26776-70-5Relevant articles and documents
Selective production of dihydroxyacetone and glyceraldehyde by photo-assisted oxidation of glycerol
Mendoza, Arisbeht,Romero, Rubí,Gutiérrez-Cedillo, Galilea P.,López-Tellez, Gustavo,Lorenzo-González, Omar,Gómez-Espinosa, Rosa María,Natividad, Reyna
, p. 149 - 154 (2020)
Glycerol is a by-product during biodiesel production and represents a potential low-cost raw material for obtaining high-cost products like Dihydroxyacetone (DHA) and glyceraldehyde (GCD) amongst others. In this work, Fe-Pillared clay (Fe-PILC) was assessed as catalyst of the selective photo-oxidation of glycerol to obtain DHA and GCD at moderate conditions (298 K and atmospheric pressure). This was conducted in a 100 mL Pyrex glass batch reactor where a Pen-Ray lamp of mercury of 5.5 W UV light (UVP) was placed at the centre. The Fe-PILC was prepared by ion exchange. The pillaring was confirmed by XRD, and a 17% w/w of Fe was determined by Atomic Absorption Spectroscopy. The active phases were established by XPS and found to be FeO and Fe3O4. The specific surface area of the clay (bentonite), determined by N2 physisorption, increased from 34 m2/g to 227 m2/g and the pore volume increased from 0.058 cm3/g to 0.106 cm3/g. The studied variables were catalyst loading and glycerol initial concentration. An experiment with TiO2 Degussa P25 was also performed as reference. It was found that by adding Fe-PILC to the glycerol oxidation system, selectivity towards DHA or GCD can be tuned. A selectivity towards DHA was found to be 87% with 0.1 g/L of Fe-Pillared after 8 h reaction. The in situ production of H2O2 was observed and therefore concluded that the glycerol oxidation occurs via a fenton process, i.e. via free radicals.
A practical synthesis of 2-butyl-4(5)-chloro-5(4)-hydroxymethyl-1H-imidazole
Shi,Frey,Tschaen,Verhoeven
, p. 2623 - 2630 (1993)
A practical process for the synthesis of 2-butyl-4-hydroxymethyl imidazole (4) followed by chlorination to provide chloroimidazole 1 in an overall 71% yield has been developed.
Cu-Al composite oxides: A highly efficient support for the selective oxidation of glycerol to 1,3-dihydroxyacetone
Ke, Yi-Hu,Wang, Xue,Qin, Hong-Yu,Liu, Hai,Yuan, Hong,Liu, Chun-Ling,Dong, Wen-Sheng
, p. 18173 - 18184 (2020)
A series of Au catalysts supported on Cu-Al composite oxides were prepared and applied for the selective catalytic oxidation of glycerol to 1,3-dihydroxyacetone (DHA) in base-free conditions. The optimal Au/CuAlO-3 catalyst (the molar ratio of Cu/Al was 5:1) exhibited the best performance, and reached the glycerol conditions of 76.7% and DHA selectivity of 97.3% under the optimized reaction conditions. The high catalytic activity of the Au/CuAlO-3 catalyst correlated to the large concentration of surface-active oxygen species, the low reduction temperature of the support, the small size of Au nanoparticles (NPs) and the interactions between Au NPs and the support. This work demonstrates that Cu-Al composite oxides are promising supports for selective catalytic oxidation of glycerol to DHA, and may offer guidelines for designing efficient support for the selective conversion of glycerol to other high value-added products. This journal is
One-Pot Homogeneous and Heterogeneous Oxidation of Glycerol to Ketomalonic Acid Mediated by TEMPO
Ciriminna, Rosaria,Pagliaro, Mario
, p. 383 - 388 (2003)
Glycerol, an increasingly abundant by-product of biodiesel production, is selectively converted to ketomalonic acid in one pot at pH 10 using NaOCl as regenerating oxidant in water at 2 °C in the presence of catalytic Br - along with the radical TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl) . The reaction can also be conducted at completion over a sol-gel silica glass doped with the nitroxyl radical. Considering the stability and versatility of such doped glasses, these materials show real promise as reusable metal-free catalysts for the conversion of a readily available and renewable biofeedstock into a highly valued compound.
A Prolific Catalyst for Selective Conversion of Neat Glycerol to Lactic Acid
Lu, Zhiyao,Demianets, Ivan,Hamze, Rasha,Terrile, Nicholas J.,Williams, Travis J.
, p. 2014 - 2017 (2016)
We report the synthesis and reactivity of a very robust iridium catalyst for glycerol to lactate conversion. The high reactivity and selectivity of this catalyst enable a sequence for the conversion of biodiesel waste stream to lactide monomers for the preparation of poly(lactic acid). Furthermore, experimental data collected with this system provide a general understanding of its reactive mechanism.
Immobilizing Systems Biocatalysis for the Selective Oxidation of Glycerol Coupled to InSitu Cofactor Recycling and Hydrogen Peroxide Elimination
Rocha-Martin, Javier,Acosta, Andreína,Guisan, Jose M.,L?pez-Gallego, Fernando
, p. 1939 - 1947 (2015)
The combination of three different enzymes immobilized rationally on the same heterofunctional carrier allowed the selective oxidation of glycerol to 1,3-dihydroxyacetone (DHA) coupled to insitu redox-cofactor recycling and H2O2 elimination. In this cascade, engineered glycerol dehydrogenase with reduced product inhibition oxidized glycerol selectively to DHA with the concomitant reduction of NAD+ to NADH. NADH oxidase regenerated the NAD+ pool by oxidizing NADH to NAD+ to form H2O2 as the byproduct. Finally, catalase eliminated H2O2 to yield water and O2 as innocuous products, which avoided the spontaneous DHA oxidation triggered by H2O2. The co-immobilization of the three enzymes on the same porous carrier allowed the insitu recycling and disproportionation of the redox cofactor and H2O2, respectively, to produce up to 9.5mM DHA, which is 18- and 6-fold higher than glycerol dehydrogenase itself and a soluble multienzyme system, respectively.
A novel glycerol valorization route: Chemoselective dehydrogenation catalyzed by iridium derivatives
Farnetti, Erica,Kaspar, Jan,Crotti, Corrado
, p. 704 - 709 (2009)
Organoiridium derivatives of the type Ir(diene)(N-N)X (diene = 1,5-hexadiene,1,5-cyclooctadiene; N-N = 2,2′-bipyridine, 1,10-phenanthroline and substituted derivatives; X = Cl, I) catalyze the hydrogen transfer reaction from glycerol to acetophenone, yielding dihydroxyacetone and phenylethanol. The catalytic reactions are performed at temperatures of 100 °C or higher, in the presence of a basic cocatalyst. The effect of experimental conditions on overall conversion and catalyst lifetime is discussed, as well as on the degradation of dihydroxyacetone, which can lead to an apparent decrease of selectivity of the catalytic reaction.
NEW MECHANISTIC PROPOSAL FOR SOME HEPTAMOLYBDATE-ION-CATALYZED ISOMERIZATIONS
Klaic, Branimir,Raza, Zlata,Sankovic, Mauricio,Sunjic, Vitomir
, p. 59 - 62 (1987)
Heptamolybdate-ion(HM)-catalyzed C(2) epimerization of D-glucose and racemization of D-glyceraldehyde proceed with comparable rates and activation parameters; HM catalyzes the isomerisation of glucal and galactal triacetates as well.For all of the above transformations, a common, new mechanism is proposed that invokes stabilization of 3-oxa-allylic cation species by the central Mo(VI) atom.
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Fernbach
, p. 1005 (1910)
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FSAB: A new fructose-6-phosphate aldolase from Escherichia coli. Cloning, over-expression and comparative kinetic characterization with FSAA
Sanchez-Moreno, Israel,Nauton, Lionel,Thery, Vincent,Pinet, Agnes,Petit, Jean-Louis,De Berardinis, Veronique,Samland, Anne K.,Guerard-Helaine, Christine,Lemaire, Marielle
, p. 9 - 14 (2012)
Fructose-6-phosphate aldolase B (FSAB) from Escherichia coli was successfully over-expressed as His-tagged recombinant protein. A decameric protein was observed as for FSAA. Unlike FSAA, FSAB is not thermally stable at temperatures higher than 60 °C. The 70% identity between the two aldolases has allowed the generation of a 3D structure which has shown a high similarity of the two active sites. Full kinetic studies towards several substrates have revealed that FSAB catalytic activity is very close to FSAA activity, corroborated by the similarity of their active sites. FSAB has been able to react with three known donors (dihydroxyacetone, hydroxyacetone and glycolaldehyde) but always slightly slower than FSAA.
Selective oxidation of glycerol to formic acid catalyzed by iron salts
Farnetti,Crotti
, p. 1 - 4 (2016)
Glycerol is oxidized by hydrogen peroxide to formic acid with excellent selectivity in the presence of iron salts. The oxidation takes place at room temperature in water; at the end of the reaction the catalytic system is still active and available to restart the oxidation.
Semicrystalline dihydroxyacetone copolymers derived from glycerol
Simon, Jeff,Olsson, Johan V.,Kim, Hyunuk,Tenney, Ian F.,Waymouth, Robert M.
, p. 9275 - 9281 (2012)
The ring-opening polymerization of glycerol-derived six-membered cyclic dimethylacetal dihydroxyacetone carbonate (MeO2DHAC) have been studied both in solution and bulk conditions with organic catalysts. The guanidine 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) was the most active catalyst in solution, whereas the thiourea/sparteine catalytic system displayed the most predictable kinetics. Ring-opening polymerization of MeO2DHAC or copolymerization with ε-caprolactone (CL) in the melt occurred readily with TBD as catalyst to afford random copolymers. Acetal deprotection afforded the polycarbonate poly(dihydroxyactone carbonate) (p(DHAC)) or poly(carbonate ester) copolymers p(DHAC-r-CL). The polycarbonate p(DHAC) is a high-melting thermoplastic with a melting point of 246 °C. The p(DHAC-r-CL) copolymers all displayed semicrystalline behavior as evidenced by DSC and WAXS analysis with Tg and Tm changing as a function of comonomer composition. These new materials could have potential use in biomedical applications or as biomass-derived thermoplastics.
Contribution of phosphate intrinsic binding energy to the enzymatic rate acceleration for triosephosphate isomerase [18]
Amyes,O'Donoghue,Richard
, p. 11325 - 11326 (2001)
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Catalytic conversion of fructose to 1,3-dihydroxyacetone under mild conditions
Huang, Hong,Lv, Jing,Meng, Xiang-Guang,Wang, Fei,Wu, Yan-Yan,Yu, Wen-Wang
, (2020)
A novel zwitterionic catalyst containing imidazole, carboxyl and amino functional groups was synthesized to catalyze the retro-aldol condensation of fructose. The catalyst displayed efficiently catalytic activity for the conversion of fructose to 1,3-dihydroxyacetone (DHA). The yield of DHA and selectivity of DHA achieved 27.9percent and 46.5percent after reaction 2 h, respectively, at pH 9.5, 85 °C. A possible catalytic mechanism was suggested. The charged functional groups on the catalyst exhibited synergistic effect and played role in electron induction and proton transfer, which leaded to a good selectivity of DHA in the conversion of fructose under mild conditions.
One-pot electrocatalytic oxidation of glycerol to DHA
Ciriminna, Rosaria,Palmisano, Giovanni,Pina, Cristina Della,Rossi, Michele,Pagliaro, Mario
, p. 6993 - 6995 (2006)
One-pot, waste-free oxidation of glycerol to 1,3-dihydroxyacetone (DHA) was achieved by simply applying a small electric potential (1.1 V vs Ag/AgCl) to a glycerol solution in water buffered at pH 9.1 in the presence of 15 mol % TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl). Prolonging the reaction time affords comparable amounts of hydroxypyruvic acid.
Selective catalytic oxidation of diglycerol
Wang, Huan,Vu, Nam Duc,Chen, Guo-Rong,Métay, Estelle,Duguet, Nicolas,Lemaire, Marc
, p. 1154 - 1159 (2021/02/26)
The selective oxidation of α,α-diglycerol was studied using oxygen as a clean oxidant in the presence of a palladium/neocuproine complex. After optimization of the reaction parameters, the mono-oxidation product was obtained with 93% NMR yield (up to 76% isolated yield). The product was named “diglycerose” considering that it mainly exists as a cyclic hemi-ketal form.
Design of a synthetic enzyme cascade for the: In vitro fixation of a C1carbon source to a functional C4sugar
Güner, Samed,Pick, André,Sieber, Volker,Wegat, Vanessa
supporting information, p. 6583 - 6590 (2021/09/10)
Realizing a sustainable future requires intensifying the waste stream conversion, such as converting the greenhouse gas carbon dioxide into value-added products. In this paper, we focus on utilizing formaldehyde as a C1 carbon source for enzymatic C-C bond formation. Formaldehyde can be sustainably derived from other C1 feedstocks, and in this work, we designed a synthetic enzyme cascade for producing the functional C4 sugar erythrulose. This involved tailoring the enzyme formolase, which was optimized for fusing formaldehyde, from a three-carbon producer (dihydroxyacetone) to sets of variants with enhanced two-carbon (glycolaldehyde) or four-carbon (erythrulose) activity. To achieve this, a high-throughput combinatorial screening was developed, and every single variant was evaluated in terms of glycolaldehyde, dihydroxyacetone and erythrulose activity. By applying the two most promising variants in an enzyme cascade, we were able to show for the first time production of ERY starting from a C1 carbon source. In addition, we demonstrated that one of our tailored formolase variants was able to convert 25.0 g L-1 glycolaldehyde to 24.6 g L-1 erythrulose (98% theoretical yield) in a fully atom-economic biocatalytic process. This represents the highest achieved in vitro concentration of erythrulose to date.
