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US 6,440,711B1 56 similar alcohols to the oxides of metals or non-metals such as aluminum, titanium, Zirconium, niobium, hafnium, chromium, vanadium, tungsten, molybdenum, iron, tin, phosphorus, sodium, calcium, and boron, or combinations thereof, are candidates for precursors of the sol-gels of this invention. Nevertheless, tetramethylorthosilicate (TMOS) has been found to be a particularly useful precursor, and tetraethylorthosilicate(TEOS) andotheractivesiliconcom pounds are preferred as Well. Theprecursorissubjectedtoaseriesofhydrolysisand 10 polymeriZation reactions to form the “sol”—a colloidal suspension. Thin ?lms can be deposited on a substrate such as by spin-coating or dip-coating, ifso desired. Upon casting the “sol” in a mold, a “Wet gel” is formed. The Wet gel can bedriedandheateduntiladensematerialforms.HoWever, 15 if the liquid in a Wet gel is extracted under a supercritical condition, a highly porous and extremely loW-density mate rial called an “aerogel” is formed. The resulting porous materialisreferredtoasa“sol-gelglass.”The averagepore diameterinsol-gelglasstypicallyrangesfrom2nmto200 20 nm. The pores are interconnected and may be doped With almost any gas, liquid or solid. The EnZymes Acombination offormate dehydrogenase (FmDH), form from carbon dioxide to methanol consumes an electron that must be donated from some source. HoWever, if a free electron isprovided, itmay be introduced atany of a number of sites on the enZymes, resulting in undesirable side reac tions.Therefore,fortheaforementionedreactionstoproceed as described, a mechanism to deliver the electron to the appropriate sites on the enZymes is desired. Thus, it is preferredthatsuchamechanismfordonatingelectrons,such as a carrier that delivers the electron to the enZymes site speci?cally,beincludedWiththematrix(orWater)asWell. CofactorsoftheenZymesprovidesuchsite-speci?cdelivery and so are the preferred terminal electron donors. Ithas been found that reduced nicotinamide adenine dinucleotide (NADH) is especially Well-suited to act as a terminal electron donor for each of the three reduction reactions. Thus,theoverallsynthesismaybeshoWnschematicallyas in FIG. 1. As notedabove,theconventionaldirectionoftheseriesof reduction reactions carried out in this invention is actually thereverseofthatcarriedoutherein;thatis,conventionally, thereactionstendtooxidation,WhichWouldresultforma tion of carbon dioxide from methanol. HoWever, ithas been found that the thermodynamics of the reactions can be shifted so that the reverse reactions (that is, the reductions) are favored if the reduced cofactor is present in great excess ofthatcalledforbythestoichiometryoftheoxidation reactions.As canbe seenfrom FIG. 1forthecaseofNADH, thestiochiometrycallsforthreemolesofNADH forcon version of one mole of carbon dioxide to one mole of methanol. Thus, Where the electron donor is NADH, for example, the reactions herein should be carried out in the presenceofabout3,000molesofNADH permolecarbon dioxide converted. VieWing itdifferently, itcan be seen also from FIG. 1, that the reactions scheme yields three moles of NAD+ permoleofcarbondioxideconverted,andsotheratio ofNADH toNAD+ shouldbemaintainedontheorderof 1,000ormore. aldehydedehydrogenase(FaldDH),andalcoholdehydroge 25 nase enZymes has been found to be an especially effective combination of enZymes for catalyZing the ordered series of reductions, although it is believed that methanol dehydrogenase enZymes may be substituted for the alcohol dehydrogenase enZymes. The series of reduction reactions 30 catalyZed by the enZymes has been found to proceed as folloWs.First,theformatedehydrogenaseenZyme(e.g.,EC. 1.2.1.2,EC 1.2.1.43,orEC 1.2.2.3)inducesaformate catalyZed reduction of the carbon dioxide to formate. The formaldehydedehydrogenaseenZyme(e.g.,EC.1.2.1.46)35 thencatalyZesthereductionoftheformatetoformaldehyde. And the alcohol dehydrogenase enZyme (e.g., EC. 1.1.1.1, EC. 1.1.1.2,EC. 1.1.1.71,orE.C.1.1.99.8)thencatalyZes the reduction of the formaldehyde to methanol. Of course, variationsoftheseenZymes,andevenmutantvariations,that 40 maintain the described catalytic functionality may be employed in place of any or all of these enZymes. It is therefore contemplated that such site-speci?c variants may be employed in place of the preferred enZymes Without departingfromthescopeofthisinventionanddiscussion45 processofthesubjectinventioniscarriedoutinanaqueous herein of the noted dehydrogenase enZymes is intended to encompass such variants as Well. Incorporation of the EnZymes in the Matrix In the subject invention, the matrix is doped With the combination of enZymes discussed above. US. Pat. No. 50 5,200,334 to Dunn et al., incorporated herein by reference, describes a sol-gel process for the preparation of porous glass structures having active biological material such as protein entrapped therein, and notes that encapsulated or entrappedenZymesareusedamicro-catalysts.Althoughthe 55 patent noWhere discloses or suggests the use of dehydroge nase enZymes, or particularly those dehydrogenase enZymes identi?ed above, according to the present invention, the enZymes employed in this invention may be encapsulated intoasol-gelglassbytheproceduredescribedinUS.Pat.60 No. 5,200,334. It has been found that use of enZymes trapped in a sol-gel matrix is three-to-four times more ef?cient at converting carbon dioxide to methanol than is the use of a mere solution of the enZymes. TheTerminalElectronDonor 65 As can be seen from the reaction scheme illustrated in FIG. 1, each of the reduction steps in the reaction scheme system, from the terminal electron donor. Ifthey are derived from the Water, itmay be preferred that the extraction of the hydrogen ion be accompanied by some other process to generate the ions or to compensate for the rami?cations of the extraction. In other Words, the continual removal of hydrogenionsfromtheWatermightincreasethepH thereof, requiring—at leastatsome point—adjustment doWnWard of the pH, such as by the addition or incorporation of a buffer or acid. Generation of the hydrogen ions from the Water may be carried out, for example, electrochemically, by addition of hydrogen gas, or by conversion of the Water to oxygen gas. The conversion of Water to oxygen gas may be accomplished, for example, photosynthetically, as Will be discussedbeloWWithrespecttoregenerationoftheelectron donor. In that case, as Will be discussed beloW, the hydrogen ionsconsumed inthereductionreactionsmay be suppliedby the terminal electron donor, and the photosynthetic reaction may in turn serve to replenish the hydrogen ions to the terminalelectrondonorratherthanthephotosyntheticreac tion supplying the hydrogen ions directly to the reduction reactions. The Hydrogen Ion Donor Although each reduction reaction in the overall scheme of this invention consumes tWo hydrogen ions, it is not nec essary that the method include addition of a separate hydro gen ion donor for that sole and speci?c purpose. The hydrogen ions consumed in each of the reduction reactions may be derived from another additive (such as an acid), or from some other mechanism for supplying the ions but, alternatively, they may be derived from the Water itselfifthePDF Image | DEHYDROGENASE ENZYMATIC SYNTHESIS OF METHANOL
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