367-47-5Relevant academic research and scientific papers
Phosphorylation Catalyzed by Dihydroxyacetone Kinase
Gauss, Dominik,Sánchez-Moreno, Israel,Oroz-Guinea, Isabel,García-Junceda, Eduardo,Wohlgemuth, Roland
, p. 2892 - 2895 (2018)
Site- and enantioselective kinases have been very useful catalysts for biocatalytic phosphorylations in straightforward syntheses of phosphorylated metabolites. Biocatalytic phosphorylations catalyzed by recombinant dihydroxyacetone kinase beyond the dihydroxyacetone substrate have been investigated with quantitative 31P NMR spectroscopy using pyruvate-kinase-catalyzed ATP regeneration. A nearly 100 % conversion of d-glyceraldehyde to d-glyceraldehyde 3-phosphate has been found. Interestingly, with pure l-glyceraldehyde as substrate, practically no formation of l-glyceraldehyde 3-phosphate was observed.
Catalytic wet air oxidation of D-glucose by perovskite type oxides (Fe, Co, Mn) for the synthesis of value-added chemicals
Geobaldo, Francesco,Pirone, Raffaele,Russo, Nunzio,Scelfo, Simone
, (2022/03/15)
The conversion of common biomasses derived, as D-glucose, into value-added chemicals has received highest attention in the last few years. Among all processes, the catalytic wet air oxidation (CWAO) of derived biomasses using noble metal-based heterogeneo
Photothermal strategy for the highly efficient conversion of glucose into lactic acid at low temperatures over a hybrid multifunctional multi-walled carbon nanotube/layered double hydroxide catalyst
Duo, Jia,Jin, Binbin,Jin, Fangming,Shi, Xiaoyu,Wang, Tianfu,Ye, Xin,Zhong, Heng
, p. 813 - 822 (2022/02/09)
The conversion of carbohydrates into lactic acid has attracted increasing attention owing to the broad applications of lactic acid. However, the current methods of thermochemical conversion commonly suffer from limited selectivity or the need for harsh conditions. Herein, a light-driven system of highly selective conversion of glucose into lactic acid at low temperatures was developed. By constructing a hybrid multifunctional multi-walled carbon nanotube/layered double hydroxide composite catalyst (CNT/LDHs), the highest lactic acid yield of 88.6% with 90.0% selectivity was achieved. The performance of CNT/LDHs for lactic acid production from glucose is attributed to the following factors: (i) CNTs generate a strong heating center under irradiation, providing heat for converting glucose into lactic acid; (ii) LDHs catalyze glucose isomerization, in which the photoinduced OVs (Lewis acid) in LDHs under irradiation further improve the catalytic activity; and (iii) in a heterogeneous-homogeneous synergistically catalytic system (LDHs-OH-), OH- ions are concentrated in LDHs, forming strong base sites to catalyze subsequent cascade reactions.
Selective Reductive Dimerization of CO2into Glycolaldehyde
Zhang, Dan,Jarava-Barrera, Carlos,Bontemps, Sébastien
, p. 4568 - 4575 (2021/05/04)
The selective dimerization of CO2 into glycolaldehyde is achieved in a one-pot two-step process via formaldehyde as a key intermediate. The first step concerns the iron-catalyzed selective reduction of CO2 into formaldehyde via formation and controlled hydrolysis of a bis(boryl)acetal compound. The second step concerns the carbene-catalyzed C-C bond formation to afford glycolaldehyde. Both carbon atoms of glycolaldehyde arise from CO2 as proven by the labeling experiment with 13CO2. This hybrid organometallic/organic catalytic system employs mild conditions (1 atm of CO2, 25 to 80 °C in less than 3 h) and low catalytic loadings (1 and 2.5%, respectively). Glycolaldehyde is obtained in 53% overall yield. The appealing reactivity of glycolaldehyde is exemplified (i) in a dimerization process leading to C4 aldose compounds and (ii) in a tri-component Petasis-Borono-Mannich reaction generating C-N and C-C bonds in one process.
Ambient base-free glycerol oxidation over bimetallic PdFe/SiO2 by in situ generated active oxygen species
Underhill, Ricci,Douthwaite, Mark,Lewis, Richard J.,Miedziak, Peter J.,Armstrong, Robert D.,Morgan, David J.,Freakley, Simon J.,Davies, Thomas,Folli, Andrea,Murphy, Damien M.,He, Qian,Akdim, Ouardia,Edwards, Jennifer K.,Hutchings, Graham J.
, p. 303 - 324 (2021/01/07)
Low temperature oxidation of alcohols over heterogeneous catalysts is exceptionally challenging, particularly under neutral conditions. Herein, we report on an efficient, base-free method to oxidise glycerol over a 0.5%Pd-0.5%Fe/SiO2 catalyst at ambient temperature in the presence of gaseous H2 and O2. The exceptional catalytic performance was attributed to the in situ formation of highly reactive surface-bound oxygenated species, which promote the dehydrogenation on the alcohol. The PdFe bimetallic catalyst was determined to be significantly more active than corresponding monometallic analogues, highlighting the important role both metals have in this oxidative transformation. Fe leaching was confirmed to occur over the course of the reaction but sequestering experiments, involving the addition of bare carbon to the reactions, confirmed that the reaction was predominantly heterogeneous in nature. Investigations with electron paramagnetic resonance spectroscopy suggested that the reactivity in the early stages was mediated by surface-bound reactive oxygen species; no homogeneous radical species were observed in solution. This theory was further evidenced by a direct H2O2 synthesis study, which confirmed that the presence of Fe in the bimetallic catalyst neither improved the synthesis of H2O2 nor promoted its decomposition over the PdFe/SiO2 catalyst.
Earth-abundant manganese oxide nanoneedle as highly efficient electrocatalyst for selective glycerol electro-oxidation to dihydroxyacetone
Chiang, Chia-Ying,Tran, Giang-Son,Vo, Truong-Giang
, p. 139 - 148 (2021/10/07)
In this study, earth-abundant manganese oxide (MnO2) was used as a catalyst for the electrocatalytic glycerol oxidation with a satisfactory yield and high selectivity under mild pH media; that is, the high current density of 6.0 mA cm?2 and selectivity of ca. 46% for dihydroxyacetone (DHA). MnO2 also exhibited reasonable durability without considerable changes for 3 h. More importantly, by combination of operando Raman and electrochemical studies, a tentative reaction pathway was also proposed. It is found that high selectivity of formic acid at low potential was due to predominant coverage of α-MnO2 on catalyst surface. Meanwhile, at high applied potential, partial transformation of α-MnO2 to δ-MnO2 causes decreasing C-C bond cleavage, leading to high DHA selectivity. The results of this work not only demonstrate that MnO2 holds promise as an efficient electrocatalyst for selectively producing DHA but also provides realistic details on electrochemically generated species under working condition.
Enantioselective Reductive Oligomerization of Carbon Dioxide into l-Erythrulose via a Chemoenzymatic Catalysis
Bontemps, Sébastien,Clapés, Pere,Desmons, Sarah,Dumon, Claire,Fauré, Régis,Grayson-Steel, Katie,Hurtado, John,Nu?ez-Dallos, Nelson,Vendier, Laure
supporting information, p. 16274 - 16283 (2021/10/12)
A cell-free enantioselective transformation of the carbon atom of CO2has never been reported. In the urgent context of transforming CO2into products of high value, the enantiocontrolled synthesis of chiral compounds from CO2would be highly desirable. Using an original hybrid chemoenzymatic catalytic process, we report herein the reductive oligomerization of CO2into C3(dihydroxyacetone, DHA) and C4(l-erythrulose) carbohydrates, with perfect enantioselectivity of the latter chiral product. This was achieved with the key intermediacy of formaldehyde. CO2is first reduced selectively by 4e-by an iron-catalyzed hydroboration reaction, leading to the isolation and complete characterization of a new bis(boryl)acetal compound derived from dimesitylborane. In an aqueous buffer solution at 30 °C, this compound readily releases formaldehyde, which is then involved in selective enzymatic transformations, giving rise either (i) to DHA using a formolase (FLS) catalysis or (ii) to l-erythrulose with a cascade reaction combining FLS and d-fructose-6-phosphate aldolase (FSA) A129S variant. Finally, the nature of the synthesized products is noteworthy, since carbohydrates are of high interest for the chemical and pharmaceutical industries. The present results prove that the cell-freede novosynthesis of carbohydrates from CO2as a sustainable carbon source is a possible alternative pathway in addition to the intensely studied biomass extraction andde novosyntheses from fossil resources.
Electrochemical Activation of Galactose Oxidase: Mechanistic Studies and Synthetic Applications
Fryszkowska, Anna,Klapars, Artis,Marshall, Nicholas,Ruccolo, Serge,Strotman, Neil A.,Zhang, Shaoguang
, p. 7270 - 7280 (2021/06/30)
The enzyme galactose oxidase (GOase) is a copper radical oxidase that catalyzes the aerobic oxidation of primary alcohols to the aldehydes and has been utilized to that end in large-scale pharmaceutical processes. To maintain its catalytic activity and ensure high substrate conversion, GOase needs to be continuously (re)activated by 1e- oxidation of the constantly formed out-of-cycle species (GOasesemi) to the catalytically active state (GOaseox). In this work, we report an electrochemical activation method for GOase that replaces the previously used expensive horseradish peroxidase activator in a GOase-catalyzed oxidation reaction. First, the formation of GOaseox of a specifically engineered variant via nonenzymatic oxidation of GOasesemi was studied by UV-vis spectroscopy. Second, electrochemical oxidation of GOase by mediators was studied using cyclic voltammetry. The electron-transfer rates between GOase and various mediators at different pH values were determined, showing a dependence on both the redox potential of the mediator and the pH. This observation suggests that the oxidation of GOase by mediators at pH 7-9 likely occurs via a concerted proton-coupled electron-transfer (PCET) mechanism under anaerobic conditions. Finally, this electrochemical GOase activation method was successfully applied to the development of a bioelectrocatalytic GOase-mediated aerobic oxidation of benzyl alcohol derivatives, cinnamyl alcohol, and aliphatic polyols, including the desymmetrizing oxidation of 2-ethynylglycerol, a key step in the biocatalytic cascade used to prepare the promising HIV therapeutic islatravir.
Converging conversion - using promiscuous biocatalysts for the cell-free synthesis of chemicals from heterogeneous biomass
Pick, André,Sieber, Volker,Sutiono, Samuel
supporting information, p. 3656 - 3663 (2021/06/06)
Production of chemicals from lignocellulosic biomass has been proposed as a suitable replacement to petrochemicals. However, one inherent challenge of biomass utilization is the heterogeneity of the substrate resulting in the presence of mixed sugars after hydrolysis. Fermentation of mixed sugars often leads to poor yield and generation of multiple by-products, thus complicating the subsequent downstream processing. System biocatalysis has thus been developed in recent years to address this challenge. In this work, several novel enzymes with broad substrate promiscuity were identified using a sequence-based discovery approach as suitable biocatalysts in a conversion ofd-xylose andl-arabinose, two major constituents of hemicellulose found in plant biomass. These promiscuous enzymes enabled simultaneous biotransformation ofd-xylose andl-arabinose to yield 1,4-butanediol (BDO) with a maximum production rate of 3 g L?1h?1and a yield of >95%. This model system was further adapted toward the production of α-ketoglutarate (2-KG) from the pentoses using O2as a cosubstrate for cofactor recycling reaching a maximum production rate of 4.2 g L?1h?1and a yield of 99%. To verify the potential applicability of our system, we attempted to scale up the BDO and 2-KG production fromd-xylose andl-arabinose. Simple optimization and reaction engineering allowed us to obtain BDO and 2-KG titers of 18 g L?1and 42 g L?1, with theoretical yields of >75% and >99%, respectively. One of the promiscuous enzymes identified together with auxiliary promiscuous enzymes was also suitable for stereoconvergent synthesis from a mixture ofd-glucose andd-galactose, predominant sugars found in food waste streams and microalgae biomass.
Photocatalytic hydrogenation of nitrobenzene to aniline over titanium(iv) oxide using various saccharides instead of hydrogen gas
Aono, Yushiro,Ikeuchi, Kazuma,Imamura, Kazuya,Onda, Ayumu,Oto, Takahiro,Sakamoto, Yuki
, p. 32300 - 32304 (2021/12/02)
Bare TiO2 photocatalyst almost quantitatively converted nitrobenzene to aniline with various saccharides without the use of hydrogen gas. Although aniline was formed when any saccharide was used, the use of disaccharides (lactose, maltose, and sucrose) de
