The present invention relates to pharmaceutical compositions containing, as active ingredient, a compound of formula:

The present invention relates to pharmaceutical compositions containing, as active ingredient, at least one compound of formula:
or one of its pharmaceutically acceptable salts, to the novel derivatives of formula (I), to their pharmaceutically acceptable salts and to their preparation as well as to their use in treating various disorders of the nervous system.
R3 represent phenyl radicals, R1 represents a radical xe2x80x94N(R5)xe2x80x94Yxe2x80x94R6, Y is SO2, R5 represents a methyl radical and R6 represents a phenyl radical is described as a synthesis intermediate in Patent WO 99/01451. The other compounds and their pharmaceutically acceptable salts are novel and as such form parts of the invention.
In formula (I)
R1 represents a radical xe2x80x94NHCOR4 or xe2x80x94N(R5)xe2x80x94Yxe2x80x94R6,
Y is CO or SO2,
R2 and R3, which are identical or different, represent either an aromatic selected from phenyl, naphthyl and indenyl, these aromatics being unsubstituted or substituted with one or more halogen atoms or alkyl, alkoxy, formyl, hydroxyl, trifluoromethyl, trifluoro-methoxy, xe2x80x94CO-alk, cyano, xe2x80x94COOH, xe2x80x94COOalk, xe2x80x94CONR7R8, xe2x80x94COxe2x80x94NHxe2x80x94NR9R10, alkylsulfanyl, alkylsulfinyl, alkyl-sulfonyl, alkylsulfanylalkyl, alkylsulfinylalkyl, alkylsulfonylalkyl, hydroxyalkyl or -alk-NR7R8 radicals; or a heteroaromatic selected from benzofuryl, benzothiazolyl, benzothienyl, benzoxazolyl, chromanyl, 2,3-dihydrobenzofuryl, 2,3-dihydrobenzothienyl, pyrimidinyl, furyl, imidazolyl, isochromanyl, isoquinolyl, pyrrolyl, pyridyl, quinolyl, 1,2,3,4-tetrahydro-isoquinolyl, thiazolyl and thienyl rings, it being possible for these heteroaromatics to be unsubstituted or substituted with a halogen atom or an alkyl, alkoxy, hydroxyl, trifluoromethyl, trifluoromethoxy, cyano, xe2x80x94COOH, xe2x80x94COOalk, xe2x80x94COxe2x80x94NHxe2x80x94NR9R10, xe2x80x94CONR7R8, -alk-NR9R10, alkylsulfanyl, alkylsulfinyl, alkylsulfonyl, alkylsulfanylalkyl, alkylsulfinylalkyl, alkylsulfonylalkyl or hydroxyalkyl radical,
R4 represents a radical -alk-SO2xe2x80x94R11, -alk-SO2xe2x80x94CHxe2x95x90CHxe2x80x94R11, Het substituted with xe2x80x94SO2xe2x80x94R11 or phenyl substituted with xe2x80x94SO2xe2x80x94R11 or -alk-SO2xe2x80x94R11,
R5 represents a hydrogen atom or an alkyl radical,
R6 represents a phenylalkyl, Het or Ar radical,
R7 and R8, which are identical or different, represent a hydrogen atom or an alkyl radical or alternatively R7 and R8 together form with the nitrogen atom to which they are attached a 3- to 10-membered saturated mono- or bicyclic heterocycle, optionally containing another heteroatom selected from oxygen, sulfur and nitrogen and being optionally substituted with one or more alkyl radicals,
R9 and R10, which are identical or different, represent a hydrogen atom or an alkyl, xe2x80x94COOalk, cycloalkyl, alkylcycloalkyl, -alk-O-alk or hydroxyalkyl radical or alternatively R9 and R10 together form with the nitrogen atom to which they are attached a 3- to 10-membered saturated or unsaturated mono- or bicyclic heterocycle, optionally containing another heteroatom selected from oxygen, sulfur and nitrogen and being optionally substituted with one or more alkyl, xe2x80x94COalk, xe2x80x94COOalk, xe2x80x94COxe2x80x94NHalk, xe2x80x94CSxe2x80x94NHalk, oxo, hydroxyalkyl, -alk-O-alk or xe2x80x94COxe2x80x94NH2 radicals,
R11 represents an alkyl, Ar or Het radical,
Ar represents a phenyl, naphthyl or indenyl radical, these radicals being optionally substituted with one or more halogen atoms or alkyl, alkoxy, cyano, xe2x80x94CO-alk, xe2x80x94COOH, xe2x80x94COOalk, xe2x80x94CONR12R13, xe2x80x94COxe2x80x94NHxe2x80x94NR14R15, alkylsulfanyl, alkylsulfinyl, alkylsulfonyl, -alk-NR14R15, xe2x80x94NR14R15, alkylthioalkyl, formyl, hydroxyl, hydroxyalkyl, Het, xe2x80x94O-alk-NH-cycloalkyl, OCF3, CF3, xe2x80x94NHxe2x80x94CO-alk, xe2x80x94SO2NH2, xe2x80x94NHxe2x80x94COCH3, xe2x80x94NHxe2x80x94COOalk or Het radicals, or alternatively, on 2 adjacent carbon atoms, with a dioxymethylene,
Het represents a 3- to 10-membered unsaturated or saturated mono- or bicyclic heterocycle containing one or more heteroatoms selected from oxygen, sulfur and nitrogen optionally substituted with one or more halogen atoms or alkyl, alkoxy, vinyl, alkoxycarbonyl, oxo, hydroxyl, OCF3 or CF3 radicals, the nitrogen-containing heterocycles being optionally in their N-oxidized form,
R12 and R13, which are identical or different, represent a hydrogen atom or an alkyl radical or alternatively R12 and R13 together form with the nitrogen atom to which they are attached a 3- to 10-membered saturated mono- or bicyclic heterocycle, optionally containing another heteroatom selected from oxygen, sulfur and nitrogen and being optionally substituted with one or more alkyl radicals,
R14 and R15, which are identical or different, represent a hydrogen atom or an alkyl, xe2x80x94COOalk, cycloalkyl, alkylcycloalkyl, -alk-O-alk or hydroxyalkyl radical or alternatively R14 and R15 together form with the nitrogen atom to which they are attached a 3- to 10-membered saturated or unsaturated mono- or bicyclic heterocycle, optionally containing another heteroatom selected from oxygen, sulfur and nitrogen and being optionally substituted with one or more alkyl, xe2x80x94COalk, xe2x80x94COOalk, xe2x80x94COxe2x80x94NHalk, xe2x80x94CSxe2x80x94NHalk, oxo, hydroxyalkyl, -alk-O-alk or xe2x80x94COxe2x80x94NH2 radicals,
alk represents an alkyl or alkylene radical.
In the preceding definitions and in those which follow, unless otherwise stated, the alkyl and alkylene radicals and portions and the alkoxy radicals and portions are in the form of a straight or branched chain and contain 1 to 6 carbon atoms and the cycloalkyl radicals contain 3 to 10 carbon atoms.
Among the alkyl radicals, there may be mentioned the methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, pentyl and hexyl radicals. Among the alkoxy radicals, there may be mentioned the methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy and pentyloxy radicals.
Among the cycloalkyl radicals, there may be mentioned the cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl radicals.
The term halogen comprises chlorine, fluorine, bromine and iodine.
Among the heterocycles represented by Het, the following heterocycles may be mentioned: benzimidazole, benzoxazole, benzothiazole, benzothiophene, cinnoline, thiophene, quinazoline, quinoxaline, quinoline, pyrazole, pyrrole, pyridine, imidazole, indole, isoquinoline, pyrimidine, thiazole, thiadiazole, piperidine, piperazine, pyrrolidine, triazole, furan, tetrahydroisoquinoline, tetrahydroquinoline, these heterocycles being optionally substituted with one or more halogen atoms or alkyl, alkoxy, vinyl, alkoxycarbonyl, oxo, hydroxyl, OCF3 or CF3 radicals.
The compounds of formula (I) may be provided in the form of enantiomers and of diastereoisomers. These optical isomers and mixtures thereof also form part of the invention.
Preferably, the compounds of formula (I) are those for which
R1 represents a radical xe2x80x94N(R5)xe2x80x94Yxe2x80x94R6,
Y is SO2,
R2 represents either a phenyl which is unsubstituted or substituted with one or more halogen atoms or alkyl, alkoxy, trifluoromethyl, trifluoromethoxy, cyano, xe2x80x94CONR7R8, hydroxyalkyl or -alk-NR7R8 radicals; or a heteroaromatic selected from the pyridyl, pyrimidyl, thiazolyl and thienyl rings, it being possible for these heteroaromatics to be unsubstituted or substituted with a halogen atom or an alkyl, alkoxy, hydroxyl, trifluoromethyl, trifluoromethoxy, xe2x80x94CONR7R8, -alk-NR9R10, alkylsulfanyl, alkylsulfinyl, alkylsulfonyl or hydroxyalkyl radical,
R3 represents either a phenyl which is unsubstituted or substituted with one or more halogen atoms or alkyl, alkoxy, trifluoromethyl, trifluoromethoxy, cyano, xe2x80x94CONR7R8, hydroxyalkyl or -alk-NR7R8 radicals; or a heteroaromatic selected from the pyridyl, pyrimidyl, thiazolyl and thienyl rings, it being possible for these heteroaromatics to be unsubstituted or substituted with a halogen atom or an alkyl, alkoxy, hydroxyl, trifluoromethyl, trifluoromethoxy, xe2x80x94CONR7R8, -alk-NR9R10, alkylsulfanyl, alkylsulfinyl, alkylsulfonyl or hydroxyalkyl radical,
R5 represents a hydrogen atom or an alkyl radical,
R6 represents a naphthyl, phenylalkyl, Het or phenyl radical optionally substituted with one or more halogen atoms or alkyl, alkoxy, cyano, xe2x80x94CO-alk, COOalk, xe2x80x94CONR12R13, -alk-NR14R15, xe2x80x94NR14R15, hydroxyl, hydroxyalkyl, Het, OCF3, CF3, xe2x80x94NHxe2x80x94CO-alk, xe2x80x94SO2NH2 or xe2x80x94NHxe2x80x94COOalk radicals, or alternatively, on 2 adjacent carbon atoms, with dioxymethylene,
R7 and R8, which are identical or different, represent a hydrogen atom or an alkyl radical or alternatively R7 and R8 together form with the nitrogen atom to which they are attached a 3- to 10-membered saturated mono- or bicyclic heterocycle, optionally containing another heteroatom selected from oxygen, sulfur and nitrogen and being optionally substituted with one or more alkyl radicals,
R9 and R10, which are identical or different, represent a hydrogen atom or an alkyl, cycloalkyl, alkylcycloalkyl or hydroxyalkyl radical or alternatively R9 and R10 together form with the nitrogen atom to which they are attached a 3- to 10-membered saturated or unsaturated mono- or bicyclic heterocycle, optionally containing another heteroatom selected from oxygen, sulfur and nitrogen and being optionally substituted with one or more alkyl, oxo or xe2x80x94COxe2x80x94NH2 radicals,
R12 and R13, which are identical or different, represent a hydrogen atom or an alkyl radical or alternatively R12 and R13 together form with the nitrogen atom to which they are attached a 3- to 10-membered saturated mono- or bicyclic heterocycle, optionally containing another heteroatom selected from oxygen, sulfur and nitrogen and being optionally substituted with one or more alkyl radicals,
R14 and R15, which are identical or different, represent a hydrogen atom or an alkyl, cycloalkyl, alkylcycloalkyl or hydroxyalkyl radical or alternatively R14 and R15 together form with the nitrogen atom to which they are attached a 3- to 10-membered saturated or unsaturated mono- or bicyclic heterocycle, optionally containing another heteroatom selected from oxygen, sulfur and nitrogen and being optionally substituted with one or more alkyl, oxo, hydroxyalkyl or xe2x80x94COxe2x80x94NH2 radicals,
Het represents a 3- to 10-membered unsaturated or saturated mono- or bicyclic heterocycle containing one or more heteroatoms selected from oxygen, sulfur and nitrogen optionally substituted with one or more halogen atoms or alkyl, alkoxy, vinyl, alkoxycarbonyl, oxo or hydroxyl radicals, the nitrogen-containing heterocycles being optionally in their N-oxidized form and, preferably, Het represents a heterocycle selected from the following heterocycles: benzimidazole, benzoxazole, benzothiazole, benzothiophene, thiophene, quinazoline, quinoxaline, quinoline, pyrrole, pyridine, imidazole, indole, isoquinoline, pyrimidine, thiazole, thiadiazole, furan, tetrahydroisoquinoline and tetrahydroquinoline, these heterocycles being optionally substituted with one or more halogen atoms or alkyl, alkoxy, vinyl, oxo, hydroxyl, OCF3 or CF3 radicals.
Still more preferably, the compounds of formula (I) are selected from the following compounds:
R1 represents a radical xe2x80x94N(R5)xe2x80x94Yxe2x80x94R6,
Y is SO2,
R2 represents either a phenyl which is unsubstituted or substituted with one or more halogen atoms or alkyl, alkoxy, trifluoromethyl, trifluoromethoxy or hydroxyalkyl radicals; or a heteroaromatic selected from pyridyl and pyrimidyl rings, it being possible for these heteroaromatics to be unsubstituted or substituted with a halogen atom or an alkyl, alkoxy, hydroxyl, trifluoromethyl or trifluoromethoxy radical,
R3 represents either a phenyl which is unsubstituted or substituted with one or more halogen atoms or alkyl, alkoxy, trifluoromethyl, trifluoromethoxy or hydroxyalkyl radicals; or a heteroaromatic selected from pyridyl and pyrimidyl rings, it being possible for these heteroaromatics to be unsubstituted or substituted with a halogen atom or an alkyl, alkoxy, hydroxyl, trifluoromethyl or trifluoromethoxy radical,
R5 represents a hydrogen atom or an alkyl radical,
R6 represents a naphthyl, phenylalkyl, Het or phenyl radical optionally substituted with one or more halogen atoms or alkyl, alkoxy, xe2x80x94NR14R15, hydroxyl, hydroxyalkyl, OCF3, CF3 or xe2x80x94SO2NH2 radicals, or alternatively, on 2 adjacent carbon atoms, with dioxymethylene,
R14 and R15, which are identical or different, represent a hydrogen atom or an alkyl, cycloalkyl, alkylcycloalkyl or hydroxyalkyl radical or alternatively R14 and R15 together form with the nitrogen atom to which they are attached a 3- to 10-membered saturated or unsaturated mono- or bicyclic heterocycle, optionally containing another heteroatom selected from oxygen, sulfur and nitrogen and being optionally substituted with one or more alkyl, oxo, hydroxyalkyl or xe2x80x94COxe2x80x94NH2 radicals,
Het represents a 3- to 10-membered unsaturated or saturated mono- or bicyclic heterocycle containing one or more heteroatoms selected from oxygen, sulfur and nitrogen optionally substituted with one or more halogen atoms or alkyl, alkoxy, vinyl, alkoxycarbonyl, oxo or hydroxyl radicals, the nitrogen-containing heterocycles being optionally in their N-oxidized form and, preferably, Het represents a heterocycle selected from the following heterocycles: benzimidazole, benzoxazole, benzothiazole, benzothiophene, thiophene, quinoline, pyrrole, pyridine, pyrimidine, thiazole, thiadiazole, furan, tetrahydroisoquinoline and tetrahydroquinoline, these heterocycles being optionally substituted with one or more halogen atoms or alkyl, alkoxy, vinyl, oxo, hydroxyl, OCF3 or CF3 radicals.
The compounds of formula (I) for which R1 represents a radical xe2x80x94NHCOR4 may be prepared according to the following reaction scheme:
In these formulae, R2, R3 and R4 have the same meanings as in formula (I).
Step a is generally carried out in an inert solvent such as tetrahydrofuran, dioxane, a chlorinated solvent (for example dichloromethane or chloroform), at a temperature of between 15 and 30xc2x0 C., in the presence of a base such as a trialkylamine (for example triethylamine or dipropylethylamine) or in pyridine, at a temperature of between 0 and 30xc2x0 C.
Step b is preferably carried out in methanol, in an autoclave, at a temperature of between 50 and 70xc2x0 C.
Step c is generally carried out in the presence of a condensing agent used in peptide chemistry, such as a carbodiimide (for example 1-(3-dimethylamiopropyl)-3-ethylcarbodiimide or N,Nxe2x80x2-dicyclohexylcarbodiimide) or N,Nxe2x80x2carbonyl-diimidazole, in an inert solvent such as an ether (for example tetrahydrofuran or dioxane), an amide (dimethylformamide) or a chlorinated solvent (for example methylene chloride, 1,2-dichloroethane or chloroform) at a temperature of between 0xc2x0 C. and the boiling point of the reaction mixture. It is also possible to use a reactive derivative of the acid such as an acid chloride, optionally in the presence of an acid acceptor such as a nitrogen-containing organic base (for example trialkylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene or 1,5-diazabicyclo[4.3.0]-non-5-ene), in a solvent as cited above, or a mixture of these solvents, at a temperature of between 0xc2x0 C. and the boiling point of the reaction mixture.
The derivatives R4COOH are commercially available or may be obtained according to the methods described in R. C. LAROCK, Comprehensive Organic Transformations, VCH editor.
The azetidinols of formula 1 may be obtained by application or adaptation of the methods described by KATRITZKY A. R. et al., J. Heterocycl. Chem., 271 (1994) or DAVE P. R., J. Org. Chem., 61, 5453 (1996) and in the examples. The procedure is generally carried out according to the following reaction scheme:
in these formulae, R2 and R3 have the same meanings as in formula (I) and Hal represents a chlorine or bromine atom.
In step A, the procedure is preferably carried out in an inert solvent such as a 1-4C aliphatic alcohol (for example ethanol or methanol), optionally in the presence of an alkali metal hydroxide, at the boiling point of the reaction medium.
In step B, the reduction is generally carried out by means of lithium aluminum hydride, in tetrahydrofuran at the boiling point of the reaction medium.
In step C, the procedure is preferably carried out in an inert solvent such as a 1-4C aliphatic alcohol (for example ethanol or methanol), in the presence of sodium hydrogen carbonate, at a temperature of between 20xc2x0 C. and the boiling point of the reaction medium.
In step D, the procedure is carried out according to the method described by GRISAR M. et al. in J. Med. Chem., 885 (1973). The magnesium compound of the brominated derivative is formed and then the nitrile is caused to react, in an ether such as ethyl ether, at a temperature of between 0xc2x0 C. and the boiling point of the reaction medium. After hydrolysis with an alcohol, the intermediate imine is reduced in situ with sodium borohydride at a temperature of between 0xc2x0 C. and the boiling point of the reaction medium.
The derivatives R2xe2x80x94COxe2x80x94R3 are commercially available or may be obtained by application or adaptation of the methods described by KUNDER N. G. et al. J. Chem. Soc. Perkin Trans 1, 2815 (1997); MORENO-MARRAS M., Eur. J. Med. Chem., 23 (5) 477 (1988); SKINNER et al., J. Med. Chem., 14 (6) 546 (1971); HURN N. K., Tet. Lett., 36 (52) 9453 (1995); MEDICI A. et al., Tet. Lett., 24 (28) 2901 (1983); RIECKE R. D. et al., J. Org. Chem., 62 (20) 6921 (1997); KNABE J. et al., Arch. Pharm., 306 (9) 648 (1973); CONSONNI R. et al., J. Chem. Soc. Perkin Trans 1, 1809 (1996); FR-96-2481 and JP-94-261393.
The derivatives R3Br are commercially available or may be obtained by application or adaptation of the methods described by BRANDSMA L. et al., Synth. Comm., 20 (11) 1697 and 3153 (1990); LEMAIRE M. et al., Synth. Comm., 24 (1) 95 (1994); GODA H. et al., Synthesis, 9 849 (1992); BAEUERLE P. et al., J. Chem. Soc. Perkin Trans 2, 489 (1993).
The derivatives R2CN are commercially available or may be obtained by application or adaptation of the methods described by BOUYSSOU P. et al., J. Het. Chem., 29 (4) 895 (1992); SUZUKI N. et al., J. Chem. Soc. Chem. Comm., 1523 (1984); MARBURG S. et al., J. Het. Chem., 17 1333 (1980); PERCEC V. et al., J. Org. Chem., 60 (21) 6895 (1995).
The compounds of formula (I) for which R1 represents a radical xe2x80x94N(R5)xe2x80x94Yxe2x80x94R6 may be prepared according to the following reaction scheme:
in these formulae, Y, R2, R3 and R6 have the same meanings as in formula (I), Hal represents a halogen atom and, preferably, an iodine, chlorine or bromine atom.
Step a is generally carried out in an inert solvent such as tetrahydrofuran, dioxane or a chlorinated solvent (for example dichloromethane or chloroform), in the presence of an amine such as a trialkylamine (for example triethylamine), at a temperature of between 5xc2x0 C. and 20xc2x0 C.
Step b is generally carried out in an inert solvent such as tetrahydrofuran, in the presence of sodium hydride, at a temperature of 0xc2x0 C. and the boiling point of the reaction medium.
The Hal-SO2R6 derivatives are commercially available or may be obtained by halogenation of the corresponding sulfonic acids, in particular in situ in the presence of chlorosulfonyl isocyanate and alcohol, in a halogenated solvent (for example dichloromethane or chloroform).
The Hal-COxe2x80x94R6 derivatives are commercially available or may be prepared according to the methods described in R. C. LAROCK, Comprehensive Organic Transformations, VCH editor.
The compounds of formula (I) may also be prepared according to the following reaction scheme:
In these formulae, R1, R2 and R3 have the same meanings as in formula (I) and Ph represents a phenyl.
Step a is generally carried out in an alcohol such as methanol, in the presence of sodium borohydride, at a temperature in the region of 20xc2x0 C.
In step b, the magnesium compound of the brominated derivative is prepared and it is caused to react, in an inert solvent such as ethyl ether or tetrahydrofuran, at a temperature of between 0xc2x0 C. and the boiling point of the reaction medium.
Step c is carried out by means of a halogenating agent such as hydrobromic acid, thionyl bromide, thionyl chloride, a mixture of triphenylphosphine and carbon tetrabromide or tetrachloride, in acetic acid or an inert solvent such as dichloromethane, chloroform, carbon tetrachloride or toluene, at a temperature of between 0xc2x0 C. and the boiling point of the reaction medium.
Step d is carried out by means of hydrogen, in the presence of palladized charcoal, in an alcohol such as methanol, at a temperature in the region of 20xc2x0 C.
Step e is carried out in an inert solvent such as acetonitrile, in the presence of an alkali metal carbonate (for example potassium carbonate) and potassium iodide, at a temperature of between 20xc2x0 C. and the boiling point of the reaction medium.
The derivatives R3Br and the derivatives R2xe2x80x94CHO are commercially available or may be obtained according to the methods described for example by R. C. LAROCK, Comprehensive Organic Transformations, VCH editor.
The compounds of formula (I) for which R1 represents a radical xe2x80x94N(R5)xe2x80x94Yxe2x80x94R6 in which R6 is a phenyl radical substituted with a hydroxyl radical may also be prepared by hydrolysis of a corresponding compound of formula (I) for which R1 represents a radical xe2x80x94N(R5)xe2x80x94Yxe2x80x94R6 in which R6 is a phenyl radical substituted with an alkoxy radical.
This hydrolysis is generally carried out in an inert solvent such as a chlorinated solvent (for example dichloromethane or chloroform), by means of boron tribromide, at a temperature in the region of 20xc2x0 C.
The compounds of formula (I) for which R1 represents a radical xe2x80x94N(R5)xe2x80x94Yxe2x80x94R6 in which R6 is a phenyl radical substituted with a hydroxy(1C)alkyl radical may also be prepared by the action of diisobutylaluminum hydride on a corresponding compound of formula (I) for which R1 represents a radical xe2x80x94N(R5)xe2x80x94Yxe2x80x94R6 in which R6 is a phenyl radical substituted with an alkoxycarbonyl radical.
This reaction is generally carried out in an inert solvent such as toluene, by means of diisopropyl-aluminum hydride, at a temperature of between xe2x88x9250xc2x0 C. and 25xc2x0 C.
The compounds of formula (I) for which R1 represents a radical xe2x80x94N(R5)xe2x80x94Yxe2x80x94R6 in which R6 is a phenyl radical substituted with a 1-pyrrolidinyl radical may also be prepared by the action of pyrrolidine and of a corresponding compound of formula (I) for which R1 represents a radical xe2x80x94N(R5)xe2x80x94Yxe2x80x94R6 in which R6 is a phenyl radical substituted with a fluorine atom.
This reaction is preferably carried out in an inert solvent such as dimethyl sulfoxide, at a temperature of 90xc2x0 C.
It is understood for persons skilled in the art that, to carry out the processes according to the invention which are described above, it may be necessary to introduce groups protecting amino, hydroxyl and carboxyl functions in order to avoid side reactions. These groups are those which allow removal without affecting the rest of the molecule. As examples of groups protecting the amino function, there may be mentioned tert-butyl or methyl carbamates which may be regenerated using iodotrimethylsilane or allyl using palladium catalysts. As examples of groups protecting the hydroxyl function, there may be mentioned triethylsilyl and tert-butyldimethylsilyl which may be regenerated using tetrabutylammonium fluoride or alternatively asymmetric acetals (methoxymethyl or tetrahydropyranyl for example) with regeneration using hydrochloric acid. As groups protecting carboxyl functions, there may be mentioned esters (allyl or benzyl for example), oxazoles and 2-alkyl-1,3-oxazolines. Other protecting groups which can be used are described by GREENE T. W. et al., Protecting Groups in Organic Synthesis, second edition, 1991, John Wiley and Sons.
The compounds of formula (I) may be purified by the customary known methods, for example by crystallization, chromatography or extraction.
The enantiomers of the compounds of formula (I) may be obtained by resolution of the racemates for example by chromatography on a chiral column according to PIRCKLE W. H. et al., Asymmetric synthesis, Vol. 1, Academic Press (1983) or by formation of salts or by synthesis from chiral precursors. The diastereoisomers may be prepared according to known conventional methods (crystallization, chromatography or from chiral precursors).
The compounds of formula (I) may be optionally converted to addition salts with an inorganic or organic acid by the action of such an acid in an organic solvent such as an alcohol, a ketone, an ether or a chlorinated solvent. These salts also form part of the invention.
As examples of pharmaceutically acceptable salts, the following salts may be mentioned: benzenesulfonate, hydrobromide, hydrochloride, citrate, ethanesulfonate, fumarate, gluconate, iodate, isethionate, maleate, methanesulfonate, methylene-bis-∃-oxynaphthoate, nitrate, oxalate, pamoate, phosphate, salicylate, succinate, sulfate, tartrate, theophyllineacetate and p-toluenesulfonate.
The compounds of formula (I) exhibit advantageous pharmacological properties. These compounds possess a high affinity for the cannabinoid receptors and particularly those of the CB1 type. They are CB1-receptor antagonists and are therefore useful in the treatment and prevention of disorders affecting the central nervous system, the immune system, the cardiovascular or endocrine system, the respiratory system, the gastrointestinal apparatus and reproductive disorders (Hollister, Pharm. Rev.; 38, 1986, 1-20, Reny and Sinha, Prog. Drug Res., 36, 71-114 (1991), Consroe and Sandyk, in Marijuana/Cannabinoids, Neurobiology and Neurophysiology, 459, Murphy L. and Barthe A. Eds, CRC Press, 1992).
Accordingly, these compounds may be used for the treatment or prevention of psychoses including schizophrenia, anxiety disorders, depression, epilepsy, neurodegeneration, cerebellar and spinocerebellar disorders, cognitive disorders, cranial trauma, panic attacks, peripheral neuropathies, glaucomas, migraine, Parkinson""s disease, Alzheimer""s disease, Huntington""s chorea, Raynaud""s syndrome, tremor, obsessive-compulsive disorder, senile dementia, thymic disorders, Tourette""s syndrome, tardive dyskinesia, bipolar disorders, cancers, movement disorders induced by medicaments, dystonia, endotoxemic shocks, hemorrhagic shocks, hypotension, insomnia, immunological diseases, multiple sclerosis, vomiting, asthma, appetite disorders (bulimia, anorexia), obesity, memory disorders, in weaning from chronic treatments and alcohol or drug abuse (opioids, barbiturates, cannabis, cocaine, amphetamine, phencyclide, hallucinogens, benzodiazepines for example), as analgesics or potentiators of the analgesic activity of the narcotic and nonnarcotic drugs. They may also be used for the treatment or prevention of intestinal transit.
The affinity of the compounds of formula (I) for the cannabis receptors has been determined according to the method described by KUSTER J. E., STEVENSON J. I., WARD S. J., D""AMBRA T. E., HAYCOCK D. A. in J. Pharmacol. Exp. Ther., 264 1352-1363 (1993).
In this test, the IC50 of the compounds of formula (I) is less than or equal to 1000 nM.
Their antagonist activity has been shown by means of the model of hypothermia induced by an agonist of the cannabis receptors (CP-55940) in mice, according to the method described by Pertwee R. G. in Marijuana, Harvey D. J. eds, 84 Oxford IRL Press, 263-277 (1985).
In this test, the ED50 of the compounds of formula (I) is less than or equal to 50 mg/kg.
The compounds of formula (I) exhibit low toxicity. Their LD50 is greater than 40 mg/kg by the subcutaneous route in mice.
The following examples illustrate the invention.

Pharmaceutical compositions containing 3-aminoazetidine derivatives, novel derivatives and their preparation

Abstract: in which R1 represents a radical xe2x80x94NHCOR4 or xe2x80x94N(R5)xe2x80x94Yxe2x80x94R6, Y is CO or SO2, R4 represents a radical -alk-SO2xe2x80x94R11, -alk-SO2xe2x80x94CHxe2x95x90CHxe2x80x94R11 or Het substituted with xe2x80x94SO2xe2x80x94R11 or a phenyl radical substituted with xe2x80x94SO2xe2x80x94R11 or -alk-SO2xe2x80x94R11, R5 represents a hydrogen atom or an alkyl radical, R6 represents a phenylalkyl, Het or Ar radical, to the novel derivatives of formula (I) and to their preparation, as well s to their use in treating various disorders of the nervous system.


A window assembly includes fixed panes, a sliding pane, and a vehicle mounting frame. The mounting frame includes a unitary, substantially full-circumference frame member. The frame member includes a show surface that may extend above or below a window opening opened and closed by the sliding pane. A reinforcement is at least partially embedded in the frame member and has a portion located behind the show surface. Interior surfaces of the fixed panes may be molded to the frame member, and the exterior surface of the fixed panes may free of the frame. A laterally outboard portion of the peripheral edge of each fixed pane may be covered by the frame member.

Window assemblies which are pre-assembled prior to installation are widely used in motor vehicle manufacture and other applications. Pre-assembly of the glazing unit for simple insertion into a recessed window opening in a vehicle body during vehicle assembly has been found to yield substantial cost and quality advantages. Such window assemblies intended for use as rear windows for pickup truck cabs, for example, typically include a frame holding one or more fixed panes and a slidable pane. In the past, windows assemblies have had an undesirably bulky appearance poorly integrated into the exterior surface of the vehicle or other structure. Exemplary of known window assemblies are those shown and described in U.S. Pat. No. 5,522,191 and U.S. Pat. No. 7,003,916, each of which is hereby incorporated by reference in its entirety for all purposes.
It is an object of the present invention to provide improved multi-pane window assemblies. It is a particular object of at least certain embodiments to provide multi-pane modular window assemblies having fixed and slidably mounted panes and presenting a substantially flush overall appearance. Additional objects and advantages of the multi-pane window assemblies disclosed here will be apparent to those skilled in the art from the following disclosure.

Multi-pane window assembly with two-sided frame and sliding pane


Provided is a hydrogen storage alloy which is characterized in that two or more crystal phases having different crystal structures are layered in a c-axis direction of the crystal structures. The hydrogen storage alloy is further characterized in that a difference between a maximum value and a minimum value of a lattice constant a in the crystal structures of the laminated two or more crystal phases is 0.03 Å or less.

A hydrogen storage alloy is an alloy capable of safely and easily storing hydrogen as an energy source and has drawn an attention as a new energy conversion and storage material and its application fields are in a wide range, e.g., hydrogen storage and transportation, heat storage and transportation, heat-mechanical energy conversion, separation and purification of hydrogen, isolation of hydrogen isotopes, batteries using hydrogen as active materials, catalysts for synthetic chemical, temperature sensors, and so forth.
For example, a nickel-metal hydride battery using a hydrogen storage alloy as a negative electrode material has characteristics such as (a) high capacity; (b) durability to overcharge and over discharge; (c) capability of charging and discharging at high efficiency; (d) cleanness and has been actively investigated to have further improved capabilities (improvement of retention ratio of capacity in the case of repeating charge and discharge, that is, cycle life, improved capacity of the battery, etc.).
So far, an AB5 type rare earth-Ni-based alloy having a CaCu5 type crystal structure has been put into practical use as an electrode material for a nickel-metal hydride battery, one application example of such a hydrogen storage alloy; however the discharge capacity reaches almost a limit of about 300 mAh/g and presently it becomes difficult to further improve the capacity.
Further, as a new hydrogen storage alloy, a rare earth metal-Mg—Ni based alloy, for example, LaCaMgNi9 alloys (Patent Document 1) having a PuNi3 type crystal structure have drawn attention and it is reported that a discharge capacity exceeding that of an AB5 type alloy can be obtained by using these alloy for electrode materials.
It is also reported that in addition of the crystal phase having the AB5 type crystal structure, electrode materials of hydrogen storage alloys containing a crystal phase of AB2 type crystal structure such as MgCu2 type or rare earth metal-Mg—Ni type alloys containing, as a main phase, the crystal phase having Ce2Ni7 type, CeNi3 type, or Gd2Co7 type crystal structure have high hydrogen storage capacities and show good hydrogen release characteristics (Patent Document 2).
Furthermore, with respect to alloys having Ce5Co19 type crystal structure, it is reported that electrodes complexed with rare earth-Ni alloy having a CaCu5 type crystal structure are excellent in hydrogenation reaction speed (Patent Document 3).
Patent Document 1: Japanese Patent No. 3015885
Patent Document 2: Japanese Patent Application Laid-Open (JP-A) No. 11-323469
Patent Document 3: Japanese Patent No. 3490871

Hydrogen storage alloy, hydrogen storage alloy electrode, secondary battery, and method for producing hydrogen storage alloy

National Institute of Advanced Industrial Science and Technology


Shelf assemblies, methods for assembling shelf assemblies, and refrigerator appliances are provided. A shelf assembly includes a fixed shelf, the fixed shelf including a pair of guides that each extend along a lateral direction. The shelf assembly further includes a movable shelf slidably mounted to the fixed shelf, the movable shelf including a pair of guides that each extend along the lateral direction. In an extended position, the pair of guides of the movable shelf cantilever from the pair of guides of the fixed shelf.

Refrigerator appliances generally include a cabinet that defines a chilled chamber for receipt of food items for storage. Refrigerator appliances also generally include various combinations of shelves, bins, and drawers positioned within the chilled chamber to assist with storage of food items therein. Certain refrigerator appliances include adjustable shelves that permit an appliance user to adjust the shelves between various configurations. For example, adjustable shelves can permit the appliance user to adjust a height or a length of the shelves.
Certain adjustable shelves include a fixed glass plate and a movable glass plate that can slide below the fixed glass plate. Such adjustable shelves can include brackets that support the glass plates within the chilled chamber. Generally, such brackets are connected to each other with cross-bars that extend between the brackets below the glass plates. Additionally, such brackets typically extend beyond the fixed plate to support the movable plate when the plate is in an extended position.
Adjustable shelves having such brackets and cross-bars have certain drawbacks. For example, cross-bars can consume valuable storage space below the adjustable shelves. Also, cross-bars can be visually unappealing or unattractive. Further, cross-bars can be expensive and add to the overall cost of the refrigerator appliance. Brackets or other extended structures which support the movable plate when in the extended position remain extended past the fixed plate even when the movable plate has been retracted, thus additionally consuming valuable storage space in front of the shelves and limiting the size of items to be stored.
Accordingly, a refrigerator appliance with features for securely and reliably mounting an adjustable shelf within a refrigerator appliance, as well as methods for assembling such shelf, would be useful. In particular, a refrigerator appliance with features for mounting an adjustable shelf within a refrigerator appliance and associated assembly methods that does not require cross-bars and that do not require brackets or other extended structures to support movable plates thereof would be useful.

Shelf assemblies for refrigerator appliances and methods for assembling same


A vehicular torsion bar suspension device, which comprises a front torsion bar spring and a rear torsion bar spring respectively installed at front and rear suspensions of the vehicle. The opposite ends of the front and rear torsion bar springs on the same side are connected mutually by a connection mechanism, and are connected with a vehicle frame through a positioning device. The connection mechanism is mounted between the front and rear torsion bar springs on the same side, so that a linkage relationship is established between the front and rear torsion bar springs. The device improves the vibration situation of the vehicle when driving the vehicle on an uneven ground, and prevents the vehicle frame and vehicle body skeleton from suffering torsional force. As a result, the usage life of the vehicle is prolonged.

1. Field of Invention
The present invention pertains to a vehicle suspension device, especially, a vehicular torsion bar suspension device.
2. Description of Related Arts
Nowadays, there are two types of suspension system. One is non-independent suspension; the other is independent suspension. The axle of the independent suspension is divided into two sections. Each wheel is independently mounted through a spiral spring under the vehicle frame; as a result, when bumping happens to one wheel, the other wheel will not be affected, and thereby the vibrations of the vehicle body will be reduced drastically and accordingly improve the comfortability effectively; especially, when driving in a highway, the running stability will be increase as well. However, this type of suspension structure has complicated structure, little carrying ability; and correspondingly, it makes the drive system and steering system of the vehicle get more complicated. Thus, current sedans have adopted the independent suspension system and have become a development trend.
The independent suspension has varieties of structures, such as sliding pillar type, MacPherson type, link type and etc. There are three types of metallic springs among these independent suspensions; they are spiral spring, leaf spring and torsion bar spring. The spiral spring got the name from its spiral line, and has advantages of light weight and small volume; when the shock force resulting from the road surface acts on the wheels, the spiral spring will be distorted and absorb the kinetic energy of the wheels and convert it into the potential energy of the spiral spring; accordingly the impact of the shock from road surface on the vehicle body will be decreased. The middle part of the leaf spring is fixed through a U-shape bolt to the axle; the spring eyes at two ends are hinged to the bracket of the vehicle frame through a peg; in this way, the axle and vehicle body are connected through the leaf spring; as a result, when the shock force resulting from the road surface acts on wheels, the leaf plate will be distorted and therefore bring the effect of buffering and shock absorption. The torsion bar spring has one end fixedly connected with the vehicle frame and the other end connected with the control arm of the suspension in order to fulfill the shock absorption by virtue of the torsion distortion of the torsion bar. Seen from the transverse section, the torsion bar spring has the circular type, tubular type, rectangular type, stacked type, combined type and etc. The circular torsion bar is applied the most. It takes on the shape of a rod, with two ends being able to be processed into the shape of spline, hexagon and etc., so as to fix one end to the vehicle frame and the other end to the wheels through the control arm. The torsion bar is made of alloy spring steel, which has very good elasticity and is subject to distortion and restoring; actually, it plays the same role as the spiral spring but with different form. When the vehicle is running, the wheels will jolt up and down due to the uneven road, and the control arm will also move up and down accordingly. When the wheels jolts up, the control arm moves up, so that the torsion bar is forced to distort and meanwhile absorb the shock energy. When the shock force gets less, the natural restoring capability of the bar is able to restore rapidly to its original position, and in turn makes wheels back to on the ground, preventing the vehicle from bumping.
Because the torsion bar spring bears only sheering force, a coil spring with the same weight can absorb more than double energy of a leaf plate with the same weight. The torsion bar spring is applied in automobiles in two ways; one is the longitudinal device and the other is the transverse device, the latter being used more often. In the longitudinal device, the torsion bar is used to substitute for the leaf spring and coil spring, which take up more rooms; for example, in the front suspension of vehicle type, Toyota Hiace, Zace, Surf, the torsion bar spring is used to match the A arm type of suspension system. The torsion bar of a transverse device is used to balance the acted force of the left and right wheels and as a balancing bar of anti-tilting, with the exception of fewer vehicle types that use the torsion bar to substitute for the coil spring.
In current auto suspension devices, the torsion bar spring is usually installed on the front suspension device of an automobile. Its front and rear elastic components are independent of each other in between, without any influence and connection. Even if the vibration direction of the front and rear wheels of the automobile is opposite, the impact the automobile gets will not be increased and the body will move in the manner that the front body goes up and the rear body goes down; moreover, when four wheels are not in a same surface or a pair of diagonal wheels bears a bigger force, the body and frame will get a certain amount of torque force; therefore, the current suspension structure still have the following pitfalls, e.g., elastic components are likely subject to be broken, the body and frame is likely subject to be distorted, and so on. In addition, articles carried in vehicles might be damaged and the passengers will feel uncomfortable.

Shizuishan Jinhui Scientific Technology and Trading Co., Ltd


A superconducting quantum interference device (SQUID) for mobile magnetic sensing applications comprising: at least two Josephson junction electrically connected to a superconducting loop; and a resistive element connected in series with one of the Josephson junctions in the superconducting loop. The resistive element is disposed in the same superconducting loop as the at least two Josephson junctions.

Superconducting Quantum Interference Devices (SQUIDs) are comprised of tiny loops of superconducting material in which Josephson junctions are placed in the loop path. A Josephson junction is a region of material that provides a weak link between two fully superconducting regions. The direct current (DC) SQUID has two symmetrical Josephson junctions. They are able to sense extremely small magnetic fields. Non-uniforms arrays of DC SQUIDs and DC bi-SQUIDs, which are DC SQUIDs with an additional Josephson junction bisecting the superconducting loop, have been modeled in different array designs and coupling schemes to determine their linearity and sensing capacities and have been fabricated in low temperature superconducting materials. A SQUID-based sensor detects minute magnetic fields and is decoupled from the size of the signal's wavelength. Hence the device can sense signals in the DC-GHz range, but still be contained fully on a ˜1×1 cm chip.
SQUID sensors require a magnetic flux bias in order to operate. DC SQUIDs are sensitive devices that may be used for measuring vector components and spatial gradients of magnetic fields, as well as an ability to resolve tiny changes in large signals. These features are particularly useful and have already been implemented in many applications such as low-noise amplifiers, biomagnetic research, nondestructive evaluations, and geomagnetic exploration. In order for the SQUID sensor to function while moving some way is needed to mitigate the changes in the earth's magnetic field due to the movement of the sensor.

SQUID having integrated resistive element

United States Government as represented by the Secretary of the Navy


Various embodiments are described of a liquid-powered dynamometric generator built into a shoe, which has at least two layers as part of its sole. The first or lower layer of the sole is a pad formed of an elastomeric material which contains a liquid within a set of chambers, one in the heel area and one in the toe area of the sole. The ambulatory foot movement inside the shoe puts pressure on the fluid and makes it flow from one chamber area to another. Contained between the chambers is a turbine that is mounted on rotary bearings and positioned within the path of the fluid flow. Due to foot motion, the fluid will flow in an oscillatory fashion while ambulating and thereby cause the turbine to turn. The second or top layer of the sole is a pad that contains one or more dynamometric generators that are coupled by mechanical or magnetic systems to the first layer, such that the action of fluid flow in the first layer imparts rotary motion to the turbine, thereby resulting in the generation of electricity within the second layer. The coupling system(s) may also include gearing or other drive componentry to increase or decrease the speed of the turbine relative to the speed of fluid flow. Electrical energy is therefore generated from the ambulatory motion and can be stored within a rechargeable battery or capacitor, and can be utilized directly for multiple purposes, such as to supply energy to lighting, heating, cooling, computing or communications equipment.

1. Field of the Invention
The present invention relates generally to a dynamometric product built into the sole of a shoe that generates electrical energy from the action of walking.
Specifically, the invention comprises two layers, one of which has a liquid-filled area with a liquid powered turbine and the other layer containing an electrical generator or generators which are powered by the liquid turbine responding to the liquid movement in the first layer. These two layers are molded or otherwise connected to a shoe sole.
2. Related Art
U.S. Pat. Nos. 5,495,682 and 5,167,082, both by Chen describe and claim another type of dynamometric generator and energy storage means built into the sole of a shoe. This invention utilizes a lever actuator connected to a pivoting platform which moves with the action of raising and lowering the heel of the foot while ambulating. While this device is useful in generating electrical energy, it is dissimilar to the invention described herein, and lacks certain ergonomic and functional benefits that will become apparent from the detailed description which follows.

Shoe sole with liquid-powered electrical generator


The invention is related to a microstrip line structure, which comprises: a first microstrip line and a second microstrip line, paralleled with the first mircostrip line for transferring a transmission signal, and a plurality of grooves periodically arranged on both sides of the second microstrip line by using subwavelength, and each period length in the plurality of grooves is smaller than the wavelength of the transmission signal.

In recent years, as the electronic systems become more rapid and highly integrated, problems in the circuit design such as loss, crosstalk, reflection, and so on become more and more serious. Especially, there exist a great amount of parallel interconnection lines, which will bring about great coupling effect if they are to close to each other. For example, the signal on the transmission line would be distorted because of the crosstalk between lines. Also, the characteristic impedances of the transmission lines changes as a result of the crosstalk. When the signal is transferred in the transmission channel, it will generate the electromagnetic coupling so as to affect the neighboring circuit lines, and also it increases the coupling voltage and the coupling current on the interference signal. If the crosstalk is too large, it will effect the operation effectively of the circuit so as to generate the miss trigger of the circuit and damage the circuit. Beside, it always increase the intervals between the microstrip lines or control the raise and fall of the digital to suppress the crosstalk in high-speed circuit systems and system boards when the circuit lines are designed as the curved lines according to the actual requirement and design. However, this act still does not effectively solve the problem of the crosstalk.
For the reason that conventional technique could not effectively solve the issue of the crosstalk between the circuit lines, a need has arisen to propose a novel microstrip line structure capable of effectively solving the problem of the crosstalk.


The present invention provides a motor driving method, a battery pack, and a semiconductor device capable of variable-controlling a bus voltage from a battery pack. A battery pack outputting a bus voltage to a positive voltage node using a negative voltage node as a reference, an inverter unit converting the bus voltage to AC voltage by switching according to a PWM signal and driving a motor, and a motor control unit generating the PWM signal are used. The motor control unit outputs a voltage instruction signal for instructing the bus voltage toward the battery pack. The battery pack variable-controls the number of cells coupled in parallel between the positive voltage node and the negative voltage node so as to obtain the bus voltage according to the voltage instruction signal.

The present disclosure relates to a motor driving method, a battery pack, and a semiconductor device and relates to, for example, a technique at the time of driving a motor by a PWM (Pulse Width Modulation) signal by using power from a battery pack and a technique of a control IC (Integrated Circuit) provided in the battery pack.
For example, patent literature 1 discloses a configuration in which a switch for charging/discharging is coupled to each of electric cells in parallel in an assembled battery in which a plurality of electric cells are coupled in series. Patent literatures 2, 3, and 4 disclose a technique of providing a DC/DC converter circuit and an inverter circuit and controlling a motor by using PWM control or PAM (Pulse Amplitude Modulation).

Motor driving method, battery pack and semiconductor device


A hydraulic fastener for mounting bearing assemblies on the end of a roll in a rolling mill stand. The fastener includes a hydraulic ring cylinder component having a front face directed toward a roll and an inner cylindrical surface adapted to fit onto a reduced diameter end section of the roll. A chamber extends about the circumference of the cylinder component and is open at the front face. A hydraulic ring piston component is slidably received in this chamber and has an inner face. A retaining ring is threadedly mounted in the cylinder component to hold at least a substantial portion of the piston in the chamber. Passageways are provided in the cylinder component for injecting grease into the chamber and into a space formed between the inner face of the piston and an opposing face of the chamber. A split ring is secured on the end section of the roll to retain the cylinder component in place. Zero-leakage two-directional seals are arranged between the cylinder component and the piston at both radially inner and radially outer sides of the piston to prevent escape of said grease.

This invention relates to forming rolls used in metal forming and in particular to the supporting mechanism for the bearing arrangement used to rotatably mount the large, heavy rolls, commonly called back-up and work rolls.
It is well known to mount a main roll of a rolling mill in top and bottom chalks in which are mounted suitable bearings. At the outboard and inboard end of the bearings are provided collars. In one known arrangement, the outboard collar has a bearing retainer extending around its circumference, which retainer is held in place by bolts threaded into the chalks. A thrust collar bears against the axial outer face of the outboard collar. Extending about the inboard collar is a seal ring that is mounted by bolts to the chalks.
It is also known to use plane bearings (usually babbit) to rotatably support the large rolls in a rolling mill. These bearings which use a large quantity of oil in order to operate can be used in conjunction with tapered roller bearings mounted axially outwardly from the plane bearing. The inner bearing support is held in place by the use of a split ring that is threaded on the outside and that is mounted in a circumferential recess formed in the roll end. The split ring is held in place by a complete exterior ring having internal threads and it is this exterior ring that actually bears against the side of the inner bearing support. The end of the roll and its exterior ring are covered by a protective cap. This arrangement for mounting bearings on the end of the rolls has several inherent disadvantages including the fact that the threads on the rings can be easily damaged and there is a possibility of injury to workmen because of the known method for tightening the threaded exterior ring (this method employs a pin and cable). The known methods for mounting the bearings is time consuming and it will be appreciated that it is important to reduce the downtime for these rolling mills as much as possible in view of the cost of such mills.
The use of a device known as "a hydraulic nut" is known in rolling mill construction, particularly in the construction of prestressed roll stands. The device can consist of ring-shaped members, namely a cylinder and a piston. In one known arrangement in a rolling mill, one of these members is directly connected with a tie rod by means of a clamp nut and is displaced with the expansion of the tie rod under hydraulic stressing, the other member resting against a support. For example a hydraulic stressing device as shown in U.S. Pat. No. 3,588,044 issued Jun. 28, 1971 to E. G. Reichrath and O. K. Buchheit. The device taught in this patent specification consists of a ring cylinder and a ring piston surrounding a tie rod. The piston is pressed downwardly by means of screw bolts and is connected directly through a divided ring with the end of the tie rod by engaging beneath a protruberance at the end of the tie rod. Fluid pressure is used to actually expand the tie rod in order to clamp the components together with a selected clamping force.
U.S. Pat. No. 4,581,911 issued Apr. 15, 1986 to Y. Shinomoto describes a cantilever-type rolling mill having a pair of roll shafts rotatably supported in a roll housing. The rolling mill includes a tension member provided axially through the center of the roll shaft and having the outer end thereof projecting out of the roll shaft. There is a roll compressing tool detachably engageable with the projecting end of the tension member, which tool incorporates a hydraulic piston-cylinder. The tool has a nut member threadably fitted on the outer periphery of the cylinder. An extraction ring interlocks the roll unit with the tool. An oil pressure passage in the cylinder communicates with an annular groove located at the inner end of the piston. In order to mount the roll unit, this unit is mounted on the tool by the use of the extraction ring and then the unit and the tool are fitted onto the roll shaft using a jig. Clearly this known hydraulic piston-cylinder mechanism is not used to hold any bearing arrangement for the end of the roll in place.
The hydraulic piston-cylinder mechanism or nut is single acting, that is, it cannot be pressurized hydraulically in more than one direction. It is pressurized during the mounting or assembly operation only and after this operation is completed, the pressure in this hydraulic nut is removed.
Although it is believed by the applicants that the use of hydraulic nuts to mount the bearing arrangement for a roll in a rolling mill has been proposed in the past, such proposals have not met with widespread commercial success. Some of these proposals have been in practice unworkable and because of the high cost of rolling mills in general, this industry has been reluctant to accept and adopt new construction techniques for these mills, at least until a new construction has proven itself as being a definite improvement.
A drawing produced by the Timken Company shows a hydraulic nut arrangement for holding in place a tapered four roll T.O.O. roller bearing mounted on the reduced end of a work roll. The hydraulic nut is formed by two ring-shaped inner and outer sections. The outer ring section has a L-shaped cross-section and it is this section that bears against a further ring member whose inner end bears against the inner bearing support. Two ring-shaped seals appear to be provided between the contacting surfaces of the inner and outer ring sections that form the hydraulic nut. Another ring member is mounted on the outer end of the roll to bear against the outer end of the inner ring section and hold the section against axially outward movement.
It is an object of the present invention to provide a hydraulic fastener for mounting one end of a roll in a rolling mill stand, said fastener being reliable and relatively easy to construct and to use.
It is a further object of the invention to provide a hydraulic fastener which can be used not only to mount one end of a roll in a rolling mill stand but which is kept under pressure during operation of the rolling mill.


The invention generally relates to a foot activated dispenser and more particularly to a foot activated dispenser for dispensing a liquid product such as a skin care product (i.e. hand soap, hand sanitizer, surgical scrub, lotion, etc.). More specifically, the foot activated dispenser includes a bladder connected to tubing that is connected to a piston pump. The piston pump is located within a shroud that is removably attached to a wall bracket. The wall bracket includes a bottle retainer for holding a bottle having a pump.

Dispensers for dispensing liquid products, such as hand soaps are generally known. See U.S. patent application Ser. No. 10/336,054 filed on Jan. 2, 2003. There are many types of dispensers, however, two common dispensers include a pump attached to a bottle, or a wall mounted dispenser. With a pump attached to a bottle, the product to be dispensed is located in the bottle (typically a plastic bottle) and a hand operated pump is attached to the bottle such that a user pushes on the top of the pump to dispense product out of the pump. With a wall mounted dispenser, the dispenser is operated by a user walking up to the dispenser and pushing a hand operated bar to dispense product.
These dispensers are often placed in locations where hand care is important, or where the likelihood of contacting microorganisms and other soils is high, for example in a public restroom or hospital facility. Over time, the surface that a user contacts to dispense product (i.e. the pump or the hand operated bar) becomes a source of germs and contaminants. Therefore, it is desirable to have a dispenser where operation of the dispenser is "hands free" so that a user does not have to touch the dispenser in order to dispense product.
It is against this background that the present invention has been made.


A wireless switch or sensor is provided that includes a radio frequency (RF) transponder including a narrowband receiver operable to generate power from a received narrowband RF signal and an ultra wideband (UWB) transmitter operable to transmit UWB pulses using the generated power.

Environments such as homes and offices require numerous switches for actuating devices such as lamps and HVAC equipment. A conventional home thus includes costly wiring between all the switch controls and the various power sinks such as lights, heaters, computers, radio and TV sets, and so on. In addition to the cost associated with wires, maintenance and installations, positioning of the switches and fixtures need to be predetermined at the time of installation. In mobile environments such as cars other factors like the weight of the copper saved in the wiring of the switches is, in and of itself, enough motivation for having a wireless network of passive switches. Copper wiring is not only expensive but also heavy; saving copper results in lower manufacturing cost and better fuel economy.
Inside cars and similar environments, the position of switches, control knobs and sensors is crucial in maintaining functional, user-friendly operation and esthetically appealing instrumentation layout. The esthetic aspects of such placements as well as the practical difficulties in providing wired connections to all such switches and sensors, e.g. through the steering wheel and hard to reach structures, present considerable design difficulties.
To eliminate the cost of installing wires between the switch and the device being actuated by the switch, various wireless switches have been developed. Similarly, wireless sensors have been developed to eliminate the need for wires between the sensors and the control systems requiring information from the sensors. One type of conventional wireless switches uses a narrowband data link to power up the switch such that the switch can manipulate the narrowband incident signal or field to convey the switch state accordingly. Such wireless switches include traditional passive radios such as backscattering or magnetically coupling RFID transponders.
Another group of solutions use a transducer to convert the mechanical energy imparted by the user actuating the switch into the required electrical energy needed for generating a narrowband RF carrier, see e.g. U.S. Pat. No. 7,245,062. But both conventional narrowband RFID approaches and transducer approaches suffer from multipath and sensor collisions.
Accordingly, there is a need in the art for improved wireless switches and sensors.


Electrooptic devices (100, 600, 700) include a left handed (102, 708) and right handed (104, 710) cholesteric phase liquid crystal layers. Electrodes (120, 122, 124, 126, 602, 604) or magnetic coils (704, 706) are used to apply electric or magnetic fields perpendicular to helical axes of the cholesteric phase liquid crystal layers. The fields lengthen the helical pitch of the liquid crystal layers thereby shifting the reflectance of the liquid crystal layers to longer wavelengths. Spectral reflectance of both left and right hand polarized light is controlled by the electrooptic devices.

The present invention relates in general to electrooptic devices. More particularly, the present invention relates to devices for switching and/or selectively filtering light signals.
In recent decades, land line communications including voice and data networks have shifted from electrical transmission mediums such as twisted pairs to optical fiber transmission mediums. As this trend continues there is an interest reducing the reliance on electrical signal processing within networks, with an ultimate goal of employing all-optical networks.
One type of component that is useful in optical networking is an optical cross connect. Optical cross connects are used to selectively connect light signals received at an input to one of a plurality of signal outputs.
Microelectromechanical system (MEMS) type optical interconnects that use moveable mirrors have been used. However the manufacture of such devices is costly and complex. Furthermore MEMS reliability is of concern.
Another type of optical interconnect that is based on an adaptation of ink jet technology has also been proposed. However, such interconnects are also quite complex.
Apart from the field of communication, there are various uses of optical filters, including for example for spectroscopy, optical remote sensing, optical lithography, and photochemistry. One of the more widely used types of precision optical filter employs a multi-layer stack of thin solid dielectric films. The spectral characteristics such as spectral reflectance and spectral transmittance of multi-layer thin film filters are determined by the number of layers thickness of each layer and index of refraction of each layer. The fabrication of such filters ordinarily involves time consuming and costly deposition processes.


A vehicular cargo restraint assembly includes a support platform. A plurality of panels are each movably coupled to the support platform. Each of the panels is independently movable between a first position wherein the panel is flat against the support platform, and a second position wherein the panel is offset from the support platform and configured to prevent the movement of cargo within a vehicle cabin.

In an effort to increase available cargo space, vehicles may offer stowable seating assemblies and increased trunk space. However, the cargo may shift and slide in the vehicle cabin when the vehicle is in motion and the cargo is unrestrained, thereby potentially damaging the cargo. Additionally, cargo management systems that secure the cargo can take up considerable space, thus limiting the amount and the size of the cargo that a vehicle is able to stow. As such, there is a need to tailor the cargo space of a vehicle in order to optimize the carrying capacity of the vehicle cabin while effectively securing the cargo in place. The present disclosure is intended to satisfy this need.


A locking strut for use on sliding doors, windows and other sliding closures. The locking strut is supplementary to any closure lock. The strut has at least one receiver in the bottom surface to receive one or more guide rails included in the guide channel of the casement. The apparatus also preferably includes a hold or holds that allow easier insertion and handling. One strut may be used in the casement both when the sliding door is in the open position and the closed position. This is allowed by having one end received in the casement upright in a first orientation for a first slider position. The other end does not fit within the casement in a second slider position. This allows the strut to serve as both a supplementary locking device and as a threshold cover to exclude debris from the guide channel when the slider is open.

It is commonly known that so-called sliding doors, such as sliding glass or window doors, are relatively easily displaced and removed from the outside of a building or room. This is true even though the door may be locked. This has led to many burglaries where access to a home, business or other location has been surreptitiously made by a burglar using a removable sliding door or other closure.
It has been previously known to cut a piece of wood to the desired length of the space between the moving sash and the casement that forms the surrounding framework of the closure. Such pieces serve to form a locking device. Such wooden locking devices are inserted between the closed sliding door sash and the casement of the door assembly. This is helpful in that the known methods for easy displacement and removal of the sliding door are much more difficult or impossible without breaking the glass and removing the wooden strut locking device.
Although such supplementary wooden strut locking devices are commonly used, they lack ascetic appeal and are often a slight embarassment for the homeowner. They also have no features which make storage convenient for the supplementary locking device and they serve no other purpose.
These limitations are greater problems when the door is in frequent use between open and a double-locked condition (wherein both the regular door lock and the supplementary strut lock) are both desirably used and engaged. Thus, it is typical for the security strut to be stood in the corner or next to the door for ready use when the property owner is ready to leave the premises and again seeks to fully secure the structure.
Thus, there remains a long-felt need in this technical art for an improved, economical, easy-to-use and ascetically pleasing device and related methods which help in securing sliding doors, windows and similar closures against forced entry by burglars.

Combined security strut apparatus and threshold cover for sliding doors and windows


Embodiments of a torsion stop deployment system for utilization onboard an airborne object are provided. In one embodiment, the torsion stop deployment system includes a deployable element hingedly coupled to the airborne object and rotatable from a non-deployed position to a deployed position. The torsion stop deployment system further includes a torsion bar member, which is fixedly coupled to the airborne object and which resiliently resists the rotation of the deployable element to reduce shock to the airborne object during deployment of the deployable element.

Missiles are commonly equipped with deployable flight control surfaces that provide aerodynamic guidance during flight. More recently, smaller projectiles (e.g., artillery shells) and modular components adapted to be mounted to smaller projectiles (e.g., fuse guidance kits) have also been equipped with deployable flight control surfaces. The deployable flight control surfaces often assume the form of a plurality of fins hingedly mounted to the projectile body. Each fin is rotatable between a non-deployed position, in which the fin resides against or within the projectile body, and a deployed position, in which the fin extends radially outward from the projectile body. Each fin is biased toward the deployed position by a mechanical biasing means (commonly referred to as a "deploy energy assembly") and/or by centrifugal forces acting on the projectile as it spins during flight. In many cases, an onboard restraint system prevents the fins from rotating into the deployed position until the desired time of deployment, which may occur shortly after projectile launch or firing. Alternatively, the walls of a storage container may prevent the fins from rotating into the deployed position until the projectile is removed from the container. After the fins are released from the non-deployed position, the fins rotate toward the deployed position and are secured therein by an onboard locking mechanism. By initially maintaining the fins in a non-deployed position, the fins are protected from physical damage that might otherwise in the course of soldier handling. In addition, initial fin stowage allows denser packaging of airframes.
It is typically desirable for fin deployment to occur in an extremely abbreviated time frame; e.g., on the order of a few fractions of a second. Thus, to achieve rapid fin deployment, deploy energy assemblies conventionally utilize one or more springs that store a significant amount of potential energy in their deformed state and that rapidly accelerate each fin from the non-deployed position through the deployed position. While enabling rapid fin deployment, conventional deployment systems that rapidly accelerate the fin through the deployed position can be disadvantageous for two primary reasons. First, onboard locking mechanisms of the type described above typically rely on precision alignment between mating components, such as spring-loaded pins, to secure the fin in the deployed position. When the rotational speed of the fin through the deployed position is excessively high, the onboard locking mechanism may have difficulty engaging the rapidly-rotating fin, which may then rotate past the desired deployed position. Fin over-rotation impacts the desired aerodynamic effects of the flight control surface and typically cannot be corrected by conventional deploy energy assemblies, which provide a unidirectional bias through the deployed position. As a second disadvantage, when the rapidly-rotating fin is abruptly arrested in the deployed position by the onboard locking mechanism, a significant mechanical shock or disturbance is produced and emanates through the projectile. Such a mechanical shock can potentially damage auxiliary components onboard the projectile and/or introduce inaccuracies into projectile guidance.
There thus exists an ongoing need to provide embodiments of a deployment system suitable for utilization with projectiles (or other airborne object) that enables rapid deployment of flight control surfaces (or other deployable elements) while overcoming the above-noted limitations associated with conventional deployment systems. In particular, it would be desirable to provide embodiments of a deployment system that reliably locks flight control surfaces in a precise position during rapid deployment, that returns the flight control surfaces to the deployed position should over-rotation occur, and that minimizes disturbances generated when the flight control surfaces are secured in the deployed position. Other desirable features and characteristics of the present invention will become apparent from the subsequent Detailed Description and the appended Claims, taken in conjunction with the accompanying Drawings and this Background.

Torsion stop deployment system for airborne object


A polishing slurry used in chemical mechanical polishing of a barrier layer and an interlayer dielectric film in a semiconductor integrated circuit includes an abrasive, an oxidizer, an anticorrosive, an acid, a surfactant and an inclusion compound. The polishing slurry has a pH of less than 5. The resulting polishing slurry contains a solid abrasive used in barrier CMP for polishing a barrier layer made of a metallic barrier material, has excellent storage stability, achieves a good polishing rate in various films to be polished such as the barrier layer, and is capable of independently controlling the polishing rate with respect to the various films to be polished while further suppressing agglomeration of the abrasive particles.

The present invention relates to a polishing slurry that may be used in the step of manufacturing semiconductor devices. The invention more specifically relates to a polishing slurry that may be advantageously used to polish mainly a barrier layer formed from a metallic barrier material and an interlayer dielectric film in planarization carried out in the step of forming interconnections in semiconductor devices.
In the development of semiconductor devices typified by semiconductor integrated circuits (hereinafter referred to as "LSI devices"), the trend toward smaller sizes and higher processing speeds has created a need in recent years for higher density and higher integration by the adoption of miniaturization and multilayer constructions of interconnections. Various techniques are being used to this end, including chemical mechanical polishing (hereinafter referred to as "CMP"). CMP is an essential technique for carrying out, for example, the surface planarization of a film to be processed (e.g., an interlayer dielectric film), plug formation, and buried metal interconnect formation, and this technology is used to carry out substrate planarization, to remove surplus metal thin film during the formation of interconnections and to remove surplus barrier layer on the dielectric film.
CMP generally involves attaching a polishing pad onto a circular platen, impregnating the surface of the polishing pad with a polishing slurry, pressing the front side of a substrate (wafer) against the pad, and rotating both the platen and the substrate while applying a predetermined pressure (polishing pressure) from the back side of the substrate so as to planarize the front side of the substrate by the mechanical friction that arises.
In the manufacture of semiconductor devices such as LSIs, fine interconnections are formed in multiple layers, and when interconnections of metals such as copper are formed in each layer, films of barrier metals such as Ta, TaN, Ti and TiN are formed in advance in order to prevent the wiring material from diffusing to the interlayer dielectric film while improving the adhesion of the wiring material.
In order to form each interconnection layer, CMP of a metal film (hereinafter referred to as "metal film CMP") is carried out in one stage or multiple stages to remove surplus wiring material deposited by plating or other method. Then, CMP for removing metallic barrier materials (barrier metals) exposed at the surface by the metal film CMP is usually carried out. However, the metal film CMP suffers from problems such as dishing (excessive polishing of interconnection portions) and also erosion.
In order to suppress such dishing, it is required, in the barrier metal CMP following the metal film CMP, to finally form interconnection layers having reduced irregularities due to, for example, dishing and erosion by adjusting the polishing rate in the metal interconnection portions and the polishing rate in the barrier metal portions. In other words, in cases where the barrier metal and the interlayer dielectric film are polished at a relatively lower polishing rate than the metal wiring material, the interconnection portions are polished more quickly to cause dishing, resulting in erosion. It is desirable for the barrier metal and the insulating layer to be polished at a reasonably high rate in order to prevent these defects. The foregoing dishing very often occurs in the metal film CMP, and the dishing having occurred in the metal film CMP can be reduced by polishing the barrier metal and interlayer dielectric film in the barrier metal CMP at a higher polishing rate than the metal wiring material. Such a high polishing rate will bring about an increased throughput of the barrier metal CMP.
The metal polishing slurry used in CMP typically includes an abrasive (such as alumina, silica, ceric oxide or zirconia) and an oxidizer (such as hydrogen peroxide, persulfuric acid, hypochlorous acid or nitric acid). It is believed that polishing takes place with oxidization of the metal surface by the oxidizer and removal of the resulting oxide film by the abrasive.
However, CMP conducted by using such polishing slurry containing the solid abrasive is associated with the risk of scratches formed by the polishing (scratches), excessive polishing of the entire polishing surface (thinning), deformation of the polished metal surface in the shape of a dish (dishing), and excessive polishing of the insulator between metal interconnections and dish-shape deformation of a plurality of metal interconnection surfaces (erosion).
Various studies as described below have been made for such polishing slurry containing a solid abrasive.
Specifically, a CMP polishing agent and a polishing method for the purpose of polishing at a high rate while hardly causing polishing scratches (see, for example, JP 2003-17446 A), a polishing composition and a polishing method with which the cleaning property was improved in CMP (see, for example, JP 2003-142435 A), and a polishing composition for preventing polishing abrasive particles from agglomerating (see, for example, JP 2000-84832 A) have been proposed.


An oscillating device includes an oscillating substrate of a non-linear optical crystal and having an incident face where a pump wave and an idler wave are made incident; a first waveguide provided in the oscillating substrate and between the incident face and an interacting part of the pump wave and idler waves; and a second waveguide provided in the oscillating substrate and between the incident face and the interacting part. The first waveguide guides the pump wave and the second waveguide guides the idler wave.

1. Field of the Invention
The present invention relates to a device of oscillating so-called terahertz wave.
2. Description of Related Art
Terahertz waves are electromagnetic waves generally having a frequency of 0.1 THz to 10 THz, and are expected for basic fields such as physical properties, electrospectroscopy, bioscience, chemistry and pharmaceutical science and for applied fields of atmospheric environmental assessment, security, material test, food test and communication.
As a device for oscillating terahertz waves, it has been developed a backward wave oscillator (BOW) and photomixing in several hundreds GHz band and free electron energy laser, p-Ge laser and quantum cascade laser (QCL) for 1 THz or more. These devices, however, have problems in the miniaturization and improvement of output power.
On the other hand, it has been recently developed a device for oscillating a wide-band terahertz wave with an optical switch or rectification using a femtosecond laser as a light source and applied for time domain spectroscopy (TDS) or the like.
According to "Basis and applications of terahertz wave" published by Kogyo Chosa Kai, 2005 and authored by Jun-ich NISHIZAWA, pages 105 to 115, stimulated Raman scattering (referred to as Polariton stimulated scattering) is caused by Polariton, which is hybrid wave of optically active transverse wave lattice vibration (TO Phonon) and terahertz wave in a crystal. It is thereby strongly generated parametric interactions of three kinds of waves, which are pump wave, idler wave and terahertz wave. As a result, when the pump wave exceeds a predetermined threshold value, idler and terahertz waves having coherency comparable with that of the pump wave are to be oscillated. Polariton stimulated scattering is observed in polar crystals such as LiNbO3, LiTaO3, GaP or the like. LiNbO3 has properties that (1) it is transparent in light wave region in a wide range (0.4 nm to 5.5 μm) and (2) resistive against optical damage, so that terahertz wave can be oscillated at a high output power.
Japanese Patent Publication No. H09-146131A discloses a device of oscillating terahertz wave using a z-plate of LiNbO3. The principle of oscillation of terahertz wave will be described referring to FIG. 1. FIG. 1 shows a main face 5a of a substrate 5 viewed from the above. The substrate 5 includes an incident face 5c of pump wave, an emitting face 5d of the pump wave, and side faces 5b and 5e. For example, a light source 1 irradiates the pump wave 3 onto the substrate and a light source 2 irradiates an idler wave 4. The pump wave 3 (frequency ω1), idler wave (frequency ω2) and polariton (terahertz wave: frequency ωT) satisfy law of conservation of energy (ω1=ω2+ωT) and law of conservation of momentum (noncollinear phase matching condition: k1=k2+kth), so that polariton stimulated scattering is observed. In this case, due to the scattering property, the frequencies of the idler wave 4 and terahertz wave 7 are decided depending on the angles α and θ of the pump wave 3 with respect to the optical axis.
According to the method, typically, the phase matching condition is satisfied when an angle α of wave vector k1 of the pump wave 3 and wave vector k2 of the idler wave is 0.5° to 1° and the terahertz wave 7 was oscillated (wavelength of 100 to 300 μm, frequency of 3 THz to 1 THz) at a high efficiency. Further, it is described that the terahertz wave is oscillated at an angle of 65 to 66° with respect to the idler wave.
Further, according to K. Kawase, M. Sato, T. Taniuchi, and H. Ito, (Appl. Phys. Lett.,) 68, PP. 2483, 1996, it is described that the intensity of the idler wave as well as that of the terahertz wave can be improved by constituting a resonator with the idler wave (terahertz wave parametric oscillation: TPO). In this case, by changing the angle α in a range of 1 to 2°, the terahertz wave of 0.97 THz to 2.2 THz can be oscillated. A y-plate of LiNbO3 crystal is used and silicon prism is pressed on a surface of the crystal so that (1) the terahertz wave can be drawn to the air at a high efficiency, (2) the fluctuation of the outgoing angle can be reduced (low dependency on wavelength) and (3) the terahertz wave having high directivity can be oscillated.
When such outer resonator is used, the spectrum line width of the oscillated idler wave becomes large (several hundreds GHz), so that it is difficult to generate terahertz wave having a frequency of 0.3 THz or lower generated by difference frequency. Because of this, the following two kinds of laser light sources have been used for generating the terahertz wave having a frequency of, for example, 0.3 THz or lower.
That is, according to Japanese Patent Publication No. 2002-72269A, an exciting laser light having a single frequency is irradiated and an idler wave having a single frequency is used for optical injection to generate terahertz wave having a high output power and whose spectrum line width can be reduced. A silicon prism is, however, used for drawing the terahertz wave.
According to "Cherenkov-type phase-matched widely tunable THz-Wave generation using lithium niobate waveguide" (the 56'th Applied Physics Related Association Conference, Proceedings, 2009 spring, Tsukuba University, 30p-P1-3), a slab optical waveguide of a y-plate or a z-plate of lithium niobate is applied to wide-band tuning of terahertz wave light source. It will be described referring to FIG. 2. A pump wave 3 and idler wave 4 are made incident onto an incident face 9c of an optical waveguide of a substrate 9, which is composed of a y-plate made of lithium niobate doped with magnesium oxide. 9a represents an upper face, 9f represents a bottom face and 9e represents a side face. Although it is described that the thickness of the slab optical waveguide is 3.8 μm, the detail is not described. According to the method, (1) the thickness of the slab optical waveguide 9 is made 3.8 μm to confine the exciting light in the slab optical waveguide 9 to reduce the phase mismatch, (2) the thickness of the substrate 9 is lowered to oscillate the terahertz wave from the crystal surface and to avoid the absorption of the terahertz wave 7 into the crystal, and (3) a prism 6 is provided on the upper face 1a of the substrate 1 to draw the terahertz wave 7.

Electromagnetic wave oscillating devices


A method is provided for coating an optoelectronic chip-on-board module, including a flat substrate populated with one or more optoelectronic components, having a transparent, UV-resistant, and temperature-resistant coating made of one or more silicones. A corresponding optoelectronic chip-on-board module and a system having multiple optoelectronic chip-on-board modules are also provided. The method includes the following steps: a) preheating the substrate to be coated to a first temperature; b) applying on the preheated substrate a dam that encloses a surface area or partial area of the substrate to be coated, the dam being made of a first, heat-curable, highly reactive silicone that cures at the first temperature; c) filling the surface area or partial area of the substrate enclosed by the dam with a liquid second silicone; and d) curing the second silicone.

The invention relates to a method for coating an optoelectronic chip-on-board module, which comprises a flat substrate populated with one or more optoelectronic components, having a transparent, UV-resistant, and temperature-resistant coating made of one or more silicones. The invention also relates to a corresponding optoelectronic chip-on-board module and to a system having several optoelectronic chip-on-board modules.
Optoelectronic chip-on-board modules of this general class are used, for example, as illuminating elements, as high-power UV LED lamps, as photovoltaic modules, as sensors, or the like. The optoelectronic components used here are, in the scope of the invention, but not exclusively, LEDs or photodiodes in the form of chips or other components arranged in the chip-on-board module on a flat substrate, that is, a metal, ceramic, or silicon substrate, a metal core or FR4 circuit board, a glass substrate, a plastic substrate, or the like. These chip-on-board modules must be protected from mechanical damage and corrosion. For this purpose, the most compact and light-weight solutions possible are desired.
A protection in the form of housings on chip-on-board modules is often expensive and technologically complicated. One practical alternative for the protection of chip-on-board modules is a flat encapsulation of the components with a plastic-based encapsulation or casting material. Together with other functional components, such as circuit boards and contacting elements, the optoelectronic components in chip-on-board modules are protected, together with a flat substrate, from mechanical damage and corrosion by coatings.
Typically, epoxy resins are used for this purpose. These are deposited as an encapsulation material, initially as a fluid and then cured by heat and/or radiation. Since the encapsulation material is initially a fluid, the encapsulation material must be prevented from flowing away. This is typically realized by a mold or a fixed frame.
The so-called "dam and fill" method forms one alternative here, wherein initially a plastic dam is applied on the substrate of the chip-on-board module, the dam enclosing an area of the substrate in which a fluid filling compound made of epoxy resin is then filled. This compound is cured. The dam and filling compound together form the coating of the module. For generating the dam, in this method, a viscous polymer is deposited with a dispensing device or drawn out and then cured, so that encapsulation material can be cast on the surface enclosed by the dam, without this material flowing away.
The plastic dam generated in this manner, however, is not transparent. Therefore, the luminous radiation intensity or light sensitivity of optoelectronic chip-on-board modules coated in this manner, that is, chip-on-board modules populated with optoelectronic components, such as LEDs or photodiodes, is adversely affected toward the edge.
One class of additional materials that can be used as a dam in a "dam and fill" method is the class of thixotropic epoxy resins. These are used for this purpose, for example, in the manufacture of chip cards. Thixotropic epoxy resins are treated so that their viscosity depends on the mechanical force application and its duration. Therefore, the application of force on the dam liquefies the thixotropic epoxy resins, and the relaxation of the material after emerging from a nozzle subsequently solidifies it. Thus, they are well suited for generating a stable dam in a "dam and fill" method. Epoxy resins, however, are not UV-resistant and therefore are unstable in a high-power UV LED module or also under intense solar irradiation with UV components, like those in photovoltaic cells. They age quickly under UV loading and are destroyed.
Up to now no method for realizing a flat coating for chip-on-board modules has been known in which materials, which are both UV-resistant and also temperature-resistant and are likewise transparent for electromagnetic radiation from the ultraviolet to the infrared spectral range, are used both in the surface areas and also the edge areas of the encapsulation material.
Other solutions, for example the adhesion of a glass frame or a glass dome, which are transparent, UV-resistant, and temperature-resistant, require a very complicated installation of the frame and a compactness of the frame that is hard to produce. Such a solution is also associated with a greater weight than a "dam and fill" solution. For rigid glass materials, a usually required adaptation of the thermal expansion coefficients of the composite materials also represents another hurdle, especially when the subsequent products are exposed to thermal cycles.
For a combination solution made of a glass frame and an encapsulation with a suitable non-epoxy resin-based material, such as a temperature-resistant and UV-resistant silicone, very small gaps between the frame and substrate can have the effect that the silicone, which has strong creeping properties, can run out during the casting. Space for the frame also must be provided on the substrate. This adversely affects the best possible utilization of the substrate surface and/or a desired stackability.
For the use of chip-on-board technology for the production of high-power UV LED modules that emit over a planar area or of photodiode arrays, a flat encapsulation that avoids the mentioned disadvantages is advantageous. For reasons of optical efficiency and best possible stackability of modules, the encapsulation should have transparent faces and also edge areas. High temperature resistance and UV resistance are likewise relevant both for the production of corresponding optoelectronic components and also for long-term, stable functioning.

Method for coating an optoelectronic chip-on-board module and optoelectronic chip-on-board module


The present invention relates to a delta-sigma-modulator and a delta-sigma-A/D converter. By speeding up the settling time constant of an integrator at the last stage with a simple configuration, the sampling frequency is sped up in the delta-sigma-modulator as a whole. Specifically, in the delta-sigma-modulator including multiple integrators connected in cascade, the integrator positioned at the last stage is a passive integrator not using an amplifier circuit, and one or more integrators positioned at stages preceding the last stage by one or more stages are active SC integrators using amplifier circuits and switched capacitor circuits, respectively. Also, each of the integrators performs integral calculation by alternately repeating a first operation phase to charge a sampling capacitor by sampling an input signal, and a second operation phase to perform a summing integration by transferring an electric charge charged in the sampling capacitor to an integration capacitor.

Conventionally, ΔΣ-A/D converters have been known as high-resolution A/D conversion methods (see, for example, Patent Document 1). A ΔΣ-A/D converter includes a ΔΣ-modulator provided at a preceding stage and a digital filter provided at a following stage. The ΔΣ-modulator converts an analog input signal by quantizing the signal with a comparatively coarse number of bits such as one bit or several bits, and outputs the quantized output value (digital signal sequence). In addition, the digital filter removes a quantization error difference from the digital signal sequence, which is the output signal from the ΔΣ-modulator, and performs final digital output.
The ΔΣ-modulator includes a difference signal generator to generate a difference signal between the analog input signal and a feedback signal; an integrator to amplify and to output the difference signal; a quantizer to quantize the output signal from the integrator, by comparing the output signal with a predetermined threshold value; and a D/A converter to apply digital-analog conversion to the output signal from the quantizer to generate the feedback signal. In the ΔΣ-modulator described in Patent Document 1, the integrator includes multiple integrators connected in cascade. Each of the integrators is an active SC integrator using an operational amplifier and a switched capacitor circuit, and includes a sampling capacitor to sample the input signal, and an integration capacitor to execute summing integration with transferred electric charge that has been charged in the sampling capacitor. In each of the integrators, sampling by the sampling capacitor (sampling phase) and integration by the integration capacitor (integration phase) are performed alternately and repeatedly. With such operations, summing integration is performed over differences between the analog input signal and the quantized output at the integrator.
Also, for example, if two stages of integrators are connected in cascade, during an integration phase of the first-stage integrator, the input terminal of the operational amplifier is connected with the first-stage sampling capacitor, whereas the output terminal of the operational amplifier is disconnected from the second-stage sampling capacitor. Also, during a sampling phase of the second-stage integrator, the input terminal of the first-stage operational amplifier is disconnected from the first-stage sampling capacitor, whereas the output terminal of the first-stage operational amplifier is connected with the second-stage sampling capacitor. Configured as such, assuming that the first-stage sampling capacitor and the second-stage sampling capacitor are alternately connected with the operational amplifier of the first-stage integrator, and also assuming that both sampling capacitors are not simultaneously connected with the integrator, then, the drive capability of the operational amplifier is relaxed because the settling time constant of the operational amplifier during an integral operation of the operational amplifier is equalized with the settling time constant in a sampling operation at the next stage.


A cover for an image sensor array is disclosed. The cover includes a plate formed of substantially transparent material and placed adjacent to the image sensor array. The plate has a plurality of surfaces and forms a lensing structure. At least one of the plurality of surfaces is contoured into a lensing surface capable of performing an imaging improvement or enhancement function.

The present specification generally relates to image sensor arrays, and particularly to a contoured-surface cover plate for such image sensor arrays.
When a sensor array is mounted on an image sensor assembly such as a digital camera system, the sensor array is sealed for protection by bonding a cover plate on the assembly over the sensor array. Often, the cover plate is a flat piece of transparent material, such as glass, plastic or plexiglass, which provides protection only from the environment. The cover plate offers little in terms of optical enhancement.
On the other hand, competition for cheap camera systems is driving demand for high quality optics at a low price. However, such high quality optics are difficult to design and fabricate without the use of multiple lensing elements. Therefore, the use of multiple lensing elements often drives the price up. In addition, the lensing elements, once fabricated, must be mounted and aligned to the camera system at fairly tight tolerances in positioning, focus, and attitude. This also adds to the overall cost of the camera system.

Contoured surface cover plate for image sensor array