WO1999023240A1 - Method of producing oxidized starch - Google Patents

Method of producing oxidized starch Download PDF

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Publication number
WO1999023240A1
WO1999023240A1 PCT/FI1998/000860 FI9800860W WO9923240A1 WO 1999023240 A1 WO1999023240 A1 WO 1999023240A1 FI 9800860 W FI9800860 W FI 9800860W WO 9923240 A1 WO9923240 A1 WO 9923240A1
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Prior art keywords
starch
tempo
oxidized
oxidizing agent
laccase
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PCT/FI1998/000860
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Finnish (fi)
French (fr)
Inventor
Liisa Viikari
Marja-Leena Niku-Paavola
Johanna Buchert
Pirkko Forssell
Anita Teleman
Kristiina Kruus
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Valtion Teknillinen Tutkimuskeskus
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Priority to AU10350/99A priority Critical patent/AU1035099A/en
Publication of WO1999023240A1 publication Critical patent/WO1999023240A1/en

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    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P19/00—Preparation of compounds containing saccharide radicals
    • C12P19/04—Polysaccharides, i.e. compounds containing more than five saccharide radicals attached to each other by glycosidic bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B31/00—Preparation of derivatives of starch
    • C08B31/18—Oxidised starch

Definitions

  • the present invention concerns a method for producing oxidized starch according to the preamble of claim 1.
  • a starch-containing substrate starch is contacted with a reagent that produces oxoammonium ion in the presence of an oxidative agent.
  • the reaction is preferably carried out in a liquid medium and the reaction product is separated from the medium after the reaction, washed and dried.
  • Starch is a naturally occuring polymer, whose derivatives are used as fillers, for gluing and in coating in the paper and board industry. Oxidized starch derivatives as well as starch esters and cationized starch are used for surface sizing of paper, for improving strength and printing properties and as adhesives in coating to bind the pigment particles together and onto the base paper.
  • starch is oxidized primarily with the aid of inorganic oxidizing agents, such as sodium hypochlorite, the viscosity of the starch dispersion being decreased to a suitable level and part of the hydroxyl groups of the starch being oxidized to carbonyl and carboxylic groups.
  • Uronic acid groups are obtained from the primary hydroxyl groups by oxidizing.
  • the carboxylic groups increase the stability of the viscosity of the dispersion.
  • oxidation methods are hampered by the problem that the oxidation is not specific enough for primary OH-groups.
  • the secondary OH-groups are oxidized to some extent.
  • the oxidation of the secondary OH-groups leads to the breaking of the polymer chain, depolymerisation. Because of this more specific methods for oxidizing starch and other biosaccharides have been sought for a long time.
  • the very selective TEMPO derivative represents an interesting alternative for oxidation.
  • the TEMPO radical may, according to literature, be oxidized with the aid of hypohalites, such as hypochlorite and hypobromite.
  • the oxidized TEMPO oxidizes different primary alcohol groups to carboxyls.
  • the TEMPO-radical (2,2,6, 6-tetramethyl piperidine-1-oxyl) has been found to oxidize with a high selectivity the primary OH-groups of carbohydrate polymers.
  • the actual oxidizing agent is the oxoammonium ion (nitrosonium ion), which is obtained by oxidizing TEMPO first with the aid of hypohalites, such as hypochlorite and hypobromite.
  • the oxoammonium ion oxidizes the primary OH-groups of the carbohydrates to carbonyls which may be oxidized further to carboxyls.
  • TEMPO and the derivatives thereof have previously been used for oxidizing the primary hydroxyl groups of alcohols and diols to aldehydes and carboxyls as well as for oxidizing aliphatic and aromatic aldehydes to carboxyls.
  • additional catalysts have been present and the reaction has taken place in an alkaline two phase system (3-5).
  • TEMPO has also been used for oxidizing different polysaccharides, such as starch in an aqueous phase (6-9).
  • the primary oxidizing agent has been the already mentioned hypochlorite and a catalytic amount of sodium bromide, a stronger oxidizing agent, hypobromite, being produced when these react.
  • the method has been stated to exhibit high selectivity and efficiency. Hydrated aldehydes in aqueous solution are produced as intermediates; the aldehydes are further oxidized to carboxyls (7-9).
  • a problem of prior art is that hypochlorite is not only expensive, but also harmful to the environment. This creates problems when operating on an industrial scale. Enzyme treatment presented in reference (12) is carried out at anaerobic conditions and the technical solution in question is not suitable to large scale production, either. It is an object of the present invention to eliminate the problems of the prior art and to provide a completely new method for selective oxidation of starch. In particular, the aim of the present invention is to provide an entirely new process for oxidizing starting materials containing starch by using a reagent which produces an oxoammonium ion, such as TEMPO, the regenerating oxidizing agent of the reagent being an oxidizing agent which does not contain halides.
  • a reagent which produces an oxoammonium ion such as TEMPO
  • the invention is based on the idea that TEMPO is oxidized with the aid of an oxidizing enzyme.
  • Suitable oxidizing enzymes are phenoloxidases, in particular laccase and peroxidases.
  • hypochlorite is used as regenerating oxidizing agent and, according to Figure IB, oxygen.
  • a catalytic amount of bromide is brought to the reaction. Bromide oxidizes to hypobromite which is a stronger oxidizing agent than hypochlorite.
  • hydrogen peroxide may be used as electron acceptor instead of oxygen.
  • oxidizing (oxidative) enzymes are used.
  • enzymes that catalyze the oxidizing of phenolic groups are used. These enzymes are oxidoreductases, such as oxidases and peroxidases. "Oxidases” are enzymes that catalyze oxidation reaction by using molecular oxygen as their substrate while “peroxidases” are enzymes that catalyze oxidation reactions by using hydrogen peroxide as their substrate. Phenoloxidases (E.C. 1.10.3.2 benzenedioloxygen oxidoreductase) catalyze the oxidation of o- and p- substituted phenolic hydroxyl and amino/amine groups in monomeric and polymeric aromatic compounds.
  • oxidoreductases such as oxidases and peroxidases.
  • Oxidases are enzymes that catalyze oxidation reaction by using molecular oxygen as their substrate
  • peroxidases are enzymes that catalyze oxidation reactions by using hydrogen peroxide as their substrate.
  • oxidases As specific examples of oxidases the following can be mentioned: laccases (E.C. 1.10.3.2), cathecoloxidases (E.C. 1.10.3.1), tyrocinases (E.C. 1.14.18.1) and bilirubineoxidases (E.C. 1.3.3.5).
  • Laccases can be produced by white rot fungi, in particular with Trametes (previously Coriolus) versicolor or hilluta or villosa strains.
  • Other known micro-organisms producing laccase are the different strains of following mold: Agaricus, Armillaria, Aspergillus, Botrytis, Fusarium, Lentinus, Monocillium, Neurospora, Phlebia, Polyporus, Podospora, Pycnoporus and Schizophyllum.
  • the invention is, however, not limited to the indicated origins of enzymes nor to a specific isolation method, and the enzymes may be obtained by other means.
  • the enzymes may be obtained by other means.
  • the starch to be oxidized may be any natural starch possessing an amylose/amylopectine ratio of 1 :0...0: 1.
  • sources of starch may be mentioned tuber-bearing plants and cereal such as potato, wheat, barley, oat, pea, corn, rice, sago and tapioka.
  • the amount of laccase in the oxidation may be approximately 1...1000 nkat/g of starch.
  • the concentration of starch may vary on a large range, it may be, e.g., 5...35% (v/w).
  • the oxidation is conducted in the liquid phase, since TEMPO is water soluble preferably in water, at a temperature in the range of 10 to 70 °C, preferably 20 to 40 °C and at a pH in the range of 4 to 9.
  • the amount of TEMPO is 0.01 to 50 wt-%, preferably approximately 0.1 to 20 wt-% of the amount of starch.
  • the reaction is conducted by dissolving a selected amount of TEMPO (in the form of a stabile nitroxyl radical) in water, to which starch is suspended.
  • the dry-content of the suspension is usually set to approximately 0.1 to 20 wt-%.
  • Buffer may be added to water to set the pH of the reaction medium to a desired, suitable in view of laccase treatment, value (over 4).
  • oxygen is fed to the reaction mixture, either as gas or as air while simultaneously mixing the composition. Depending on the amount of the material to be oxidized, the feeding of oxygen lasts usually approximately 10 min - 24 h.
  • the oxidized starch is separated by filtration from the liquid, washed and dried.
  • TEMPO is oxidized with hydrogen peroxide.
  • starch is obtained, a part of the primary OH-groups of which having been converted to carbonyl and carboxyl groups.
  • the ratio of carbonyl groups to carboxyl groups is 1...5.
  • the molar mass of starch possibly decreases as a result of the oxidation, but is usually still over 300.000 g/mol, e.g., at least 400.000 g/mol.
  • Oxidized starch can be used as such as an additive in paper making in the wet end of a paper machine or as a coating material. Due to the carbonyl groups, the starch is made reactive and thus the product may also be further oxidized and the carbonyl groups may be further modified.
  • TEMPO oxidation catalyzed by TEMPO
  • 0.3 g TEMPO was dissolved in water, 30 g starch was suspended to the solution and 12 g NaBr was added. The temperature of the reaction mixture was adjusted to 0 °C. Another mixture with 345 ml 8 % hypochlorite was prepared, pH was adjusted with 3 M hydrochloric acid to a value of 10.8 and the temperature of the solution was adjusted to 0 °C. The solution was added in one batch to the solution containing starch and incubated for 2 h. During the incubation the pH of the solution was controlled and, if necessary, adjusted back to a value of 10 - 11 with 0.5 M NaOH. The reaction was stopped by adding 60 ml 96% ethanol and adjusting thereafter the pH of suspension to 7. The starch was separated and washed with 1000 ml water and dried at room temperature.
  • Native potato starch was oxidized by using TEMPO as a intermediate medium and laccase enzyme as an oxidizer.
  • Enzyme Trametes hirsuta D 443 -fungus laccase, growth medium. The activity was defined by using ABTS-substrate (10).
  • a 5 % suspension with a pH of 5.0 was prepared of 35 g native potato starch.
  • TEMPO 3.5 g was dissolved in the buffer, starch was added and suspended to the liquid phase, after which laccase was added (dosage 200 nkat g starch).
  • the reaction was oxidized with an oxygen flow for 3 h at room temperature and simultaneous mixing with a magnetic stirrer.
  • the starch was removed by filtration and washed with 1000 ml water. After washing, the starch was dried at room temperature.
  • oxidized starch both chemically and laccase-TEMPO oxidized were slightly smaller than the molecular weight of native potato starch.
  • the geling properties of oxidized starch were determined with Bohl's VOR rheometer (oscillation method). The samples were cooled from 90 °C to 20 °C at a rate of 1 °C/min. The measurements were made in 15 % starch solutions. Laccase-TEMPO and commercial oxidized starch did not gel in the measuring conditions.
  • Starch was oxidized with different dosages of laccase and TEMPO.
  • the properties of oxidized starch (molecular weight distribution, geling properties, structure) were determined according to example 3. It was discovered that by varying the dosages of TEMPO and laccase the modification degree of the starch may be altered and thus also the gel properties and molecular weight properties change.

Abstract

The invention concerns a method for producing oxidized starch. According to the method, the starting material containing starch is contacted with a reagent producing oxoammonium ion, in particular 2,2,6,6,-tetramethylpiperidin-1-oxyl, in the presence of an oxidizing agent. According to the invention, an oxidative enzyme, such as laccase, is used as the oxidizing agent. By using laccase as the oxidizing agent is achieved quite selective oxidation while avoiding the halide-containing reagents that are considered harmful to the environment.

Description

Method of producing oxidized starch
The present invention concerns a method for producing oxidized starch according to the preamble of claim 1.
According to a method of this kind a starch-containing substrate starch is contacted with a reagent that produces oxoammonium ion in the presence of an oxidative agent. The reaction is preferably carried out in a liquid medium and the reaction product is separated from the medium after the reaction, washed and dried.
Starch is a naturally occuring polymer, whose derivatives are used as fillers, for gluing and in coating in the paper and board industry. Oxidized starch derivatives as well as starch esters and cationized starch are used for surface sizing of paper, for improving strength and printing properties and as adhesives in coating to bind the pigment particles together and onto the base paper.
Industrially, starch is oxidized primarily with the aid of inorganic oxidizing agents, such as sodium hypochlorite, the viscosity of the starch dispersion being decreased to a suitable level and part of the hydroxyl groups of the starch being oxidized to carbonyl and carboxylic groups. Uronic acid groups are obtained from the primary hydroxyl groups by oxidizing. The carboxylic groups increase the stability of the viscosity of the dispersion. As alternative procedures for oxidizing with hypochlorite, the use of hydrogen peroxide, bromine, periodate, ozone and oxygen have been proposed, of which oxidation using hydrogen peroxide is the most promising alternative (1-2).
Conventional oxidation methods are hampered by the problem that the oxidation is not specific enough for primary OH-groups. In the chemical oxidation procedures, in addition to the primary OH-groups, also the secondary OH-groups are oxidized to some extent. The oxidation of the secondary OH-groups leads to the breaking of the polymer chain, depolymerisation. Because of this more specific methods for oxidizing starch and other biosaccharides have been sought for a long time. The very selective TEMPO derivative represents an interesting alternative for oxidation. The TEMPO radical may, according to literature, be oxidized with the aid of hypohalites, such as hypochlorite and hypobromite. The oxidized TEMPO oxidizes different primary alcohol groups to carboxyls.
The TEMPO-radical (2,2,6, 6-tetramethyl piperidine-1-oxyl) has been found to oxidize with a high selectivity the primary OH-groups of carbohydrate polymers. The actual oxidizing agent is the oxoammonium ion (nitrosonium ion), which is obtained by oxidizing TEMPO first with the aid of hypohalites, such as hypochlorite and hypobromite. The oxoammonium ion oxidizes the primary OH-groups of the carbohydrates to carbonyls which may be oxidized further to carboxyls.
TEMPO and the derivatives thereof have previously been used for oxidizing the primary hydroxyl groups of alcohols and diols to aldehydes and carboxyls as well as for oxidizing aliphatic and aromatic aldehydes to carboxyls. In these cases, also additional catalysts have been present and the reaction has taken place in an alkaline two phase system (3-5). TEMPO has also been used for oxidizing different polysaccharides, such as starch in an aqueous phase (6-9). In these cases, the primary oxidizing agent has been the already mentioned hypochlorite and a catalytic amount of sodium bromide, a stronger oxidizing agent, hypobromite, being produced when these react.
The method has been stated to exhibit high selectivity and efficiency. Hydrated aldehydes in aqueous solution are produced as intermediates; the aldehydes are further oxidized to carboxyls (7-9).
There are also known technical solutions where TEMPO has been oxidized with a superoxide which has been produced with enzymes (12).
A problem of prior art is that hypochlorite is not only expensive, but also harmful to the environment. This creates problems when operating on an industrial scale. Enzyme treatment presented in reference (12) is carried out at anaerobic conditions and the technical solution in question is not suitable to large scale production, either. It is an object of the present invention to eliminate the problems of the prior art and to provide a completely new method for selective oxidation of starch. In particular, the aim of the present invention is to provide an entirely new process for oxidizing starting materials containing starch by using a reagent which produces an oxoammonium ion, such as TEMPO, the regenerating oxidizing agent of the reagent being an oxidizing agent which does not contain halides.
The invention is based on the idea that TEMPO is oxidized with the aid of an oxidizing enzyme. Suitable oxidizing enzymes are phenoloxidases, in particular laccase and peroxidases. Thus, the oxidation of starch can be conducted in a more environmentally friendly way with enzymes and TEMPO than oxidation with chemical oxidizing agents.
More specifically, the technical solution of the present invention is mainly characterized by what is stated in the characterizing part of claim 1.
A number of considerable advantages are obtained with the aid of the present invention. Thus, a quite selective oxidation is obtained, both carboxyl and carbonyl groups being obtained in a suitable proportion. The halide-containing materials that are considered environmentally problematic can be eliminated by using phenoloxidase as regenerating oxidizing agent. Oxygen functions as final electron acceptor, when the building up of difficult by-products in the reaction system is avoided, which facilitates the removal and purification of the product. Similarly, when using an oxidizing enzyme, such as phenoloxidase, as regenerating oxidizing agent, mild reaction conditions, such as neutral or almost neutral pH and low temperature may be used.
Next, the invention will be more closely examined with the aid of a detailed description and a number of working examples. In the description reference is made to the enclosed drawing, which schematically depicts the reactions of TEMPO in the oxidation system. Figure 1 A presents the oxidation of TEMPO resulting from the chemical oxidizing agents and Figure IB gives a corresponding presentation of a solution according to the present invention, in which the oxidation is obtained by using an enzyme.
As is apparent from Figures 1 A and IB, the stabile nitroxyl radical (stage 1) is oxidized to oxoammonium ion (stage 2) which oxidizes the alcohol group (RCH OH) to, e.g., aldehyde (RCHO), the oxoammonium ion being at the same time reduced to hydroxyl amine (stage 3).
According to Figure 1 A, hypochlorite is used as regenerating oxidizing agent and, according to Figure IB, oxygen. In the first case, also a catalytic amount of bromide is brought to the reaction. Bromide oxidizes to hypobromite which is a stronger oxidizing agent than hypochlorite. When using peroxidases, hydrogen peroxide may be used as electron acceptor instead of oxygen.
As already mentioned, in the invention, oxidizing (oxidative) enzymes are used.
Preferably, enzymes that catalyze the oxidizing of phenolic groups are used. These enzymes are oxidoreductases, such as oxidases and peroxidases. "Oxidases" are enzymes that catalyze oxidation reaction by using molecular oxygen as their substrate while "peroxidases" are enzymes that catalyze oxidation reactions by using hydrogen peroxide as their substrate. Phenoloxidases (E.C. 1.10.3.2 benzenedioloxygen oxidoreductase) catalyze the oxidation of o- and p- substituted phenolic hydroxyl and amino/amine groups in monomeric and polymeric aromatic compounds.
As specific examples of oxidases the following can be mentioned: laccases (E.C. 1.10.3.2), cathecoloxidases (E.C. 1.10.3.1), tyrocinases (E.C. 1.14.18.1) and bilirubineoxidases (E.C. 1.3.3.5).
It is particularly preferred to use phenoloxidases, in particular laccases, in the invention. Laccases can be produced by white rot fungi, in particular with Trametes (previously Coriolus) versicolor or hilluta or villosa strains. Other known micro-organisms producing laccase are the different strains of following mold: Agaricus, Armillaria, Aspergillus, Botrytis, Fusarium, Lentinus, Monocillium, Neurospora, Phlebia, Polyporus, Podospora, Pycnoporus and Schizophyllum.
The invention is, however, not limited to the indicated origins of enzymes nor to a specific isolation method, and the enzymes may be obtained by other means. Thus it is possible to produce oxidative enzymes with microorganisms that are mutated and genetically built to produce the desired enzyme, or with other host strains to which the genes that code the enzyme are removed.
The starch to be oxidized may be any natural starch possessing an amylose/amylopectine ratio of 1 :0...0: 1. As examples of such sources of starch may be mentioned tuber-bearing plants and cereal such as potato, wheat, barley, oat, pea, corn, rice, sago and tapioka.
The amount of laccase in the oxidation may be approximately 1...1000 nkat/g of starch. The concentration of starch may vary on a large range, it may be, e.g., 5...35% (v/w). The oxidation is conducted in the liquid phase, since TEMPO is water soluble preferably in water, at a temperature in the range of 10 to 70 °C, preferably 20 to 40 °C and at a pH in the range of 4 to 9. The amount of TEMPO is 0.01 to 50 wt-%, preferably approximately 0.1 to 20 wt-% of the amount of starch.
In practice, the reaction is conducted by dissolving a selected amount of TEMPO (in the form of a stabile nitroxyl radical) in water, to which starch is suspended. The dry-content of the suspension is usually set to approximately 0.1 to 20 wt-%. Buffer may be added to water to set the pH of the reaction medium to a desired, suitable in view of laccase treatment, value (over 4). After the addition of laccase, oxygen is fed to the reaction mixture, either as gas or as air while simultaneously mixing the composition. Depending on the amount of the material to be oxidized, the feeding of oxygen lasts usually approximately 10 min - 24 h. After the reaction the oxidized starch is separated by filtration from the liquid, washed and dried.
As already mentioned, when using peroxidases, TEMPO is oxidized with hydrogen peroxide.
As a result of oxidation according to the invention starch is obtained, a part of the primary OH-groups of which having been converted to carbonyl and carboxyl groups. Typically, according to the present method the ratio of carbonyl groups to carboxyl groups is 1...5. The molar mass of starch possibly decreases as a result of the oxidation, but is usually still over 300.000 g/mol, e.g., at least 400.000 g/mol. Oxidized starch can be used as such as an additive in paper making in the wet end of a paper machine or as a coating material. Due to the carbonyl groups, the starch is made reactive and thus the product may also be further oxidized and the carbonyl groups may be further modified.
The following non-limiting examples illustrate the invention.
Example 1 (Comparative example) Chemical oxidation
The oxidation catalyzed by TEMPO was carried out as follows:
0.3 g TEMPO was dissolved in water, 30 g starch was suspended to the solution and 12 g NaBr was added. The temperature of the reaction mixture was adjusted to 0 °C. Another mixture with 345 ml 8 % hypochlorite was prepared, pH was adjusted with 3 M hydrochloric acid to a value of 10.8 and the temperature of the solution was adjusted to 0 °C. The solution was added in one batch to the solution containing starch and incubated for 2 h. During the incubation the pH of the solution was controlled and, if necessary, adjusted back to a value of 10 - 11 with 0.5 M NaOH. The reaction was stopped by adding 60 ml 96% ethanol and adjusting thereafter the pH of suspension to 7. The starch was separated and washed with 1000 ml water and dried at room temperature.
Example 2
The lacchase-TEMPO-oxidation of starch
Native potato starch was oxidized by using TEMPO as a intermediate medium and laccase enzyme as an oxidizer.
Enzyme: Trametes hirsuta D 443 -fungus laccase, growth medium. The activity was defined by using ABTS-substrate (10).
In 0.1 M NaAc buffer a 5 % suspension with a pH of 5.0 was prepared of 35 g native potato starch. TEMPO (3.5 g) was dissolved in the buffer, starch was added and suspended to the liquid phase, after which laccase was added (dosage 200 nkat g starch). The reaction was oxidized with an oxygen flow for 3 h at room temperature and simultaneous mixing with a magnetic stirrer. The starch was removed by filtration and washed with 1000 ml water. After washing, the starch was dried at room temperature.
Example 3
The properties of oxidized starch
Carboxyl and carbonyl groups were formed in starch both by chemical oxidation and laccase-TEMPO oxidation. The results are presented in the table below:
Starch COOH/ 100 glucose unit CHO/ 100 glucose unit native potato starch 0.47 - 0.52 0 chemical TEMPO oxidation 1.07 - 10.3 2.56 - 11.0 laccase-TEMPO oxidation 1.02 2.99
The molecular weights of oxidized starch (both chemically and laccase-TEMPO oxidized) were slightly smaller than the molecular weight of native potato starch.
The geling properties of oxidized starch were determined with Bohl's VOR rheometer (oscillation method). The samples were cooled from 90 °C to 20 °C at a rate of 1 °C/min. The measurements were made in 15 % starch solutions. Laccase-TEMPO and commercial oxidized starch did not gel in the measuring conditions.
Example 4
Starch was oxidized with different dosages of laccase and TEMPO. The properties of oxidized starch (molecular weight distribution, geling properties, structure) were determined according to example 3. It was discovered that by varying the dosages of TEMPO and laccase the modification degree of the starch may be altered and thus also the gel properties and molecular weight properties change. Literature:
1. Forssell, P., Hamunen, A., Autio, K., Suortti, T. & Poutanen,K. Starch 47, 371-377 (1995).
2. Parovuori,P., Hamunen,A., Forssell, P., Autio,K. & Poutanen , K. Starch 47, 19-23 (1995).
3. Anelli, P.L., Biffi, C, Montanari, F. & Quici,S. J.Org. Chem. 52, 2559 (1987)
4. Anelli, P.L., Banfi, S., Montanari, F. & Quici,S. J.Org. Chem.,54, 2970(1989)
5. Kabalka, G.W., Chatla, N., Wadgaonkar, P.P. & Deshpande, S.M. Synth. Comm., 20.1617 (1990).
6. deNooy, A.E.J., Besemer, A.C. & van Bekkum, H. Recl.Trav.Chim. Pays-Bas 113, 165- 166 (1994).
7. de Nooy, A.E.J., Besemer, A.C. & van Bekkum, H. Carbohydrate Res. 269, 89-98 (1995).
8. Besemer, A.C & de Nooy, A.E.J. PCT WO 95/07303.
9. Chang, P.S. & Robyt, J.F. J. Carboh. Chem., 15, 819-830 (1996).
10. Niku-Paavola, M.-L., E. Karhunen, P. Salola, and V. Raunio. Biochem. J. 254, 877-884 (1988).
11. Smith, R. J. in Starch: Chemistry and Technology, Eds.R.L. Whistler & E.F. Paschall, Vol II, Academic Press, Inc., New York 1967, pp.620-625.
12. Krishna et al., 1992, Proc.Natl.Acad.Sci.USA, Vol 89, pp.5537-5541

Claims

Claims:
1. A method of producing oxidized starch, comprising contacting the starting material containing starch with a reagent producing oxoammonium ion in the presence of an oxidizing agent, characterized in that an oxidative enzyme is used as the oxidizing agent.
2. A method according to claim 1 , characterized in that phenoloxidase is used as the oxidizing enzyme.
3. A method according to claim 1 or 2, characterized in that the reaction is conducted in liquid medium and the reaction product is separated from the medium after the reaction and conducted to further treatment for purification.
4. A method according to any of claims 1-3, characterized in that as the reagent producing oxoammonium ion, 2,2,6,6-tetramethylpiperidin-l-oxyl is used and laccase is used as a regenerating oxidizing agent reacting with it.
5. A method according to any of claims 1-4, characterized in that laccase of Trametes-, Agaricus-, Armillaria-, Aspergillus-, Botrytis-, Fusarium-, Lentinus-, Monocillium-, Neurospora-, Phlebia-, Polyporus-, Podospora-, Pycnoporus- or Schizophyllum- strain is used as peroxidase.
6. A method according to any of claims 1 -3, characterized in that as the reagent producing oxoammonium ion, 2,2,6,6-tetramethylpiperidin-l-oxyl (TEMPO) is used and peroxidase is used as a regenerating oxidizing agent reacting with it.
7. A method according to any of claims 1 -3, characterized in that starch is oxidized to obtain aldehyde or carboxyl groups in particular to the primary OH group.
8. Modification of starch with oxidized TEMPO.
9. Modification according to claim 8, characterized in that TEMPO is oxidized enzymatically.
10. Modification according to claim 8 or 9, characterized in that TEMPO is oxidized with the aid of laccase.
11. Modification according to claim 8 or 9, characterized in that TEMPO is oxidized with the aid of peroxidase.
12. The use of modified starch handled with TEMPO as an additive in paper making, in the wet end of a paper machine or as coating material.
PCT/FI1998/000860 1997-11-04 1998-11-04 Method of producing oxidized starch WO1999023240A1 (en)

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WO2001000681A1 (en) * 1999-06-30 2001-01-04 Sca Hygiene Products Zeist B.V. Process for selective oxidation of primary alcohols
US6228126B1 (en) 1999-08-17 2001-05-08 National Starch And Chemical Investment Holding Corporation Paper prepared from aldehyde modified cellulose pulp and the method of making the pulp
WO2001034657A1 (en) * 1999-11-08 2001-05-17 Sca Hygiene Products Zeist B.V. Process of oxidising primary alcohols
EP1149846A1 (en) * 2000-04-25 2001-10-31 SCA Hygiene Products Zeist B.V. Oxidation of polysaccharides with nitroxyls
US6319361B1 (en) 1996-03-28 2001-11-20 The Procter & Gamble Company Paper products having wet strength from aldehyde-functionalized cellulosic fibers and polymers
US6322632B1 (en) 2000-02-18 2001-11-27 Archer-Daniels-Midland Corporation Method for producing oxidized starch
US6368456B1 (en) 1999-08-17 2002-04-09 National Starch And Chemical Investment Holding Corporation Method of making paper from aldehyde modified cellulose pulp with selected additives
US6409881B1 (en) 1999-11-08 2002-06-25 Sca Hygiene Products Gmbh Metal-crosslinkable oxidized cellulose-containing fibrous materials and products made therefrom
US6540876B1 (en) 2000-05-19 2003-04-01 National Starch And Chemical Ivnestment Holding Corporation Use of amide or imide co-catalysts for nitroxide mediated oxidation
WO2003040190A1 (en) * 2001-11-07 2003-05-15 Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek, Tno Process for oxidising dialdehyde polysaccharides
US6582559B2 (en) 2000-05-04 2003-06-24 Sca Hygiene Products Zeist B.V. Aldehyde-containing polymers as wet strength additives
US6586588B1 (en) 1999-08-17 2003-07-01 National Starch And Chemical Investment Holding Corporation Polysaccharide aldehydes prepared by oxidation method and used as strength additives in papermaking
US6635755B1 (en) 1999-11-08 2003-10-21 Sca Hygiene Products Gmbh Oxidized polymeric carbohydrates and products made thereof
US6695950B1 (en) 1999-08-17 2004-02-24 National Starch And Chemical Investment Holding Corporation Aldehyde modified cellulose pulp for the preparation of high strength paper products
JP2004512805A (en) * 1999-02-24 2004-04-30 ネーデルランドセ・オルガニザテイエ・フール・テゲパスト−ナトウールベテンシヤツペリーク・オンデルツエク・テイエヌオー Method for selective oxidation of primary alcohol and novel carbohydrate aldehyde
US6824645B2 (en) 1999-02-24 2004-11-30 Sca Hygiene Products Gmbh Oxidized cellulose-containing fibrous materials and products made therefrom
WO2005059152A1 (en) * 2003-12-18 2005-06-30 Cerestar Holding B.V. Oxidation of carbohydrates by means of peroxidases and nitroxy radicals
GB2417029A (en) * 2004-08-11 2006-02-15 Sca Hygiene Prod Ab Oxidation of hydroxyl groups using nitrosonium ions
KR100637451B1 (en) 2005-02-28 2006-10-23 한양대학교 산학협력단 Preparing method of Oxidized Oat ?-Glucan
US7138035B2 (en) 2001-05-08 2006-11-21 National Starch And Chemical Investment Holding Corporation Process for the selective modification of carbohydrates by peroxidase catalyzed oxidation
US7247722B2 (en) 1999-08-17 2007-07-24 National Starch And Chemical Investment Holding Corporation Polysaccharide aldehydes prepared by oxidation method and used as strength additives in papermaking
US7259218B2 (en) 2005-02-17 2007-08-21 The Procter + Gamble Company Processes for making temporary wet strength additives
US7691233B2 (en) 2003-10-16 2010-04-06 The Procter & Gamble Company Temporary wet strength additives
US7879994B2 (en) 2003-11-28 2011-02-01 Eastman Chemical Company Cellulose interpolymers and method of oxidation
US8802398B2 (en) 2008-04-30 2014-08-12 Dupont Nutrition Biosciences Aps Oxidation process
US9376648B2 (en) 2008-04-07 2016-06-28 The Procter & Gamble Company Foam manipulation compositions containing fine particles
CN110846231A (en) * 2019-12-03 2020-02-28 安徽农业大学 High-yield laccase fungus mucormycoma hirsutum La-7 and application thereof
CN114191601A (en) * 2021-11-25 2022-03-18 华南理工大学 Starch gel hemostatic material based on 3D printing technology and preparation method and application thereof

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Cited By (45)

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US6319361B1 (en) 1996-03-28 2001-11-20 The Procter & Gamble Company Paper products having wet strength from aldehyde-functionalized cellulosic fibers and polymers
US6824645B2 (en) 1999-02-24 2004-11-30 Sca Hygiene Products Gmbh Oxidized cellulose-containing fibrous materials and products made therefrom
JP2004512805A (en) * 1999-02-24 2004-04-30 ネーデルランドセ・オルガニザテイエ・フール・テゲパスト−ナトウールベテンシヤツペリーク・オンデルツエク・テイエヌオー Method for selective oxidation of primary alcohol and novel carbohydrate aldehyde
WO2001000681A1 (en) * 1999-06-30 2001-01-04 Sca Hygiene Products Zeist B.V. Process for selective oxidation of primary alcohols
US6695950B1 (en) 1999-08-17 2004-02-24 National Starch And Chemical Investment Holding Corporation Aldehyde modified cellulose pulp for the preparation of high strength paper products
US6586588B1 (en) 1999-08-17 2003-07-01 National Starch And Chemical Investment Holding Corporation Polysaccharide aldehydes prepared by oxidation method and used as strength additives in papermaking
US6368456B1 (en) 1999-08-17 2002-04-09 National Starch And Chemical Investment Holding Corporation Method of making paper from aldehyde modified cellulose pulp with selected additives
US6228126B1 (en) 1999-08-17 2001-05-08 National Starch And Chemical Investment Holding Corporation Paper prepared from aldehyde modified cellulose pulp and the method of making the pulp
US7247722B2 (en) 1999-08-17 2007-07-24 National Starch And Chemical Investment Holding Corporation Polysaccharide aldehydes prepared by oxidation method and used as strength additives in papermaking
US6562195B2 (en) 1999-08-17 2003-05-13 National Starch And Chemical Investment Holding Corporation Paper prepared from aldehyde modified cellulose pulp
US6635755B1 (en) 1999-11-08 2003-10-21 Sca Hygiene Products Gmbh Oxidized polymeric carbohydrates and products made thereof
US6987181B2 (en) 1999-11-08 2006-01-17 Sca Hygiene Products Gmbh Oxidized polymeric carbohydrates and products made thereof
WO2001034657A1 (en) * 1999-11-08 2001-05-17 Sca Hygiene Products Zeist B.V. Process of oxidising primary alcohols
US6770755B1 (en) 1999-11-08 2004-08-03 Sca Hygiene Products Zeist B.V. Process of oxidizing primary alcohols
US6409881B1 (en) 1999-11-08 2002-06-25 Sca Hygiene Products Gmbh Metal-crosslinkable oxidized cellulose-containing fibrous materials and products made therefrom
US6322632B1 (en) 2000-02-18 2001-11-27 Archer-Daniels-Midland Corporation Method for producing oxidized starch
EP1149846A1 (en) * 2000-04-25 2001-10-31 SCA Hygiene Products Zeist B.V. Oxidation of polysaccharides with nitroxyls
US6608229B2 (en) 2000-04-25 2003-08-19 Sca Hygiene Products Zeist B.V. Oxidation of polysaccharides with nitroxyls
US6582559B2 (en) 2000-05-04 2003-06-24 Sca Hygiene Products Zeist B.V. Aldehyde-containing polymers as wet strength additives
US6896725B2 (en) 2000-05-04 2005-05-24 Sca Hygiene Products Zeist B.V. Aldehyde-containing polymers as wet strength additives
US6540876B1 (en) 2000-05-19 2003-04-01 National Starch And Chemical Ivnestment Holding Corporation Use of amide or imide co-catalysts for nitroxide mediated oxidation
US7138035B2 (en) 2001-05-08 2006-11-21 National Starch And Chemical Investment Holding Corporation Process for the selective modification of carbohydrates by peroxidase catalyzed oxidation
WO2003040190A1 (en) * 2001-11-07 2003-05-15 Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek, Tno Process for oxidising dialdehyde polysaccharides
US7691233B2 (en) 2003-10-16 2010-04-06 The Procter & Gamble Company Temporary wet strength additives
US9243072B2 (en) 2003-11-28 2016-01-26 Eastman Chemical Company Cellulose interpolymers and method of oxidation
US9150665B2 (en) 2003-11-28 2015-10-06 Eastman Chemical Company Cellulose interpolymers and method of oxidation
US8816066B2 (en) 2003-11-28 2014-08-26 Eastman Chemical Company Cellulose interpolymers and methods of oxidation
US9040685B2 (en) 2003-11-28 2015-05-26 Eastman Chemical Company Cellulose interpolymers and method of oxidation
US9040683B2 (en) 2003-11-28 2015-05-26 Eastman Chemical Company Cellulose interpolymers and method of oxidation
US9040684B2 (en) 2003-11-28 2015-05-26 Eastman Chemical Company Cellulose interpolymers and method of oxidation
US7879994B2 (en) 2003-11-28 2011-02-01 Eastman Chemical Company Cellulose interpolymers and method of oxidation
WO2005059152A1 (en) * 2003-12-18 2005-06-30 Cerestar Holding B.V. Oxidation of carbohydrates by means of peroxidases and nitroxy radicals
US7517675B2 (en) 2003-12-18 2009-04-14 Cerestar Holding B.V. Oxidation of carbohydrates by means of peroxidases and nitroxy radicals
GB2417029A (en) * 2004-08-11 2006-02-15 Sca Hygiene Prod Ab Oxidation of hydroxyl groups using nitrosonium ions
WO2006015847A1 (en) * 2004-08-11 2006-02-16 Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno Process for the enzymatic oxidation of a substrate comprising a primary hydroxyl group
US7625989B2 (en) 2005-02-17 2009-12-01 The Procter & Gamble Company Processes for making temporary wet strength additives
US7598331B2 (en) 2005-02-17 2009-10-06 The Procter & Gamble Company Processes for making temporary wet strength additives
US7259218B2 (en) 2005-02-17 2007-08-21 The Procter + Gamble Company Processes for making temporary wet strength additives
KR100637451B1 (en) 2005-02-28 2006-10-23 한양대학교 산학협력단 Preparing method of Oxidized Oat ?-Glucan
US9376648B2 (en) 2008-04-07 2016-06-28 The Procter & Gamble Company Foam manipulation compositions containing fine particles
US8802398B2 (en) 2008-04-30 2014-08-12 Dupont Nutrition Biosciences Aps Oxidation process
CN110846231A (en) * 2019-12-03 2020-02-28 安徽农业大学 High-yield laccase fungus mucormycoma hirsutum La-7 and application thereof
CN110846231B (en) * 2019-12-03 2020-11-27 安徽农业大学 Laccase-producing fungus mucormycoma hirsutum La-7 and application thereof
CN114191601A (en) * 2021-11-25 2022-03-18 华南理工大学 Starch gel hemostatic material based on 3D printing technology and preparation method and application thereof
CN114191601B (en) * 2021-11-25 2022-05-24 华南理工大学 Starch gel hemostatic material based on 3D printing technology and preparation method and application thereof

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