• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    A process for the enzymatic production of D-fructose from D-glucose in a one-pot reaction, wherein D-glucose is enzymatically oxidized to D-glucosone and D-glucosone is enzymatically reduced to D-fructose and the use of the D-fructose so produced of furan derivatives.
    公开号:AT513928A1
    申请号:T50091/2013
    申请日:2013-02-06
    公开日:2014-08-15
    发明作者:Ortwin Mag Ertl；Marta Dr Sut；Martina Dr Brandner
    申请人:Annikki Gmbh；
    IPC主号:
    专利说明:

    1 A17301
    Process for the preparation of fructose
    The present invention relates to a process for producing D-fructose from D-glucose. For the industrial production of D-fructose, a two-step process has conventionally been used, in which D-glucose is obtained by hydrolysis of polysaccharides, e.g. Starch, prepared and then the isomerization of the D-glucose thus obtained is carried out to D-fructose. By isomerization of D-glucose, 42% D-fructose, 50% D-glucose and about 8% residual polysaccharides can be obtained. A problem with this is that isolation of pure D-fructose from this mixture requires the use of costly and expensive purification techniques.
    An alternative to the production of D-fructose by isomerization of D-glucose is a method in which D-glucose is converted to D-fructose in one enzymatic and one chemical step.
    Overall, a large number of different methods for the production of D-fructose from D-glucose are known.
    For example, e.g. a reduction of D-glucosone to D-fructose, which in most cases has been carried out chemically, as described for example in EP 1048672. In this process, the D-fructose is prepared by catalytic hydrogenation of a high dry matter glucosone solution using particular pressure and temperature conditions.
    US4321324 describes the production of D-glucosone from D-glucose in an enzymatic step in which D-glucose is oxidized by a pyranose-2-oxidase to D-glucosone and the resulting hydrogen peroxide is separated by a semipermeable membrane. 2/16 2
    The reduction of D-glucosone to D-fructose enzymatically by reductase has been described e.g. in the book "Microbial Transformation of non-steroid cyclic compounds" by Kieslich, Georg Thieme Publishers, Stuttgart 1976 and proposed in Biochem J. 1997 Sep 15; 326 683-92 it has been described that a xylose reductase from Candida tenuis can reduce D-glucosone to D-fructose.
    The production of D-fructose by isomerization of D-glucose in two steps (enzymatic and chemical) was e.g. in US4246347. According to the method described therein, D-glucose was first enzymatically converted to D-glucosone using a pyranose-2-oxidase. The resulting hydrogen peroxide was separated and reused, or degraded by a catalase. In a second step, resulting D-glucosone was converted by hydrogenation to D-fructose. 2% glucose was used in this process and the two steps were carried out separately. The problems with the processes are the high pressure and the high temperatures as well as low concentrations of used substrates.
    Known processes for the preparation / isomerization of D-fructose from D-glucose usually have various disadvantages. Thus, for example, an efficient conversion of the substrate with high selectivity is usually only possible with the use of high pressures and temperatures and the formation of contaminating by-products which are difficult to separate off is not easy to avoid.
    It has now surprisingly found a method which allows efficient conversion of the substrate with high selectivity and without the use of high pressures and temperatures, wherein the formation of contaminating by-products can be largely avoided, so that the separation of the substrate from the product is not necessary and The use of complex and expensive cleaning techniques can be dispensed with.
    In one aspect, the present invention provides a process for producing D-fructose from D-glucose which is characterized by oxidizing D-glucose enzymatically to D-glucosone in a one-pot reaction and b) D-glucosone is enzymatically reduced to D-fructose.
    A method provided by the present invention is also referred to herein as a method according to the present invention.
    The present invention thus relates to a process for the preparation of D-fructose from D-glucose in a one-pot reaction in two enzymatic steps:
    An enzymatic oxidation of D-glucose to D-glucosone, followed by an enzymatic reduction of D-glucosone to D-fructose, which proceeds according to the following Reaction Scheme 1:
    Reaction Scheme 1
    H. H. .0
    H HO H H
    --OH --H - OH - OH CH 2 OH
    HO H H
    1 = 0 -H-OH -OH
    HO H H
    CH2OH
    CH 2 OH = 0 - H - OH - OH CH 2 OH D-glucose D-glucosone D-fructose
    A method of the present invention provides a novel enzymatic ability to produce D-fructose without the need for separation and purification of residual D-glucose. Compared to currently used techniques, the present invention represents a significant improvement of the process for the production of D-fructose from D-glucose. In contrast to existing processes, compounds are both enzymatically oxidized and enzymatically reduced without having to isolate an intermediate product. At the same time significantly higher substrate concentrations can be used and also a higher conversion can be achieved than was possible in previously used method. 4/16 4
    Suitable sources of D-glucose in a process of the present invention are, for example, enzymatic or non-enzymatic hydrolysates of starch, in particular corn starch, enzymatic or non-enzymatic hydrolysates of sucrose or enzymatic or non-enzymatic hydrolysates of cellulose. Cellulose that can be used in a process of the present invention can be obtained, for example, from biomass, preferably from lignocellulosic biomass, such as wood, straw, such as wheat straw, corn straw, bagasse, sisal, energy grasses. For enzymatic hydrolysis of corn starch, for. B. amylases are used. For the enzymatic cleavage of sucrose z. B. invertases. For the enzymatic cleavage of cellulose z. As cellulases are used. For example, an acid-catalyzed cleavage is suitable for the nonenzymatic cleavage of said multiple sugars.
    A process of the present invention is preferably carried out in an aqueous system. It is also possible to add a buffer (system) to the aqueous system. Suitable buffers (systems) are known and include conventional buffers (systems), for example, acetate, potassium phosphate, Tris-HCl and glycine buffers. Preferably, a buffer used in a process of the present invention has a pH of from 5 to 10.5, preferably from 6 to 9.5. To stabilize the enzymes, stabilizers, e.g. conventional stabilizers, such as ions, e.g. Mg 2+, or other additives, e.g. conventional additives, such as glycerol, are added.
    In a process of the present invention, oxygen is required for the oxidation of D-glucose to D-glucosone. This oxygen can be introduced as usual and e.g. be provided by contact with ambient air or by increased oxygen supply, for example by compressed air or the introduction of pure oxygen.
    A process according to the invention is carried out at suitable temperatures, e.g. may depend on the enzymes used. Suitable temperatures include 10 ° C to 70 ° C, preferably 20 ° C to 50 ° C, e.g. 20 ° C to 45 ° C a 5/16 5
    As a "one-pot reaction" herein is meant a process in which oxidation reaction and reduction reaction are carried out in the same reaction mixture without isolation of intermediates, in particular in the two involved in product formation enzymatic redox reactions and an enzymatic system for cofactor regeneration in a reaction mixture be carried out without isolating an intermediate. In this case, either all the enzymes involved can be added simultaneously or only a portion of the enzymes is added, e.g. the enzyme (s) for step a) and, with a time lag, another part of the enzymes, e.g. the enzyme (s) for step b). Prior to the addition of the second part of the enzymes, the enzymes already present in the reaction mixture may be inactivated, e.g. with a common method, e.g. Increase the temperature, for example to 65 ° C for 10 min.
    In a particular aspect, a process according to the present invention is characterized in that the process is carried out without isolation of intermediates.
    The oxidation of D-glucose to D-glucosone in a process according to the invention is enzymatic, namely by enzymatic catalysis, and can be carried out according to a known method. The oxidation is preferably carried out by catalysis with an oxidase, in particular with a pyranose-2-oxidase.
    Suitable oxidases are known and include common oxidases such as pyranose-2-oxidases. Pyranose-2-oxidases are e.g. available from Coriolus sp., Aspergillus sp. or Polyporus obtusus.
    A particular embodiment of the process according to the present invention is characterized in that the oxidation of D-glucose to D-glucosone is catalyzed by a pyranose-2-oxidase.
    The reaction of pyranose-2-oxidase produces H2O2, which is removed from the reaction mixture. The removal of H2O2 can be carried out by conventional methods and is preferably carried out enzymatically, e.g. with the help of a catalase. For example, a catalase is added to the reaction mixture. 6/16 6
    A particular embodiment of the method according to the present invention is characterized in that the resulting H2O2 is removed with the aid of a catalase.
    Suitable catalases are known and are available, for example, from Aspergillus sp., Corynebacterium glutümicum or from bovine liver.
    The enzymatic reduction of D-glucosone to D-fructose in a method according to the invention may be carried out by a suitable method, e.g. by a conventional method, or as described herein. As the enzyme for reduction, suitable, e.g. conventional enzymes which are suitable for the reduction of substrates are used. Suitable enzymes include, for example, reductases, especially xylose reductases.
    Suitable xylose reductases are known and are available, for example, from Candida tropicalis, Candida parapsilosis or Debariomyces hansenii.
    A particular embodiment of the method according to the present invention is characterized in that a xylose reductase is used for the reduction of D-glucosone to D-fructose.
    In a process according to the present invention, preference is given to using a redox cofactor, in particular NAD (P) H / NAD (P) +; in particular, NAD (P) H is used as redox cofactor in the reduction of D-glucosone to D-fructose , NAD + denotes the oxidized form and NADH denotes the reduced form of nicotinamide adenine dinucleotide, while NADP + denotes the oxidized form and NADPH denotes the reduced form of nicotinamide adenine dinucleotide phosphate. By using a cell lysate of the microorganism expressing the enzymes involved, e.g. E. coli, e.g. E. coli BL21 (DE 3), which contains the required NAD (P), may be u.U. If the redox cofactors NAD (P) + and / or NAD (P) H are added in the reaction of D-glucose to D-fructose, the added concentration in a process of the present invention is usually 0.001 mM to 10 mM, preferably from 0.01 mM to 1 mM. 7/16 7
    A particular embodiment of the process according to the present invention is characterized in that, in particular in the reduction of D-glucosone, redox cofactors, in particular NAD (P) H, are used, in particular that the enzyme used in step b) is used, NADP (H) is dependent.
    Redox cofactors can be regenerated, namely recycled, by a suitable cofactor regeneration system, with the cofactors being converted back to their original form.
    A particular embodiment of the process according to the present invention is characterized in that used redox cofactors are subjected to recycling, in particular by a suitable cofactor regeneration system.
    The regeneration of redox cofactors generally requires the presence of a suitable co-substrate that is consumed during the regeneration of the redox cofactors. Co-substrates which can be used, for example, using the co-factors NAD (P) H / NAD (P) + include, e.g. Alcohols such as isopropyl alcohol (2-propanol, IPA), lactic acid and its salts, pyruvic acid and its salts, oxygen, hydrogen and / or formic acid and salts thereof.
    In a particular aspect, a method of the present invention is characterized in that the redox cofactor in the use of the co-factors NAD (P) H / NAD (P) +, in particular in the reduction of D-glucosone, using a Co -Substrates, in particular selected from an alcohol, lactic acid and its salts, pyruvic acid and its salts, oxygen, hydrogen and / or formic acid and its salts, is regenerated.
    A particular embodiment of a process according to the present invention is characterized in that co-substrates are used in the regeneration of the redox cofactors, in particular in the reduction of D-glucosone to D-fructose. 8/16 8
    In the regeneration of redox co-factors, a redox enzyme is used. Redox enzymes that may be considered as redox cofactors using NAD (P) H / NAD (P) + include, for example, dehydrogenases, e.g. Alcohol dehydrogenases, lactate dehydrogenases, formate dehydrogenases, preferably alcohol dehydrogenases. Suitable alcohol dehydrogenases are known and include e.g. an alcohol dehydrogenase obtainable from Lactobacillus kefir.
    In a further particular embodiment of the process according to the present invention, the redox cofactor is regenerated by a redox enzyme, in particular by an alcohol dehydrogenase.
    Enzymes can be used in a method according to the present invention as such, optionally in the form of cell lysates, optionally as recombinantly overexpressed proteins, for example as E. coli recombinantly overexpressed proteins, wherein preferably the corresponding cell lysates are used without further purification can. Depending on the enzyme to be produced, other microorganisms may also be used for expression, e.g. Microorganisms known to those skilled in the art. Solid components of the respective microorganisms can either be separated in a process of the present invention or used in the reaction (e.g., whole cell biocatalysts). It is also possible to use culture supernatants or lysates of microorganisms which already have sufficient enzyme activity without recombinant DNA technology. The enzyme unit 1 U corresponds to that amount of enzyme that is required to implement 1 micromolar substrate per minute.
    In one method of the present invention, both one or more enzymes, as well as one or more redox cofactor (s) can be used in the conversion of D-glucose to D-fructose, either in soluble form or immobilized on carriers (solids).
    In a further aspect, a process according to the present invention is characterized in that it is according to the following reaction scheme 2 9/16 9 D-glucose
    O o2 + H- HO- H- H-
    -OH
    -H -OH
    Pyranose 2-oxidase
    -OH
    'OH h2o2 catalase c D-glucosone D-fructose OH H20 + 1/2 02
    Acetone isopropanol in the LkADH an alcohol dehydrogenase, in particular an alcohol dehydrogenase from Lactobacillus kefir. which is NADP (H) dependent means expires. D-fructose obtained according to the present invention may be prepared from the reaction mixture, e.g. be isolated by a conventional method, for example by crystallization. D-fructose is an important feedstock for further processing in the chemical industry. For example, D-fructose may be known to be in furan derivatives such as e.g. Flydroxymethylfurfural (HMF) of the formula
    Hydroxymethylfurfural (HMF) are further processed.
    Hydroxymethylfurfural is known to be a starting material for the preparation of 2,5-furandicarboxylic acid (FDCA) of formula 10/16 10
    10 ο HO
    OH ο 2,5-furandicarboxylic acid (FDCA) which is known to be suitable as a monomer for the preparation of polymers such as polyethylene furanoate (PEF). PEF can be used in a similar manner as polyethylene terephthalate (PET), for example for the production of hollow bodies, in particular bottles, e.g. Beverage bottles, bottles for cosmetics or bottles for detergents. With simultaneous use of ethylene glycol from regenerative sources and FDCA, which is accessible from IIMF. made in a process according to the present invention, PEF can be obtained which consists entirely of renewable raw materials.
    In a particular embodiment of the process of the present invention, the fructose produced is further transformed into furan derivatives, e.g. Hydroxymethylfurfural (HMF) of the formula
    O HO
    implemented.
    In the following examples, all temperatures in degrees are Celsius (° C). The enzyme unit "1 U" corresponds to the amount of enzyme required to convert 1 pmol of substrate per min. The following abbreviations are used: h min
    Hour (s) Minute (s) 11/16 11
    example 1
    Bioconversion of D-glucose to D-glucosone by pyranose oxidase using catalase to remove the resulting H2O2
    A 0.5 ml batch contains 2.5% (w / v) D-glucose and 1 U pyranose-2-oxidase (Sigma Aldrich). To convert the H2O2 formed in this reaction, 50 U catalase (Sigma Aldrich) is used, which converts the resulting II2O2 to H2O + V2 O2. The reaction is carried out in Tris-HCl buffer (50 mM, pH 7.0) at 30 ° C with continuous shaking (850 rpm). An open system is used to provide adequate oxygen delivery. After 48 h, 99% of D-glucose had been converted to D-glucosone.
    Example 2
    Bioconversion of D-glucosone to D-fructose by xylose reductase using an alcohol dehydrogenase-dependent cofactor regeneration system
    A 0.5 ml batch contains 2.5% (w / v) D-glucosone and 10 U of recombinant xylose reductase from Candida tropicalis (overexpressed in E. coli BL21 (DE3)). For the regeneration of NADPH, 10 U of the recombinant alcohol dehydrogenase from Lactobacillus kefir (overexpressed in E. coli BL21 (DE3)) and initially 5% (w / v) 2-propanol are used. The reaction is carried out without addition of NADPH. The cofactor is available from the cell extract of E. coli BL21 (DE3) used to express xylose reductase and alcohol dehydrogenase. The reaction is carried out in Tris-HCl buffer (50 mM, pH 7.0) at 30 ° C with continuous shaking (850 rpm). An open system is used to allow the evaporation of acetone and to shift the reaction towards D-fructose. 2.5% (w / v) IPA after 6 h, 5% IPA (w / v) after 18 h and 2.5% (w / v) IPA are dosed in after 24 h. After 48 h, ~ 90% of D-glucosone had been converted to D-fructose.
    Example 3
    Bioconversion of D-glucose to D-glucosone and on to D-fructose in a one-pot reaction (two consecutive steps without isolation of 12/16 12
    Intermediate) using an alcohol dehydrogenase-dependent Kofakor regeneration system
    A 0.5 ml batch contains 2.5% (w / v) D-glucose and 1 U pyranose-2-oxidase (Sigma Aldrich). To convert the H2O2 formed in this reaction, 50 U catalase is used, which converts the resulting H2O2 to H2O + ¥ 2 O2. The reaction is carried out in Tris-HCl buffer (50 mM, pH 7.0) at 30 ° C with continuous shaking (850 rpm). Furthermore, an open system is used to achieve adequate oxygen delivery. After 24 hours, the reaction mixture is heated to 65 ° C for 10 minutes to deactivate the enzymes. Subsequently, 10 U of the recombinant xylose reductase from Candida tropicalis (overexpressed in E. coli BL21 (DE3)) are added to the reaction mixture. For the regeneration of NADPH, 10 U of the recombinant alcohol dehydrogenase from Lactobacillus kefir (overexpressed in E. coli BL21 (DE3)) and initially 5% (w / v) 2-propanol are used. The reaction is carried out without addition of NADPH. The cofactor is available from the cell extract of E. coli BL21 (DE3) used to express recombinant xylose reductase and recombinant alcohol dehydrogenase. The reaction is carried out at 30 ° C with continuous shaking (850 rpm). An open system is used to allow the evaporation of acetone and to shift the reaction towards D-fructose. 2.5% (w / v) IPA after 6 h, 5% (w / v) IPA after 18 h and 2.5% (w / v) IPA are dosed in after 24 h. After 48 h, 91% of the D-glucose used had been converted to D-fructose. 13/16
    权利要求:
    Claims (11)
    [1]
    1. A process for the preparation of D-fructose from D-glucose, characterized in that in a one-pot reaction a) D-glucose enzymatically oxidized to D-glucosone, and b) D-glucosone enzymatically reduced to D-fructose becomes.
    [2]
    2. The method according to claim 1, characterized in that the method is carried out without isolation of intermediates.
    [3]
    3. The method according to any one of claims 1 or 2, characterized in that the oxidation of D-glucose to D-glucosone is catalyzed by a pyranose-2-oxidase.
    [4]
    4. The method according to claim 3, characterized in that the resulting 1¾¾ is removed by means of a catalase.
    [5]
    5. The method according to any one of claims 1 to 4, characterized in that for the reduction of D-glucosone to D-fructose a xylose ReduktaSe is used.
    [6]
    6. The method according to any one of claims 1 to 5, characterized in that, in particular in the reduction of D-glucosone to D-fructose, redox cofactors, in particular NAD (P) H, are used, in particular, that the enzyme in the Step b) is used, NADP (H) is dependent.
    [7]
    7. The method according to claim 6, characterized in that used redox cofactors are subjected to recycling, in particular by a suitable cofactor Regeneri erungs system.
    [8]
    8. The method according to any one of claim 6 or 7, characterized in that the redox cofactor when using the co-factors NAD (P) H / NAD (P) +, in particular in the reduction of D-glucosone to D-fructose , using a co-substrate, in particular selected from an alcohol, lactic acid and its salts, pyruvic acid and its salts, oxygen, hydrogen and / or formic acid and salts thereof, is regenerated
    [9]
    9. The method according to any one of claims 6 to 8, wherein the redox cofactor is regenerated by a redox enzyme, in particular by an alcohol dehydrogenase.
    [10]
    10. The method according to any one of claims 1 to 9, characterized in that it according to the following reaction scheme 2 D-glucose O 02 + H-HO-H-H-OH-H-OH pyranose-2-Qxidase - »-OH l OH h2o2 catalase D-GlucOSon D-fructose OH H20 + 1/2 02

    Acetone isopropanol in which LkADH means an alcohol dehydrogenase, in particular an alcohol dehydrogenase from Lactobacillus kefir, which is NADP (H) -dependent.
    [11]
    11. The method according to any one of claims 1 to 10, characterized in that the D-fructose prepared is further reacted to Furanderivaten. 15/16
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    WO1981003666A1|1980-06-18|1981-12-24|Standard Brands Inc|Process for making fructose|
    EP0098533A2|1982-06-30|1984-01-18|NABISCO BRANDS, Inc.|Process for production of glucosone|
    US4246347A|1979-05-29|1981-01-20|Cetus Corporation|Process for the production of fructose|
    US4321324A|1980-06-18|1982-03-23|Standard Brands Incorporated|Process for making glucosone|
    US5225339A|1992-02-26|1993-07-06|The Scripps Research Institute|Lactobacillus kefir alcohol dehydrogenase|
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    US7939681B2|2006-08-07|2011-05-10|Battelle Memorial Institute|Methods for conversion of carbohydrates in ionic liquids to value-added chemicals|
    TW201343623A|2012-02-07|2013-11-01|Annikki Gmbh|Process for the enzymatic regeneration of redox cofactors|CN107556345A|2017-08-24|2018-01-09|北京林业大学|A kind of method that enzymatic combination chemical catalysis prepares fructose or mannitol|
    EP3839054A1|2019-12-20|2021-06-23|Cascat GmbH|Production of fructose from oligo- and/or polysaccharides|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    ATA50091/2013A|AT513928B1|2013-02-06|2013-02-06|Process for the preparation of fructose|ATA50091/2013A| AT513928B1|2013-02-06|2013-02-06|Process for the preparation of fructose|
    US14/763,678| US10113192B2|2013-02-06|2014-02-05|Method for producing fructose|
    AU2014214038A| AU2014214038B2|2013-02-06|2014-02-05|Method for producing fructose|
    PL14703332T| PL2954062T3|2013-02-06|2014-02-05|Process for producing fructose|
    PCT/EP2014/052230| WO2014122167A1|2013-02-06|2014-02-05|Method for producing fructose|
    EP14703332.8A| EP2954062B1|2013-02-06|2014-02-05|Process for producing fructose|
    RS20180911A| RS57530B1|2013-02-06|2014-02-05|Process for producing fructose|
    TR2018/10706T| TR201810706T4|2013-02-06|2014-02-05|Method for the production of fructose.|
    ES14703332.8T| ES2683208T3|2013-02-06|2014-02-05|Procedure for the production of fructose|
    DK14703332.8T| DK2954062T3|2013-02-06|2014-02-05|Process for producing fructose|
    CA2900310A| CA2900310C|2013-02-06|2014-02-05|Method for producing fructose|
    HUE14703332A| HUE038656T2|2013-02-06|2014-02-05|Process for producing fructose|
    HRP20181223TT| HRP20181223T1|2013-02-06|2018-08-01|Process for producing fructose|
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