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Novel catalytic activities of oxidoreductases for oxidation and or bleaching

USPTO Application #: 20060054290
Title: Novel catalytic activities of oxidoreductases for oxidation and or bleaching
Abstract: A new enzyme-based process for oxidation and/or bleaching is described, comprising of oxidoreductases such as laccases and/or peroxidases—seperately or in combination—in the presence of their respective co-substrates like O2, air, H2O2, organic peroxides, peracids etc. and comprising of enhancer compounds from the class of oxocarbons, from the class of urazoles and hydrazides, from the class of hydantoins and the class of nitril (Cyan)-compounds, and comprising additionally of carbonyl compounds such as ketones, aldehyds, whereby the combination of enzyme, co-substrate, enhancer compound and carbonyl compound generate active oxygen species like dioxiranes, dioxetanes, peroxy-compounds etc. or form other reactive compounds or transition states like radicals (kation radicals, anion radicals) or reactive (red/ox-active) neutral compounds as oxidizing and/or bleaching agents. (end of abstract)



Agent: Dr Hans-peter Call - Ubach-palenberg, DE
Inventor: Hans-Peter Call
USPTO Applicaton #: 20060054290 - Class: 162001000 (USPTO)

Related Patent Categories: Paper Making And Fiber Liberation, Processes Of Chemical Liberation, Recovery Or Purification Of Natural Cellulose Or Fibrous Material

Novel catalytic activities of oxidoreductases for oxidation and or bleaching description/claims


The Patent Description & Claims data below is from USPTO Patent Application 20060054290, Novel catalytic activities of oxidoreductases for oxidation and or bleaching.

Brief Patent Description - Full Patent Description - Patent Application Claims
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[0001] It is wellknown, that enzymes like e.g. peroxidases, especially horseradish peroxidase (HRP), lignin peroxidases and manganese peroxidases and also special oxidases such as laccases, which all belong to the lignolytic enzymes, can oxidize a huge variety of different substrates either in the presence of H.sub.2O.sub.2, organic peroxides or peracids (peroxidases) or in the presence of air or O.sub.2 (oxidases/laccases).

[0002] During the last years several applications of the mentioned enzymes were published or patented like e.g. their use as mild oxidants in the chemical synthesis or in food field, as decolorizing oxidants of dyes e.g. in waste waters, as labeling-enzymes for special analysis approaches and in biosensors etc.

[0003] Furthermore some applications were published and patented referring to enzymes which work together with special mediator compounds (WO96/18770/, WO 94/29510, WO 94/12619, WO 94/12620 und WO 94/12621).

[0004] In these cases the preferred enzyme is mostly laccase, an enzyme which is today commercial available.

[0005] On the one hand these mediator compounds make possible an oxidation of substrates with higher oxidation potential, they normally cannot be oxidized by laccases alone; and on the other hand they cause that the so-called laccase mediator system--due to the fact that the mediator compounds are free-diffusible and low-molecular--can also degradate substrates in not freely accessable substances such as e.g. lignin in pulp fibres. Free enzymes wouldn't cause any significant substrate degradation due to their--besides the low oxidation power--too large molecule size.

[0006] Besides these laccase-based enzymatic approaches only the manganes peroxidase systems (MnP-systems) which can be found in withe-rotting fungi and work with the aid of chelated Mn.sup.2+ as natural mediator can be applied as an in-vivo-system for lignin degradation in pulps. The main drawbacks regarding the performance of these systems are on the one hand their strong sensitivity against H.sub.2O.sub.2 as co-oxidant and on the other hand the difficulties in production of the enzymes. These difficulties have made a use in a larger scale and therefore a commercialization impossible.

[0007] Due to the too large molecular weight which makes a penetration into the fibres impossible (see above) und due to the fact that there are so far no specific mediator compounds have Due to the too large molecular weight which makes a penetration into the fibres impossible (see above) und due to the fact that there are so far no specific mediator compounds have been found, the use of lignin peroxidase causes no delignification but a lignin polymerisation.

[0008] Despite the good performance of laccase- mediator-systems (LMS) and the very good selectivity i.e. good pulp properties which can be obtained, a) the high price mainly of the mediator compounds b) their necessary relatively high dosages (the reactions are stochiometric and not catalytic) and c) the oftenly existing environmental risks due to the possible toxicity of the mediator compounds prevent the broad implementation of these systems.

[0009] On the other side there is a great demand for alternative bleaching systems mainly due to the necessity for closed mill loops which can only difficult be obtained (because of e.g. of the corrosion problems) with the aid of ECF-bleaching (elemental chlorine free bleaching) with chlorine dioxide as main bleaching agent.

[0010] Therefore it is the target of the present invention to provide an oxidation-/bleaching system which hasn't the disadvantages of the mentioned state-of-the-art systems.

[0011] This can be solved by providing a new process for oxidation and/or bleaching comprising of

ACCORDING TO THE INVENTION

[0012] oxidoreductases such as laccases and/or peroxidases--seperately or in combination--in the presence of their respective co-substrates like O.sub.2, air, H.sub.2O.sub.2, organic peroxides, peracids etc. and comprising of

[0013] enhancer compounds from the class of oxocarbons, from the class of urazoles and hydrazides, from the class of hydantoins and the class of nitril (Cyan)-compounds, and comprising additionally of

[0014] carbonyl compounds such as ketones, aldehyds,

[0015] whereby the combination of enzyme, co-substrate, enhancer compound and carbonyl compound generate active oxygen species like dioxiranes, dioxetanes, peroxy-compounds etc. or form (according e.g. to the literature: K. Deuchert et. al., Angewandte Chemie 90, S. 927-938, 1978) also other reactive compounds or transition states like radicals (kation radicals, anion radicals) or reactive (red/ox-active) neutreal compounds as oxidizing and/or bleaching agents.

[0016] As oxocarbon compounds such compounds are preferably used as cited in the literature: Chemie in unserer Zeit, 16. Jahrgang 1982, Nr. 2, S. 57-67 inclusivly of the therein quoted literature preferably: R.West et al., Oxocarbons and their Reactions, in J. Zabicky ed., "The chemistry of the Carbonyl Group", Wyley (Interscience), 1970; R.West, Oxocarbons,

[0017] Academic

[0018] Press, 1980 und Rompp Chemie Lexikon, Thieme Verlag, 1995, S. 3175-3177.

[0019] Particularly preferred are carbonyl compounds of the general formula I, such as .alpha.-hydroxycarbonyl compounds of general formula Ia, .alpha.-dicarbonyl compounds of general formula lb, .beta.-hydroxycarbonyl compounds of general formula Ic and .beta.-dicarbonyl compounds of general formula Id: wherein R.sup.1 to R.sup.8 independently of one another are selected from the group consisting of hydrogen, a halogen, an alkyl group, an alkyloxy group, an aryl group, an aryloxy group, a hydroxy group, an oxo group, a formyl group, a thioxo group, a mercapto group, an alkylthio group, a sulfeno group, a sulfino group, a sulfo group, a sulfamoyl group, an amino group, an imino group, an amido group, an amidino group, a hydroxycarbamoyl group, a hydroximino group, a nitroso group, a nitro group and a hydrazono group, with R.sup.1 and R.sup.2; R.sup.3 and R.sup.4; R.sup.5 and R.sup.6; and R.sup.7 and R.sup.8 possibly being linked together to form a single group, and wherein n is greater than or equal to 1;

[0020] particularly preferred are such compounds of general formula II (linear compounds with double bonds/enols): wherein R.sup.9 and R.sup.10, independently of one another, are selected from the group consisting of hydrogen, a halogen, an alkyl group, an alkyloxy group, an aryl group, an aryloxy group, a hydroxy group, an oxo group, a formyl group, a thioxo group, a mercapto group, an alkylthio group, a sulfeno group, a sulfino group, a sulfo group, a sulfamoyl group, an amino group, an imino group, an amido group, an amidino group, a hydroxycarbamoyl group, a hydroximino group, a nitroso group, a nitro group and a hydrazono group, and R.sup.9 and R.sup.10 are possibly linked together to form a single group;

[0021] Furthermore preferred are such compounds of general structure III (cyclic compounds, groups not OH, derivatives of squaric acid, OH group derivatized): wherein R.sup.11 and R.sup.12, independently of one another are selected from the group consisting of hydrogen, a halogen, an alkyl group, an alkyloxy group, an aryl group, an aryloxy group, a hydroxy group, an oxo group, a formyl group, a thioxo group, a mercapto group, an alkylthio group, a sulfeno group, a sulfino group, a sulfo group, a sulfamoyl group, an amino group, an imino group, an amido group, an amidino group, a hydroxycarbamoyl group, a hydroximino group, a nitroso group, a nitro group and a hydrazono group, and m is greater than or equal to 0. Particularly preferred are cyclic oxocarbon compounds of the general formula IV (general sum formula: C.sub.xO.sub.x wherin x=>3.

[0022] Struktur element:

[0023] p.gtoreq.0.

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