498-07-7Relevant articles and documents
A one-pot reaction for biorefinery: Combination of solid acid and base catalysts for direct production of 5-hydroxymethylfurfural from saccharides
Takagaki, Atsushi,Ohara, Mika,Nishimura, Shun,Ebitani, Kohki
, p. 6276 - 6278 (2009)
5-Hydroxymethylfurfural (HMF), one of the most important intermediates derived from biomass, was directly produced from monosaccharides (fructose and glucose) and disaccharides (sucrose and cellobiose) by a simple one-pot reaction including hydrolysis, isomerization and dehydration using solid acid and base catalysts under mild conditions.
Uncatalysed wet oxidation of d-glucose with hydrogen peroxide and its combination with hydrothermal electrolysis
Moreno, Teresa,Kouzaki, Goushi,Sasaki, Mitsuru,Goto, Motonobu,Cocero, María José
, p. 33 - 38 (2012)
An increasing interest in biomass as a renewable feedstock for the chemical industry has risen over the last decades, and glucose, the monomer unit of cellulose, has been widely studied as a source material to produce value-added products such as carboxylic acids, mainly gluconic and formic. In this work, the non-catalysed wet oxidation of glucose using hydrogen peroxide has been analysed, obtaining molar yields to gluconic and formic acids up to 15% and 64%, respectively. Glucose conversion was generally between 40 and 50%, reaching over 80% under the highest temperature (200°C). An appropriate choice of temperature can tune product distribution as well as reaction rates. The interaction of the wet oxidation with an electrolytic reaction was also analysed.
Sulfonic acid-functionalized carbon coated red mud as an efficient catalyst for the direct production of 5-HMF from D-glucose under microwave irradiation
Das, Bikashbindu,Mohanty, Kaustubha
, (2021)
Though suitable for the fructose conversion to 5-hydroxymethylfurfural (5-HMF), sulfonated carbon catalysts are inefficient for the direct glucose transformation to 5-HMF due to the lack of appropriate Lewis acids. Here, we have reported an efficient and inexpensive catalyst by suitably modifying red mud (RM), a by-product from the aluminum industry. The AD-1:1/SO3H catalyst produced by the acid (HCl) treatment, carbon coating, and SO3H grafting on RM exhibited enhanced surface area, mesoporous characteristics, and suitable Lewis and Bronsted acid sites. The XRD, FTIR, and XPS analysis suggested Fe2(SO4)3, Fe2O3, and various carbon functionalities as the major active components in the AD-1:1/SO3H catalyst. The NH3-TPD analysis revealed an appreciable acid site density of 6.8 mmol g?1. Under microwave heating at 180 °C, 30 min, and 90:10 DMSO/water weight percentage ratio, the catalyst produced a D-glucose conversion and 5-HMF yield of 93.05 % and 51.5 %, respectively.
Producing Glucose 6-phosphate from cellulosic biomass: Structural insights into levoglucosan bioconversion
Bacik, John-Paul,Klesmith, Justin R.,Whitehead, Timothy A.,Jarboe, Laura R.,Unkefer, Clifford J.,Mark, Brian L.,Michalczyk, Ryszard
, p. 26638 - 26648 (2015)
The most abundant carbohydrate product of cellulosic biomass pyrolysis is the anhydrosugar levoglucosan (1, 6-anhydro-β-D-glucopyranose), which can be converted to glucose 6-phosphate by levoglucosan kinase (LGK). In addition to the canonical kinase phosphotransfer reaction, the conversion requires cleavage of the 1, 6-anhydro ring to allow ATP-dependent phosphorylation of the sugar O6 atom. Using x-ray crystallography, we show that LGK binds two magnesium ions in the active site that are additionally coordinated with the nucleotide and water molecules to result in ideal octahedral coordination. To further verify the metal binding sites, we co-crystallized LGK in the presence of manganese instead of magnesium and solved the structure de novo using the anomalous signal from four manganese atoms in the dimeric structure. The first metal is required for catalysis, whereas our work suggests that the second is either required or significantly promotes the catalytic rate. Although the enzyme binds its sugar substrate in a similar orientation to the structurally related 1, 6-anhydro-N-acetylmuramic acid kinase (AnmK), it forms markedly fewer bonding interactions with the substrate. In this orientation, the sugar is in an optimal position to couple phosphorylation with ring cleavage. We also observed a second alternate binding orientation for levoglucosan, and in these structures, ADP was found to bind with lower affinity. These combined observations provide an explanation for the high Km of LGK for levoglucosan. Greater knowledge of the factors that contribute to the catalytic efficiency of LGK can be used to improve applications of this enzyme for levoglucosan-derived biofuel production.
Free energy landscape for glucose condensation and dehydration reactions in dimethyl sulfoxide and the effects of solvent
Qian, Xianghong,Liu, Dajiang
, p. 50 - 60 (2014)
The mechanisms and free energy surfaces (FES) for the initial critical steps during proton-catalyzed glucose condensation and dehydration reactions were elucidated in dimethyl sulfoxide (DMSO) using Car-Parrinello molecular dynamics (CPMD) coupled with me
Glucose to value-added chemicals: Anhydroglucose formation by selective dehydration over solid acid catalysts
Takagaki, Atsushi,Ebitani, Kohki
, p. 650 - 651 (2009)
Selective dehydration of glucose to anhydroglucoses, 1,6-anhydro-β-D- glucopyranose (levoglucosan) and 1,6-anhydro-β-D-glucofuranose, which are highly value-added intermediates for drugs, polymers, and surfactants was performed. Solid acids with sulfonic acid groups like Amberlyst-15 were found to effectively produce anhydroglucoses in polar aprotic solvents. Copyright
Isotope labeling studies on the formation of 5-(hydroxymethyl)-2- furaldehyde (HMF) from sucrose by pyrolysis-GC/MS
Locas, Carolina Perez,Yaylayan, Varoujan A.
, p. 6717 - 6723 (2008)
Although it is generally assumed that the reactivity of sucrose, a nonreducing sugar, in the Maillard reaction is due to its hydrolysis into free glucose and fructose, however, no direct evidence has been provided for this pathway, especially in dry and high temperature systems. Using specifically Relabeled sucrose at C-1 of the fructose moiety, HMF formation was studied at different temperatures. Under dry pyrolytic conditions and at temperatures above 250°C, 90% of HMF originated from fructose moiety and only 10% originated from glucose. Alternatively, when sucrose was refluxed in acidic methanol at 65°C, 100% of HMF was generated from the glucose moiety. Moreover, the relative efficiency of the known HMF precursor 3-deoxyglucosone to generate HMF was compared to that of glucose, fructose and sucrose. Glucose exhibited a much lower conversion rate than 3-deoxyglucosone, however, both fructose and sucrose showed much higher conversion rates than 3-deoxyglucosone thus precluding it as a major precursor of HMF in fructose and sucrose solutions. Based on the data generated, a mechanism of HMF formation from sucrose is proposed. According to this proposal sucrose degrades into glucose and a very reactive fructofuranosyl cation. In dry systems this cation can be effectively converted directly into HMF.
Syntheses of 5-hydroxymethylfurfural and levoglucosan by selective dehydration of glucose using solid acid and base catalysts
Ohara, Mika,Takagaki, Atsushi,Nishimura, Shun,Ebitani, Kohki
, p. 149 - 155 (2010)
Selective dehydration of glucose, the most abundant monosaccharide, was examined using a solid acid catalyst individually or a combination of solid acid and base catalysts to form anhydroglucose (levoglucosan) or 5-hydroxymethylfurfural (HMF), respectively. Glucose was dehydrated to anhydroglucose by acid catalysis in polar aprotic solvents including N,N-dimethylformamide. Amberlyst-15, a strongly acidic ion-exchange resin, functioned as an efficient solid acid catalyst for anhydroglucose production with high selectivity. In the presence of solid base, aldose-ketose isomerization of glucose to fructose preferentially occurred by base catalysis, even in coexistence with the solid acid, resulting in successive dehydration of fructose to 5-hydroxymethylfurfural by acid catalysis with high yield in a one-pot reaction. A combination of Amberlyst-15 and hydrotalcite, an anionic layered clay, afforded high HMF selectivity under a moderate reaction temperature, owing to prevention of anhydroglucose formation.
Production of solubilized carbohydrate from cellulose using non-catalytic, supercritical depolymerization in polar aprotic solvents
Ghosh, Arpa,Brown, Robert C.,Bai, Xianglan
, p. 1023 - 1031 (2016)
We report yields of solubilized and depolymerized carbohydrate from solvent processing of cellulose as high as 94% without use of catalysts. Cellulose was converted using a variety of polar aprotic solvents at supercritical conditions, including 1,4-dioxane, ethyl acetate, tetrahydrofuran, methyl iso-butyl ketone, acetone, acetonitrile, and gamma-valerolactone. Maximum yield of solubilized products from cellulose, defined as both depolymerized carbohydrate and products of carbohydrate dehydration, was 72 to 98% at 350 °C for reaction times of 8-16 min. In all cases solvents were recovered with high efficiency. Levoglucosan was the most prevalent solubilized carbohydrate product with yields reaching 41% and 34% in acetonitrile and gamma-valerolactone, respectively. Levoglucosan yields increased with increasing polar solubility parameter, corresponding to decreasing activation energy for cellulose depolymerization.
Biochemical Characterization and Mechanistic Analysis of the Levoglucosan Kinase from Lipomyces starkeyi
Rother, Christina,Gutmann, Alexander,Gudiminchi, Ramakrishna,Weber, Hansj?rg,Lepak, Alexander,Nidetzky, Bernd
, p. 596 - 603 (2018)
Levoglucosan kinase (LGK) catalyzes the simultaneous hydrolysis and phosphorylation of levoglucosan (1,6-anhydro-β-d-glucopyranose) in the presence of Mg2+–ATP. For the Lipomyces starkeyi LGK, we show here with real-time in situ NMR spectroscopy at 10 °C and pH 7.0 that the enzymatic reaction proceeds with inversion of anomeric stereochemistry, resulting in the formation of α-d-glucose-6-phosphate in a manner reminiscent of an inverting β-glycoside hydrolase. Kinetic characterization revealed the Mg2+ concentration for optimum activity (20–50 mm), the apparent binding of levoglucosan (Km=180 mm) and ATP (Km=1.0 mm), as well as the inhibition by ADP (Ki=0.45 mm) and d-glucose-6-phosphate (IC50=56 mm). The enzyme was highly specific for levoglucosan and exhibited weak ATPase activity in the absence of substrate. The equilibrium conversion of levoglucosan and ATP lay far on the product side, and no enzymatic back reaction from d-glucose-6-phosphate and ADP was observed under a broad range of conditions. 6-Phospho-α-d-glucopyranosyl fluoride and 6-phospho-1,5-anhydro-2-deoxy-d-arabino-hex-1-enitol (6-phospho-d-glucal) were synthesized as probes for the enzymatic mechanism but proved inactive with the enzyme in the presence of ADP. The pyranose ring flip 4C1→1C4 required for 1,6-anhydro-product synthesis from d-glucose-6-phosphate probably presents a major thermodynamic restriction to the back reaction of the enzyme.
