WO1994012620A1 - Enhancement of enzyme reactions - Google Patents
Enhancement of enzyme reactions Download PDFInfo
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- WO1994012620A1 WO1994012620A1 PCT/DK1993/000394 DK9300394W WO9412620A1 WO 1994012620 A1 WO1994012620 A1 WO 1994012620A1 DK 9300394 W DK9300394 W DK 9300394W WO 9412620 A1 WO9412620 A1 WO 9412620A1
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- peroxidase
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- hydrogen peroxide
- enhancing agent
- enzyme
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- C12N9/00—Enzymes; Proenzymes; Compositions thereof; Processes for preparing, activating, inhibiting, separating or purifying enzymes
- C12N9/0004—Oxidoreductases (1.)
- C12N9/0065—Oxidoreductases (1.) acting on hydrogen peroxide as acceptor (1.11)
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- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2086—Hydroxy carboxylic acids-salts thereof
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- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
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- C11D3/28—Heterocyclic compounds containing nitrogen in the ring
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- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
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- C11D3/30—Amines; Substituted amines ; Quaternized amines
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- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/34—Organic compounds containing sulfur
- C11D3/349—Organic compounds containing sulfur additionally containing nitrogen atoms, e.g. nitro, nitroso, amino, imino, nitrilo, nitrile groups containing compounds or their derivatives or thio urea
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- 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
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- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2003—Alcohols; Phenols
- C11D3/2006—Monohydric alcohols
- C11D3/2034—Monohydric alcohols aromatic
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- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/34—Organic compounds containing sulfur
- C11D3/3418—Toluene -, xylene -, cumene -, benzene - or naphthalene sulfonates or sulfates
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- 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
- C11D3/34—Organic compounds containing sulfur
- C11D3/3463—Organic compounds containing sulfur containing thio sulfate or sulfite groups
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- 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
- C11D3/34—Organic compounds containing sulfur
- C11D3/3472—Organic compounds containing sulfur additionally containing -COOH groups or derivatives thereof
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- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/34—Organic compounds containing sulfur
- C11D3/3481—Organic compounds containing sulfur containing sulfur in a heterocyclic ring, e.g. sultones or sulfolanes
Definitions
- This invention relates to activation of enzymes. More specifically, the invention relates to peroxidase enhancing agents.
- the invention also relates to methods of oxidizing a substrate with a source of hydrogen peroxide in the presence of a peroxidase enzyme and a peroxidase enhancing agent. More specifically, the invention relates to a method of bleaching of dye in solutions, to a method of inhibiting the transfer of a textile dye from a dyed fabric to another fabric when said fabrics are washed together in a wash liquor, to a method of bleaching of lignin-containing material, in particular bleach ⁇ ing of pulp for paper production, to a method of treatment of waste water from pulp manufacturing, and to a method of enzymatic polymerization and/or modification of lignin or lignin containing material.
- Peroxidases are enzymes that catalyse the oxidation of a substrate (an electron or hydrogen donor) with hydrogen peroxide.
- Such enzymes are known from microbial, plant and animal origins, e.g. peroxidase from Coprinus cinereus (cf. e.g. EP 179,486). They are typically hemopro- teins, i.e. they contain a heme as a prosthetic group.
- Use of peroxidase together with hydrogen peroxide or a hydrogen peroxide precursor has been suggested e.g. in bleach ⁇ ing of pulp for paper production, in treatment of waste water from pulp production, for improved bleaching in laundry detergents, for dye transfer inhibition during laundering, and for lignin modification, e.g. in particle board production.
- ABTS 2,2'-azino-bis(3-ethylbenzothiazoline-6- sulfonate)
- Boehringer Mannheim supplied by Boehringer Mannheim, is a chromogenic substrate, and a common peroxidase and phenol oxidase assay agent.
- These enzymes catalyse the oxidation of ABTS by hydrogen peroxide and dioxygen, respectively, producing a greenish-blue colour, which process may be monitored photo ⁇ metrically.
- ABTS has been found to form a stable radical cation when oxidized by a laccase enzyme (polyphenol oxidase, EC 1.10.3.2), and has been proposed to act as a redox mediator for oxidation of non-phenolic lignin model compounds [Bourbonnais R, Paice M G; FEBS Lett (1990) 267 99-102].
- a laccase enzyme polyphenol oxidase, EC 1.10.3.2
- ABTS redox mediator for oxidation of non-phenolic lignin model compounds
- oxidizable substrates e.g. metal ions and phenolic compounds such as 7-hydroxycoumarin (7HCm) , vanillin (VAN) , and p-hydroxybenzenesulfonate (pHBS)
- accelerators or enhancers able to enhance bleaching reactions (cf. e.g. WO 92/18683, WO 92/18687, and Kato M and Shimizu S. Plant Cell Physiol. 1985 26 (7), pp. 1291-1301 (cf. Table 1 in particular) , or Saunders B C, et al., Peroxidase, London, 1964, p. 141 ff) .
- the present invention provides an agent for enhancing the activity of a peroxidase enzyme, the agent being described by the general formula
- the invention provides a method of inhibiting the transfer of a textile dye from a dyed fabric to another fabric when said fabrics are washed together in a wash liquor, the method comprising treatment of the wash liquor with a peroxidase enzyme in the presence of a source of hydrogen peroxide and in presence of a peroxidase enhancing agent of the invention.
- the invention provides a detergent additive capable of inhibiting the transfer of a textile dye from a dyed fabric to another fabric when said fabrics are washed together in a wash liquor, the detergent additive comprising an enzyme exhibiting peroxidase activity, a source of hydrogen peroxide and a peroxidase enhancing agent of the invention.
- the invention provides a detergent composition capable of inhibiting the transfer of a textile dye from a dyed fabric to another fabric when said fabrics are washed together in a wash liquor, the detergent composition comprising an enzyme exhibiting peroxidase ac ⁇ tivity, a source of hydrogen peroxide, and a peroxidase enhancing agent of the invention.
- the invention provides a method of bleaching of lignin-containing material, in particular bleach- ing of pulp for paper production, the method comprising treatment of the lignin or lignin containing material with a peroxidase enzyme in the presence of a source of hydrogen peroxide and in the presence of a peroxidase enhancing agent of the invention.
- the invention provides a method of enzymatic polymerization and/or modification of lignin or lignin containing material, the method comprising treatment of the lignin or lignin containing material with a peroxidase enzyme in the presence of a source of hydrogen peroxide and in presence of a peroxidase enhancing agent of the invention.
- the invention provides a method of treatment of waste water, e.g. waste water from the chemical or pharmaceutical industry, the method comprising treatment of the waste water with a peroxidase enzyme in the presence of a source of hydrogen peroxide and in the presence of a peroxidase enhancing agent of the invention.
- Fig. 1 shows the substituents II, III, IV, and V, of the general formula I according to the invention
- Fig. 2 shows a comparison of a peroxidase enhancing agent of the invention (ABTS) and pHBS, applied to bleaching of Methyl Orange by a Coprinus cinereus peroxidase (1: pHBS, 20 ⁇ M H 2 0 2 ; 2 : pHBS , 200 ⁇ M H 2 0 2 ; 3 : ABTS , 20 ⁇ M H 2 0 2 ; 4 : ABTS , 200 ⁇ M H 2 0 2 ) ;
- ABTS peroxidase enhancing agent of the invention
- Fig. 3 shows accelerated bleaching of Methyl Orange by a Coprinus cinereus peroxidase in the presence of varying
- ABTS (l: 0 ⁇ M ABTS; 2: 1 ⁇ M ABTS; 3: 5 ⁇ M ABTS; and 4: 10 ⁇ M
- Fig. 4 shows a comparison of the initial bleaching rates during bleaching of Direct Blue 1 (DB1) at pH 10.5 (D ABTS, 1 10 nM peroxidase; ⁇ VAN, 100 nM peroxidase; ⁇ 7HCm, 100 nM peroxidase; A pHBS, 100 nM peroxidase) ; and
- Fig. 5 shows a comparison of the initial bleaching rates during bleaching of DB1 at pH 8.8 (and pH 10.5) (D ABTS pH 8.8; ⁇ VAN pH 8.8; ⁇ 7HCm pH 8.8; 0 ABTS pH 10.5; and A pHBS pH 158.8) .
- the present invention relates to the use of a known chemical compound for enhancing the activity of peroxidase 20 enzymes. Accordingly, the invention provides an agent capable of enhancing the effect of a peroxidase enzyme.
- the agent is an azino compound described by the general formula I:
- the peroxidase enhancing agent of the invention may be in free form or in the form of an addition salt.
- the substituent groups R 1 , R 2 , R 3 , and R 4 which may be identical or different, independently represents hydrogen, halogen, a hydroxy group, a C.,-C 3 alkyl group, or a sulfo group.
- the halogen is fluoro, chloro, or bromo.
- the C 1 -C 3 alkyl group is methyl, ethyl, propyl, or isopropyl.
- the substituent group R 5 represents halogen, a hydroxy group, a C,-C 3 alkoxy group, a C,- C 3 alkyl group, or an amino group.
- a peroxidase enhancing agent of the invention is 2,2'-azino-bis(3-ethyl- benzothiazoline-6-sulfonate) .
- This compound abbreviated ABTS, is a chromogenic substrate, and a common peroxidase and phenol oxidase assay agent.
- ABTS contrary to the enhancers known and described above, is capable of acting as a peroxidase enhancing agent at highly alkaline conditions, i.e. above pH 9.
- This feature allows ABTS to be implemented into e.g. detergent compositions, intended for performance in the range pH 7-13, particularly the range pH 8- 12, preferably the range pH 9-11.
- the invention provides a method of oxidizing a substrate with a source of hydrogen peroxide in the presence of a peroxidase enzyme, the method being characterized by the presence of a peroxidase enhancing agent of the general formula
- substituents the symbols A and B which may be identical or different, independently represents any of the substituents II, III, IV, and V, presented in Fig. 1; in which substituents the symbols X and Y, which may be identical or different, independently represents carbon, nitrogen, which nitrogen may be unsubstituted or substituted with a substituent group R 5 , sulfur, oxygen, selenium or tellurium; and in which substituents the substituent groups R 1 , R 2 , R 3 , and R 4 , which may be identical or different, independently represents hydrogen, halogen, a hydroxy group, a C ⁇ C j alkoxy group, a formyl group, a carboxy group, a sulfo group, a nitro group, a C,,-C 5 alkyl group, which alkyl group may furthermore be saturated or unsaturated, or an amino group, which amino group may furthermore be unsubstituted or substituted once or twice with a substituent group R 5 ; which substituent group
- the peroxidase enhancing agent of the invention may be in free form or in the form of an addition salt.
- the substituent groups R , R 2 , R 3 , and R 4 which may be identical or different, independently represents hydrogen, halogen, a hydroxy group, a C.,-C 3 alkyl group, or a sulfo group.
- the halogen is fluoro, chloro, or bromo.
- the C,-C 3 alkyl group is methyl, ethyl, propyl, or isopropyl.
- the substituent group R 5 represents halogen, a hydroxy group, a C.-C 3 alkoxy group, a C,- C 3 alkyl group, or an amino group.
- the peroxidase enhancing agent of the invention is 2,2'-azino-bis(3-ethyl- benzothiazoline-6-sulfonate) (ABTS) .
- the enzyme employed in the method of the invention may be any peroxidase enzyme comprised by the enzyme classification EC 1.11.1.7. Such enzymes are known from microbial, plant and animal origins.
- the peroxidase employed in the method of the invention is producible by plants (e.g. horseradish peroxidase) or microorganisms such as fungi or bacteria.
- the peroxidase is derived from Coprinus. e.g. C. cinereus or C. macrorhizus. or from Bacillus, e.g. B. pumilus, particularly a peroxidase according to PCT/DK 90/00260.
- the peroxidase may furthermore be one which is produc ⁇ ible by a method comprising cultivating a host cell transformed with a recombinant DNA vector which carries a DNA sequence encoding said peroxidase as well as DNA sequences encoding functions permitting the expression of the DNA sequence encoding the peroxidase, in a culture medium under conditions permitting the expression of the peroxidase and recovering the peroxidase from the culture.
- a recombinantly produced peroxidase is a peroxidase derived from a Coprinus sp. , in particular Coprinus macrorhizus or cinereus according to WO 92/16634.
- the peroxidase enhancing agent of the invention may be present in concentrations of from 0.01 to 100 ⁇ M, more prefer ⁇ red 0.1 to 50 ⁇ M, most preferred 1 to 10 ⁇ M.
- the source of hydrogen peroxide may be hydrogen peroxide or a hydrogen peroxide precursor, e.g. percarbonate or per ⁇ borate, or a hydrogen peroxide generating enzyme system, e.g. an oxidase and a substrate for the oxidase.
- Hydrogen peroxide may be added at the beginning or during the process, e.g. in an amount of 0.001-5 mM, particularly 0.01-1 mM.
- Coprinus peroxidase 0.01-0.25 mM H 2 0 2 is preferred, and with B. pumilus peroxidase 0.1-1 mM H 2 0 2 .
- Methods according to the invention of oxidizing a substrate with a source of hydrogen peroxide in the presence of a peroxidase enzyme find various industrial applications.
- the method of the invention finds application for bleaching of dye in solutions.
- the method of the invention finds application for dye transfer inhibition, e.g. for treatment of dyed textiles (cf. e.g. WO 92/18687) or during laundering (cf. e.g. WO 91/05839) .
- the invention provides a method for inhibiting the transfer of a textile dye from a dyed fabric to another fabric when said fabrics are washed together in a wash liquor, the method comprising treatment of the wash liquor with a peroxidase enzyme in the presence of a source of hydrogen peroxide, and the presence of a peroxidase enhancing agent of the invention.
- the textile dye may be a synthetic dye such as an azo dye, or a natural or na ⁇ ture-identical dye.
- the method of the invention finds application in bleaching of pulp for paper production.
- the use of a peroxidase together with hydrogen peroxide or a hydrogen peroxide precursor in bleaching of paper pulp has been de ⁇ scribed in e.g. SE 88/0673 and US 4,690,895.
- the invention provides a method for bleaching of lignin-containing material, in particular bleach ⁇ ing of pulp for paper production, which method comprises treatment of the lignin or lignin containing material with a peroxidase enzyme in the presence of a source of hydrogen peroxide and in the presence of a peroxidase enhancing agent of the invention.
- the method of the invention finds application for lignin modification, e.g. in particle board production.
- Binders for producing wood composites such as fibre boards and particle boards can be made from peroxidase treated lignin (cf. US 4,432,921).
- the invention provides a method for enzymatic polymerization and/or modification of lignin or lignin containing material, which method comprises treatment of the lignin or lignin containing material with a peroxidase enzyme in the presence of a source of hydrogen peroxide, and the presence of a peroxidase enhancing agent of the invention.
- the method of the invention finds application in treatment of waste water e.g. waste water from the chemical or pharmaceutical industry, from dye manufac ⁇ turing, from the textile industry, or from pulp production (cf. e.g. US 4,623,465, or JP-A 2-31887).
- the invention provides a method for treatment of waste water from dye manufacturing, from textile industry, or from pulp manufacturing, the method comprising treatment of the waste water with a peroxidase enzyme in the presence of a source of hydrogen peroxide and in the presence of a peroxidase enhancing agent of the invention.
- the peroxidase enhancing agent may be added as a component of a detergent composition.
- the invention provides a detergent additive capable of inhibiting the transfer of a textile dye from a dyed fabric to another fabric when said fabrics are washed together in a wash liquor, the detergent additive comprising an enzyme exhibiting peroxidase activity, a source of hydrogen peroxide, and a peroxidase enhancing agent of the invention.
- the detergent additive may additionally comprise one or more other enzymes conventionally used in detergents, such as proteases, Upases, amylases, or cellulases.
- the detergent additive is provided in the form of a granulate, preferably a non-dusting granulate, a liquid, in particular a stabilized liquid, a slurry, or in a protected form.
- the invention provides a detergent composition capable of inhibiting the transfer of a textile dye from a dyed fabric to another fabric when said fabrics are washed together in a wash liquor, the detergent composition comprising an enzyme exhibiting peroxidase ac ⁇ tivity, a source of hydrogen peroxide and a peroxidase enhanc ⁇ ing agent of the invention.
- the peroxidase enhancing agent of the invention may be included in the detergent as a part of a peroxidase system, comprising a peroxidase enzyme, a source of hydrogen peroxide, and the peroxidase enhancing agent of the invention.
- the peroxidase system may be included in the detergent composition in the form of a non-dusting granulate, a liquid, in particular a stabilized liquid, or in a protected form.
- Non- dusting granulates may be produced, e.g. as disclosed in US 4,106,991 and 4,661,452 (both to Novo Industri A/S) and may optionally be coated by methods known in the art.
- Liquid enzyme preparations may, for instance, be stabilized by adding a polyol such as propylene glycol, a sugar or sugar alcohol, lactic acid or boric acid according to established methods. Other enzyme stabilizers are well known in the art.
- a protected form of the peroxidase system may be prepared according to the method disclosed in EP 238,216.
- the detergent composition of the invention may be in any convenient form, e.g. as powder, granules or liquid.
- a liquid detergent may be aqueous, typically containing up to 90% water and 0-20% organic solvent.
- the detergent composition comprises surfactants which may be anionic, nonionic, cationic, amphoteric or a mixture of these types.
- the detergent will usually contain 0-50% anionic surfactant such as linear alkylbenzenesulfonate (LAS) , alpha- olefinsulfonate (AOS) , alkyl sulfate (AS) , alcohol ether sulfate (AES) or soap. It may also contain 0-40% nonionic surfactant such as nonyl phenol ethoxylate or alcohol ethoxy- late. Furthermore, it may contain a polyhydroxy fatty acid amide surfactant (e.g. as described in WO 92/06154) .
- the pH (measured in aqueous detergent solution) will usually be neutral or alkaline, e.g. 7-11.
- the detergent may contain 1-40% of a detergent builder such as zeolite, phosphate, phosphonate, citrate, NTA, EDTA or DTPA, alkenyl succinic anhydride, or silicate, or it may be unbuilt (i.e. essentially free of a detergent builder). It may also contain other conventional detergent ingredients, e.g. fabric conditioners, foam boosters, bleaching agents, e.g.
- the detergent composition may additionally comprise one or more other enzymes conventionally used in detergents such as proteases, lipases, amylases, and cellulases.
- a detergent composition formulated as a nonaqueous detergent liquid comprising a liquid nonionic surfactant consisting essentially of linear alkoxylated primary alcohol, phosphate builder, alkali, with a pH in use adjusted to a value between about 7 and 10.5.
- a liquid compact detergent comprising 5-65% by weight of surfactant, 0-50% by weight of builder and 0-30% by weight of electrolyte.
- Methyl Orange (Merck) catalysed by a recombinantly produced Coprinus cinereus peroxidase (rCiP) , obtained according to WO 92/16634, and hydrogen peroxide in the presence of 2,2'-azino-bis(3-ethylb- enzothiazoline-6-sulfonate) (ABTS, supplied by Boehringer Mannheim) or para-hydroxybenzene sulfonate (pHBS, supplied by Sigma) is shown in Fig. 2. The following conditions were used:
- Reagents were mixed in a 1 cm cuvette, and the bleaching was started by addition of hydrogen peroxide.
- the bleaching was detected spectrophotometrically at 465 nm, which is the ab ⁇ sorption peak of this dye. Bleaching was followed with respect to time over a span of 10 in.
- Methyl Orange Accelerated bleaching of Methyl Orange (Merck) catalysed by a recombinantly produced Coprinus cinereus peroxidase (rCiP) , obtained according to WO 92/16634, and hydrogen peroxide in the presence of varying concentrations of 2,2'- azino-bis(3-ethylbenzothiazoline-6-sulfonate) (ABTS, supplied by Boehringer Mannheim) is shown in Fig. 3. The following conditions were used:
- Reagents were mixed in a 1 cm cuvette, and the bleaching was started by addition of hydrogen peroxide.
- the bleaching was detected spectrophotometrically at 610 nm, which is the ab ⁇ sorption peak of this dye. Bleaching was followed for 10 minutes, and the bleaching rates (- ⁇ mAbs/min) were determined from the initial (linear) reduction in absorbance.
- the detergent solution for the washing trial was made up using 4.5 g/1 of a commercially available European high-pH powder detergent containing no bleach and no optical bright- ener.
- the water used was tap water mixed with demineralized water in the ratio 1:2; the mixture had a hardness equivalent to approx. 1.1 mM Ca 2+ .
- Textile load Approx. 6 g nylon dyed with acid Red 151 and 1 g white cotton per litre washing liquor
- Peroxidase Recombinantly produced Coprinus cinereus peroxidase, obtained ac ⁇ cording to WO 92/16634, at 5 nM
- test pieces were rinsed thoroughly in cold tap water and dried in the dark overnight, after which the remission measurements were performed. Treatments with various concentrations of the two enhancers yielded the following results:
- the peroxidase system with 1 ⁇ M enhancer provided no significant dye transfer inhibition (reference without peroxidase system not included here) .
- the ABTS system has an effect already at 5 ⁇ M of enhan ⁇ cer, whereas the pHBS system does not; and at 20 ⁇ M enhancer, the ABTS system has a much larger effect than the pHBS system.
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP6512668A JPH08503371A (en) | 1992-12-01 | 1993-12-01 | Enhancing the enzymatic reaction |
EP94900786A EP0677102A1 (en) | 1992-12-01 | 1993-12-01 | Enhancement of enzyme reactions |
BR9307575A BR9307575A (en) | 1992-12-01 | 1993-12-01 | Agent to improve the activity of a peroxidase enzyme process to oxidize a detergent additive substrate detergent composition |
FI952647A FI952647A (en) | 1992-12-01 | 1995-05-31 | Enhancement of enzyme reactions |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DK921441A DK144192D0 (en) | 1992-12-01 | 1992-12-01 | ENZYMER ACTIVATION |
DK1441/92 | 1993-10-26 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1994012620A1 true WO1994012620A1 (en) | 1994-06-09 |
Family
ID=8104867
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/DK1993/000394 WO1994012620A1 (en) | 1992-12-01 | 1993-12-01 | Enhancement of enzyme reactions |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP0677102A1 (en) |
JP (1) | JPH08503371A (en) |
BR (1) | BR9307575A (en) |
CA (1) | CA2150563A1 (en) |
DK (1) | DK144192D0 (en) |
FI (1) | FI952647A (en) |
WO (1) | WO1994012620A1 (en) |
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WO1995033040A1 (en) * | 1994-05-31 | 1995-12-07 | The Procter & Gamble Company | Dye transfer inhibition system containing a peroxidase/accelerator system |
WO1997006244A1 (en) * | 1995-08-08 | 1997-02-20 | Ciba Specialty Chemicals Holding Inc. | Method for enhancing the activity of an enzyme, compounds showing enzyme activity enhancement, and detergents containing such compounds |
WO1997041215A1 (en) * | 1996-04-29 | 1997-11-06 | Novo Nordisk A/S | Non-aqueous, liquid, enzyme-containing compositions |
US5691193A (en) * | 1993-02-25 | 1997-11-25 | Pulp And Paper Research Institute Of Canada | Non-chlorine bleaching of kraft pulp |
US5700769A (en) * | 1992-12-01 | 1997-12-23 | Novo Nordisk A/S | Enhancement of enzyme reactions |
WO1998023716A2 (en) * | 1996-11-25 | 1998-06-04 | Unilever N.V. | Enzymatic oxidation process |
WO1999031155A1 (en) * | 1997-12-17 | 1999-06-24 | Stockhausen Gmbh & Co. Kg | Method for grafting lignin, polymerizates produced according to the method and the utilization thereof |
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 |
WO2001010195A1 (en) * | 1999-08-10 | 2001-02-15 | Novozymes A/S | Reduction of malodour in soiled animal litter |
US6225275B1 (en) | 1997-06-10 | 2001-05-01 | Lever Brothers Company, Division Of Conopco, Inc. | Method for enhancing the activity of an enzyme |
WO2001034750A1 (en) * | 1999-11-11 | 2001-05-17 | Unilever N.V. | Method and composition for enhancing the activity of an enzyme |
WO2001034749A1 (en) * | 1999-11-11 | 2001-05-17 | Unilever N.V. | Method and composition for enhancing the activity of an enzyme |
WO2001092454A1 (en) * | 2000-05-31 | 2001-12-06 | Unilever N.V. | Enzymatic oxidation composition and process |
WO2002036724A1 (en) * | 2000-10-31 | 2002-05-10 | Unilever N.V. | Oxidation process and composition |
US6417151B1 (en) | 1997-04-04 | 2002-07-09 | Henkel Kommanditgesellschaft Auf Aktien | Activators for peroxide compounds in detergents and cleaning agents |
US6518231B2 (en) | 2000-12-18 | 2003-02-11 | Unilever Home & Personal Care Usa, Division Of Conopco, Inc. | Enhancement of air bleaching catalysts |
US6592867B2 (en) * | 1998-11-09 | 2003-07-15 | Novozymes A/S | Antimicrobial composition containing an oxidoreductase and an enhancer of the N-hydroxyanilide-type |
US6610172B1 (en) | 1999-05-06 | 2003-08-26 | Novozymes A/S | Process for treating pulp with laccase and a mediator to increase paper wet strength |
US6818149B2 (en) | 2000-12-15 | 2004-11-16 | Unilever Home & Personal Care Usa, Division Of Conopco, Inc. | Ligand and complex for catalytically bleaching a substrate |
US6866687B2 (en) | 2002-09-27 | 2005-03-15 | Unilever Home & Personal Care Usa, A Division Of Conopco, Inc. | Composition and method for bleaching a substrate |
WO2005103372A3 (en) * | 2004-04-26 | 2006-03-16 | Call Krimhild | Oxidative, reductive, hydrolytic and other enzymatic systems for oxidizing, reducing, coating, coupling or cross-linking natural and artificial fiber materials, plastic materials or other natural or artificial monomer to polymer materials |
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- 1992-12-01 DK DK921441A patent/DK144192D0/en not_active IP Right Cessation
-
1993
- 1993-12-01 WO PCT/DK1993/000394 patent/WO1994012620A1/en not_active Application Discontinuation
- 1993-12-01 JP JP6512668A patent/JPH08503371A/en active Pending
- 1993-12-01 EP EP94900786A patent/EP0677102A1/en not_active Withdrawn
- 1993-12-01 CA CA002150563A patent/CA2150563A1/en not_active Abandoned
- 1993-12-01 BR BR9307575A patent/BR9307575A/en not_active Application Discontinuation
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1995
- 1995-05-31 FI FI952647A patent/FI952647A/en not_active Application Discontinuation
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US3893803A (en) * | 1972-10-10 | 1975-07-08 | Procter & Gamble | Hair dyeing premixes containing peroxidase enzymes stabilized with heme complexing agents |
DD147368A1 (en) * | 1979-11-23 | 1981-04-01 | Baerbel Porstmann | METHOD OF INCREASING THE ACTIVITY OF SEA-RETROSPECT PEROXIDASE |
US4432921A (en) * | 1980-10-08 | 1984-02-21 | Gesellschaft Fur Biotechnologische Forschung | Process for producing a binder for wood materials |
US4623465A (en) * | 1981-04-20 | 1986-11-18 | Massachusetts Institute Of Technology | Removal of combined organic substances from aqueous solutions |
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Cited By (36)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5700769A (en) * | 1992-12-01 | 1997-12-23 | Novo Nordisk A/S | Enhancement of enzyme reactions |
US5691193A (en) * | 1993-02-25 | 1997-11-25 | Pulp And Paper Research Institute Of Canada | Non-chlorine bleaching of kraft pulp |
WO1995033040A1 (en) * | 1994-05-31 | 1995-12-07 | The Procter & Gamble Company | Dye transfer inhibition system containing a peroxidase/accelerator system |
WO1997006244A1 (en) * | 1995-08-08 | 1997-02-20 | Ciba Specialty Chemicals Holding Inc. | Method for enhancing the activity of an enzyme, compounds showing enzyme activity enhancement, and detergents containing such compounds |
WO1997041215A1 (en) * | 1996-04-29 | 1997-11-06 | Novo Nordisk A/S | Non-aqueous, liquid, enzyme-containing compositions |
US6355461B2 (en) | 1996-04-29 | 2002-03-12 | Novozymes A/S | Non-aqueous, liquid, enzyme-containing compositions |
WO1998023716A2 (en) * | 1996-11-25 | 1998-06-04 | Unilever N.V. | Enzymatic oxidation process |
WO1998023716A3 (en) * | 1996-11-25 | 1998-10-08 | Unilever Nv | Enzymatic oxidation process |
US6080573A (en) * | 1996-11-25 | 2000-06-27 | Lever Brothers Company, Division Of Conopco, Inc. | Enzymatic oxidation process |
US6417151B1 (en) | 1997-04-04 | 2002-07-09 | Henkel Kommanditgesellschaft Auf Aktien | Activators for peroxide compounds in detergents and cleaning agents |
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 |
WO1999031155A1 (en) * | 1997-12-17 | 1999-06-24 | Stockhausen Gmbh & Co. Kg | Method for grafting lignin, polymerizates produced according to the method and the utilization thereof |
US6593460B1 (en) * | 1997-12-17 | 2003-07-15 | Stockhausen Gmbh & Co Kg | Method for grafting lignin, polymerizates produced according to the method and the utilization thereof |
US6592867B2 (en) * | 1998-11-09 | 2003-07-15 | Novozymes A/S | Antimicrobial composition containing an oxidoreductase and an enhancer of the N-hydroxyanilide-type |
US6610172B1 (en) | 1999-05-06 | 2003-08-26 | Novozymes A/S | Process for treating pulp with laccase and a mediator to increase paper wet strength |
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 |
WO2001010195A1 (en) * | 1999-08-10 | 2001-02-15 | Novozymes A/S | Reduction of malodour in soiled animal litter |
WO2001034750A1 (en) * | 1999-11-11 | 2001-05-17 | Unilever N.V. | Method and composition 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 |
WO2001034749A1 (en) * | 1999-11-11 | 2001-05-17 | Unilever N.V. | Method and composition for enhancing the activity of an enzyme |
WO2001092454A1 (en) * | 2000-05-31 | 2001-12-06 | Unilever N.V. | Enzymatic oxidation composition and process |
WO2002036724A1 (en) * | 2000-10-31 | 2002-05-10 | Unilever N.V. | Oxidation process and composition |
US6689738B2 (en) | 2000-10-31 | 2004-02-10 | Unilever Home And Personal Care Usa Division Of Conopco, Inc. | Oxidation process and composition |
US6818149B2 (en) | 2000-12-15 | 2004-11-16 | Unilever Home & Personal Care Usa, Division Of Conopco, Inc. | Ligand and complex for catalytically bleaching a substrate |
US6518231B2 (en) | 2000-12-18 | 2003-02-11 | Unilever Home & Personal Care Usa, Division Of Conopco, Inc. | Enhancement of air bleaching catalysts |
US6866687B2 (en) | 2002-09-27 | 2005-03-15 | Unilever Home & Personal Care Usa, A Division Of Conopco, Inc. | Composition and method for bleaching a substrate |
WO2005103372A3 (en) * | 2004-04-26 | 2006-03-16 | Call Krimhild | Oxidative, reductive, hydrolytic and other enzymatic systems for oxidizing, reducing, coating, coupling or cross-linking natural and artificial fiber materials, plastic materials or other natural or artificial monomer to polymer materials |
WO2013040991A1 (en) * | 2011-09-23 | 2013-03-28 | Novozymes A/S | Color modification of textile |
US9670614B2 (en) | 2011-09-23 | 2017-06-06 | Novozymes A/S | Color modification of textile |
US11208675B2 (en) | 2016-07-13 | 2021-12-28 | Kikkoman Corporation | Reaction accelerating agent |
EP4053328A1 (en) | 2021-03-02 | 2022-09-07 | CHT Germany GmbH | Combined bleaching treatment for textiles |
WO2022184584A1 (en) | 2021-03-02 | 2022-09-09 | CHT Germany GmbH | Combined bleaching treatment for textiles |
Also Published As
Publication number | Publication date |
---|---|
DK144192D0 (en) | 1992-12-01 |
FI952647A0 (en) | 1995-05-31 |
EP0677102A1 (en) | 1995-10-18 |
BR9307575A (en) | 1999-06-15 |
FI952647A (en) | 1995-05-31 |
JPH08503371A (en) | 1996-04-16 |
CA2150563A1 (en) | 1994-06-09 |
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