WO1997006244A1 - Method for enhancing the activity of an enzyme, compounds showing enzyme activity enhancement, and detergents containing such compounds - Google Patents

Method for enhancing the activity of an enzyme, compounds showing enzyme activity enhancement, and detergents containing such compounds Download PDF

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Publication number
WO1997006244A1
WO1997006244A1 PCT/EP1996/003333 EP9603333W WO9706244A1 WO 1997006244 A1 WO1997006244 A1 WO 1997006244A1 EP 9603333 W EP9603333 W EP 9603333W WO 9706244 A1 WO9706244 A1 WO 9706244A1
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WO
WIPO (PCT)
Prior art keywords
formula
enzyme
compound
detergent
compounds
Prior art date
Application number
PCT/EP1996/003333
Other languages
English (en)
French (fr)
Inventor
Rudolf Zink
Ian John Fletcher
Beat Freiermuth
Klaus Huber
Original Assignee
Ciba Specialty Chemicals Holding Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from GBGB9516244.2A external-priority patent/GB9516244D0/en
Priority claimed from GBGB9525992.5A external-priority patent/GB9525992D0/en
Application filed by Ciba Specialty Chemicals Holding Inc. filed Critical Ciba Specialty Chemicals Holding Inc.
Priority to EP96927059A priority Critical patent/EP0843723A1/en
Priority to AU67022/96A priority patent/AU6702296A/en
Priority to JP9508085A priority patent/JPH11508136A/ja
Publication of WO1997006244A1 publication Critical patent/WO1997006244A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/44—Oxygen and nitrogen or sulfur and nitrogen atoms
    • C07D231/52—Oxygen atom in position 3 and nitrogen atom in position 5, or vice versa
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/28—Heterocyclic compounds containing nitrogen in the ring
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38654—Preparations containing enzymes, e.g. protease or amylase containing oxidase or reductase
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3245—Aminoacids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/34—Organic compounds containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N9/00—Enzymes; Proenzymes; Compositions thereof; Processes for preparing, activating, inhibiting, separating or purifying enzymes
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C5/00—Other processes for obtaining cellulose, e.g. cooking cotton linters ; Processes characterised by the choice of cellulose-containing starting materials
    • D21C5/005—Treatment of cellulose-containing material with microorganisms or enzymes
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/10—Bleaching ; Apparatus therefor
    • D21C9/1026—Other features in bleaching processes
    • D21C9/1036—Use of compounds accelerating or improving the efficiency of the processes

Definitions

  • the present invention relates to a method of enhancing the activity of an enzyme with an enhancing agent for the enzyme and to the use of the enzyme of enhanced activity in a degradation process.
  • the use is known of a peroxidase enzyme in the bleaching of pulp for paper production, in the bleaching of textiles during washing, in the inhibition of dye transfer during washing and in the modification, breakdown or bleaching of lignin, especially during the production of paper pulp.
  • the peroxidase enzyme is conventionally used together with hydrogen peroxide or a compound capable of producing hydrogen peroxide in situ.
  • ABTS exhibits an excellent performance as a mediator for the bleaching of undesired dyestuffs, e.g. in the inhibition of dye transfer during washing, it is itself a dyestuff and suffers from the disadvantage that, after effecting its bleaching action, residual amounts of ABTS always remain in the treatment system.
  • WO 94/12621 proposes naphthalene compounds which are optionally substituted by a wide variety of groups in all possible positions on the naphthalene nucleus.
  • the disclosed substituent groups do not include the nitroso group.
  • WO 94/29510 there is described a process for modifying, breaking down or bleaching lignin using oxidation catalysts and suitable oxidizing agents.
  • the catalysts are used in combination with an aliphatic, cycloaliphatic, heterocyclic or aromatic compound containing NO-, NOH- or H-N(R)-OH groups (in which R is not defined).
  • N-hydroxy heterocyclic compounds such as hydroxybenzotriazole appear to be preferred.
  • No aromatic compounds containing a nitroso group are specifically mentioned.
  • 1 -Hydroxybenzotriazole is indeed an excellent mediator. It is probably not sufficiently economic, however, for use in bleaching applications. Moreover, during enzyme reaction involving 1 -hydroxybenzotriazole, there is obtained the by-product benzotriazole, which has been found to be mutagenic.
  • the present invention provides, as a first aspect, a method for enhancing the activity of an enzyme, comprising the use of the enzyme in combination with a mediator compound having the formula:
  • A is a (hetero)aromatic residue
  • Y is an -SH or, preferably, an -OH group
  • Z is a water-solubilising group, preferably a group - SO 2 NH 2 , -CO 2 M or -SO3M in which M is hydrogen or a cation
  • x is 1 or 2, preferably 1
  • y is 1 , 2 or 3, preferably 1
  • z is 0, 1 , 2, 3 or 4, preferably 0, 1 or 2.
  • the mediator compound of formula (1) may be present in any of its possible tautomeric forms and/or transition metal complex forms.
  • the mediator compound of formula (1) is preferably in the form of an iron, manganese or cobalt metal complex.
  • the residue A may also contain one or more further substituents such as CrC 4 alkyl, C ⁇ - C 4 alkoxy, halogen and nitro groups.
  • the enzyme component may be any oxidoreductase or any fraction or synthetic mimic of such an enzyme.
  • enzyme mimics are meant compounds which simulate the prosthetic group of an oxidoreductase.
  • oxidoreductases include oxidases, peroxidases, lignin peroxidases, manganese peroxidases and, in particular, laccases and laccase related enzymes.
  • the peroxidase enzyme may be any of those comprised by the enzyme classification EC 1.11.1.7, or any peroxidase activity-exhibiting fragment derived from such enzyme.
  • synthetic or semi-synthetic derivatives of such enzymes such as those comprising porphyrin ring systems or microperoxidases which are described, e.g., in US- 4077768, EP-537381 , WO 91/05858 or WO 92/16634.
  • Other relevant enzymes are peroxidase-active fragments derived from cytochromes, hemoglobin or peroxidase enzymes, or synthetic or semi-synthetic derivatives thereof such as iron porphins, iron po ⁇ hyrins, iron phthalocyanine and derivatives thereof.
  • Such enzymes may be derived from animal, vegetable or microbial sources.
  • the laccase or related laccase enzyme may be any of those comprised by the enzyme classification EC 1.10.3.2, any catechol oxidase enzyme comprised by the enzyme classification EC 1.10.3.1 , any bilirubin oxidase enzyme comprised by the enzyme classification EC 1.3.3.5 or any monophenol monooxygenase enzyme comprised by the enzyme classification EC 1.14.99.1.
  • the laccase or related laccase enzyme may also be one which can be produced by cultivation of a host cell transformed with a recombinant DNA vector carrying a DNA sequence encoding the laccase and carrying DNA sequences encoding functions allowing the expression of the DNA sequence encoding the laccase.
  • the cultivation may be conducted in a culture medium under conditions which permit the expression of the laccase enzyme.
  • the laccase may be recovered from the culture medium.
  • the laccases are preferably produced from white rotting fungi, especially Phanerochaete chtysosporium and Coriolus (Trametes) versicolor.
  • A may be a purely aromatic residue, preferably a phenyl residue or, especially, a naphthyl residue, or it may be a heteroaromatic residue, that is an aromatic residue containing one or more heteroatoms, preferably nitrogen, oxygen or sulfur atoms, such a pyrimidine or coumarin residue, or an aromatic residue substituted with a heterocyclic residue.
  • aromatic and heteroaromatic residues A include mono- and polycyclic residues.
  • Examples of preferred purely aromatic mediator compounds of formula (1 ) are those having the formula:
  • Preferred purely aromatic compounds of formula (2) are those having the formula:
  • Me is a transition metal and p is the valency of the transition metal Me.
  • heteroaromatic mediator compounds of formula (1) are pyrimidine derivatives having the formula:
  • M when M is a cation, it is preferably an alkali metal cation, especially a sodium cation, or a cation formed from an amine.
  • Particularly preferred purely aromatic mediator compounds of formula (1) include those having one of the formulae:
  • the mediator compounds are mostly known compounds and can be obtained commercially or by methods which are well known.
  • the compound of formula (10), however, is a new compound and, as such, forms a second aspect of the present invention " .
  • the present invention provides, as a third aspect, a process for the degradation of a substrate comprising contacting the substrate with a bleach liquor comprising an oxidizing agent, an enzyme and a mediator for the enzyme, according to the first aspect of the present invention.
  • the oxidizing agent used in the degradation process according to the present invention is preferably hydrogen peroxide or a compound capable of producing hydrogen peroxide in situ, such as a perborate, a percarbonate, a peroxycarboxylic acid or a salt thereof.
  • the oxidizing agent used in the degradation process according to the present invention is preferably oxygen, conveniently supplied as air or pure oxygen, optionally with the application of pressure.
  • the degradation process of the invention may also include the addition of hemicellulases, cellulases, pectinases, amylases and lipases to the reaction mixture. Mixtures of two or more enzymes may also be used and, under certain circumstances, synergistic effects may be observed with the use of such mixtures of enzymes.
  • the oxidizing agent is preferably added at the start of the degradation process and preferably in an amount of from 0.0001 to 5.0% by weight, more preferably from 0.01 to 1.0% by weight, based on the total weight of the substrate to be degraded.
  • the degradation process according to the present invention is preferably applied to the degraditive bleaching of pulp for paper production; in the degraditive bleaching of stains on a) textiles during washing thereof with laundry detergents or on b) dishes during washing thereof with dishwashing detergents; in the modification, breakdown or bleaching of lignin, especially during the production of paper pulp; in the degradation of organic material such as a dyestuff in waste water; and in the degraditive bleaching of migrating dyes in a washing process, so that inhibition of transfer of such dyes during washing is effected.
  • the process of the present invention When the process of the present invention is applied to degraditive bleaching of pulp, the process is generally conveniently operated at a temperature in the range of from 25-80°C, preferably at a temperature in the range of from 40-60°C
  • the process is preferably conducted in the presence of air or oxygen and at a pressure ranging from normal pressure up to 10 bar excess pressure.
  • the consistency of the process reaction mixture preferably ranges from 0.5-40%.
  • the process of the present invention may be applied to the production of pulps in general.
  • the process may be used for the delignification (bleaching) of sulfate-, sulfite-, organosolve- and wood pulp.
  • the present invention further provides a method for the degraditive bleaching of stains on a) textiles during washing thereof with laundry detergents or on b) dishes during washing thereof with dishwashing detergents, comprising washing the textiles or dishes with a laundry or dishwashing detergent which contains an enzyme having enhanced activity by the addition of a mediator compound of formula (1) according to the present invention.
  • the present invention also provides a method for inhibiting the re-absorption of migrating dyes in the wash liquor, comprising introducing into a wash liquor containing a peroxide detergent, from 0.001 to 150 mg, per litre of wash liquor, of an enzyme having enhanced activity by the addition of a mediator compound of formula (1 ) according to the present invention.
  • the method of the present invention When the method of the present invention is applied to the degraditive bleaching of stains on textiles during washing thereof with laundry detergents, or for inhibiting the re-absorption of migrating dyes in the wash liquor, comprising introducing into a wash liquor containing a peroxide detergent, the method is generally conveniently operated at a temperature in the range of from 15-80°C, preferably at a temperature in the range of from 25-50°C.
  • the present invention further provides a detergent composition
  • a detergent composition comprising: i) 5-90%,preferably 5-70% of A) an anionic surfactant and/or B) a nonionic surfactant; ii) 5-70%, preferably 5-50%, especially 5-40% of C) a builder; iii) 0.01-30%, preferably 1-12% of D) a peroxide; and iv) 0.001-2%, preferably 0.02-2% of E) an enzyme having enhanced activity by the addition of a mediator compound of formula (1 ) according to the present invention, each by weight, based on the total weight of the detergent.
  • Each of components A) to E) may be a single compound or a mixture of compounds.
  • the detergent may be formulated as a solid; or as a non-aqueous liquid detergent, containing not more than 5, preferably 0-1 wt.% of water, and based on a suspension of a builder in a non-ionic surfactant, as described, e.g., in GB-A-2158454.
  • the detergent is in powder or granulate form.
  • Such powder or granulate forms may be produced by firstly forming a base powder by spray-drying an aqueous slurry containing all the said components , apart from the components D) and E); then adding the components D) and E) by dry-blending them into the base powder.
  • the component E) may be added to an aqueous slurry containing components A), B) and C), followed by spray-drying the slurry prior to dry- blending component D) into the mixture.
  • component B) is not present, or is only partly present in an aqueous slurry containing components A) and C); component E) is incorporated into component B), which is then added to the spray-dried base powder; and finally component D) is dry-blended into the mixture.
  • the anionic surfactant component A) may be, e.g., a sulphate, sulphonate or carboxylate surfactant, or a mixture of these.
  • Preferred sulphates are alkyl sulphates having 12-22 carbon atoms in the alkyl radical, optionally in combination with alkyl ethoxy sulphates having 10-20 carbon atoms in the alkyl radical.
  • Preferred sulphonates include alkyl benzene sulphonates having 9-15 carbon atoms in the alkyl radical.
  • the cation is preferably an alkali metal, especially sodium.
  • Preferred carboxylates are alkali metal sarcosinates of formula R-CO(R')CH 2 COOM 1 in which R is alkyl or alkenyl having 9-17 carbon atoms in the alkyl or alkenyl radical, R 1 is C ⁇ -C alkyl and M 1 is alkali metal.
  • the nonionic surfactant component B) may be, e.g., a condensate of ethylene oxide with a Cg-C t5 primary alcohol having 3-8 moles of ethylene oxide per mole.
  • the builder component C) may be an alkali metal phosphate, especially a tripolyphosphate; a carbonate or bicarbonate, especially the sodium salts thereof; a silicate; an aluminosilicate; a polycarboxylate; a polycarboxylic acid; an organic phosphonate; or an aminoalkylene poly (alkylene phosphonate); or a mixture of these.
  • Preferred silicates are crystalline layered sodium silicates of the formula NaHSimO 2 m + ⁇ or Na 2 Si m O 2m+ i.pH O in which m is a number from 1.9 to 4 and p is 0 to 20.
  • aluminosilicates are the commercially-available synthetic materials designated as Zeolites A, B, X, and HS, or mixtures of these. Zeolite A is preferred.
  • Preferred polycarboxylates include hydroxypolycarboxyla.es, in particular citrates, polyacrylates and their copolymers with maleic anhydride.
  • Preferred polycarboxylic acids include nitrilotriacetic acid and ethylene diamine tetra-acetic acid.
  • Preferred organic phosphonates or aminoalkylene poly (alkylene phosphonates) are alkali metal ethane 1 -hydroxy diphosphonates, nitrilo trimethylene phosphonates, ethylene diamine tetra methylene phosphonates and diethylene triamine penta methylene phosphonates.
  • the peroxide component D) may be any organic or inorganic peroxide compound, described in the literature or available on the market, which bleaches textiles at conventional washing temperatures, e.g. temperatures in the range of from 10°C. to 90°C.
  • the organic peroxides are, for example, monoperoxides or polyperoxides having alkyl chains of at least 3, preferably 6 to 20, carbon atoms; in particular diperoxydicarboxylates having 6 to 12 C atoms, such as diperoxyperazelates, diperoxypersebacates, diperoxyphthalates and/or diperoxydodecanedioates, especially their corresponding free acids, are of interest.
  • Peroxides can have different crystalline forms and/or different degrees of hydration. They may be used in admixture with other organic or inorganic salts, thereby improving their stability to storage.
  • the addition of the peroxides to the detergent is effected, in particular, by mixing the components, for example by means of screw-metering systems and/or fluidized bed mixers.
  • the detergents may contain, in addition to the combination according to the invention, one or more of fluorescent whitening agents, such as a bis-triazinylamino-stilbene-disulphonic acid, a bis-triazolyl-stilbene-disulphonic acid, a bis-styryl-biphenyl, a bis- benzofuranylbiphenyl, a bis-benzoxalyl derivative, a bis-benzimidazolyl derivative, a coumarine derivative or a pyrazoline derivative; soil suspending agents, for example sodium carboxymethylcellulose; salts for adjusting the pH, for example alkali or alkaline earth metal silicates; foam regulators, for example soap; salts for adjusting the spray drying and granulating properties, for example sodium sulphate; perfumes; and also,
  • a particularly preferred detergent co-additive is a polymer known to be useful in preventing the transfer of labile dyes between fabrics during the washing cycle.
  • Preferred examples of such polymers are polyvinyl pyrrolidones, optionally modified by the inclusion of an anionic or cationic substituent, especially those having a molecular weight in the range from 5000 to 60,000, in particular from 10,00 to 50,000.
  • such polymer is used in an amount ranging from 0.05 to 5%, preferably 0.2-1.7% by weight, based on the weight of the detergent.
  • CI.Direct Blue 1 The oxidation of CI.Direct Blue 1 is monitored spectroscopically at 610 nm (the absorption peak of the dye) in a spectrophotometer.
  • the reagents are added, using a pipette, in the following sequence, to a cuvette having a layer thickness of 1 cm: acetate buffer pH 5
  • test mediators used according to the present invention are those having the following formulae:
  • the mixture is stirred with the tip of the pipette for about 15 seconds. 20 seconds after the addition of the enzyme, the spectroscopic measurement at 610 nm is commenced and the spectrum is monitored for 8 minutes.
  • the temperature of the reagents and the cuvette is set at 25°C. Each experiment is conducted at pH 5. The volume of liquid in the cuvette is adjusted to 3 ml for each experiment by adding the necessary amount of water.
  • the concentration unit U ( ⁇ mol/min) given for the laccase is defined in Bourbonnais et al., in FEBS letters (1990) 267, No.1 , 99-102 (supra).
  • the results of the dye oxidation tests, showing the optical density (OD) measurements at 0 and at 8 minutes, and the rate of increase (initial gradient) of the respective OD curves, are set out in the following Table 2.
  • the rate of dye oxidation obtained with the mediators used according to the invention is clearly greatly superior to that in the control experiment or using the known mediator HOBT.
  • This mediator solution is dissolved in 20 mis of water.
  • This mediator solution together with 4 mis of a 0.5% by weight aqueous solution of EDTA and - mis of water are then added to the pulp in order to provide, in the mixture, a concentration of 5 mg of the mediator compound of formula (10) per g of pulp and a concentration of 2 mg of EDTA per g of pulp. Over a period of 60 seconds, the resulting mixture is thoroughly homogenized.
  • the kneaded mixture is placed in a steel container from which the air is then evacuated using a water jet pump.
  • the container is then charged with oxygen to a pressure of 3 bar.
  • the container is then heated at 50°C. for 225 minutes and subsequently the oxygen is removed using a water jet pump.
  • the reaction mixture is washed with 1 litre of warm (50°C.) water in a Buchner funnel; then extracted with a warm (70°C) aqueous NaOH solution, using 2 g of NaOH per 100 g of pulp; and finally re-washed with 1 litre of warm (50°C.) water in a Buchner funnel.
  • the total weight of the alkaline mixture (including 10 g of pulp) is then adjusted to 100 g by the addition of further water.
  • the Kappa number of the washed material is then determined according to the test method SCAN-C 1 :77 of the Scandinavian Pulp and Paper Board. Compared with the initial Kappa number, a Kappa number reduction of 26% is obtained.
  • wash liquids are made up containing, in 25 mis of water, a) a borax buffer (pH 9) or a commercial detergent; b) a peroxidase from horse radish (Fluka No. 77333) dissolved in a phosphate buffer (pH 6); and c) the compound of formula (101).
  • the wash liquor is pre-heated to 40°C.
  • Test cotton swatches are immersed in the respective wash liquids and then 5 mis of an aqueous solution, also pre-heated to 40°C, of Cibacron Marine C-B dye and hydrogen peroxide are added.
  • the total volume in the wash container is 30 mis.
  • 1 U of Fluka No. 77333 corresponds to the amount of enzyme which oxidizes 1 ⁇ mol of ABTS per minute at pH 6 and at 25°C.

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  • Chemical & Material Sciences (AREA)
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PCT/EP1996/003333 1995-08-08 1996-07-29 Method for enhancing the activity of an enzyme, compounds showing enzyme activity enhancement, and detergents containing such compounds WO1997006244A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP96927059A EP0843723A1 (en) 1995-08-08 1996-07-29 Method for enhancing the activity of an enzyme, compounds showing enzyme activity enhancement, and detergents containing such compounds
AU67022/96A AU6702296A (en) 1995-08-08 1996-07-29 Method for enhancing the activity of an enzyme, compounds showing enzyme activity enhancement, and detergents containing such compounds
JP9508085A JPH11508136A (ja) 1995-08-08 1996-07-29 酵素の活性を増強する方法、酵素活性増強組成物、およびかかる化合物を含有する洗剤

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GBGB9516244.2A GB9516244D0 (en) 1995-08-08 1995-08-08 Enzyme activity enhancement
GB9516244.2 1995-12-20
GBGB9525992.5A GB9525992D0 (en) 1995-12-20 1995-12-20 Enzyme activity enhancement
GB9525992.5 1995-12-20

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WO1997006244A1 true WO1997006244A1 (en) 1997-02-20

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EP (1) EP0843723A1 (ja)
JP (1) JPH11508136A (ja)
AU (1) AU6702296A (ja)
GB (1) GB2304107A (ja)
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WO1998051772A1 (de) * 1997-05-12 1998-11-19 Call, Krimhild Enzymatisches bleichsystem mit neuen enzymwirkungsverstärkenden verbindungen
EP0905306A1 (de) * 1997-09-26 1999-03-31 Consortium für elektrochemische Industrie GmbH Mehrkomponentensystem zum Verändern, Abbau oder Bleichen von Lignin, ligninhaltigen Materialien sowie Verfahren zu seiner Anwendung
WO1999016962A1 (de) * 1997-09-27 1999-04-08 Degussa-Hüls Aktiengesellschaft Verfahren zum delignifizieren und bleichen von zellstoffen unter verwendung elektrochemisch oxidierter organischer verbindungen
EP1055409A1 (fr) * 1999-05-28 2000-11-29 L'oreal Compositioin de teinture d'oxydation des fibres kératiniques et procédé de teinture mettant en oeuvre cette composition
FR2794364A1 (fr) * 1999-06-01 2000-12-08 Oreal Composition de teinture d'oxydation des fibres keratiniques et procede de teinture mettant en oeuvre cette composition
US6169065B1 (en) 1997-09-08 2001-01-02 Lever Brothers Company Division Of Conopco Company Method for the activity of an enzyme
WO2001000769A1 (en) * 1999-06-23 2001-01-04 Unilever N.V. Method and composition for enhancing the activity of an enzyme
WO2001000768A1 (en) * 1999-06-23 2001-01-04 Unilever N.V. Bleaching detergent compositions
US6225275B1 (en) 1997-06-10 2001-05-01 Lever Brothers Company, Division Of Conopco, Inc. Method for enhancing the activity of an enzyme
US6384007B1 (en) 1999-11-11 2002-05-07 Unilever Home & Personal Usa Division Of Conopco, Inc. Method and composition for enhancing the activity of an enzyme
WO2002099023A2 (de) * 2001-06-05 2002-12-12 Call, Krimhild Enzymatische systeme zur generierung aktiver sauerstoffspezies zur reaktion mit anderen precursern zur oxidation und/oder bleiche
US6660128B1 (en) 1998-04-16 2003-12-09 Pulp And Paper Research Institute Of Canada Oxidase process for pulp
DE19820947B4 (de) * 1997-05-12 2005-12-01 Call, Krimhild Enzymatisches Bleichsystem mit neuen enzymwirkungsverstärkenden Verbindungen zum Verändern, Abbau oder Bleichen von Lignin, ligninhaltigen Materialien oder Verändern oder Abbau von Kohle sowie Verfahren unter Verwendung des Bleichsystems

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AU7924200A (en) * 2000-03-01 2001-09-12 Lucas Huybrechts Tooth whitening products and procedures
FR2811888A1 (fr) * 2000-07-21 2002-01-25 Oreal Composition a base d'enzymes pour la decoloration des fibres keratiniques et procede de decoloration
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Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998051772A1 (de) * 1997-05-12 1998-11-19 Call, Krimhild Enzymatisches bleichsystem mit neuen enzymwirkungsverstärkenden verbindungen
DE19820947B4 (de) * 1997-05-12 2005-12-01 Call, Krimhild Enzymatisches Bleichsystem mit neuen enzymwirkungsverstärkenden Verbindungen zum Verändern, Abbau oder Bleichen von Lignin, ligninhaltigen Materialien oder Verändern oder Abbau von Kohle sowie Verfahren unter Verwendung des Bleichsystems
US6225275B1 (en) 1997-06-10 2001-05-01 Lever Brothers Company, Division Of Conopco, Inc. Method for enhancing the activity of an enzyme
US6169065B1 (en) 1997-09-08 2001-01-02 Lever Brothers Company Division Of Conopco Company Method for the activity of an enzyme
EP0905306A1 (de) * 1997-09-26 1999-03-31 Consortium für elektrochemische Industrie GmbH Mehrkomponentensystem zum Verändern, Abbau oder Bleichen von Lignin, ligninhaltigen Materialien sowie Verfahren zu seiner Anwendung
US6242245B1 (en) 1997-09-26 2001-06-05 Consortium für elektrochemische Industrie GmbH Multicomponent system for modifying, degrading or bleaching lignin or lignin-containing materials, and processes for its use
WO1999016962A1 (de) * 1997-09-27 1999-04-08 Degussa-Hüls Aktiengesellschaft Verfahren zum delignifizieren und bleichen von zellstoffen unter verwendung elektrochemisch oxidierter organischer verbindungen
US6660128B1 (en) 1998-04-16 2003-12-09 Pulp And Paper Research Institute Of Canada Oxidase process for pulp
EP1055409A1 (fr) * 1999-05-28 2000-11-29 L'oreal Compositioin de teinture d'oxydation des fibres kératiniques et procédé de teinture mettant en oeuvre cette composition
FR2794022A1 (fr) * 1999-05-28 2000-12-01 Oreal Composition de teinture d'oxydation des fibres keratiniques et procede de teinture mettant en oeuvre cette composition
FR2794364A1 (fr) * 1999-06-01 2000-12-08 Oreal Composition de teinture d'oxydation des fibres keratiniques et procede de teinture mettant en oeuvre cette composition
EP1062938A1 (fr) * 1999-06-01 2000-12-27 L'oreal Composition de teinture d'oxydation des fibres kératiniques et procédé de teinture
WO2001000769A1 (en) * 1999-06-23 2001-01-04 Unilever N.V. Method and composition for enhancing the activity of an enzyme
US6380146B1 (en) 1999-06-23 2002-04-30 Unilever Home & Personal Care Usa A Division Of Conopco, Inc. Bleaching detergent compositions
US6323014B1 (en) 1999-06-23 2001-11-27 Unilever Home & Personal Care Division Of Conopco, Inc. Method and composition for enhancing the activity of an enzyme
WO2001000768A1 (en) * 1999-06-23 2001-01-04 Unilever N.V. Bleaching detergent compositions
US6384007B1 (en) 1999-11-11 2002-05-07 Unilever Home & Personal Usa Division Of Conopco, Inc. Method and composition for enhancing the activity of an enzyme
WO2002099023A2 (de) * 2001-06-05 2002-12-12 Call, Krimhild Enzymatische systeme zur generierung aktiver sauerstoffspezies zur reaktion mit anderen precursern zur oxidation und/oder bleiche
WO2002099023A3 (de) * 2001-06-05 2003-05-30 Call Krimhild Enzymatische systeme zur generierung aktiver sauerstoffspezies zur reaktion mit anderen precursern zur oxidation und/oder bleiche

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JPH11508136A (ja) 1999-07-21
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GB2304107A (en) 1997-03-12
AU6702296A (en) 1997-03-05

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