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US 6,440,711B1 78 RegenerationoftheTerminalElectronDonorand/orHydro gen Ion Donor Asnotedabove,NADH hasbeenfoundtobeanexcellent terminal electron donor and hydrogen ion donor in the process of this invention. HoWever, NADH is relatively expensive.Therefore,itisdesirablethatifNADH isused, thattheNADH beregeneratedsothatitcanberecycledfor repeated use. Surprisingly, it has been found not that only cantheNADH indeedberegeneratedfromtheNAD",but thatitcanberegeneratedsimplyand“automatically”With out a need for any additional steps that Would involve, for example, removal of the NAD+ from the reaction vessel, extra treatment and return to the reaction vessel and Without any signi?cant interference With the reduction reactions of thisinvention.Inparticular,ithasbeendiscoveredthat15 describedinEnZymaticConversionofCarbonDioxideto oflight,theNADH canberegeneratedandrecycledauto matically and continuously. Techniques for extraction of green plant PSII are Well knoWn. See, for example, Structural,BiochemicalandBiophysicalCharacterizationof FourOxygen-EvolvingPhotosystemIPreparationsfrom Spinach, T. Dunahay et al., Biochemica et Biophysica Acta, 764 (1984) 179—193. Thus, upon extraction and incorporation of the PSII preparations into the reduction system of this invention and exposureofthePSIIpreparationstolightthePSIIprepara tionsseemtousetheNAD+ asanelectron-acceptorinplace oftheacceptorquinoneofgreenplants.As aresult,thePSII preparation photo-oxidizes the Water in the system to oxy gen(OZ),releasinghydrogenionsandelectronsandthereby converting the NAD+ back to NADH. See FIG. 2 for a schematic representation. According to the overall reaction, therefore, carbon dioxide, Water and light are converted to methanol and oxygen. The reaction scheme has been found to run—apparently—inde?nitely on the initial doses of the enZyme-containingmatrix,NADHandPSII,requiringonly40 oftheinvention.OtherembodimentsWiththescopeofthe carbon dioxide, Water and light as input ?oWs thereafter, and producing oxygen and methanol. Thus, the process closely mimics natural photosynthesis Wherein photo-generated electrons produced from the oxidation of Water synthesiZe hydrocarbons from carbon dioxide. The reactions With NADH regeneration and recycling have been carried out With green plant PSII, but it is believed that bacteria pho tosystem can be used in similar manner as Well. The extracted photosystem preparation may be incorpo ratedintothereactionschemeofthisinventionbysoaking the matrix in a suspension of the extracted photosystem preparationsothatitdiffusesthroughthematrix,addingthe extracted photosystem preparation directly to the matrix containing mixture for carrying out the process of this invention, or both. Because the photosystem reaction is activated by exposure to light, it is advantageous for the matrix to be transparent, so that the light can be transmittal Without undue interference to the photosystem preparation. Other alternatives for regeneration of the electron donor, hydrogeniondonororboth,andparticularly,NADH, are available as Well and Will be readily apparent to those of ordinaryskillintheartuponreadingthisspeci?cation,based on the recognition that What is required is a method for producing or introducing electrons and hydrogen ions. For example,hydrogengasmaybebubblingthroughthesystem, thereby effecting the reduction NAD++H2—>NADH+H+. This additional production of hydrogen ions may also be claims herein Will be apparent to one skilled in the art from considerationofthespeci?cationorpracticeoftheinvention as disclosed herein. It is intended that the speci?cation, together With the examples, be considered exemplary only, 45 Withthescopeandspiritoftheinventionbeingindicatedby the claims Which folloW the examples. EXAMPLE 1 EnZymatic conversion of carbon dioxide to methanol Was 50 attemptedinsolutionphaseWithanenZymestocksolution comprising 10 mg/mL of each of the formate, formaldehyde and alcohol dehydrogenase enZymes dissolved in 0.1 M phosphatebufferatpH 7.ReactionmixturesWereprepared byadding1.0mL oftheenZymestocksolutionto1.0mL of 55 various concentrations of NADH solution in polystyrene cuvettessuchthatthe?nalconcentrationofNADH inthe cuvettes varied from 0.025 to 0.1 M. The cuvettes Were covered With Para?lm to prevent extensive loss of methanol formed by evaporation, and gaseous CO2 Was then bubbled 60 throughthissolutionfor3hoursusingasmallnoZZleWith anoutletdiameterofabout0.5mm andthroughaholeinthe Para?lm. The extended time ofbubbling of CO2 ensured that the reaction Was alloWed to go to completion and that equilibrium Was established. Quantitative measurement of 65 methanolWascarriedoutWithgaschromatography(GC).A calibration curve Was established for aqueous methanolic solutions With knoWn concentrations of methanol ranging seen as an additional bene?t in that reduction of carbon dioxide to methanol consumes three hydrogen ions per carbon dioxide molecule. Other techniques for supplying additional electrons and hydrogen ions Will also be readily apparent. For example, electrons can be produced electrochemically, electrolytic processes may be used to produce the hydrogen ions from the Water as Well as electrons, electroactive sol-gels may be produced by doping With metals or electrically conductive 10 polymers, or photoactive inorganic components such as titanium oxide may be employed. Contacting the EnZymne-Containing Matrix With Carbon Dioxide photosystem I (PSII) preparations, Which contain chloro phyll and an O2-evolving complex, can be extracted from green plants such as spinach and by simply adding the extracted PSII preparation to the reaction vessel—or to the matrixitself—andcarryingoutthereactionsinthepresence20 WaterandHCltoformamixturethatisthensonicatedto In a preferred embodiment, a sol-gel matrix is prepared as Methanol: Enhanced Methanol Production in Silica Sol-Gel Matrices, R. Obert and B. Dave (the inventor herein), J.Am. Chem. Soc. 1999, 121, 12192—12193. In summary, the gel may be prepared by mixing tetramethoxysilane precursor, formasol.Thesolisaddedtoastockofthecombinationof enZymes described above inbuffer(pH 7) and iftheNADH is to be regenerated by means of a PSII system, a suspension ofPSIIparticlesareaddedtothesol.WhereNADH isused 25 astheterminalelectronandhydrogendonor,theresulting gelisalloWed toage and immersed inasolutionofNADH toalloWtheNADH moleculestodiffuseintothegel.The resultinggelcontainingthethreeenZymesofthisinvention, the NADH and the PSII system may be crushed to a 30 particulateorpoWderformandmaintainedinsuspensionin Water held in a reaction vessel such as a CSTR. Carbondioxide,suchasatmosphericcarbondioxide,may be bubbled under constant positive pressure through the Water and so diffused through the matrix and contacted With 35 the enZymes entrapped in the matrix. Remaining carbon dioxide and resulting methanol then diffuse out of the matrix and through the Water for collection by distillation and the recirculation of the aqueous fraction, if so desired. The folloWing examples describe preferred embodimentsPDF Image | DEHYDROGENASE ENZYMATIC SYNTHESIS OF METHANOL
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