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US 6,440,711B1 12 DEHYDROGENASE ENZYMATIC SYNTHESIS OF METHANOL BACKGROUND OF THE INVENTION (1) Field of the Invention The present invention relates to chemical reductions cata lyZed by dehydrogenase enZymes and more particularly to the implementation of such reductions in the synthesis of methanol. (2) Description of the Related Art Methanol isused inaWide range ofapplications.Among such applications may be noted itsuse in the production of formaldehyde, in automotive anti-freeZe, in a variety of chemical syntheses, as a general solvent, as an aviation fuel (for Water injection), as a denaturant for ethyl alcohol, and as a dehydrator for natural gas. Conventional techniques for the production of methanol include high-pressure catalytic synthesis from carbon monoxide and hydrogen, partial oxi dation of natural gas hydrocarbons, and puri?cation of pyroligneous acid resulting from destructive distillation of Wood. 15 ideisreportedtohavebeenreducedtoformateviacarbonate formation in a reaction requiring strict anaerobic conditions to prevent oxygen-induced oxidation of the NADH. Parkinson and Weaver also describe the production of formate via the formate dehydrogenase catalyZed reduction of carbon dioxide. Photoelectrochemical Pumping of EnZy matic CO2 Reduction, Nature 309, 148 (1984). In their process, Parkinson and Weaver report that a 150 Watt tungsten/halogen lamp generated electrons from the semi conductor indium phosphide to reduce methyl viologen (MV2+), Which they state mediated the enZyme linked reduction of carbon dioxide to formate. Parkinson and Weaver state that an electrochemical reaction Was used to reduce MV2+. Mandler and Willner discuss relaying photoinduced elec trons generated by the (Ru(bpy)3)2"/l\/IV2+ system to an electron transfer molecule such as 2-mercaptoethanol or cystine. Photochemical Fixation of Carbon Dioxide: EnZy micPhotosynthesisofMalic,Aspartic,Isocitric,andFormic Acids in Arti?cial Media, J. Chemical Soc., Perkin Trans., 997 (1988). According to Mandler and Willner, the 2-mercaptoethanolsoenergiZedreducedNADP+to generate NADPH, Which mediated the enZyme-induced carboxyla tion of pyruvate to malate. LikeWise, Mandler and Willner shoWthatcysteineiscapableofdonatingelectronsinthe formatedehydrogenase-inducedreactionofCO2 toformate. Mandler and Willner note that the formate dehydrogenase activityisproblematicbecauseitdecaysrapidlyuponexpo sure to light, and postulate that since the decarboxylation of formicacidissoenergeticallyfavorable,NADH istooWeak a reducer to enable ef?cient production of formate. KuWabata et al. describe the sequential reduction of carbon dioxide to methanol by use of formate dehydroge nase and methanol dehydrogenase enZymes, Wherein elec trons are generated electrochemically and either pyrrolo quinolinequinone (PQQ) or MV2+ is used as the electron carrier. Thus, the KuWabata et al. technique is an electrolytic processthatrequireseverythingessentialtosuchprocesses, including an elecrolytic bath, electrodes, and electrical cur rentinput,andalsorequiresuseofPPQ orMV2+. Moreover, KuWabata et al. report that the electrolysis had to be carried out in the dark to maintain the durability of the formate dehydrogenase enZyme. Accordingly, a neW technique for synthesis of methanol, andespeciallyconversionofcarbondioxidetomethanol, that alleviates such draWbacks isdesired. In particular, a loW temperature, highly ef?cient technique for production of methanol from carbon dioxide isdesired. SUMMARY OF THE INVENTION Brie?y, therefore, the present invention is directed to a novel method for conversion of carbon dioxide to methanol. According to the method, a combination of formate dehy drogenaseenZymes,formaldehydedehydrogenaseenZymes and either alcohol dehydrogenase enZymes or methanol dehydrogenase enZymes is contacted With the carbon diox ide in the presence of a terminal electron donor to produce the methanol. Preferably, the enZymes are ?xed in a microporous matrix such as a sol-gel and the terminal electron donor is a cofactor of the enZymes, such as reduced nicotinamide adenine dinucleotide (Which can also donate hydrogen ions to the reductions as Well) matrix. In a most preferred embodiment, the invention also contemplates a mechanism for regeneration of the terminal electron donor for reuse. Thissynthesisismade up ofaseriesofsynthesissteps, fromcarbondioxidetoformate,fromformatetoformalde Various techniques for synthesiZing methanol from car bon dioxide are also knoWn. As noted in EnZymatic Con versionofCarbonDioxidetoMethanol:EnhancedMethanol 25 Production in Silica Sol-Gel Matrices, J.Amer. Chem. Soc. 1999, 121, 12192—12193 (publishedon theWorld Wide Web on Dec. 9, 1999), partial hydrogenation of carbon dioxide has been carried out by means of heterogeneous catalysis, electro-catalysis,andphotocatalysis,Withoxide-basedcata lysts being used predominantly for industrial ?xation of carbon dioxide. Derivation of methanol from carbon dioxide has several obvious advantages. For example, carbon dioxide is 35 plentiful, readily available (indeed, omnipresent), and extremelyinexpensive,tosaytheleast.Inaddition,Whereas use of many resources may lead to undesirable depletion of that resource, rising levels of carbon dioxide have been associated With What has been referred to as the “green house” effect, Which has been theoriZed to be a contributing factortoglobalWarming.Thus,moderateremovalofcarbon dioxide from the atmosphere is vieWed as bene?cial rather than detrimental. HoWever,conventionalmethodsforsynthesiZingmetha 45 nol from carbon dioxide also suffer from certain draWbacks. Such draWbacks include inefficiencies, costs, high energy consumption, and the need for special equipment adapted for high temperature or highly corrosive environments. For example, one common commercial method of methanol synthesis is by reduction of carbon dioxide in the presence of oxide catalysts. HoWever, this synthesis produces par tialy reduced species as by-products, thereby not only creating impurities but also resulting in limited conversion ef?ciency. Moreover, the process is carried out at high 55 temperatures,requiringspecialequipmentforaccommodat ing and maintaining such temperatures as Well as high energy input. Various other procedures for reduction of carbon dioxide byenZyme-catalyZedreactionsalsohavebeendescribed,but such processes either have not been directed to methanol production or involve various draWbacks. Thus, for example,inCO2ReductiontoFormatebyNADH Catalysed by Formate Dehydrogenase from Pseudomonas oxalaticus, Ruschigetal.,Eur.J.Biochem.70,325—330(1976),adirect 65 reductionofcarbondioxidebyformatedehydrogenaseusing substrateamountsofNADH isdisclosed.ThecarbondioxPDF Image | DEHYDROGENASE ENZYMATIC SYNTHESIS OF METHANOL
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