Hybrid Technologies for an Enhanced Carbon Recycling Based on the Enzymatic Reduction of CO<sub>2</sub> to Methanol in Water: Chemical and Photochemical NADH Regeneration

Dibenedetto, Angela; Stufano, Paolo; Macyk, Wojciech; Baran, Tomasz; Fragale, Carlo; Costa, Mirco; Aresta, Michele

doi:10.1002/cssc.201100484

Cited by 102 publications

(92 citation statements)

References 15 publications

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“…An attractive liquid fuel, requiring a six electron reduction of carbon dioxide, is methanol [39]. Biocatalytic synthesis of methanol from CO 2 involving a set of different dehydrogenase enzymes as catalysts has already been demonstrated and optimized [40][41][42]. Such an exergonic catalytic dark-reaction, however, requires continuous supply with the twoelectron reduced nucleotide cofactors NADPH or NADH.…”

Section: Subsequent Dark-reactionsmentioning

confidence: 98%

Recent progress in homogeneous multielectron transfer photocatalysis and artificial photosynthetic solar energy conversion

Knör

2015

Coordination Chemistry Reviews

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Section: Subsequent Dark-reactionsmentioning

confidence: 98%

Recent progress in homogeneous multielectron transfer photocatalysis and artificial photosynthetic solar energy conversion

Knör

2015

Coordination Chemistry Reviews

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“…To date, photocatalysis has shown great potential for photodegradation of environmental pollutants [8–9]. Most interesting is that photocatalysis may play a relevant role in the conversion of large quantities of CO 2 into fuel by using water or waste organics as the hydrogen source [7,10–11]. Therefore, integrated photochemical CO 2 reduction/organic oxidation and H 2 O splitting have received significant interest due to their potential environmental and resource preservation benefits [12–13].…”

Section: Introductionmentioning

confidence: 99%

An integrated photocatalytic/enzymatic system for the reduction of CO₂ to methanol in bioglycerol–water

Aresta¹,

Dibenedetto²,

Baran³

et al. 2014

Beilstein J. Org. Chem.

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SummaryA hybrid enzymatic/photocatalytic approach for the conversion of CO2 into methanol is described. For the approach discussed here, the production of one mol of CH3OH from CO2 requires three enzymes and the consumption of three mol of NADH. Regeneration of the cofactor NADH from NAD+ was achieved by using visible-light-active, heterogeneous, TiO2-based photocatalysts. The efficiency of the regeneration process is enhanced by using a Rh(III)-complex for facilitating the electron and hydride transfer from the H-donor (water or a water–glycerol solution) to NAD+. This resulted in the production of 100 to 1000 mol of CH3OH from one mol of NADH, providing the possibility for practical application.

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“…7 The capability of regenerating 1,4-NADH has been the subject of intense studies by enzymatic, chemical, photochemical, or electrochemical reactions. 8,9 Recently, NADH/NAD + regeneration under mild conditions in aqueous media has been studied. 10,11 Significant attention has focused on transition metal complexes as catalysts for regeneration of NADH via hydrogenation 10 (H 2 ) or transfer hydrogenation using 2-propanol, 12 glycerol, 13 phosphate, 14 formic acid together with a base, 15 or formate 11 as the hydride source in water.…”

Section: ■ Introductionmentioning

confidence: 99%

Improved Catalytic Activity of Ruthenium–Arene Complexes in the Reduction of NAD⁺

et al. 2012

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A series of neutral Ru II half-sandwich complexes of the type [(η 6 -arene)Ru(N,N′)Cl] where the arene is para-cymene (p-cym), hexamethylbenzene (hmb), biphenyl (bip), or benzene (bn) and N,N′ is N-(2-aminoethyl)-4-(trifluoromethyl)benzenesulfonamide (TfEn), N-(2-aminoethyl)-4-toluenesulfonamide (TsEn), or N-(2-aminoethyl)-methylenesulfonamide (MsEn) were synthesized and characterized. X-ray crystal structures of [(p-cym) The coordination of formate and subsequent CO 2 elimination to generate the hydride were modeled computationally by density functional theory (DFT). CO 2 elimination occurs via a two-step process with the coordinated formate first twisting to present its hydrogen toward the metal center. The computed barriers for CO 2 release for arene = benzene follow the order MsEn > TsEn > TfEn, and for the MsEn system the barrier followed bn < hmb, both consistent with the observed rates. The effect of methanol on transfer hydrogenation rates in aqueous solution was investigated. A study of pH dependence of the reaction in D 2 O gave the optimum pH* as 7.2 with a TOF of 1.58 h −1 for 2. The series of compounds reported here show an improvement in the catalytic activity by an order of magnitude compared to the ethylenediamine analogues. ■ INTRODUCTIONThe coenzyme nicotinamide adenine dinucleotide (NAD + ) and its reduced form 1,4-NADH have crucial roles in many cellular metabolic processes such as regulation of energy metabolism, antioxidative function, DNA repair and transcription, immunological functions, and cell death. 1 The coenzymes are involved in many other processes, acting as substrates and cofactors for enzymes such as NAD + ligases, oxidoreductases, polymerases, and deacetylases involved in biosynthesis.The coenzymes NAD + /NADH have been studied intensively during the past few years. It has been demonstrated that changes in metabolism result in fluctuations in the ratio NAD + / NADH or, conversely, changes in the ratio can produce metabolic changes. 2 In some cases alterations in the cellular redox status have been shown to play an important role in cell death, and therefore the coenzymes have become possible drug targets for chronic or autoimmune diseases such as Parkinson's, hepatitis C, diabetic vascular dysfunction, hyperglycemia, and cancer. 3 The concentration of NAD + and the ratio NAD + /NADH have been shown to be very important for cancer cells. On the one hand, due to their active metabolism, cancer cells generate high levels of oxidizing species and, therefore, they are under constant oxidative stress. 4 This makes cancer cells more dependent on redox regulatory systems and more sensitive to variations in the NAD + /NADH ratio. On the other hand, NAD + is required as a substrate for many enzymatic reactions such as ADP-ribosylation, which is crucial for genome stability and DNA repair. 3 Due to the up-regulation of some enzymes required for the biosynthesis of NAD + in cancer cells, a

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Hybrid Technologies for an Enhanced Carbon Recycling Based on the Enzymatic Reduction of CO₂ to Methanol in Water: Chemical and Photochemical NADH Regeneration

Cited by 102 publications

References 15 publications

Recent progress in homogeneous multielectron transfer photocatalysis and artificial photosynthetic solar energy conversion

Recent progress in homogeneous multielectron transfer photocatalysis and artificial photosynthetic solar energy conversion

An integrated photocatalytic/enzymatic system for the reduction of CO₂ to methanol in bioglycerol–water

Improved Catalytic Activity of Ruthenium–Arene Complexes in the Reduction of NAD⁺

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Hybrid Technologies for an Enhanced Carbon Recycling Based on the Enzymatic Reduction of CO2 to Methanol in Water: Chemical and Photochemical NADH Regeneration

Cited by 102 publications

References 15 publications

Recent progress in homogeneous multielectron transfer photocatalysis and artificial photosynthetic solar energy conversion

Recent progress in homogeneous multielectron transfer photocatalysis and artificial photosynthetic solar energy conversion

An integrated photocatalytic/enzymatic system for the reduction of CO2 to methanol in bioglycerol–water

Improved Catalytic Activity of Ruthenium–Arene Complexes in the Reduction of NAD+

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Hybrid Technologies for an Enhanced Carbon Recycling Based on the Enzymatic Reduction of CO₂ to Methanol in Water: Chemical and Photochemical NADH Regeneration

An integrated photocatalytic/enzymatic system for the reduction of CO₂ to methanol in bioglycerol–water

Improved Catalytic Activity of Ruthenium–Arene Complexes in the Reduction of NAD⁺