase, but in the free state, which agent is distributed in said bath, which latter may possibly be set in motion, b) the aqueous reaction bath is separated into a fraction which is enriched in agent of enzymic catalysis in solid and divided phase and into a fraction which lacks said agent of catalysis and from which the treatment agent is obtained. 2. The process as claimed in claim 1, characterized in that the agent of enzymic catalysis is introduced, in the state of a solid and divided phase, into the reaction bath. 3. The process as claimed in claim 1, characterized in that the agent of enzymic catalysis is introduced, in liquid phase, into the reaction bath. 4. The process as claimed in claim 1, characterized in that the oxidizable substrate is introduced, where appropriate in aqueous phase, into the aqueous reaction bath. 5. The process as claimed in claim 1, characterized in that the oxygen donor is introduced, where appropriate in aqueous phase, into the aqueous reaction bath. 6. The process as claimed in claim 1, characterized in that the agent of enzyme catalysis is discharged from the reaction bath. 7. The process as claimed in claim 1, characterized in that it is performed continuously or discontinuously. 8. The process as claimed in claim 1, characterized in that the agent of enzymic catalysis is suspended, in solid phase, in the reaction bath in the form of an emulsion and an emulsifying agent is introduced, where appropriate, into said bath. 9. The process as claimed in claim 1, characterized in that aggregates of solid particles which are inert vis-á-vis the agent of enzymic catalysis are formed in the aqueous reaction bath, with said aggregates comprising or incorporating said agent of catalysis in the free state and said aggregates being distributed in the aqueous reaction bath, by means of which said bath is separated, during step (b), into a fraction which is enriched in aggregate and a fraction which is devoid of aggregate and from which the treatment agent is obtained. 10. The process as claimed in claim 9, characterized in that the aggregates are floccules and a flocculating agent, for example an anionic or cationic flocculating agent, is introduced into the reaction bath. 11. The process as claimed in claim 9, characterized in that the aggregates are coagulates and a coagulating agent is introduced into the reaction bath. 12. The process as claimed in claim 9, characterized in that a coagulating agent and a flocculating agent is introduced into the reaction bath. 13. The process as claimed in claim 1, characterized in that a thickening agent is introduced into the reaction bath. 14. The process as claimed in claim 13, characterized in that the thickening agent is selected from clays, kaolin, silica or silicates. 15. The process as claimed in claim 1, characterized in that the agent of catalysis comprises a microorganism which is expressing at least one enzyme of the peroxidase type. 16. The process as claimed in claim 1, characterized in that a pH-correcting agent is introduced into the bath. 17. The process as claimed in claim 1, characterized in that an oxygen donor in the form of a supplementary enzyme system which produces hydrogen peroxide is introduced into the bath and the agent of enzymic catalysis comprises an enzyme of the oxidoreductase type in addition to the enzyme of the peroxidase type. 18. The process as claimed in claim 1, characterized in that the agent of enzymic catalysis is selected from peroxidases. 19. The process as claimed in claim 16, characterized in that the peroxidase is a lactoperoxidase. 20. The process as claimed in claim 1, characterized in that the oxidizable substrate is selected from the group consisting of sodium thiocyanate (NASCN) or potassium thiocyanate (KSCN), sodium bisulfite (NaHSO3), sodium hydrosulfite (Na2S2O4), sodium metabisulfite Na2S2O5), sodium nitrite (NaNO2), or potassium nitrite (KNO2), sodium hypochlorite (NaOCl) and potassium iodide (KI). 21. The process as claimed in claim 1, characterized in that the oxygen donor is hydrogen peroxide. 22. A group of reagents for enzymically producing a treatment agent in the fluid state which comprises, in the free state, at least one oxygenated chemical species, characterized in that it comprises an agent of enzymic catalysis and an aggregating agent in aqueous phase. 23. A group of reagents for enzymically producing a treatment agent in the fluid state which comprises, in the free state, at least one oxygenated chemical species, characterized in that it comprises an agent of enzymic catalysis and a flocculating agent in aqueous phase. 24. A group of reagents for enzymically producing a treatment agent in the fluid state which comprises, in the free state, at least one oxygenated chemical species, characterized in that it comprises an agent of enzymic catalysis and a coagulating agent in aqueous phase. 25. A group of reagents for enzymically producing a treatment agent in the fluid state which comprises, in the free state, at least one oxygenated chemical species, characterized in that it comprises an agent of enzymic catalysis and a thickening agent. 26. A group of reagents as claimed in claim 22, characterized in that the agent of enzymic catalysis is selected from peroxidases. 27. A group of reagents as claimed in claim 26, characterized in that the peroxidase is a lactoperoxidase. 28. A treatment agent in the fluid, for example liquid, state, which comprises, in the free state, as the oxygenated chemical species, at least the hypothiocyanate ion (OSCN), which is in the stable state for more than 10 hours. 29. The use, for producing a treatment agent as claimed in claim 28, of a reactor, characterized in that it comprises three or four compartments, two or three of which are stirred continuously: the first is intended to receive the agent of enzymic catalysis and optionally the coagulant and the thickening agent; it is stirred at high speed, the second optionally receives the flocculent and optionally receives the pH-correcting agent; it is stirred at low speed, the third, to which the oxidizable substrate as well as the oxygen donor are supplied, is the site of the desired enzyme reaction and is also stirred at low speed, the fourth compartment, in which the aqueous reaction bath is separated into a fraction which is enriched with agent of enzymic catalysis, in solid and divided phase, and a fraction which is devoid of said agent of catalysis and from which said treatment agent is obtained, comprises means for separating said fractions. 30. The use as claimed in claim 29, characterized in that the means for separating said fractions are selected from decantation, flotation, centrifugation, filtration and/or cyclonic separation. |
Method and device for feeding reels to a machine |
A device (2) for feeding reels (3) has a manipulator (14) having a gripping member (19) for picking up one reel (3) at a time off a pallet (16) and transferring the reel (3) to an unwinding pin (4a; 4b) on a machine (1); the gripping member (19) is enabled to pick up a reel (3) off the pallet (16) when at least one reference point (k1) of the gripping member (19) lies inside a central hole (7) of the reel (3). |
1. A method of feeding reels to a machine from a store (16) of reels (3) close to said machine (1); each reel (3) having an axis (5), an central hole (7) which is engaged by an unwinding pin (4a; 4b) on said machine (1), and two flat faces (9) perpendicular to said axis (5); and the method being characterized by determining whether at least one reference point (K1) of a gripping member (19) of a manipulator (14) lies inside the hole (7) of a reel (3) in the store (16); picking up said reel (3) by means of the gripping member (19) when the reference point (K1) lies inside the hole (7) of said reel (3); and transferring said reel (3) from said gripping member (19) to said unwinding pin (4a; 4b). 2. A method as claimed in claim 1, characterized by positioning said gripping member (19) facing one of said flat faces (9) of a reel (3); and emitting a beam of electromagnetic waves onto a reel (3) by means of an emitter (27) on said gripping member (19); said reference point (K1) being the reflection point (K1) of emitted said beam. 3. A method as claimed in claim 2, characterized in that said gripping member (19) comprises a receiver (28) located at a first distance (D1) from said emitter (27) so as to pick up the reflected beam when said flat face (9) is located at a second distance, parallel to said axis (5), from said gripping member (19), and the reflection point (K1) lies on said flat face (9). 4. A method as claimed in claim 3, characterized in that said receiver (28) comprises a number of adjacent cells (29) sensitive to electromagnetic waves, so as to pick up the reflected beam when the flat face (9) lies within a given range (I), parallel to said axis (5), about said second distance (D2) from the gripping member (19), and the reflection point (k1) lies on said flat face (9). 5. A method as claimed in claim 3 or 4, characterized by moving said gripping member (19) parallel to said flat face (9) when said receiver (28) picks up the reflected beam. 6. A method as claimed in claim 5, characterized by picking up said reel (3) when said receiver (28) does not pick up the reflected beam. 7. A method as claimed in claim 3 or 4, characterized in that said gripping member (19) comprises three distance sensors (25); each distance sensor (25) comprising a said emitter (27) and a said receiver (28); each distance sensor (25) generating a responsive reference point (K1, K2, K3); and said gripping member (19) picking up a reel (3) when none of the receivers (28) pick up the respective reflected beams. 8. A method as claimed in claim 3, characterized by positioning said gripping member (19) at the second distance (D2) from said flat face (9) or at least within a range (I) about said second distance (D2) and close to said hole (7) of a reel (3). 9. A method as claimed in claim 8, characterized by bringing said gripping member (19) into contact with said flat face (9); determining said contact by means of a sensor (26); and withdrawing said gripping member (19) perpendicularly to said flat face (9) to position the gripping member (19) at said second distance (D2) from the flat face (9) or within said range (I). 10. A device for feeding reels to a machine from a store (16) of reels (3) close to said machine (1); each reel (3) having an axis (5), a central hole (7) which is engaged by an unwinding pin (4a; 4b) on said machine (1), the device being characterized by comprising a manipulator (14) having a gripping member (19) for picking up a reel (3) from said store (16) when at least one reference point (K1) of the gripping member (19) lies inside the hole (7) of said reel (3). 11. A device as claimed in claim 10, characterized by comprising an emitter (27) located on said gripping member (19) to emit a beam of electromagnetic waves directed onto the reel (3); said reference point (K1) being a reflection point (K1) of the emitted said beam. 12. A device as claimed in claim 11, characterized by comprising a receiver (28) for picking up a reflected beam when the reflection point (K1) lies on said flat face (9), and not for picking up the reflected beam when the reflection point (K1) lies inside the hole (7). 13. A device as claimed in claim 12, characterized in that the receiver (28) is located at a first distance (D1) from said emitter (27) so as to pick up the reflected beam when said flat face (9) is located at a second distance (D2), parallel to said axis (5), from gripping member (19), and the reflection point (K1) lies on said flat face (9). 14. A device as claimed in claim 13, characterized in that said receiver (28) comprises a number of adjacent cells (29) sensitive to electromagnetic waves, so as to pick up reflected beam when the flat face (9) lies within a given range (I), parallel to said axis (5), about said second distance (D2) from the gripping member (19), and the reflection point (k1) lies on said flat face (9). 15. A device as claimed in any one of claims 12 to 14, characterized by comprising a control unit (33), which commands a movement of the manipulator (14) to move said gripping member (19) parallel to said flat face (9) when the reflection point (K1) lies on said flat face (9). 16. A device as claimed in claim 15, characterized in that said gripping member (19) comprises an annular plate (22) having suction holes (23) to pick up said reel (3) when said reflection point (K1) lies inside the hole (7) of said reel (3) and the plate (22) is positioned contacting said flat face (9). 17. A device as claimed in claim 13 or 14, characterized in that said gripping member (19) comprises three distance sensors (25); each distance sensor (25) comprising a said emitter (27) and a said receiver 28); the distance sensors (25) generating distinct respective reference points (K1, K2, K3); and said gripping member (19) picking up a reel (3) when the reference points (K1, K2, K3) all lie inside the hole (7) of the reel (3). 18. A device as claimed in claim 10, characterized by comprising a platform (15) for supporting said store (16) of reels (3) in a given position with respect to said machine (1) and to said manipulator (14). 19. A device as claimed in claim 10, characterized in that said store is a pallet (16) of reels (3). 20. A device as claimed in claim 18, characterized in that said platform (15) comprises a lifting device (20). 21. A device as claimed in claim 10, characterized in that said unwinding pin (4a, 4b) comprises a self-centering spindle (30). 22. A device as claimed in claim 21, characterized in that said self-centering spindle (30) comprises a tapered free end (31). |
<SOH> BACKGROUND ART <EOH>Cigarette packaging machines now operate at such high output rates as to require large amounts of packaging material, which is partly supplied in the form of strips wound into reels. Each reel comprises a strip of packaging material wound about a spool having a central hole, and is fitted onto an unwinding pin on the packaging machine. The strip of packaging material is unwound off the reel, and sheets of packaging material are cut off the strip and folded about groups of cigarettes. The increase in the amount of packaging material required calls for automatic reel handling to speed up reel feed to the machine, which in turn calls for determining the position of the reel to enable a reel manipulator to grip the reel by means of a gripping member and align the reel with an unwinding pin on the packaging machine. Patent EP-A-551,854 relates to a manipulator featuring a reel gripping member and for picking reels off a pallet on which the reels are arranged with their respective axes positioned vertically. The gripping member has a TV camera for picking up an image of a reel; and an arithmetic unit for processing the image data by means of an algorithm based on translation and inversion of the image to determine the coordinates of a characteristic point on the reel. Once the coordinates of the characteristic point on the reel are determined, the manipulator sets the gripping member to a given position to grip the reel correctly. Though reliable and capable of transferring a large number of reels per unit of time, the arithmetic unit of the above manipulator for processing the points in the image is relatively expensive. |
<SOH> BRIEF DESCRIPTION OF THE DRAWINGS <EOH>A number of non-limiting embodiments of the present invention will be described by way of example with reference to the accompanying drawings, in which: FIG. 1 shows a view in perspective, with parts removed for clarity, of a packaging machine featuring a reel feed device in accordance with the present invention; FIG. 2 shows a larger-scale underside view of a gripping member of the FIG. 1 device; FIGS. 3 and 4 show schematic side views of a variation of the gripping member in two operating positions with respect to a reel; FIGS. 5, 6 and 7 are schematic plan views showing the position of a gripping member of the FIG. 1 device with respect to a reel. detailed-description description="Detailed Description" end="lead"? |
Method of producing bio-fuels |
A method of producing bio-fuels by causing an enzyme to act on the oils and fats in a waste clay to decompose them into a fatty acid which is then reacted with a lower alcohol to form an ester that can be used as a bio-fuel. An environment friendly bio-fuel is obtained from the starting waste clay through a decreased number of steps without requiring cumbersome operations. |
1. A method of producing bio-fuels by causing an enzyme to act upon the oils and fats in a waste clay to decompose them into a fatty acid, and reacting the formed fatty acid with a lower alcohol to form an ester thereof that can be used as a bio-fuel. 2. A production method according to claim 1, wherein the decomposition and the reaction of the fatty acid with the lower alcohol are carried out in water or in an organic solvent. 3. A production method according to claim 1, wherein the oils and fats are those of plant oils. 4. A production method according to claim 1, wherein the enzyme is a lipase. 5. A production method according to claim 1, wherein the reaction of the fatty acid with the lower alcohol is carried out in the presence of from 25 to 250 parts by weight of water or an organic solvent per 100 parts by weight of the oils and fats. 6. A production method according to claim 2, wherein a hexane or a petroleum ether is used as the organic solvent. 7. A production method according to claim 1, wherein the reaction of the fatty acid with the lower alcohol is carried out at a temperature of from 20 to 50° C. 8. A production method according to claim 1, wherein a glyceride contained in the residual waste clay after the fatty acid is separated, is extracted and is circulated into a step of decomposition into the fatty acid or into the step of esterification. 9. A production method according to claim 1, wherein a lower alcohol with not more than 8 carbon atoms is used. |
<SOH> BACKGROUND ART <EOH>Environment friendly fuels utilizing oils and fats have been proposed in the names of bio-fuels and bio-diesels. A representative example of the bio-diesels may be obtained by causing a caustic soda and a methyl alcohol to act upon the used fry oil to esterify it with methyl. Japanese Unexamined Patent Publication (Kokai) No. 138796/1983 teaches obtaining a fuel oil that can be used for diesel engines at a low cost and in a high yield by adding an alkali aqueous solution to the starting plant oil, heating the mixture, washing the mixture with water after it has been stirred, followed by the removing-acid treatment. According to the method of saponifying the oils and fats with an alkali followed by the neutralization with an acid to liberate the fatty acid as represented by the above prior art, however, an increased number of steps are required and, besides, the alkali and the acid that are used remain in the reaction system arousing a problem in that cumbersome operation is needed for removing them. In the field of refining oils and fats, on the other hand, waste clay occluding large amounts of oils and fats are produced as by-products without, however, any effective treatment therefor but simply blending and firing them together for producing the portland cement. It has further been attempted to extract and remove oil components contained in the waste clay with an organic solvent such as hexane. However, it is difficult to remove the oil components present in the pores of white clay (fuller's earth), and no effective processing means has yet been found. |
<SOH> BRIEF DESCRIPTION OF THE DRAWINGS <EOH>FIG. 1 is a graph plotting relationships between the reaction times and the amounts of the formed ester in Example 1 (black circles in the drawing) and in Comparative Example 1 (open circles in the drawing); FIG. 2 is a graph plotting relationships between the reaction times and the amounts of the formed ester in Example 2 (black circles in the drawing) and in Comparative Example 2 (open circles in the drawing); FIG. 3 is a graph plotting relationships between the reaction times and the amounts of the formed ester in Example 3 (black circles in the drawing) and in Comparative Example 3 (open circles in the drawing); FIG. 4 is a graph plotting relationships between the reaction times and the amounts of the formed ester in Example 4 (open circles: reacted for 72 hours, black circles: reacted for 48 hours); FIG. 5 is a graph plotting relationships between the reaction times and the amounts of the formed ester in Example 5 (open circles), in Example 6 (black circles), in Example 7 (black triangles), in Example 8 (black squares), in Example 9 (open squares), in Example 10 (open triangles) and in Example 11 (open rhombuses); FIG. 6 is a graph plotting relationships between the reaction times and the amounts of the formed ester in Examples 16 to 18, the used solvents being a hexane (black triangles), a diethyl ether (black circles) and a petroleum ether (open squares); FIG. 7 is a graph plotting a relationship between the reaction time and the amount of the formed ester in Example 19; and FIG. 8 is a graph plotting a relationship between the reaction time and the amount of the formed ester in Example 20. detailed-description description="Detailed Description" end="lead"? |
Materials and methods for producing tomato yellow leaf curl virus resistance in plants |
The subject invention concerns materials and methods for providing genetically-engineered resistance in plants to tomato yellow leaf curl geminivirus using a truncated version of the replication associated protein (Rep) gene of TYLCV. Virus-resistant plants produced according to the present invention have horticulturally acceptable phenotypic traits. Methods of the invention comprise transforming a plant with a polynucleotide wherein when the polynucleotide is expressed in the plant, the transformed plant exhibits resistance to plant viral infections. An exemplified embodiment utilizes a polynucleotide comprising a truncated Rep gene derived from a Florida isolate of TYLCV-Is. The methods of the invention can be used to provide resistance to TYLCV infection in plants such as tomato and tobacco. The present invention also concerns transformed and transgenic plants and plant tissue that express a polynucleotide comprising a truncated Rep gene of TYLCV. |
1. A method for providing resistance to infection by a tomato yellow leaf curl virus (TYLCV) in a plant or plant tissue, said method comprising transforming said plant or plant tissue with a polynucleotide selected from the group consisting of: i) a polynucleotide comprising a fragment of a TYLCV Rep gene, wherein said fragment of said Rep gene consists of all or a portion of the 5′ intergenic region of a Rep gene and up to about 400 to 500 nucleotides of the 5′ coding sequence of a Rep gene, or a fragment of said polynucleotide that is capable of providing resistance to infection by said TYLCV; ii) a polynucleotide comprising a sequence that is antisense to said fragment of said TYLCV Rep gene, or a fragment of said antisense polynucleotide that is capable of providing resistance to infection; and, iii) a polynucleotide comprising a sequence that hybridizes under stringent conditions with said fragment of said TYLCV Rep gene or said sequence that is antisense to said fragment of said TYLCV Rep gene, or a fragment of said hybridizing polynucleotide that is capable of providing resistance to infection by said TYLCV. 2. The method according to claim 1, wherein said fragment of said TYLCV Rep gene is derived from TYLCV-Is. 3. The method according to claim 1, wherein said fragment of said TYLCV Rep gene is derived from a Florida isolate of TYLCV-Is. 4. The method according to claim 1, wherein said polynucleotide comprising a fragment of said TYLCV Rep gene has the nucleotide sequence shown in SEQ ID NO. 4, or a fragment of said nucleotide sequence that is capable of providing resistance to infection. 5. The method according to claim 1, wherein said polynucleotide comprising a fragment of said TYLCV Rep gene has the nucleotide sequence shown in SEQ ID NO. 6, or a fragment of said nucleotide sequence that is capable of providing resistance to infection. 6. The method according to claim 1, wherein said polynucleotide comprising a sequence that is antisense to said fragment of said TYLCV Rep gene has the nucleotide sequence shown in SEQ ID NO. 5, or a fragment of said nucleotide sequence that is capable of providing resistance to infection. 7. The method according to claim 1, wherein said polynucleotide comprising a sequence that is antisense to said fragment of said TYLCV Rep gene has the nucleotide sequence shown in SEQ ID NO. 7, or a fragment of said nucleotide sequence that is capable of providing resistance to infection. 8. The method according to claim 1, wherein said tomato yellow leaf curl virus is selected from the group consisting of TYLCV-China, TYLCV-Israel, TYLCV-Nigeria, TYLCV-Sardinia, TYLCV-southern Saudi Arabia, TYLCV-Tanzania, TYLCV-Thailand, and TYLCV-Yemen. 9. The method according to claim 8, wherein said tomato yellow leaf curl virus is TYLCV-Israel. 10. The method according to claim 1, wherein said plant or plant tissue is selected from the group consisting of tomato, tobacco, statice, petunia, lisianthus, and tomatillo. 11. The method according to claim 10, wherein said plant or plant tissue is tomato. 12. The method according to claim 10, wherein said plant or plant tissue is tobacco. 13. The method according to claim 1, wherein said plant or plant tissue is transformed with said polynucleotide by agroinfection, biolistic targeting, electroporation, or direct gene injection. 14. The method according to claim 1, wherein said polynucleotide comprises regulatory sequences operably linked to said Rep gene sequence. 15. The method according to claim 14, wherein said regulatory sequences comprise a promoter. 16. The method according to claim 15, wherein said promoter is selected from the group consisting of constitutive promoter, tissue-specific promoter, and inducible promoter. 17. The method according to claim 15, wherein said promoter is selected from the group consisting of CaMV 35S promoter, CaMV 35S2 promoter, octopine synthase promoter, nopaline synthase promoter, Ap3 promoter, heat shock 80 promoter, alfalfa histone H3.2 gene promoter, and E8 promoter. 18. The method according to claim 1, wherein said polynucleotide comprises a selectable marker gene. 19. The method according to claim 18, wherein said selectable marker gene provides for antibiotic resistance when expressed. 20. The method according to claim 19, wherein said antibiotic resistance is selected from the group consisting of resistance to G418, hygromycin, bleomycin, kanamycin, and gentamicin. 21. The method according to claim 1, wherein said polynucleotide comprises a 3′ non-translated termination sequence. 22. A transgenic or transformed plant or plant tissue having increased resistance to infection by a tomato yellow leaf curl virus (TYLCV), wherein said plant or plant tissue comprises a polynucleotide selected from the group consisting of: i) a polynucleotide comprising a fragment of a TYLCV Rep gene, wherein said fragment of said Rep gene consists of all or a portion of the 5′ intergenic region of a Rep gene and up to about 400 to 500 nucleotides of the 5′ coding sequence of a Rep gene, or a fragment of said polynucleotide that is capable of providing resistance to infection by said TYLCV; ii) a polynucleotide comprising a sequence that is antisense to said fragment of said TYLCV Rep gene, or a fragment of said antisense polynucleotide that is capable of providing resistance to infection by said TYLCV; and, iii) a polynucleotide comprising a sequence that hybridizes under stringent conditions with said fragment of said TYLCV Rep gene or said sequence that is antisense to said fragment of said TYLCV Rep gene, or a fragment of said hybridizing polynucleotide that is capable of providing resistance to infection by said TYLCV. 23. The plant or plant tissue according to claim 22, wherein said fragment of said TYLCV Rep gene is derived from TYLCV-Is. 24. The plant or plant tissue according to claim 22, wherein said fragment of said TYLCV Rep gene is derived from a Florida isolate of TYLCV-Is. 25. The plant or plant tissue according to claim 22, wherein said polynucleotide comprising a fragment of said TYLCV Rep gene has the nucleotide sequence shown in SEQ ID NO. 4, or a fragment of said nucleotide sequence that is capable of providing resistance to infection. 26. The plant or plant tissue according to claim 22, wherein said polynucleotide comprising a fragment of said TYLCV Rep gene has the nucleotide sequence shown in SEQ ID NO. 6, or a fragment of said nucleotide sequence that is capable of providing resistance to infection. 27. The plant or plant tissue according to claim 22, wherein said polynucleotide comprising a sequence that is antisense to said fragment of said TYLCV Rep gene has the nucleotide sequence shown in SEQ ID NO. 5, or a fragment of said nucleotide sequence that is capable of providing resistance to infection. 28. The plant or plant tissue according to claim 22, wherein said polynucleotide comprising a sequence that is antisense to said fragment of said TYLCV Rep gene has the nucleotide sequence shown in SEQ ID NO. 7, or a fragment of said nucleotide sequence that is capable of providing resistance to infection. 29. The plant or plant tissue according to claim 22, wherein said tomato yellow leaf curl virus is selected from the group consisting of TYLCV-China, TYLCV-Israel, TYLCV-Nigeria, TYLCV-Sardinia, TYLCV-southem Saudi Arabia, TYLCV-Tanzania, TYLCV-Thailand, and TYLCV-Yemen. 30. The plant or plant tissue according to claim 29, wherein said tomato yellow leaf curl virus is TYLCV-Israel. 31. The plant or plant tissue according to claim 22, wherein said plant or plant tissue is selected from the group consisting of tomato, tobacco, statice, petunia, lisianthus, and tomatillo. 32. The methed-plant or plant tissue according to claim 31, wherein said plant or plant tissue is tomato. 33. The plant orplant tissue according to claim 31, wherein said plant or plant tissue is tobacco. 34. The plant or plant tissue according to claim 22, wherein said plant or plant tissue is transformed with said polynucleotide by agroinfection, biolistic targeting, electroporation, or direct gene injection. 35. The plant or plant tissue according to claim 22, wherein said polynucleotide comprises regulatory sequences operably linked to said Rep gene sequence. 36. The plant or plant tissue according to claim 35, wherein said regulatory sequences comprise a promoter. 37. The plant or plant tissue according to claim 36, wherein said promoter is selected from the group consisting of constitutive promoter, tissue-specific promoter, and inducible promoter. 38. The plant or plant tissue according to claim 36, wherein said promoter is selected from the group consisting of CaMV 35S promoter, CaMV 35S2 promoter, octopine synthase promoter, nopaline synthase promoter, Ap3 promoter, heat shock 80 promoter, alfalfa histone H3.2 gene promoter, and E8 promoter. 39. The plant or plant tissue according to claim 22, wherein said polynucleotide comprises a selectable marker gene. 40. The plant or plant tissue according to claim 39, wherein said selectable marker gene provides for antibiotic resistance when expressed. 41. The plant or plant tissue according to claim 40, wherein said antibiotic resistance is selected from the group consisting of resistance to G418, hygromycin, bleomycin, kanamycin, gentamicin. 42. The plant or plant tissue according to claim 22, wherein said polynucleotide comprises a 3′ non-translated termination sequence. 43. A progeny of the plant or plant tissue of claim 22. 44. A polynucleotide selected from the group consisting of: i) a polynucleotide comprising a fragment of a TYLCV Rep gene, wherein said fragment of said Rep gene consists of all or a portion of the 5′ intergenic region of a Rep gene and up to about 400 to 5 00 nucleotides of the 5′ coding sequence of a Rep gene, or a fragment of said polynucleotide that is capable of providing resistance to infection by said TYLCV; ii) a polynucleotide comprising a sequence that is antisense to said fragment of said TYLCV Rep gene, or a fragment of said antisense polynucleotide that is capable of providing resistance to infection by said TYLCV; and, iii) a polynucleotide comprising a sequence that hybridizes under stringent conditions with said fragment of said TYLCV Rep gene or said sequence that is antisense to said fragment of said TYLCV Rep gene, or a fragment of said hybridizing polynucleotide that is capable of providing resistance to infection by said TYLCV. 45. The polynucleotide according to claim 44, wherein said fragment of said TYLCV Rep gene is derived from TYLCV-Is. 46. The polynucleotide according to claim 44, wherein said fragment of said TYLCV Rep gene is derived from a Florida isolate of TYLCV-Is. 47. The polynucleotide according to claim 44, wherein said polynucleotide comprising a fragment of said TYLCV Rep gene has the nucleotide sequence shown in SEQ ID NO. 4, or a fragment of said nucleotide sequence that is capable of providing resistance to infection. 48. The polynucleotide according to claim 44, wherein said polynucleotide comprising a fragment of said TYLCV Rep gene has the nucleotide sequence shown in SEQ ID NO. 6, or a fragment of said nucleotide sequence that is capable of providing resistance to infection. 49. The polynucleotide according to claim 44, wherein said polynucleotide comprising a sequence that is antisense to said fragment of said TYLCV Rep gene has the nucleotide sequence shown in SEQ ID NO. 5, or a fragment of said nucleotide sequence that is capable of providing resistance to infection. 50. The polynucleotide according to claim 44, wherein said polynucleotide comprising a sequence that is antisense to said fragment of said TYLCV Rep gene has the nucleotide sequence shown in SEQ ID NO. 7, or a fragment of said nucleotide sequence that is capable of providing resistance to infection. 51. The polynucleotide according to claim 44, wherein said tomato yellow leaf curl virus is selected from the group consisting of TYLCV-China, TYLCV-Israel, TYLCV-Nigeria, TYLCV-Sardinia, TYLCV-southem Saudi Arabia, TYLCV-Tanzania, TYLCV-Thailand, and TYLCV-Yemen. 52. The polynucleotide according to claim 51, wherein said tomato yellow leaf curl virus is TYLCV-Israel. 53-56. (canceled) 57. The polynucleotide according to claim 44, wherein said polynucleotide comprises regulatory sequences operably linked to said Rep gene sequence. 58. The polynucleotide according to claim 57, wherein said regulatory sequences comprise a promoter. 59. The polynucleotide according to claim 58, wherein said promoter is selected from the group consisting of constitutive promoter, tissue-specific promoter, and inducible promoter. 60. The polynucleotide according to claim 58, wherein said promoter is selected from the group consisting of CaMV 35S promoter, CaMV 35S2 promoter, octopine synthase promoter, nopaline synthase promoter, Ap3 promoter, heat shock 80 promoter, alfalfa histone H3.2 gene promoter, and E8 promoter. 61. The polynucleotide according to claim 44, wherein said polynucleotide comprises a selectable marker gene. 62. The polynucleotide according to claim 61, wherein said selectable marker gene provides for antibiotic resistance when expressed. 63. The polynucleotide according to claim 62, wherein said antibiotic resistance is selected from the group consisting of resistance to G418, hygromycin, bleomycin, kanamycin, and gentamicin. 64. The polynucleotide according to claim 44, wherein said polynucleotide comprises a 3′ non-translated termination sequence. 65. An expression vector comprising a polynucleotide of claim 44. 66. The expression vector according to claim 65, wherein said expression vector is suitable for expressing said polynucleotide in a plant. 67. A plant cell comprising in its genome a polynucleotide of claim 44. 68. A plant seed comprising in its genome a polynucleotide of claim 44. |
<SOH> BACKGROUND OF THE INVENTION <EOH>Whitefly-transmitted geminiviruses have become a major limiting factor in tomato production in Florida, the Caribbean and much of Latin America. This group of viruses is currently expanding in the Western Hemisphere, and the number of characterized geminiviruses which infect tomato in this region has increased from three to more than 17 over the last 15 years (Polston and Anderson, 1997). This expansion is continuing and reports of new epidemics are appearing almost monthly. Whitefly-transmitted viruses appear alone and in mixed infections with other geminiviruses and other viruses. Whitefly-transmitted geminiviruses are reducing tomato yields in many countries, and total crop losses are not uncommon (Polston and Anderson, 1997). In Florida, tomato production has suffered significant losses (estimated at $125 million in 1990-91) due to Tomato mottle virus (ToMoV) infection, which first appeared in 1989 and to Tomato yellow leaf curl virus (TYLCV, which has caused crop failures and increases in production costs due to increases in pesticide use. The family Geminiviridae is divided into three genera, of which the genus, Begomovirus, contains the whitefly-transmitted geminiviruses. There are two major divisions within the genus Begomovirus, those with monopartite genomes and those with bipartite genomes. The taxonomy of Begomoviruses is in a state of confusion, due to the naming of viruses based on disease symptoms before any sequence analysis has been performed. Many of these viruses cause similar symptoms in the same host, which has resulted in very different viruses having the same or related name in the literature. This is particularly true for tomato yellow leaf curl virus (TYLCV). There are eight separate and unique Begomoviruses named TYLCV. Recent suggestions to resolve this confusion have been published, though none have been adopted by all virologists, with the result that different viruses are referred to in a number of different ways. Using the scheme suggested by Fauquet and Mayo (1999), the eight viruses are identified based on the country from where the virus was first described: from China (TYLCV-Ch), from Israel (also the first one to be described) (TYLCV-Is), from Nigeria (TYLCV-Ng), from Sardinia (TYLCV-Sar), from southern Saudi Arabia (TYLCV-SSA), from Tanzania (TYLCV-Tz), from Thailand (TYLCV-Th), and from Yemen (TYLCV-Ye). Thus, while each of these viruses is named TYLCV, each of these viruses have unique sequences with less than 90% sequence homology over the genome. The geminivirus referred to as tomato yellow leaf curl virus-Israel (TYLCV-Is), which caused extensive losses to tomato production in the Dominican Republic (reviewed by Polston and Anderson, 1997), was found in Florida in 1997 (Polston et al., 1999). TYLCV-Is infection of tomato is a serious problem in the United States Florida, Georgia, Louisiana, and Mississippi), the Caribbean (The Bahamas, Cuba, Dominican Republic, Puerto Rico, and Jamaica), Mexico, Japan, Europe, and the Mediterranean (Canary Islands, Egypt, Israel, Cyprus, Italy, Spain, Portugal and Morocco). Incidences of TYLCV-Is are increasing and economic losses have been experienced as recently as fall of 1998. TYLCV-Is virus is widespread in Florida, is likely to increase over the next few years and will become a major constraint to tomato production in Florida. Currently, there are few commercial tomato cultivars on the market with resistance to infection by TYLCV-Is. The resistance is categorized as tolerance, since infected plants show no to slight symptoms and produce yields that are relatively unaffected by infection; however, the virus can still be detected in inoculated plants and these plants can serve as sources of inoculum for susceptible cultivars and crops (Lapidot et al., 2001). Geminiviruses are very difficult to economically manage in fresh market tomatoes, and practically impossible to manage in processing tomatoes. At this time, geminiviruses are managed primarily through the use of a single insecticide, imidacloprid (Bayer Agricultural Products, Kansas City, Mo.), to reduce the population of the whitefly vector. Tolerance to this insecticide has already been reported (Cahill et al., 1996; Williams et al., 1996). It may be only a matter of time before imidacloprid loses efficacy in the United States and other locations. The average Florida tomato grower spent approximately $250/acre for insecticides to control ToMoV in 1994 through 1997. These costs have increased significantly as U.S. growers' struggle to manage TYLCV-Is. In Caribbean countries geminiviruses have caused many small and medium size tomato growers to go out of business due the increases in costs of production and crop losses. In Israel, where imidacloprid resistance is present, TYLCV-Is is managed by pesticide use plus exclusion; tomatoes are produced in planthouses enclosed in whitefly-proof screening material or in screened tunnels in the field. The use of these methods is expensive and is often not an economically or horticulturally realistic alternative. The least expensive and most practical control of whitefly-transmitted geminiviruses is the use of resistant cultivars. At this time there are no commercially available resistant tomato cultivars for the geminiviruses native to the Western Hemisphere. As noted above, there are only two cultivars with tolerance to TYLCV-Is that are suitable for production in the U.S. This resistance is derived from wild species of Lycopersicon, probably L. peruvianum and L. pimpinellifolium. There are a few reports suggesting that the gene encoding the Begomovirus replication associated protein (Rep) might be used for resistance to viral infection. There has been a report that a modified ToMoV Rep mutated in an NTP-binding motif was transformed into tomato plants and demonstrated to interfere with viral replication (Stout et al., 1997). Hanson et al. (1999) analyzed phenotypes of BGYMV (bean golden yellow mosaic virus) with mutations in an NTP-binding motif of the Rep gene, and demonstrated that the NTP-binding domain is required for replication. They proposed that mutations in this motif might serve in a trans-dominant negative interference scheme for pathogen-derived resistance (also known as “dominant negative mutations”). Resistance to African cassava mosaic geminivirus (ACMV) in Nicotiana benthamiana plants was developed by transformation with ACMV Rep (Hong and Stanley, 1996). Some viral resistance has been reported using the Rep gene of the geminivirus TYLCV from Sardinia (TYLCV-Sar). However, TYLCV-Sar is a distinct virus, only distantly related to TYLCV-Is and shows significant differences in the genomic sequence (<80% homology). Noris et al (1996) found TYLCV-Sar resistance in N. benthamiana plants using the TYLCV-Sar Cl gene that encodes a protein with a truncated C-terminal (210 amino acids). However, resistance was overcome with time. Brunetti et al. (1997) transformed tomatoes with the same construct and found that high accumulation of the truncated Rep protein was required for resistance, that high accumulation resulted in a “curled” phenotype, and that the resistance did not extend to an unrelated geminivirus. Transgenic Nicotiana benthamiana plants expressing antisense RNA to the Rep gene have been observed with resistance to TYLCV-Sar infection (Bendahmane and Gronenborn, 1997). The plants transformed according to the methods of the subject invention have a normal phenotype and are expected to be high yielding as well. The present invention overcomes the expensive, time consuming, and limited options in the traditional plant breeding programs applied to generating virus resistant tomato cultivars. |
<SOH> BRIEF SUMMARY OF THE INVENTION <EOH>The subject invention concerns materials and methods for providing genetically-engineered resistance to tomato yellow leaf curl geminivirus, such as TYLCV-Israel (TYLCV-Is), in plants while maintaining acceptable phenotypic characteristics of the plant. In exemplified embodiments, the subject invention provides TYLCV-Is resistance in tomato and tobacco. Specifically, resistance is provided by transforming a plant with a truncated version of the replication associated protein (Rep) gene of TYLCV. Exemplified herein is the use of a truncated Rep gene from TYLCV-Is (Florida isolate). The full length Rep gene of TYLCV-Is encodes a virus replication related protein of approximately 357 amino acids. In an exemplified embodiment, the Rep gene used in the present methods was truncated at the 3′ end, leaving 508 nucleotides (nt) at the 5′ terminus which comprised an 82 nt intergenic sequence and a 426 nt sequence that encodes a Rep protein fragment (N-terminus) of 142 amino acids. In another embodiment, a polynucleotide that is antisense to a truncated Rep gene of the present invention is used to provide resistance to infection. The present invention demonstrates the application of genetic engineering in the development of TYLCV-Is resistance in a tomato breeding line suitable for use in a hybrid for tomato production in Florida. |
Cleaning device |
The present invention is a cleaning device (10), including an elongated substantially tubular portion (12) extending a long a first axis (A-A) and a blade element (14) attached to and extending away from the elongated tubular portion (12). The blade element (14) has a base portion (16) and an edge portion (18), and the edge portion (18) extends along a second axis (B-B), which is parallel to the first axis (A-A) of the tubular portion (12). Both the tubular portion (12) and the blade element (14) are manufactured from a flexible and deformable material having excellent memory characteristics. |
1. A cleaning device, comprising; an elongated substantially tubular portion extending along a first axis; and a blade element attached to and extending away from the elongated tubular portion, the blade element having a base portion and an edge portion, the edge portion extending along a second axis substantially parallel to the first axis of the tubular portion; wherein, the tubular portion and the blade element are substantially flexible and deformable, and wherein the tubular portion is manufactured from a material, such that, when deformed via pressure and then released, the tubular portion returns to its original position. 2. The cleaning device of claim 1, wherein the blade element is manufactured from a material, such that, when deformed via pressure and then released, the blade element returns to its original position. 4. The cleaning device of claim 1, wherein at least one of the tubular portion and the blade element are manufactured from a material that is resilient and water resistant. 5. The cleaning device of claim 1, wherein at least one of the tubular portion and the blade element are manufactured from a polymeric material. 6. The cleaning device of claim 5, wherein the polymeric material is a chemically expanded polymer in the form of a closed cell microcellular foam formulation. 7. The cleaning device of claim 5, wherein the polymeric material comprises a material selected from the group consisting of polyurethane, expanded neoprene gas, rubber compounds, silicone compounds, neoprene, vinyl nitrile neoprene, polyethylene, butyl ethylene, vinyl acetate, cross-linked polyethylene, butadiene, elastomeric sponge and synthetic closed cell sponge rubber. 8. The cleaning device of claim 1, wherein the tubular portion and the blade element are manufactured as a single, integral element from one of a pour-mold process and thermo-mold process. 9. The cleaning device of claim 1, further comprising: a first cap element positioned at least partially over a first end of the tubular portion; and a second cap element positioned at least partially over a second end of the tubular portion. 10. The cleaning device of claim 7, wherein the tubular portion is a hollow tube having a first end and a second end, the first cap element is frictionally slid at least partially over the hollow tube first end, and the second cap element is frictionally slide at least partially over the hollow tube second end. 11. A cleaning device kit, comprising: a substantially flat section of deformable material having a first end portion, a second end portion, a middle portion and a flat section width; an adhesive applied to the first end portion and the second end portion; a tubular element positioned on the middle portion; and a tubular element manufactured from a material, such that, when deformed via pressure and then released, the tubular element returns to its original position. 12. The cleaning device kit of claim 11, wherein the tubular portion has a first end and a second end and a length less than the width of the flat section. 13. The cleaning device kit of claim 12, further comprising a first cap element positioned adjacent the tubular portion first end and a second cap element positioned adjacent the tubular portion second end. 14. The cleaning device kit of claim 11, wherein at least one of the tubular portion and the blade element are manufactured from a material that is resilient and water resistant. 15. The cleaning device kit of claim 11, wherein at least one of the tubular portion and the blade element are manufactured from one of a polymeric material. 16. The cleaning device of claim 15, wherein the polymeric material is a chemically expanded polymer in the form of a closed cell microcellular foam formulation. 17. The cleaning device of claim 15, wherein the polymeric material comprises a material selected from the group consisting of polyurethane, expanded neoprene gas, rubber compounds, silicone compounds, neoprene, vinyl nitrile neoprene, polyethylene, butyl ethylene, vinyl acetate, cross-linked polyethylene, butadiene, elastomeric sponge and synthetic closed cell sponge rubber. 18. The cleaning device kit of claim 11, wherein the tubular portion is a hollow tube element. 19. A cleaning device, comprising: an elongated substantially tubular portion extending along a first axis; and a blade element attached to and extending away from the elongated tubular portion, the blade element having a base portion and an edge portion, the edge portion extending along a second axis substantially parallel to the first axis of the tubular portion; wherein, the tubular portion and the blade element are manufactured from a polymeric material comprising a synthetic closed cell sponge rubber, wherein the tubular element is manufactured from a material, such that, when deformed via pressure and then released, the tubular portion returns to its original position. 20. The cleaning device of claim 19, wherein the tubular portion and the blade element are manufactured as a single, integral element from one of a pour-mold process and thermo-mold process. |
<SOH> BACKGROUND OF THE INVENTION <EOH>1. Field of the Invention The present invention relates generally to cleaning devices and, in particular, to a flexible all-purpose cleaning device. 2. Description of Related Art There are many cleaning devices available to remove foreign substances, whether liquid or solid, from a surface. For example, a consumer may use a mop to remove liquid from a floor, a feather duster to remove dust from a surface, e.g., furniture, a rag or cloth to remove dirt and other foreign substances from surfaces, etc. Devices have also been created that remove water droplets from a surface, such as a glass, tile, or painted surfaces. One drawback in using a cloth or rag to remove water droplets from a surface is the resultant streaking and incomplete removal of the water. In order to enhance this removal, a “bladed” device having a flat edge may be used to ensure the removal of all foreign substances from the surfaces. However, these “bladed” cleaning devices often scratch the surface that the consumer desires to clean, thereby defeating the original purpose. This result is particularly defeating when the scratched surface is a painted one, such as the body of an automobile. One prior art device that has been created to overcome the drawback of possible scratching discussed above includes a flexible blade connected to a rigid gripping element. The blade is manufactured from a flexible, closed-cell foam which will not scratch a painted surface. However, the use of a rigid gripping element drastically decreases the applicability of such a cleaning device to a non-flat surface. For example, if such a cleaning device were used on the hood of a car, when passed over the hood of the car, and due to the rigid gripping element, water would remain at or around the grooved and/or curved areas. |
<SOH> SUMMARY OF THE INVENTION <EOH>It is, therefore, an object of the present invention to provide a cleaning device that overcomes the drawbacks of the prior art cleaning devices. It is another object of the present invention to provide a cleaning device that is substantially flexible and deformable, thereby allowing a non-flat or irregular surface to be thoroughly cleaned. It is a further object of the present invention to provide a cleaning device that is easy to use and inexpensive in its manufacture. The present invention is directed to a cleaning device including an elongated substantially tubular portion extending along a first axis. The cleaning device includes a blade element attached to and extending away from the elongated tubular portion, and the blade element has a base portion and an edge portion. The edge portion of the blade element extends along a second axis, which is parallel to the first axis of the tubular portion. The cleaning device, namely the elongated tubular portion and the blade element, are flexible and deformable. This cleaning device is manufactured from a material, such that when the material is deformed via pressure and then released, the blade element returns to its original position. In a preferred embodiment, the tubular portion and the blade element are manufactured from a polymeric material comprising a synthetic closed cell sponge rubber. The present invention also includes a cleaning device kit, including a substantially flat section of deformable material having a first end portion, a second end portion, a middle portion and a flat section width. The kit includes an adhesive applied to the first end portion and the second end portion, and a tubular element positioned on the middle portion. The present invention, both as to its construction and its method-of-operation, together with the additional objects and advantages thereof, will best be understood from the following description of exemplary embodiments when read in connection with the accompanying drawings. |
Method and device for transmitting data in a multi-carrier systemcomprising parallel concatenated coding and modulation |
The invention relates to a transmitter-receiver pair for improved data transmission in a multi-carrier system and to a corresponding method, according to which a chain coding is used. To this end, a transmitter has a first coding stage, a transmission-demultiplexer stage, a second coding stage, a modulator stage, a transmission multiplexer stage and a multi-carrier modulator, whereby said transmission-demultiplexer stage and the transmission multiplexer stage are controlled by a bit loading device. Similarly, the receiver has a multi-carrier demodulator, a receiver demultiplexer stage, a first decoding stage, a receiver multiplexer stage and a second decoding stage, whereby the receiver multiplexer stage and demultiplexer stage are in turn controlled by the bit loading device. |
1-25. (canceled) 26. A transmit device for data transfer in a multi-carrier system, comprising: a first encoding level for performing a first encoding on a serial data stream; a transmit demultiplexer level for dividing the encoded serial data stream into a plurality of parallel data streams; a second encoding level for performing a second encoding for the plurality of parallel data streams, resulting in a plurality of encoded parallel data streams; a modulator level for performing a QAM modulation for the plurality of encoded parallel data streams, resulting in a plurality of modulated parallel data streams; a transmit multiplexer level for rearranging the modulated parallel data streams into a serial data stream; a multi-carrier modulator for performing a pulse shaping and a copying of QAM symbols onto a multi-carrier time signal; and a bit-load device for performing a bit-load algorithm and for controlling both the transmit demultiplexer level and the transmit multiplexer level; wherein the second encoding level has a first plurality of encoders, the modulator level has a second plurality of TCM modulators for performing a plurality of different modulation procedures, and the first encoding level has a puncturer for performing a data speed adaptation of the encoded serial data stream depending on the bit-load algorithm performed. 27. A transmit device for data transfer in a multi-carrier system as claimed in claim 26, wherein the first encoding level includes an interleaver for performing an interleaving of the serial data stream. 28. A transmit device for data transfer in a multi-carrier system as claimed in claim 26, wherein the multi-carrier modulator performs at least one of an OFDM, an MC-CDMA and a CDMA modulation. 29. A receive device for data transfer in a multi-carrier system comprising: a multi-carrier demodulator for returning a transfer multi-carrier time signal in a serial sequence of QAM symbols; a received demultiplexer level for dividing the serial sequence of QAM symbols into a plurality of parallel sequences of QAM symbols; a demodulator level for performing a plurality of QAM demodulations on the parallel sequences of QAM symbols, resulting in a plurality of demodulated parallel data streams; a first decoding level for performing a first decoding of the demodulated parallel data streams for generating a parallel data stream; a receive multiplexer level for rearranging the parallel data stream into a serial data stream; a second decoding level for performing a second decoding of the serial data stream; and a bit-load device for performing a bit-load algorithm and for controlling the receive demultiplexer level and the receive multiplexer level; wherein the modulator level has a first plurality of QAM demodulators for performing a plurality of different demodulation procedures, the first decoding level has a second plurality of second decoders which are implemented as TCM demodulators, and the second decoding level has a de-puncturer for performing a data speed adaptation of the serial input data stream depending on the bit-load algorithm performed. 30. A receive device for data transfer in a multi-carrier system in claim 29, wherein the second decoding level includes a de-interleaver for reversing an interleaving of the serial input data stream. 31. A receive device for data transfer in a multi-carrier system as claimed in claim 29, wherein the multi-carrier demodulator performs at least one of OFDM, MC-CDMA and CDMA demodulation. 32. A receive device for data transfer in a multi-carrier system as claimed in claim 29, wherein the second decoding level performs a Viterbi algorithm. 33. A receive device for data transfer in a multi-carrier system as claimed in claim 29, further comprising: a transmitter chain which is a reproduction of a transmit path and generates a reproduced serial sequence of QAM symbols from the data stream which is generated by the second decoding level; an analysis unit for generating a reliability information signal depending on the reproduced serial sequence of QAM symbols and the received serial sequence of QAM symbols of a multi-carrier demodulator; and a select device for selecting a reliability information signal of a 1st to kth iteration, wherein the reliability information signal of a 1st iteration represents a function of a channel state information. 34. A receive device for data transfer in a multi-carrier system as claimed in claim 33, wherein the channel state information is derived from a channel estimation. 35. A receive device for data transfer in a multi-carrier system as claimed in claim 33, wherein the plurality of QAM demodulators and first decoders, which are implemented as TCMD modulators, are controlled depending on the selected reliability information signals. 36. A receive device for data transfer in a multi-carrier system as claimed in claim 29, wherein the second decoding level performs a soft-output Viterbi algorithm for outputting a reproduced reliability information signal. 37. A receive device for data transfer in a multi-carrier system as claimed in claim 36, further comprising: a feedback path for feeding back the reproduced reliability information signal; and a select device for selecting a reliability information signal of a 1st to kth iteration, wherein the reliability information signal of a 1st iteration represents a function of a channel state information. 38. A receive device for data transfer in a multi-carrier system as claimed in claim 37, wherein the channel state information is derived from a channel estimation. 39. A receive device for data transfer in a multi-carrier system as claimed in claim 37, wherein the plurality of post-connected first decoders are controlled depending on the selected reliability information signals. 40. A received device for data transfer in a multi-carrier system as claimed in claim 38, wherein the feedback path includes at least one of a puncturer and an interleaver, which are reproductions of a corresponding element of a transmit path. 41. A method for data transfer in a multi-carrier system, the method comprising the steps of: a) performing a first encoding on a serial data stream; b) dividing the serial data stream into a plurality of parallel data streams; c) performing a plurality of second encodings on the parallel data streams; d) performing a plurality of QAM modulations on the encoded parallel data streams; e) rearranging the QAM-modulated parallel data streams into a serial sequence of QAM symbols; f) performing a multi-carrier modulation; g) transferring the modulated data stream on at least one channel of a transfer medium; h) performing a multi-carrier demodulation for generating a serial sequence of QAM symbols; i) dividing the serial sequence of QAM symbols into a plurality of parallel sequences of QAM symbols; j) performing a plurality of QAM demodulations on the parallel sequences of QAM symbols; k) performing a plurality of first demodulations on the QAM-demodulated parallel data streams; l) rearranging the decoded parallel data streams into a serial data stream; m) performing a second decoding of the serial data stream; and n) performing a bit-load algorithm for controlling the steps b), e), i) and 1) wherein a puncturing is performed after step a) and a de-puncturing is performed before step m) depending on the bit-load algorithm which has been performed. 42. A method for data transfer in a multi-carrier system as claimed in claim 41, the method further comprising the steps of: performing an interleaving of the serial data stream following step a); and performing a reversal of the interleaving of the serial input data stream following step 1). 43. A method for data transfer in a multi-carrier system as claimed in claim 41, wherein different combinations of at least one second encoding and at least one post-connected QAM modulation are performed in steps c) and d), and different combinations of at least one first decoding and at least one pre-connected QAM demodulation are performed in steps j) and k). 44. A method for data transfer in a multi-carrier system as claimed in claim 41, wherein at least one of an OFDM, an MC-CDMA and CDMA modulation is performed in step f), and at least one of an OFDM, MC-CDMA and a CDMA demodulation is performed in step h). 45. A method for data transfer in a multi-carrier system as claimed in claim 41, wherein a Viterbi algorithm is performed in step m). 46. A method for data transfer in a multi-carrier system as claimed in claim 41, wherein step m) further includes feeding back the decoded serial data stream via a transmitter chain for generating a reproduced serial sequence of QAM symbols, generating a reliability information signal depending on the reproduced and the received serial sequence of QAM symbols, and selecting and copying a reliability information signal of a 1st to kth iteration for controlling step j), wherein the copied reliability information signal of a 1st iteration represents a function of a channel state information. 47. A method for data transfer in a multi-carrier system as claimed in claim 41, wherein a soft-output Viterbi algorithm for outputting a calculated reliability information signal is performed in step m). 48. A method for data transfer in a multi-carrier system as claimed in claim 46, wherein step m) further includes linking the calculated reliability information signal back into a feedback path, and selecting and copying a reliability information signal of a 1st to kth iteration for controlling step i), wherein the copied reliability information signal of the 1st iteration represents a function of a channel state information. 49. A method for data transfer in a multi-carrier system as claimed in claim 46, wherein the channel state information is derived from a channel estimation. 50. A method for data transfer in a multi-carrier system as claimed in claim 48, the method further comprising the step of performing at least one of a puncturing and an interleaving in the feedback path as in the transmit path. |
<SOH> BACKGROUND OF THE INVENTION <EOH>The present invention relates to a transmit and receive device for improved data transfer in a multi-carrier system, together with an associated method, and, in particular, to a transmit and receive device together with an associated method for improved data transfer in a wireless OFDM-based multi-carrier system having channels which exhibit a quasi-static behavior. Conventional digital multi-carrier systems transmit and receive digital signals using a multiplicity of carriers or sub-channels having various frequencies. In this context, a transmitter divides a transmit signal into a multiplicity of components, assigns the components to a specific carrier, encodes each carrier in accordance with its components, and transfers each carrier via one or more transfer channels. A device and a method for improved data transfer in an OFDM multi-carrier system, in which an adaptive modulation is combined with a multilevel encoding, is disclosed on pages 21.1-21.5 of the document reference “Combining Multilevel Coding and Adaptive Modulation in OFDM Systems” by M. Lampe and H. Rohling, 1 st OFDM Workshop, Sep. 21-22, 1999, Hamburg-Harburg, Germany. In this context, the multilevel encoder includes a demultiplexer for dividing a serial data stream into a multiplicity of parallel data streams, a multiplicity of parallel-arranged encoders and post-connected QAM modulators, and a multiplexer for returning data in a serial data stream. The decoder includes a multiplicity of decoders and demodulators which are arranged in parallel, and a multiplexer for returning the parallel data stream in a serial data stream. By combining this multilevel encoding with the adaptive modulation, it is possible to derive a multi-carrier system with improved data transfer properties and reduced susceptibility to failure. In accordance with the aforementioned document reference, therefore, a data grouping is partitioned and the so-called “weakest” and “strongest” bits are examined with regard to their error susceptibility, wherein on the basis of the observed properties a more or less strong error correction is applied; for example, in the form of FEC encoding procedures (Forward Error Correction). In order to reduce system complexity, the output signal of a relevant demodulator/decoding level is forwarded to the higher-order demodulator/decoder in the multilevel structure of the decoder. The encoders are the same at each level, and are merely punctured differently. A method and an arrangement for transferring data are disclosed in EP 0 991 221 A2, in which interference characteristics are specified for a selection of n channels to be used for an audio data transfer. For this, data bits of the audio data are divided into n classes on the basis of their sensitivity to errors which occur, the division being performed in such a way that the classes of bits with the highest error sensitivity are transferred on channels which are the least susceptible to interferences. In contrast, the present invention addresses the problem of creating a transmit and receive device for improved data transfer in a multi-carrier system, together with an associated method. |
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