A process for the conversion of an organic material comprising an oxidation step during which an organic material undergoes the oxidising action of an enzymatic means capable of generating hydrogen peroxide, wherein said oxidation step is carried out, wholly or partly, in the presence of 0.001% to 1% of a metal selected from ruthenium, palladium and mixtures thereof.

The present invention relates to a new process for the conversion of organic materials, particularly saccharide materials, comprising an oxidation step carried out under particular conditions, namely combining, at least at a given moment, a means of enzymatic oxidation capable of generating hydrogen peroxide and at least one particular metal, namely ruthenium and/or palladium.
The invention also relates to a process as described above comprising an additional step involving the oxidation or reduction of the material oxidised enzymatically beforehand.
In particular, the claimed process makes it possible to obtain, in a simple, rapid and inexpensive manner, organic materials, particularly those of a saccharide nature, oxidised with high selectivity then optionally reduced or re-oxidised, having numerous industrial applications, including the use as synthesis intermediates, such as glucosone, galactosone, gluconic, 2-keto-gluconic or isoascorbic acids, fructose, sorbitol, mannitol etc.
The term xe2x80x9corganic materialsxe2x80x9d within the meaning of the present invention means both saccharide materials and non-saccharide organic materials.
The latter include alcohols and organic acids of a non-saccharide nature such as, for example, lower alcohols including methanol, fatty alcohols, glycerol, cholesterol, polyvinyl alcohols, hydroxycarboxylic acids including malic acid, the respective derivatives thereof and, generally, all organic products other than saccharides which are potentially capable of being oxidised enzymatically with the concomitant production of hydrogen peroxide.
As mentioned, the process forming the subject matter of the invention may be applied advantageously to saccharide materials, this idea being in no way limiting and including linear, cyclic or branched monosaccharides, disaccharides, trisaccharides, oligosaccharides and mixtures of these products such as hydrolysates of starch, insulin or cellulose.
It may also be applied to saccharide materials which have undergone, before the characteristic step of enzymatic oxidation, at least one step involving chemical, enzymatic and/or physical modification, particularly hydrolysis, oxidation or hydrogenation and/or at least one purification step.
Preferably, the saccharide material is chosen from the group comprising monosaccharides, disaccharides, oxidised or hydrogenated derivatives of monosaccharides and disaccharides, and any mixtures of at least any two of these products, independently of the process by which such products were obtained.
Monosaccharides may consist, in particular, of pentoses or hexoses such as xylose, arabinose, ribose, glucose, galactose, mannose, sorbose or fructose.
Disaccharides may consist, in particular, of maltose, isomaltose, lactose, lactulose, cellobiose or sucrose.
As mentioned, the process according to the invention may also be applied to organic materials composed of purified or unpurified monosaccharides or disaccharides which have already been modified, particularly which have already been oxidised or hydrogenated.
The oxidised monosaccharides and disaccharides undergoing the characteristic step of enzymatic oxidation according to the invention may, in particular, correspond to the products of the oxidation, in one or more places, of the monosaccharides and disaccharides listed above and, in particular, may consist of any of gluconic, glucaric, 5-keto-gluconic, galactonic, galactaric, gulonic, maltobionic or lactobionic acids, said acids being in the free and/or lactonised and/or salt form.
The lactonised form may, by way of example, consist of a gluconolactone, a galactolactone or a gulonolactone.
The hydrogenated monosaccharides and disaccharides may, in particular, correspond to the products of relatively thorough catalytic hydrogenation of the above-mentioned monosaccharides and disaccharides.
It is widely known that monosaccharides or disaccharides, optionally oxidised or hydrogenated already, may be oxidised enzymatically, particularly by oxidoreductases capable of using oxygen as a hydrogen acceptor and hence capable of generating hydrogen peroxide (H2O2) in the reaction medium.
These are, in particular, enzymes of Group 1.1.3 as defined in the document xe2x80x9cENZYME NOMENCLATURExe2x80x9d, revised periodically by the International Union of Biochemistry and Molecular Biology. The nomenclature of such enzymes is recapitulated on pages 55 to 60 of the 1992 edition of said document.
These are, inter alia, enzymes having at least one of the glucose oxidase, hexose oxidase, galactose oxidase or pyranose oxidase activities.
Thus, reference has been made regularly, particularly for about twenty years, to the use of pyranose oxidase (also known, inter alia, as xe2x80x9cglucose 2-oxidasexe2x80x9d, xe2x80x9cpyranose: oxygen 2-oxidoreductasexe2x80x9d or more simply xe2x80x9cP2Oxe2x80x9d) for the enzymatic conversion of monosaccharides, optionally already oxidised, to their equivalents oxidised in the 2 position, and in particular for the conversion of glucose to glucosone or galactose to galactosone. These products are synthesis intermediates of great interest for obtaining products such as fructose, sorbitol, mannitol or tagatose which, on their own or in mixture, have wide fields of application, particularly in the food, pharmaceutical and chemical industries.
For several decades, there has also been wide recourse to the use of glucose oxidase (also known, inter alia, as xe2x80x9cglucose oxyhydrasexe2x80x9d, xe2x80x9cbeta-D-glucose: oxygen 1-oxidoreductasexe2x80x9d or more simply xe2x80x9cGODxe2x80x9d) for the preparation of gluconic acid, in the free, lactonised and/or salt form, from glucose.
However, one of the major disadvantages of the above-mentioned enzymes is that hydrogen peroxide is generated concomitantly and in equimolar quantities with the desired oxidised product. However, it is acknowledged that the presence of hydrogen peroxide is, on the whole, disadvantageous for the activity of an oxidoreductase such as pyranose or glucose oxidase, and efforts are generally made to remove hydrogen peroxide wholly or partly from the reaction medium during the course of the enzymatic oxidation reaction.
Various means of an enzymatic, chemical or physical nature have been proposed for removing or decreasing hydrogen peroxide or at least the adverse effects associated with the generation and presence of this compound in the complex medium which the enzymatic oxidation medium constitutes.
The means most often described consists in the use of catalase in the free or immobilised form, with a view to decomposing hydrogen peroxide enzymatically. This use is described in numerous patents such as the patents WO 81/03664 and WO 81/03666 published in 1981 in the name of STANDARD BRANDS, the subsequent patents U.S. Pat. Nos. 4,351,902, 4,423,149, 4,568,645, 4,569,910, 4,569,913, 4,569,915 and 4,650,758 in the name of CETUS CORPORATION, WO 97/24454 in the name of GENENCOR INTERNATIONAL INC and U.S. Pat. No. 5,897,995 in the name of GIST-BROCADES B.V.
The use of catalase in combination with a glucose oxidase has also been mentioned, where necessary also illustrated by examples, in the articles or patents below:
xe2x80x9cSTABILITY STUDIES ON THE IMMOBILIZED GLUCOSE OXIDASE/CATALASE ENZYME SYSTEMxe2x80x9d, R. S. CARTER et al, ENZYME ENG., (1980), 5, 321-324,
U.S. Pat. No. 4,460,686, published in 1984 in the name of BOEHRINGER INGELHEIM,
xe2x80x9cProduction of gluconic acid with immobilized glucose oxidase in airlift reactorsxe2x80x9d, K. NAKAO et al, CHEMICAL ENGINEERING SCIENCE, (NOV. 1997), VOL. 52, no. 21-22, 4127-4133.
The use of catalase in combination with another oxidoreductase, namely a glycolate oxidase (EC 22.214.171.124), has also been illustrated by examples in U.S. Pat. No. 5,262,314 published in 1993 in the name of E.I. Du Pont de Nemours and Co.
The use of catalase has also been described, inter alia, in the following recent scientific articles:
xe2x80x9cLaboratory procedures for producing 2-keto-D-glucose, 2-keto-D-xylose and 5-keto-D-fructose from D-glucose, D-xylose and L-sorbose with immobilized pyranose oxidase of Peniophoro giganteaxe2x80x9d, A. HUWIG et al, Journal of Biotechnology 32, 309-315 (1994),
xe2x80x9cA Convenient Enzymatic Procedure for the Production of Aldose-Free-D-Tagatosexe2x80x9d, D. HALTRICH et al, ANNALS NEW YORK ACADEMY OF SCIENCES, 864, 295-299 (1998),
xe2x80x9cThe CETUS Process revisited: a novel enzymatic alternative for the production of aldose-free D-fructosexe2x80x9d, C. LEITNER et al, Biocatalysis and Biotransformation, Vol., 00, 1-18 (1998).
Other routes already advocated for the removal/decrease of hydrogen peroxide or of its adverse effects in a reaction medium as envisaged here consist in the use of chemical means such as:
Manganese oxides said to be capable of decomposing H2O2 according to the article xe2x80x9cThe Immobilization of Glucose Oxidase to Manganese Oxidexe2x80x9d, Z. DUVNJAK et al, BIOTECHNOLOGY AND BIOENGINEERING, VOL. XVIII, 737-739 (1976), but which are said not to be sufficiently effective according to U.S. Pat. No. 4,460,686 mentioned above and would not, in fact, be able to act as a substitute for catalase, as follows from the examples of U.S. Pat. No. 5,262,314,
Quinine sulfate or urea which are said to be capable of stabilising glucose oxidase in the presence of H2O2 according to the article xe2x80x9cThe Influence of Peroxidexe2x80x94Stabilizing Agents on Enzyme Deactivation by H2O2xe2x80x9d, Y. K. CHO et al, BIOTECHNOLOGY AND BIOENGINEERING, VOL. XIX, 157-158 (1977),
Activated carbon which is said to be capable of inactivating H2O2 according to the article xe2x80x9cEnzyme Immobilization on Activated Carbon: Alleviation of Enzyme Deactivation by Hydrogen Peroxidexe2x80x9d, Y. K. CHO et al, BIOTECHNOLOGY AND BIOENGINEERING, VOL. XIX, 769-775 (1977) and according to the above-mentioned article by R. S. CARTER,
Alkenes which are said to be capable of xe2x80x9cconsumingxe2x80x9d H2O2 and thus forming recoverable glycols or alkoylene oxides according to U.S. Pat. No. 4,321,324 in the name of CETUS CORPORATION,
Platinum which, in the presence of P2O-producing mycelium and a dilute solution of glucose (2.5%), is said to be capable of decomposing H2O2 according to the patent WO 81/03666 mentioned above, and the use of which, as a substitute for catalase for stabilising glycolate oxidase, is advocated in U.S. Pat. No. 5,262,314 mentioned above,
Stabilisation of pyranose oxidase by amidination according to the above-mentioned U.S. Pat. No. 4,650,758,
Purification of pyranose oxidase by removing the parasitic xe2x80x9cpyranosone dehydratasexe2x80x9d activity according to the above-mentioned U.S. Pat. No. 4,569,913.
Other documents advocate the removal (of the adverse effects) of hydrogen peroxide by combining a physical means (semi-permeable membrane) with an enzymatic means (catalase) or chemical means (alkene) as described in the above-mentioned patents WO 81/03664 and U.S. Pat. No. 4,321,324.
Metals other than platinum have been advocated with a view to stabilising the activity of glucose oxidase (xe2x80x9cGODxe2x80x9d) by decomposition of hydrogen peroxide (H2O2).
This is the case, inter alia, with ruthenium, the use of which is envisaged in the above-mentioned article by R. S. CARTER. This document does not, however, specify the exact conditions of use of this metal in the oxidation reaction medium, and particularly the ruthenium content of said medium, and the ratio of glucose oxidase/catalase activity when the latter is present. On the other hand, this document underlines the gradual xe2x80x9cpoisoningxe2x80x9d of the ruthenium by the gluconic acid generated and draws conclusions about the insufficient protective effect of this metal towards GOD from the point of view of long-term industrial trials.
This insufficient ability of ruthenium to improve the stability of GOD, including immobilised GOD in the presence of catalase, is underlined in column 2, lines 46-51 of the U.S. Pat. No. 4,460,686 mentioned above.
This lack of effectiveness of ruthenium as a substitute for catalase for stabilising an oxidoreductase such as glycolate oxidase follows clearly, moreover, from the U.S. Pat. No. 5,262,314 published subsequently in 1993.
Examples 3, 5 and 13 of said patent show that this metal, even if used in a very large quantity, i.e. greater than 2.5% expressed as dry weight with respect to the dry substance of the reaction medium, or greater than 5% expressed as dry weight with respect to the dry weight of the substrate to be oxidised, does not make it possible to obtain:
high yields of oxidised substrate, these yields always being less than 35%,
a high residual xe2x80x9coxidoreductasexe2x80x9d activity, this activity also always being less than 35%.
This is the case, in particular, when ruthenium is used on an activated carbon support according to example 5 of said patent.
The use of 0.615 g of a catalyst based on 5% ruthenium on activated carbon, that is, about 5.4% ruthenium (dry/dry)with respect to the glycolic acid used, or about 2.7% ruthenium (dry/dry) expressed with respect to the dry substance of the reaction medium, allows at best the following to be obtained after 22 hours"" reaction:
a glyoxylate yield of 32.5%, and
a residual xe2x80x9cglycolate oxidasexe2x80x9d activity of 17%.
Consequently, U.S. Pat. No. 5,262,314 advocates the use of extremely large quantities of xe2x80x9cnon-enzymatic catalystsxe2x80x9d of a very varied nature such as manganese or copper oxides, ruthenium, platinum, palladium, lead, soluble salts or chelates of manganese, copper, nickel, cobalt, zinc, iron or chromium, activated carbon or certain imidazole derivatives, from the point of view of replacing the use of catalase.
More recently, consideration has been given, within the context of reactions carried out in particular pieces of equipment (airlift reactors), to substituting catalase by fine particles of palladium contained in a quantity of 4 wt. % in alginate beads having a density of around 1 g/cm3 and in which GOD is also immobilised.
The exact quantities of palladium used effectively in the reaction medium, particularly in terms of the total dry substance of said medium (including alginate beads) and/or the dry weight of the substrate alone to be oxidised (glucose) are not specified. However, it is pointed out in the last paragraph of the chapter xe2x80x9cOptimal operating conditionsxe2x80x9d on page 4132 of said document that:
the optimum initial concentration of the glucose solution is 10 g/l, and
the optimum volume ratio of the alginate beads with respect to the total volume of beads+glucose solution or xe2x80x9cgel bead contentxe2x80x9d is 0.4.
Consequently, also in view of the presumed density of said glucose solution (≈1 g/cm3) and the very low usual dry substance content of alginate beads intended to contain an enzyme (dry substance less than 20%, generally less than 10%), it is deduced by calculation that the authors advocate a quantity of palladium whatever the circumstances;
greater than 250%, expressed as dry/dry with respect to the quantity of substrate (glucose), and
greater than 15%, expressed as dry weight with respect to the total dry substance of the reaction medium (including beads).
The overall result of the above is that, in the case of glucose oxidase and glycolate oxidase, metals such as, inter alia, ruthenium or palladium cannot be effective substitutes for catalase unless, optionally, they are used in necessarily very high and hence extremely expensive quantities.
Moreover, in the case of pyranose oxidase, there is no option but to ascertain that the most recent prior art, represented by the examples of the above-mentioned CETUS CORPORATION patents and scientific articles, envisages in practice only catalase as the principal means of removing hydrogen peroxide and its adverse effects.
In particular, catalase may be physically combined with the oxidoreductase (pyranose oxidase, glucose oxidase in particular) by way of enzymatic complexes naturally present in various microorganisms or pre-mixtures of enzymes of different origins, but also by means of co-immobilisation on the same support, these variants being described, for example, in the U.S. Pat. Nos. 4,569,910, 4,650,758, 4,351,902 and 5,897,995 mentioned above.
Catalase may also be combined with bovine serum albumin (xe2x80x9cBSAxe2x80x9d acting as a stabiliser or protector of the oxidoreductase as described in the articles by HALTRICH and LEITNER mentioned above. The precise mode of action of BSA is poorly understood but, according to LEITNER this protein could, in particular, protect pyranose oxidase and also catalase from the adverse effects of glucosone. Other protective agents may consist of casein, methionine, quinine or mannitol, sorbitol or glycerol according to the U.S. Pat. No. 5,897,995.
Whatever the case, it is known that catalase is also inactivated by hydrogen peroxide and that it is necessary, in practice, to use it in large quantities, in any case in a large excess with respect to the quantities of oxidoreductases used in conjunction therewith.
The patents WO 97/24454 and U.S. Pat. No. 5,897,995 published very recently envisage ratios between the number of units of catalase and the number of units of oxidoreductase (glucose oxidase) used in the reaction medium (hereinafter known as the C/O ratios) of the order of 40-80 (WO 97/24454) or even equal to 140 (U.S. Pat. No. 5,897,995).
Finally, the articles by HALTRICH and LEITNER mentioned above advocate a CIO ratio of 1000, combined with the use of BSA in a quantity of 5 mg/ml of reaction medium, with the possibility of recycling the oxidoreductase (pyranose oxidase) and BSAxe2x80x94unlike the catalase used which is unstablexe2x80x94after their extraction from the reaction medium by ultrafiltration.
Another teaching by LEITNER relates to the fact that the platinum deposited on activated carbon cannot, in fact, be used as a substitute for catalase because its use results in a loss of more than 95% of the P2O activity under standard operating conditions.
Consequently, in spite of the cost of using catalase, no serious consideration was given, until then, to questioning the growing interest and use.
After considerable research, a new means has now been developed for the effective preparation of organic materials oxidised enzymatically such as, for example, glucosone or gluconic acid, said means making it possible, if desired, to obtain said materials in the presence of reduced or even zero quantities of catalase, and/or protective agent such as BSA.
The Applicant company has, in particular, found that, surprisingly and unexpectedly, ruthenium and palladium in small quantities could, unlike platinum in particular, be used advantageously as a substitute for catalase and allow an oxidoreductase such as pyranose or glucose oxidase to act rapidly with a high yield and excellent selectivity.
More specifically, the present invention relates to a process for the conversion of an organic material comprising an oxidation step during which an organic material undergoes the oxidising action of an enzymatic means capable of generating hydrogen peroxide, this process being characterised in that said oxidation step is carried out wholly or partly in the presence of 0.001% to 1% of a metal selected from ruthenium, palladium and mixtures thereof, these percentages being expressed as total dry weight of ruthenium and palladium with respect to the total dry weight of the reaction medium.
Advantageously, said metal is present in an amount in the range 0.005% to 0.2%
As mentioned, it is not obligatory that said metal be present in the reaction medium perfectly simultaneously with the means of enzymatic oxidation; one may be introduced into the reaction medium and/or withdrawn from the reaction medium before the other. Ruthenium and/or palladium may be introduced in any suitable forms, particularly in the immobilised form on a support, obtained by any known method, particularly impregnation or ion exchange. The support may be composed, for example, of activated carbon, peat, zeolite, titanium dioxide or a synthetic polymer of the carbon fibre type. An undeniable advantage of the process claimed here is that it allows the recycling of said metal, which is generally impossible with an ordinary catalase.
The organic materials, particularly of a saccharide nature, that may be used as a substrate for at least one of the means of enzymatic oxidation envisaged here have been described above and relate in particular to monosaccharides, disaccharides and their respective derivatives, for example, those which have already been oxidised.
The term xe2x80x9cmeans of enzymatic oxidationxe2x80x9d within the context of the present invention means, in particular, the oxidoreductases of group 1.1.3 within the meaning of the document xe2x80x9cENZYME NOMENCLATURExe2x80x9d mentioned above and mixtures of at least any two of these enzymes, it being specified that said enzymes may be used in the free form or immobilised on a support, such as they are, in the partly or wholly purified form and/or by means of organisms which synthesise said enzymes.
By way of example, the means of enzymatic oxidation may be chosen from enzymes or mixtures of enzymes having at least one of the activities of glucose oxidase, hexose oxidase, galactose oxidase, pyranose oxidase, L-sorbose oxidase, cellobiose oxidase, L-gulonolactone oxidase, L-galactononolactone oxidase, alcohol oxidase, secondary alcohol oxidase or (S)-2-hydroxyacid oxidase, and their respective equivalents, current or future.
Advantageously, the means of enzymatic oxidation has at least one of the glucose oxidase, hexose oxidase, galactose oxidase or pyranose oxidase activities.
It may be, in particular, a preparation based on partly or wholly purified enzyme(s) in the free form or immobilised on a support, having a pyranose oxidase and/or glucose oxidase activity, or based on organism(s), in the free form or immobilised on a support, which synthesise this type of enzyme(s).
Such organisms, enzymatic preparations and enzymes which may advantageously be recycled, are described in the above-mentioned patents and scientific articles which form an integral part of the present description. They may, by way of example, be derived from (consist of) any of the following organisms:
Polyporus obtusus, Trametes multicolor, Coriolus versicolor, Lenzites betulinus, Oudemansiella mucida, Aspergillus flavus capable of synthesising, inter alia, pyranose oxidase,
Aspergillus niger, Aspergillus oryzae capable of synthesising, inter alia, glucose oxidase, and all their taxonomic and/or functional equivalents, current or future, of natural origin or otherwise, resulting in particular from treatments, mutations or genetic manipulations.
Preferably, the means of enzymatic oxidation has a pyranose oxidase activity.
According to a variant of the process according to the invention, the enzymatic oxidation step is carried out in the presence of a ratio of catalase/oxidoreductase activity(C/O ratio) as specified above, of less than 1000, and particularly
less than 500, preferably less than 200, if the oxidoreductase consists of pyranose oxidase, or
less than 40 if the oxidoreductase consists of glucose oxidase.
It should be recalled here that a preparation of oxidoreductase may, despite continuous efforts to purify the enzyme, exhibit simultaneously a relatively high catalase activity which is relatively intimately associated with it physically. This is due in particular to as yet incomplete purification and/or recycling from a medium which also contained catalase. The use of said oxidoreductase may therefore involve, particularly due to its recycling, the concomitant use of an xe2x80x9cendogenousxe2x80x9d catalase activity which should be distinguished from an xe2x80x9cexogenousxe2x80x9d catalase activity, i.e. supplied in a predetermined manner, independently of the oxidoreductase activity, simultaneously or otherwise with the latter.
According to a variant of the process according to the invention, the enzymatic oxidation step is carried out in the absence of any exogenous supply of catalase activity.
According to another variant, the means of enzymatic oxidation and the metal (ruthenium and/or palladium) are immobilised on the same support.
The concentration of the organic material used as a substrate of the means of enzymatic oxidation is not subject to any particular constraint as regards the prior art. The organic material may be supplied in particular in the form of a solution having a dry substance (xe2x80x9cDSxe2x80x9d) content in the range 2% to 70%, particularly from 4% to 60%. It may be, for example, a glucose solution having a DS of more than 5%, particularly in the range 6% to 55%, which may be used as a substrate of pyranose oxidase or glucose oxidase. In practice, the enzymatic oxidation reaction is generally carried out at a temperature in the range 15xc2x0 C. to 60xc2x0 C., for example, in the range 20xc2x0 C. to 35xc2x0 C. if the means of enzymatic oxidation consists of pyranose or glucose oxidase.
The other reaction parameters are those generally found in the literature, including those concerning aeration, agitation and the pH of the reaction medium.
The Applicant company has found, however, that in the case of pyranose oxidase, the pH of the reaction mixture was advantageously above about 5.5 and particularly in the range about 5.6 to 6.5.
As mentioned, the process according to the invention makes it possible, remarkably, to obtain an oxidised material such as glucosone with a very high yield and selectivity from glucose within very short periods of time. If the means of oxidation has pyranose oxidase activity, the process according to the invention may therefore be characterised advantageously by the fact that the enzymatic oxidation step has a duration of less than 6 hours, preferably less than 5 hours.
Consequently, a new, simple, effective, inexpensive and very selective means is now available for obtaining oxidised organic materials.
This means is particularly suitable for the preparation of a saccharide composition containing at least one monosaccharide or a disaccharide, preferably selected from the group comprising glucose, galactose, mannose, xylose, sorbose, maltose, lactose and any mixtures of at least any two of these products, oxidised in at least one place and optionally lactonised, particularly for the preparation of a composition based on at least one product selected from the group comprising glucosone, galactosone, xylosone, glucosyl-glucosone, 2,5-diketo-fructose, gluconic acid, galactonic acid, 2-keto-gluconic acid, 2-keto-glucaric acid, 2,5-diketo-gluconic acid, isoascorbic acid, said acids being in the free and/or lactonised and/or salt form, and any mixtures of at least any two of said products.
Due, in particular, to their purity, the oxidised organic materials obtained in accordance with the invention may undergo advantageously, if desired, one or more subsequent modification steps, particularly of a chemical nature.
The present invention relates in particular to a process as described above, characterised in that it comprises, subsequent to the enzymatic oxidation step in the presence of ruthenium and/or palladium, at least one additional step involving the reduction or oxidation of the enzymatically oxidised, optionally purified organic material.
The reduction step may take place enzymatically as described in the articles by HALTRICH and LEITNER mentioned above. Advantageously, it is a catalytic hydrogenation step as described in the patents WO 81/03666, U.S. Pat. No. 4,321,324 and U.S. Pat. No. 4,423,149 mentioned above.
By way of example, the glucosone preparation obtained from glucose in the presence of pyranose oxidase and ruthenium and/or palladium may, particularly due to its low content of formic acid or of other species acting as catalyst poisons, undergo advantageously an additional oxidation or catalytic hydrogenation step.
Another undeniable economic advantage of the process according to the invention is, moreover, that it allows the recycling of the ruthenium and/or palladium used during the enzymatic oxidation step for the purpose of using it during a subsequent catalytic hydrogenation step.
According to one variant, this process is characterised, therefore, in that it comprises an additional catalytic hydrogenation step, continuous or batchwise, this being preferably also carried out in the presence of ruthenium and/or palladium recycled from the previous enzymatic oxidation step or not recycled.
This process may therefore be used advantageously for the preparation of a saccharide composition containing at least one product selected from the group comprising fructose, sorbitol, mannitol, tagatose, hydrogenated or not hydrogenated, glucosyl-sorbitol, glucosyl-mannitol and any mixtures of at least any two of these products.
According to another variant of the process according to the invention, the enzymatic oxidation step is carried out continuously. Thus, the organic material that has to undergo said step is introduced continuously into the reaction medium and the oxidised organic material that has undergone said step, for example, glucosone, is drawn off, also continuously, from said reaction medium.
In this case, the ruthenium and/or palladium (on a support) may be used advantageously in the form of granules which are placed in a perforated and generally fixed vessel immersed in the reaction medium. The metal granules may thus remain in continuous contact with the reaction medium.
Moreover, the oxidised organic material may, according to another variant, advantageously undergo, likewise continuously or batchwise, at least one subsequent filtration step, for example, microfiltration and/or ultrafiltration, with a view in particular to allowing the continuous or batchwise recycling of all or part of the means of enzymatic oxidation and/or the metal (ruthenium and/or palladium) used beforehand. The oxidised organic material thus purified, for example, glucosone, may then undergo, as already mentioned, a subsequent, particularly continuous, hydrogenation step.
The present invention will be described in more detail with the aid of the examples below which are in no way restrictive.

Process for the conversion of organic materials, particularly saccharide materials, comprising an enzymatic oxidation step in the presence of ruthenium or palladium


A curing component (A) containing amino groups available for reaction with epoxy resins (B), wherein the curing component (A) is a condensation product of di- or polyhydroxyaromatics (A1) with polyamines (A2) is disclosed. The curing component (A) is useful in preparing curing mixtures (C) which include the curing component (A) and at least one epoxy resin (B), whereby the curing mixtures are useful in the production of shaped articles and as coatings.

1. Field of the Invention
The present invention relates to a curing component for epoxy resins, a process for its preparation and the use thereof in curable mixtures.
2. Description of Related Art
It is known that alcohols, in particular phenol or alkylated phenols, accelerate the curing reaction between oxiranes and amino groups (cf. U.S. Pat. No. 3,366,600, EP-B 0 114 875, DE-C 10 43 629 and DE-C 20 25 343). It has proved advantageous in these case to form a single compound that combines the phenol component together with the amine component. In DE-C 15 43 754, a hydroxyaryl-substituted aliphatic carboxylic acid is linked with a polyamine via an amide bond to produce a single compound having both a phenol component and an amine component. In this process, however, one amino group of the polyamine, which is required for the amide bond, is lost for the curing operation. In DE-A 32 33 565 and EP-A 0 114 875, the reaction product of a Mannich reaction of aldehydes and polyamines with phenol or alkylphenols, for example cresols, p-tert-butylphenol or nonylphenol, is therefore proposed as the curing component, and in EP-A 0 066 447 reaction products with arylphenols, for example benzylphenol, also are proposed.
U.S. Pat. No. 2,974,121 also discloses adducts of phenols with polyamines which are used for curing epoxy resins, and in particular are used as coatings. The suitable polyamines have at least one, but not more than two amino groups per molecule, the amino groups in each case being bonded to an aliphatic carbon atom. Epoxide-amine adducts are preferred in this document. The phenols disclosed in this document are those that have in each case at least one monohydroxyphenyl group per molecule. Phenols which contain exclusively polyhydroxyphenyl groups, such as resorcinol, hydroquinone and phloroglucinol, are said to provide coatings with matt surfaces, and are therefore not useful for the present invention. The adducts disclosed in this document are formed by heating, without the addition of catalysts, to temperatures between 4 and 104.degree. C., preferably up to 52.degree. C. The adducts are salts of the acid phenol with the amine; the salt is present in an equilibrium, the phenol being liberated again during the (amine-consuming) curing reaction.
These combinations have all proved to be good, but also have disadvantages, such as, in some cases, a lack of acceleration at low temperatures (.ltoreq.10.degree.0C.) and under high atmospheric humidity, and a lack of resistance to dilute organic acids, such as, for example, acetic acid. Since all these aforementioned combinations comprise phenol or alkylated phenols, they can furthermore be employed to only a limited extent from a toxicological aspect due to the risk to the user during application. When contacted with foodstuffs, the phenols are readily extracted from the coating due to the aqueous dilute organic acids contained therein, such as acetic acid, tartaric acid or citric acid, and thus spoil the foodstuff.
DE-C 10 43 629 also mentions, in addition to the customary phenolic components, polyhydric phenols as possible reactants for curing components which can be prepared by a Mannich reaction. Compounds such as resorcinol and hydroquinone, however, produce highly crosslinked Mannich bases of undesirably high viscosity because of their high reactivity. The increased polarity of polyhydric phenols compared with monohydric phenolic components furthermore causes greater blushing of the coatings produced from them, for example during absorption of water (action of moisture).

Curing component for epoxy resins and the use thereof


The present invention is related to a shock endurable alarm lamp which is comprised of a light emitting structure and a shock proof structure. The light emitting structure is constructed from a plurality of lampshades and lamp base structures. A shock proof structure is installed on the bottom of the light emitting structure. The shock proof structure has two layers of spring structures installed on the upper and lower sides of a fixing base, and then a bolt is inserted downwards into the two layer structures for aligning the springs. Finally, a bushing covers the outside of the structure. Therefore, a shock proof structure is formed. Next, the whole structure is installed on a machine which needs an alarm lamp. The shock proof structure formed by the two sets of springs will cause oscillations induced from the machine to be absorbed, thereby sustaining the structure and stability of the alarm lamp.

1. Field of the Invention
The present invention is related to a shock endurable alarm lamp which is mainly installed on a finishing machine for alerting the operator, the shock endurable alarm lamp is comprised of a light emitted structure and a shock proof structure, said light emitted structure may be formed from a generally used lamp or a light emitted diode (LED), and the bottom of this light emitted structure is installed with a shock proof structure having a well effect of shock proof In this structure, a plurality of springs are separately installed on the upper and lower parts of the fixing base, and every two springs are aligned to each other. A bolt is penetrated through a pair of aligned two springs and then they are fixed to upper and lower fixing disks so to form two layer of good elastic shock proof structure, and then the assembled spring structure are engaged into a bush and is fixed on the nose portion of the bush, and then they are installed to a finishing machine through a pillar, By using the springs to absorb the vibration so to generate a buffer effect, thus the alarm lamp may be prevented to be destroyed by the resonance from the oscillation of finishing machine, and therefore, the lifetime of alarm lamp are prolonged.
2. Description of the Prior Art
In the field of automatic control, owing to the progress of new technology and industrialization, other then the performance of a product, the shape of the product is also a main concern for the user, now in different kinds of finishing machine, the alarm lamp is generally used, it may be used to alert the operator to pay attention to the danger in working.
As shown in FIGS. 5 and 6, in the current alarm lamp, a plurality of lamps are installed within a lamp device, after assembling, the structure are integrally installed on a finishing machine. The drawback of this design is that since the finishing machine is driven by a motor, the structure itself is assembled by different mechanic elements, thus it has no the buffer effect, naturally, a big vibration will occur, accordingly, the alarm lamp installed on said finishing machine will resonate so that the lamp device will be destroyed, therefore, the lifetime of the alarm lamp will reduce and the cost will increase.


A circuit breaker includes a pair of separable contacts forming a pole, an operating mechanism for operating the electrical contacts, an electronic trip circuit responsive to currents flowing through the pole for operating the operating mechanism in response to predetermined current conditions to open the separable contacts, and a fail-safe mechanism for operating the operating mechanism in response to a failure in the electronic trip circuit. The fail-safe mechanism includes a solenoid that is electrically connected to be energized in response to a failure in the electronic trip circuit and a linkage that operates the operating mechanism in response to operation of the solenoid. An operating arm that moves in response to the solenoid, interacts with operating mechanism to prevent resetting of the operating mechanism following actuation of the solenoid.

This invention relates to ground fault current interrupter and arc fault current interrupter circuit breakers and more particularly to such circuit breakers having a mechanism for opening the associated circuit in the event of a failure in the ground fault or arc fault trip circuit.
In small circuit breakers, commonly referred to as miniature circuit breakers, used for residential and light industrial applications, overcurrent protection is typically provided by a thermal-magnetic trip device. This trip device typically includes a bimetal strip that is heated and bends in response to a persistent overload condition. The bimetal, in turn, unlatches a spring powered operating mechanism that opens the separable contacts of the circuit breaker to interrupt current flow in the protected power system.
For short circuit protection, an armature, which is attracted by the sizable magnetic forces generated in a magnetic core by a short circuit, unlatches, or trips, the operating mechanism. As an example, the magnetic type actuation occurs when the hot line conductor becomes directly connected with ground or neutral, thereby bypassing the load. In many applications, a miniature circuit breaker may additionally provide ground fault and arc fault protection.
Ground fault current interrupter (GFCI) and arc fault current interrupter (AFCI) circuit breakers are well known in the art. Examples of ground fault and arc fault circuit breakers are disclosed in U.S. Pat. Nos. 4,081,852; 5,260,676; 5,293,522; 5,896,262; and 5,892,593. In ground fault circuit breakers, an electronic circuit typically detects leakage of current to ground and generates a ground fault trip signal. This trip signal energizes a trip solenoid, which unlatches the operating mechanism, often through deflection of the armature of the thermal-magnetic trip device.
Ground fault circuit breakers include both Class A (e.g., ground fault current of about 5 mA for people protection) and equipment protective devices (e.g., ground fault current of about 30 mA). A common type of ground fault detection circuit is the dormant oscillator detector including first and second sensor coils. The line and neutral conductors of the protected circuit pass through the first sensor coil. The output of this coil is applied through a coupling capacitor to an operational amplifier followed by a window comparator having two reference values. A line-to-ground fault causes the magnitude of the amplified signal to exceed the magnitude of the reference values and, thus, generates a trip signal. At least the neutral conductor of the protected circuit passes through the second sensor coil. A neutral-to-ground fault couples the two detector coils which causes the amplifier to oscillate, thereby resulting in the generation of the trip signal.
In conventional ground fault circuit breakers, the ground fault detection circuit is powered from the load side of the circuit breaker such that the ground fault detection circuit is not powered after the circuit breaker has detected a ground fault and, thus, has tripped. In this manner, the circuit breaker separable contacts are employed as a cut-off switch to remove power to the ground fault detection circuit and, thus, protect such detection circuit.
In the event of a failure in the electronic trip circuit, such as a component failure that disables the electronic trip circuit, the circuit breaker can remain energized after the failure. It is desirable to provide a fail-safe mechanism that would open the contacts of the breaker in the event of such failure. It is further desirable to provide a means for preventing resetting of the circuit breaker once the contacts have been opened as a result of such failure.
A circuit breaker includes a pair of separable contacts forming a pole, an operating mechanism for operating the electrical contacts, an electronic trip circuit responsive to currents flowing through the pole for operating the operating mechanism in response to predetermined conditions to open the separable contacts, and a mechanism for operating the operating mechanism in response to a failure in the electronic trip circuit. The mechanism may include a solenoid that is electrically connected to be energized in response to a failure in the electronic trip circuit and a linkage that operates the operating mechanism in response to operation of the solenoid.
When the electronic circuit breaker fails, voltage is transferred to an auxiliary solenoid, which will then activate the trip mechanism of the circuit breaker.
Circuit breakers constructed in accordance with this invention further include a mechanism for preventing resetting of the circuit breaker once the auxiliary solenoid has been activated. This disables the circuit breaker with the contacts in an open position.

Ground fault current interrupter/arc fault current interrupter circuit breaker with fail safe mechanism


BLAST search was done on the EST database by using various nucleotide sequences encoding known bromodomain motifs to discover several ESTs likely encoding bromodomain genes. Next, testicular cDNAs were PCR cloned by using primers designed based on the sequence of EST (W17142), which is one of the ESTs discovered above. By using the thus obtained PCR product as a probe, the testicular library was screened. The obtained cDNA clone was used as a probe to re-screen the testicular cDNA library, thereby successfully isolating a full-length cDNA corresponding to EST (W17142). The protein encoded by the thus isolated cDNA had, in addition to the bromodomain, several regions and domains conserved in transcription regulatory factors. Moreover, the protein interacted with proteins associated with the chromatin-mediated transcriptional regulatory mechanism and a transcription co-activator.

The bromodomain is a characteristic amino-acid motif seen in transcriptional regulatory factors and is believed to be involved in the interactions with other transcriptional regulatory factors. Proteins comprising the bromodomain, normally have one or two (Tamkun et al. (1992) Nuc. Acids Res. 20:2603; Haynes et al. (1992) Nuc. Acids Res. 20: 2603), but as many as five (Nicolas et al. (1996) Gene 175(12):233–240) bromodomain motifs. This motif has been identified in a wide range of animals, for example, in the homeotic gene (Digan et al. (1986) Dev. Biol. 114:161–169; Tamkun et al. (1992) Cell 68: 561–572) of the fruit fly (Drosophila), in the transcriptional regulatory genes of yeasts (Winston et al. (1987) Genetics 115:649–656; Laurent et al. (1991) Proc. Nat. Acad. Sci. USA 88:2687–2691) and in mammals (Denis et al. (1996) Genes and Devel. 10:261–271; Yang et al. (1996) Nature 382:319–324). According to a recent report (Jeanmougin et al. (1997) Trends Biochem. Sci. 22:151–153), 37 bromodomain genes, including 13 human genes are recorded in the database. In addition to the bromodomain motif of amino acid residues 59–63, the sequences adjacent to the motif are also structurally conserved, and furthermore, 4 α-helixes (Z, A, B, and C) are reported to be coded within the long 110 amino acids.
When these bromodomain-comprising transcriptional regulatory factors are compared, they all regulate signal-dependent transcription in actively proliferating cells (Tamkun et al. (1992) Cell 68:561–572; Haynes et al. (1992) Nuc. Acids Res. 20:2603). This characteristic implies that oncogenesis may occur when a gene encoding a bromodomain-containing protein undergoes abnormal regulation. In reality, six bromodomain genes have been experimentally proven to associate with oncogenesis. Three of these genes HRX/ALL-1 (Tkachuk et al. (1992) Cell 71:691–700; Gu et al. (1992) Cell 71:701–708); TIF1 (Miki et al. (1991) Proc. Nat. Acad. Sci. USA 88:5167–5171; Le Douarin et al. (1995) EMBO J. 14:2020–2033) and CBP (Borrow et al. (1996) Nature Genet. 14:33–41) are linked with the gene cleavage points in leukemia. All three of these proteins contain the C4HC3 (also called PHD/LAP/TRX) zinc-finger (Aasland et al. (1995) Trends Biochem. Sci. 20:56–59; Koken et al. (1995) CR Acad. Sci. III, 318:733–739; Saha et al. (1995) Proc. Nat. Acad. Sci. USA 92:9737–9741). Also, there are findings that CBP/P300 interact with p53 (Gu et al. (1997) Nature 387:819–823; Lill et al.(1997) Nature 387:823–827) and other various transcriptional factors, suggesting that CBP and the homologous gene P300 play a key-role in cancer.
The other three genes have been suggested to be linked with cancer in various ways. BRG1 interacts with retinoblastoma protein RB (Dunaief et al. (1994) Cell 79:119–130), inducing formation of flat, growth-arrested cells, and thereby showing a tumor-suppressive activity. RING3 has a homology with the fruit fly (Drosophila) growth control protein fsh (Haynes et al. (1989) Dev. Biol. 134:246–257) and is a serine-threonine kinase having endonuclear autophosphorylation activity. This activity has been reported to be linked to the growth phase of chronic and acute lymphocytic leukemia (Denis et al. (1996) Genes and Devel. 10:261–271). As for P/CAF, it has been reported to inhibit the interaction between E1A and p300/CBP (Yang et al. (1996) Nature 382:319–324). When P/CAF is exogenously expressed on HeLa cells, the cell cycle is inhibited. This is believed to be due to the disruption of the transcriptional regulation of E1A by the binding of P/CAF to p300/CBP. Similar to p300/CBP (Bannister and Kouzarides (1996) Nature 384:641–643), P/CAF has been reported to contain histone acetyl-transferase activity (Yang et al. (1996) Nature 382:319–324).
Thus, regulatory abnormalities of transcriptional regulatory factors comprising bromodomains are envisaged to be closely associated with various diseases, particularly, cancer and other cell-proliferation-linked diseases. Hence, attention has been focused on transcriptional regulatory factors comprising bromodomains in the recent years as novel targets for the treatment of cancer and other cell-proliferation-linked diseases.


A detaching apparatus is provided for detaching a connector having an elastic release tab from a mating connector socket of an electronic device. The release tab of the connector is engagable with the connector socket. The detaching apparatus includes a pivot member pivotably attached to the electronic device, and an operating member connectable with the pivot member. The operating member is manipulably rotatable together with the pivot member for pressing the release tab to disengage the connector from the connector socket of the electronic device.

1. Field of the Invention
The present invention relates to detaching apparatuses, and more particularly to a detaching apparatus for a connector.
2. Description of Related Art
With the development of electronic technology, a greater number of small-sized connectors are being used in electronic devices. However, detaching a connector from a mating connector of an electronic device by hand can be difficult and inconvenient because of limited or cramped operating space, and the connector or a wire connected with the connector is easily loosened or broken when drawing the connector out from the electronic device.
What is needed, therefore, is a detaching apparatus which can be operated to safely and easily detach a connector from a mating connector of an electronic device.

Hong Fu Jin Precision Industry (ShenZhen) Co., Ltd.


A system (100), method and computer program product for optimization of crop protection. A generator module (120) accesses one or more configuration data structures (220) wherein the one or more configuration data structures include data fields to store crop data (221), advice data (222) related to respective crop data, and crop protection product data (223) related to respective advice. Further, it accesses a plurality of code snippets (230) wherein each code snippet (231, 232, 233) has a condition which relates either to at least one property field of the one or more data structures (220) or to a result of another code snippet, and further includes generic program logic associated with the condition, and wherein each property field is used in the condition of at least one code snippet. The plurality of code snippets is applied to the one or more configuration data structures to generate an advice logic program.

Crop protection products (including at least chemical crop protection products and biological crop protection products) are used when growing crops to increase the yield. Preferably, crop protection products are chemical crop protection products." The term crop protection, as used herein, includes but is not limited to chemical crop protection, fertilization, and biological crop protection. Preferably, crop protection is chemical crop protection. Examples for chemical crop protection products are: pyraclostrobin, azoxystrobin, picoxystrobin, fluxapyroxad, cyproconazole, metconazole, epoxiconazole, mefentrifluconazole, boscalid, Kresoxim-methyl, dimoxystrobin, triticonazole, thiophanate-methyl, fipronil, broflanilide, abamectin, afidopyropen, alpha-cypermethrin, chlorfenapyr, chlorantraniliprole, cyantraniliprole, metaflumizone, pyridaben, teflubenzuron, thiamethoxam, imidacloprid, sulfoxaflor, aminopyralid, dicamba, diflufenzopyr, glyphosate, imazapyr, metazachlor, 2,4-dichlorophenoxyacetic acid (2,4-D), cinmethylin, pendimethalin, saflufenacil, tembotrione, topramezone, or products based on these active ingredients. Examples for biological crop protection products are: Bacillus amyloliquefaciens (an example for a product based on Bacillus amyloliquefaciens, strain MBI600, is Serifel®), Beauveria bassiana (an example for a product based on Beauveria bassiana is Broadband®), Bacillus firmus, Bacillus subtilis, Bradyrhizobium, Bacillus pumilus, Bacillus licheniformis, Paenibacillus polymyxa, Paenibacillus epiphyticus, Pasteuria nishizawae, Penicillium bilaiae, or products based on these microorganisms, as well as biochemical active ingredients such as fusaricidins and cis-jasmone, or products based on these active ingredients.
Crop, as used herein, is a plant or plant product that can be grown and harvested on a field. However, it is critical for an improved yield to apply the right crop protection products. for a particular crop at the right time to the right target. A crop protection product may include single Active Ingredients, combinations of Active Ingredients or combinations of Adjuvants. In other words, crop protection products, as used herein, include but are not limited to active ingredients, compositions, mixture and formulations comprising one or more active ingredients, formulants, co-formulants, adjuvants, inerts, solvents, and water. "Target" as used herein describes a particular infestation or a particular crop disease which can be treated by a crop protection measure. The crop protection measure can include the application of one or more crop protection products to the affected crop. Examples for crops are cereals, oil seed rape, corn, potatoes, sugar beets, rice, soybeans, sugarcane, cotton, fruits, vegetables, and legumes. Infestations include but are not limited to, microbial infestation insect pest infestation, weed infestation, or any challenges regarding plant health, plant nutrition or plant growth. Overall, at least several hundreds of targets are known in the art, which include weeds and, weed grasses, fungal, bacterial or viral pathogens and animalistic pests, especially insects. Many different crop protection products are available to counter such infestations or diseases. Such products can be segmented into segments, such as for example: insecticides (i), fungicides (f), herbicides (h), nitrogen stabilisators (n), growth regulators (g), nematicides, molluscicides, rodenticides, acaricides, bactericides, algaecides, antimicrobials, fertilizers, soil amendments, and soil additives. Commercially available compounds can be found in "The Pesticide Manual", 17th Edition, British Crop Protection Council (2015) among other publications, and its online database https://www.bcpc.org/product/bcpc-online-pesticide-manual-latest-version.
In some cases, where a crop is affected by one or more targets, it can be advantageous to combine multiple products into a product mix (e.g., a spray mix of respective crop protection products) which is applied to the respective crop. However, the selection of the right products depends on many factors, such as for example, the growth stage of the crop, the weather conditions, the current season, recently applied products, etc. For mixtures of protection products additional selection parameters can be compatibility of products, use rate adaption, registration restrictions, resistance issues, or preferable mode of action combination. For example, systems and methods for applying liquid mixtures are described in WO2013/087103 A1.
Once a target is detected for a particular crop on a field, it can be advantageous to determine the appropriate spray mix instantaneously. For example, the weather conditions may change making an immediate application of the spray mix in the field mandatory. As a consequence, near-real-time determination of the spray mix becomes a requirement for an efficient yield. Further, new products may become available which may cause new interdependencies to other products. This may require a complete reevaluation of all application conditions of the various products during the various growth stages of the crop. The interdependencies and conditions are so complex that a human is not able to perform a determination of appropriate product mix instructions for respective spraying appliances.

System and method for optimization of crop protection


The present invention relates to a retraction system for laparoscopic surgery. According to one embodiment of the present invention, the retraction system includes: a retraction part for holding an object or tissue to be retracted; a retraction fiber control part for retracting the retraction part at the area to be retracted by means of a retraction fiber to fix the retraction part; and an abdominal wall fixer coupled to the retraction fiber control part, wherein the abdominal wall fixer is fixed to the abdominal wall. The retraction fiber control part includes: a retraction fiber control part body having a retraction hole through which the retraction fiber connected to the retraction part passes in the lower portion thereof; and a retraction fiber fixing part disposed outside the retraction fiber control part body so as to retract the retraction fiber or fix the retraction fiber such that the retraction fiber is immovable.

In the field of a surgical operation, different from the typical laparoscopic surgery, the use of a laparoscopic surgery increases day by day after it was developed for the purpose of reducing an incised portion at a skin.
The laparoscopic surgery has features in that multiple small holes are formed at a patient's abdomen with trocars, and a surgical operation tool such as an endoscope, etc. is introduced up to an operation portion of an abdomen with the aid of trocars, so a doctor performs a surgical operation observing an operation portion of an abdomen through the endoscope.
The above mentioned laparoscopic surgery is widely applied to cholecystectomy, extirpation of choledocal stone, hepatolithectomy, gastrectomy, colectomy, small intestine resection, thyroidectomy, etc.
Among the surgical operation tools used for the sake of a laparoscopic surgery, the trocars has features in that one end of a trocars body integrally extends communicating with a channel with a certain size and comprises an insertion part which is inserted into a hole formed at the abdomen.
In almost surgical operation procedures, it is preferred to use as many work channels as possible which extend into a body for the purpose of allowing various tools to pass by when a certain tissue is observed for the sake of a diagnosis or treatment, and the tissue is treated holding it.
In the course of an abdomen procedure in a laparoscopic surgery, at least one tubular cannula or a retractor which forms a work channel is inserted into an abdominal cavity.
Here, a camera for a laparoscopic surgery connected to a monitor in an operation room can be used for the purpose of observing an operation portion. The above mentioned camera can be set up through one of the work channels.
Various laparoscopic surgery tools such as a grasper, a dissector, scissors, a retractor, etc. can be set up through at least one work channel for a surgical doctor and/or assistants to handle them in easier ways. In this case, an additional tool for the sake of retractions is necessary.
In addition, a view way in terms of surgical operation and a surgical operation itself might be interrupted now that a liver, uterus, intestine (small intestine (including duodenum), large intestine, rectum or stomach, etc) comes down into an operation region during the operations near a gallbladder or an esophagus or during the laparoscopic surgery in a pelvic cavity.
The laparoscopic tissue retractor of WO 09/047707 (Apr. 16, 2009) discloses a tissue reactor for a surgery which is generally used for a surgical operation. The above mentioned retractor has features in that a mesh barrier connected to a long shaft is inserted in the interior of an abdominal cavity for retracting organs.
For the above mentioned mesh barrier is connected with a long shaft and is handled through a channel, it may be interfered with other surgical tools which are used for the sake of an operation work through the channels, so some surgical tools may collide with each other because each tool works differently from others in a narrow channel.

Retraction system for laparoscopic surgery


A mobile terminal, data communication method, and a computer program stored in a computer-readable medium for communicating management data in a more efficient way. A management data communication interface communicates management data regularly with a management server, while an application data communication interface communicates application data with an application server on a demand basis. A data collision detector detects a collision between the management data and application data. If a collision is detected, a priority resolver determines whether to prioritize application data over management data. The management data suppressor suspends the management data communication interface when the priority resolver has determined that application data should be prioritized over management data.

1. Field of the Invention
The present invention relates to a mobile terminal, a data communication method, and a data communication program stored in a computer-readable storage medium. More particularly, the present invention relates to a mobile terminal, a data communication method, and a computer program for communicating data with servers.
2. Description of the Related Art
Mobile communications systems are widely used in recent years, not only for personal communication, but also for business activities. The latter case requires remote maintenance capabilities and operation management functions in order to prepare for potential damages caused by the loss of mobile terminals used in business, and to reduce the cost for maintenance and operations of such terminals. For this purpose, mobile terminal devices are supposed to have the capability of sending and receiving data for management purposes, besides being able to exchange data of business applications. The former class of data is referred to herein as "management data," and the latter class of data is referred to herein as "application data." Specifically, the management data communication includes uploading of operation logs and receiving push services. This kind of data is exchanged by using polling techniques.
The radio communications technologies have enabled the deployment of cellular communications services, wireless local area networks (LAN), and, in Japan, Personal Handyphone Systems (PHS). Those mobile communication environments are, however, limited in their available communication bandwidths. Frequent exchange of management data would consume the available bandwidth excessively and thus choke the communication channels of application data, resulting in communication delays and errors. Some existing specifications for mobile applications only allow a terminal device to perform a single communication session at a time. Mobile terminals using such applications would be seriously affected by the excessive traffic of management data.
A known method for avoiding the above-described problem is to classify the transmit data with different priorities and schedule their communication sessions accordingly. Specifically, the method employs transmit queues to control the flow of data (see, for example, Japanese Unexamined Patent Application Publication No. 2004-200857).
The above queue-based method, however, requires implementation of a complicated control algorithm and thus increases the size of applications since application data and management data are separately controlled. Also the response of application data communication would be worse than what users expect normally, thus making it difficult for the users to do their jobs quickly. More specifically, the use of transmit queues increases the latency of transmit data, i.e., the time lag from depression of a send button to actual transmission of data. This is because the queue-based communication control process involves the multiple steps of entering transmit data into appropriate queues, comparing the priority of each piece of data with others, and selecting data with a high priority before sending it.

Mobile terminal, method, and computer program for communicating data with servers with data collision control


In systems and methods of transmitting a data packet to a wireless device over a wireless communication link, a signal level is received of a wireless communication link between a wireless device and an access node. A data packet is divided into a first segment and a second segment according to the received signal level, and the first segment and the second segment are transmitted to the wireless device over the wireless communication link according to the signal level.

Communication over a wireless communication link can be affected by wireless link conditions, including a signal level, radio frequency interference, multipath interference, and the like. Wireless communication can also be affected by the availability of wireless link resources, which diminish as demand and resultant network congestion increases. Evaluation of wireless link conditions and efficient use of available wireless link resource are vitally important in wireless communication systems.

Transmitting a data packet over a wireless communication link


A system for and method of paper note authentication and tracking through NFC is presented. The system and method includes utilizing an authenticating device to receive paper note data using an NFC reader, transmit the paper note data to an authenticating party, receive an authentication determination and/or additional paper note data, and authenticate the paper note where the authentication determination indicates accordingly. The system and method may further include updating the paper note data upon authentication to prevent duplicate authentication attempts.

Paper note authentication is important in combating counterfeit paper notes. Paper notes may include, for example, currency, bonds, stocks, checks, notarized documents, and other certificates. Communicating authentication of a paper note may be through a variety of channels and may include a lengthy process. Moreover, authentication of a paper note may include a subjective analysis and thus, may provide varying results depending on the authenticator.

System for and method of paper note authentication and tracking through NFC


Provided are a catalyst which inhibits light paraffins form being produced in catalytic cracking of heavy hydrocarbons and which effectively produces olefins and a process in which the above catalyst is used to produce olefins from heavy hydrocarbons at a high yield. The catalyst is a catalytic cracking catalyst for catalytically cracking a hydrocarbon raw material, comprising (A) pentasil type zeolite modified with a rare earth element and zirconium and (B) faujasite type zeolite, and the process is a production process for olefin and a fuel oil, comprising bringing a heavy oil containing 50 mass % or more of a hydrocarbon fraction having a boiling point of 180° C. or higher into contact with the catalyst described above to crack it.

1. Field of the Invention
The present invention relates to a catalytic cracking catalyst comprising zeolite and a production process for olefin and a fuel oil using the same, specifically to a catalytic cracking catalyst comprising pentasil type zeolite modified with a rare earth element and zirconium and faujasite type zeolite and a process for catalytically cracking a heavy oil (containing 50% or more of a hydrocarbon fraction having a boiling point of 180° C. or higher) by using the above catalytic cracking catalyst to produce olefins (particularly propylene) and a fuel oil.
2. Description of the Related Art
Light olefins, particularly propylene are an important material as a basic raw material for various chemical products. A process in which light hydrocarbon such as butane and naphtha is used as a raw material and cracked in a tubular furnace of an external heating type by heating under steam atmosphere has so far widely been carried out as a production process for light olefins. However, the above process has the economically disadvantageous points that a high temperature of 800° C. or higher is required in order to enhance an olefin yield and that this makes it inevitable to use expensive apparatus materials. Further, carried out as well is a process in which olefins such as propylene are produced as by-products together with a fuel oil from a heavy oily by fluid catalytic cracking (hereinafter abbreviated as FCC) using a zeolite catalyst. However, the problem that light paraffins having a low value are produced in larger quantities is involved therein.
A process in which a hydrocarbon fraction is catalytically cracked using a catalyst comprising Y type zeolite and pentasil type zeolite containing phosphorus, magnesium and the like to produce light olefins is disclosed in patent document 1. Examples in which a hydrocarbon fraction having a distillation range of 229 to 340° C. is catalytically cracked to produce olefins having 2 to 4 carbon atoms in a proportion of 13 to 14 mass % are described in the examples (Table 2) of the above document. In this case, however, "cracking gas" accounts for about 27 mass %, and light paraffins having a low value which are obtained by deducting an amount of olefins having 2 to 4 carbon atoms from a "cracking gas" amount are produced in as large proportion as 13 to 14 mass %.
A process in which a hydrocarbon fraction is catalytically cracked using a catalyst comprising phosphorus and rare earth-containing zeolite of a high silica content having a pentasil structure and Y type zeolite to produce light olefins is disclosed in patent document 2. Examples in which a hydrocarbon fraction having a distillation range of 243 to 507° C. is catalytically cracked to produce olefins having 2 to 4 carbon atoms in a proportion of 37.1 mass % (ethylene: 5.32 mass %, propylene: 18.31 mass %, butenes: 13.47 mass %) are described in the examples (Table 4) of the above document. In this case, "cracking gas" accounts for 49.24 mass %, and it can be found that light paraffins having a low value which are obtained by deducting an amount of olefins having 2 to 4 carbon atoms from a "cracking gas" amount are produced in a proportion of 12.14 mass %.
A process in which a hydrocarbon fraction is catalytically cracked using a catalyst comprising high silica content zeolite containing a specific amount of a rare earth element and Y type zeolites (REY, high silica Y) to produce gasoline and light olefins is disclosed in patent document 3. An example in which hydrocarbon having a boiling point of 291° C. or higher is catalytically cracked to produce 8.6 mass % of propylene and 7.28 mass % of butenes is described in the example (Table 6, Example 1) of the above document. However, a production amount of propane is 3.03 mass %, and a production amount of butanes is 10.11 mass %. Thus, a production amount of light paraffins having a low value is large as well.
Further, known as well is a catalytic cracking process which is carried out using an ordinary FCC catalyst mixed with a catalyst containing ZSM-5 type zeolite as an additive for producing olefins. A catalytic cracking process in which a physical mixture of Y type zeolite and ZSM-5 type zeolite is used as a catalyst is disclosed in patent document 4. An example in which vacuum gas oil (VGO) is catalytically cracked to produce 17.8 mass % of propylene and 13.8 mass % of butenes is described in the examples (Table 2) of the above document. However, paraffins having 2 to 4 carbon atoms account for 14.6 mass %, and a lot of light paraffins is produced.
Results obtained by catalytically cracking a heavy oil with a commercial FCC catalyst mixed with an additive containing ZSM-5 are disclosed in non-patent document 1. The production amounts of propylene and butene are 6% and 5.8% respectively (11.8% in total), and a production amount of light paraffins (dry gas+LPG−propylene−butene) other than the above is 6.2%. Thus, a production proportion (light paraffins/(dry gas+LPG)) is as high as about 34%.
An example in which butane is cracked by using pentasil type zeolite modified with a rare earth element and zirconium to produce 14 to 22 mass % of propylene is disclosed in patent document 5. However, light hydrocarbons such as butane and naphtha are assumed as the raw material, and applicability thereof to a heavy oil is not described.
Further, processes in which a heavy oil is catalytically cracked by using a fluidized bed reactor of a down flow type to produce olefin and a fuel oil are disclosed (patent documents 6, 7 and 8). However, such a large amount of a catalyst that a catalyst/raw material oil ratio (C/O ratio) is 20 to 40 is required, and an amount of light paraffins is still large (patent document 8, Table 2: propylene/propane ratio=10.5).
As described above, the existing situation is that a catalyst which inhibits light paraffins having a low value from being produced to effectively produce olefins in catalytic cracking of heavy hydrocarbons has not yet been found.    Patent document 1: Japanese Patent Application Laid-Open No. 192431/1999    Patent document 2: Japanese Patent Application Laid-Open (through PCT) No. 504817/1997    Patent document 3: U.S. Pat. No. 5,358,918    Patent document 4: Japanese Patent Application Laid-Open No. 220466/1994    Patent document 5: Japanese Patent Application Laid-Open No. 143373/2004    Patent document 6: Japanese Patent Application Laid-Open No. 60453/1998    Patent document 7: Japanese Patent Application Laid-Open No. 241764/2002    Patent document 8: Japanese Patent Application Laid-Open No. 29620/2005    Non-patent document 1: Shokubai-Kasei-Gihou, Vol. 17, p. 15 to 24, 2000

Catalytic cracking catalyst for heavy oil and production process for olefin and fuel oil

Research Association of Refinery Integration for Group-Operation


A method of predicting a fault in a rolling bearing, the rolling bearing including inner and outer rings and rolling bodies evenly angularly distributed therebetween, the method comprising: processing (in the DSP system 8) a position signal (x(t)) indicative of a relative angular position of the inner ring with respect to the outer rings, and a vibration signal (y(t)) (by the accelerometer 7) indicative of speed-related vibrations in the rolling bearing, such that they correspond to either an angular displacement of the rolling bodies equal to an integer number of angular gaps between adjacent rolling bodies or an integer number of complete rotations of the inner ring with respect to the outer ring; space sampling (in the ND acquisition board 9) the processed vibration signal (y(t)) based on the processed position signal (x(t)); and predicting a fault in the rolling bearing based on the space-sampled vibration signal (y(t)).

As is known, on a factory floor of a food packaging plant, several specifically-aimed processes are generally performed, including incoming food and packaging material storage, food processing, food packaging, and package warehousing. With specific reference to pourable food products, food packaging is performed in Packaging Lines, each of which is an assembly of machines and equipments for the production and handling of packages, and includes a Filling Machine for the production of sealed packages, followed by one or more defined configurations of downstream Distribution Equipments such as, accumulators, straw applicators, film wrappers, and cardboard packers, connected to the Filling Machine via Conveyors, for the handling of the packages.
A typical example of this type of packages is the parallelepiped-shaped package for liquid or pourable food products known as Tetra Brik Aseptic®, which is made by folding and sealing a laminated web of packaging material.
The packaging material has a multilayer sheet structure substantially comprising one or more stiffening and strengthening base layers typically made of a fibrous material, e.g. paper, or mineral-filled polypropylene material, covered on both sides with a number of heat-seal plastic material layers, e.g. polyethylene film. In the case of aseptic packages for long-storage products, such as UHT milk, the packaging material also comprises a gas- and light-barrier material layer, e.g. aluminium foil or ethyl vinyl alcohol (EVOH) film, which is superimposed on a heat-seal plastic material layer, and is in turn covered with another heat-seal plastic material layer forming the inner face of the package eventually contacting the food product.
Packages of this sort are produced on fully automatic Filling Machines, wherein a continuous vertical tube is formed from the web-fed packaging material; which is sterilized by applying a chemical sterilizing agent such as a hydrogen peroxide solution, which, once sterilization is completed, is removed, e.g. evaporated by heating, from the surfaces of the packaging material; and the sterilized web is maintained in a closed, sterile environment, and is folded and sealed longitudinally to form the vertical tube. The tube is then filled downwards with the sterilized or sterile-processed pourable food product, and is fed along a vertical path to a forming station, where it is gripped along equally spaced cross sections by a jaw system including two or more pairs of jaws, which act cyclically and successively on the tube, and seal the packaging material of tube to form a continuous strip of pillow packs connected to one another by transverse sealing strips. Pillow packs are separated from one another by cutting the relative sealing strips, and are conveyed to a final folding station where they are folded mechanically into the finished, e.g. substantially parallelepiped-shaped, packages.
Alternatively, the packaging material may be cut into blanks, which are formed into packages on forming spindles, and the packages are filled with food product and sealed. One example of this type of package is the so-called "gable-top" package known as Tetra Rex®.
In these Packaging Lines, several components are operated by (electric) servomotors, which, although valuable in several respects, are affected by malfunctions, one of the major causes of which is the breakdown of the rolling bearings supporting the shaft of the servomotors due to fatigue or wear. While fatigue can be statistically characterized in a standard way that leads to the so-called L10 rating of the bearings, wear is a subtler phenomenon, known in the literature as pitting or brinelling, that creates localized damages, the onset of which may (pseudo)randomly appear during the expected lifetime of the component, followed by a relatively quick degradation phase that leads to the complete breakdown. As a result, periodic replacement of these components is a strategy that may be successful only to prevent fatigue-related failures, whereas it will be almost useless against wear-related failures.
Other kinds of preventive periodic maintenance activities, such as cleaning and lubrication, may be effective in reducing bearing wear, as usually wear is characterized by the contamination of the bearing lubricant which in turn worsens the bearing health. Such contamination may come from the exterior (e.g. the bearing is placed in a hostile environment) but may also be due to internal causes (e.g. due to small flakes of material that the revolving elements lose during operation).
Ultimately, however, the only way to prevent wear-related breakdown is condition-based monitoring of the bearing health status; such maintenance strategy is mainly possible thanks to the fact that once the bearing approaches failure, it becomes noisy and vibrates as a warning sign of the impending breakdown: if this sign is detected timely it gives the operator a time frame that typically ranges from days to even weeks (depending on the bearing and the application) to plan a maintenance activity and substitute the bearing without impacting production time.
It may be appreciated that vibration analysis is an important part of industrial predictive maintenance programs so that wear and damages in the rolling bearings can be discovered and repaired before the machine breaks down, thus reducing operating and maintenance costs.
Empirical evaluation of the vibration level of a bearing is an error-prone activity that may lead to significantly underestimate or overestimate the remaining lifetime of the component, and also to mistake for a bearing damage a noise that is due to a completely different cause (e.g. a shaft imbalance). For this reason, the scientific community has striven to provide a scientific characterization of bearing faults, and nowadays a rich literature can be found on this topic.
The basic idea is associating each failure mode of a bearing with a characteristic frequency signature, that can be extracted from a vibration signal via an appropriate analysis. In particular, traditional vibration analysis is based on the fact that if there is a localized damage on one of the bearing surfaces, it will cause a series of impacts during bearing rotation; moreover, such impacts are periodic assuming that the servomotor is rotating at constant speed. In fact, a kinematic analysis of the bearing shows that, assuming that no slip is present, the component is quite similar to an epicyclic gear; in other words there is a fixed "transmission ratio" between the servomotor shaft and all the other moving parts of the bearing, and this leads to the fundamental equation of vibration analysis:fd=kdfr  (1)which shows that fd, the damage frequency (which is actually the frequency of such impacts) depends linearly on the rotation frequency fr by means of a damage coefficient kd which is none other than the transmission ratio between the servomotor shaft and the moving part on which the damage is located. Such coefficients are well-known in the literature and are given by:
                              k          d                =                  {                                                                                1                      2                                                                                (                                              1                        -                                                                                B                              d                                                                                P                              d                                                                                cos                                                                                θ                                                                    )                                                        =                                      k                    g                                                                                for                                                                                cage                                                                                faults                                                                                1                      2                                                                                N                                                                    (                                                  1                          -                                                                                B                                d                                                                                P                                d                                                                                cos                                                                                θ                                                                          )                                                                              =                                      k                    e                                                                                for                                                                                outer                                                                                ring                                                                                faults                                                                                1                      2                                                                                N                                                                    (                                                  1                          +                                                                                B                                d                                                                                P                                d                                                                                cos                                                                                θ                                                                          )                                                                              =                                      k                    i                                                                                for                                                                                inner                                                                                ring                                                                                faults                                                                                1                      2                                                                                B                        d                                                                    P                        d                                                                                N                                                                    [                                                  1                          -                                                                                (                                                                                B                                    d                                                                                P                                    d                                                                                cos                                                                                θ                                                            )                                                        2                                                                          ]                                                                              =                                      k                    v                                                                                for                                                                                ball                                                                                faults                                                                                (        2        )            where Bd, Pd are ball and pitch diameter, N is the number of revolving elements, θ is an angle that indicates a possible misalignment between inner and outer rings (or rings) as a result of mounting operations (typical values are between 0 and 10 degrees), and wherein the subscript d relates in general to damage frequencies, while subscripts g, e, i and v relate to specific kinds of damage, namely in the inner and outer rings, in the balls evenly angularly spaced apart between the inner and outer rings, and in the cage which retains the balls and which rotates jointly, i.e., at the same speed, with the balls.
The repercussions of this phenomenon on the spectrum of a vibration signal can be easily understood using the basic properties of Fourier transforms: if a single impact is considered, in the time domain this can be represented as a forcing action d(t) of impulsive nature and finite duration T, which tends to an ideal Dirac impulse function δ(t) as T→0; likewise, the spectrum D(f) of said signal will be characterized by a bandwidth that will tend to infinity as d(t) approaches the ideal impulse case (whose Fourier transform is constant over all frequencies).
During the actual component operation the forcing action u(t) will be a periodic repetition at the damage frequency of the original impulse d(t):
                              u                                (            t            )                          =                              ∑                          j              =                              -                ∞                                      ∞                                          d                                      (                              t                -                                  j                                                                                T                    d                                                              )                                                          (        3        )
By virtue of the properties of the Fourier transform, periodic repetition in time equates to sampling in frequency, which means that the spectrum U(f) of the forcing action that a localized damage applies to the bearing is a discrete spectrum, obtained by sampling the original impulse spectrum D(f):
                              U                                (            f            )                          =                              ∑                          j              =                              -                ∞                                      ∞                                                        D                                            (                f                )                                                                δ                                            (                                  f                  -                                      j                                                                                f                      d                                                                      )                                                                        (        4        )
In practice, this means that the frequency signature of the damage in the vibration signal is a sequence of peaks separated by the characteristic damage frequency of the bearing part damaged.
In general, however, the spectrum of a vibration signal acquired on a bearing does not reproduce exactly U(f); it can be rather represented as:Y(f)=G(f)H(f)U(f)+N(f)  (5)where G(f) is the transfer function of the mechanical assembly, H(f) is the sensor (usually an accelerometer) sensitivity function, and N(f) is any kind of noise superimposed to the fault signal. The spectrum of Y(f) as such may not therefore be the best signal to look at in order to identify a damage signature; the usual procedure to obtain a signal with better signal-to-noiseratio is called envelope analysis and is based on the following assumptions: there exist a frequency band [f1, f2] such that:                |G(f)|>>1, that is we are near a mechanical resonance        |H(f)|>>1, that is we are in the operational range of the sensor        |N(f)|<<1, which means in practice that we have to look for higher harmonics of the signal U(f).
The latter statement is motivated by the fact that usually mechanical noise is higher at low frequencies. There are some exceptions to this rule, for example noise due to gearing attached to the motor, and in this case it is necessary to resort to more advanced known filtering techniques. If the above hypotheses are satisfied, by band-pass filtering in the frequency band [f1, f2] and demodulation of Y(f) it is possible to obtain a signal where some peaks are clearly visible, spaced by fd.
Summing up, classical vibration analysis is based upon the following hypotheses:                there is a localized damage on a bearing;        the motor the bearing is attached to rotates at a constant speed;        there is no slip during the relative motion of the bearing elements;        during the motor operation, the damage causes a series of short-duration impacts, that generate a train of spikes in the frequency spectrum of the vibration signal with a certain periodicity; and        there is a frequency band where the signal-to-noise ratio is such that the train of impulses is detectable.
If these conditions are not verified, the train of peaks may be smeared so that it is not recognizable anymore, or can be hidden among other kinds of noise. Moreover, the fact that the angle θ in (2) is almost impossible to measure under practical circumstances adds some difficulties to the task, as each fd is actually variable in the range of admissible θ's. Most research in the field has historically been focused to signal processing techniques to obtain better signal-to-noise ratios or to cope with smearing of the peaks due to small fluctuations of velocity or the presence of slip.
Despite the basic assumption of constant rotation speed of the servomotors still holds true for many applications, it proves to be a huge limitation in the field of automatic machines, where usually a number of servomotors are employed as electric cams and operated at a variable speed in order to obtain variable speed profiles of the actuated elements. In particular, as servomotors, usually AC brushless motors, tend to appear more and more often in recent machine designs thanks to their performance being much higher than the mechanical solutions for machine motion in time required to reconfigure the motion profile, in these applications any rolling bearing fault prediction based on frequency signature determined via the above-described classical vibration analysis proves to be unsatisfactory.
In order to extend the above-described classical vibration analysis based on the constant rotation speed assumption to cope with applications in which the rotation speed of the servomotors varies over time, a so-called Order Tracking (OT) vibration analysis has been proposed, which is a frequency analysis that uses multiples, commonly referred to as orders, of the rotation speed, instead of absolute frequencies (Hz) as the frequency base, and is useful for machine condition monitoring because it can easily identify speed-related vibrations such as shaft defects and bearing wear. For a detailed discussion of this technique, reference may be made to R. Potter, A new order tracking method for rotating machinery, Sound and Vibration 24, 1990, 30-34, and K. Fyfe, E. Munck, Analysis of computed order tracking, Mechanical System and Signal Processing 11(2), 1997, 187-205.
Order Tracking is based on a constant spatial sampling approach, according to which the vibration signal is sampled at constant angular increments (i.e. uniform Δθ), and hence at a frequency proportional to the bearing rotation speed. Traditional order tracking accomplishes this task by using a variable-time data acquisition system, wherein a time-sampling is performed at a frequency which is varied proportionally to the bearing rotation speed. Computed order tracking (COT), instead, accomplishes this task by using a constant-time data acquisition system, wherein the vibration signal is first time-sampled at a constant frequency (i.e. constant-time sampling with uniform Δt), and then the sampled data are digitally spatially re-sampled at constant angular increments (i.e. constant-space sampling with uniform Δθ) to provide the desired constant Δθ data. Therefore, Order Tracking maps real time reference t to a modified time reference τ such that the vibration signal is seen as if it were generated piece-wise by a bearing rotating at a constant speed. This mapping results in a modified vibration signal where the frequency signature of a given typology of damage can be found, and in a rolling bearing fault being satisfactorily predicted.