470-23-5Relevant articles and documents
Hybrid Organic–Inorganic Anatase as a Bifunctional Catalyst for Enhanced Production of 5-Hydroxymethylfurfural from Glucose in Water
Lanziano, Carlos A. S.,Moya, Silvia F.,Barrett, Dean. H.,Teixeira-Neto, Erico,Guirardello, Reginaldo,de Souto da Silva, Felipe,Rinaldi, Roberto,Rodella, Cristiane B.
, p. 872 - 880 (2018)
Hybrid organic–inorganic anatase (hybrid-TiO2) is prepared by a facile hydrothermal synthesis method employing citric acid. The synthetic approach results in a high surface-area nanocrystalline anatase polymorph of TiO2. The uncalcin
Analysis of the hydrolysis of inulin using real time 1H NMR spectroscopy
Barclay, Thomas,Ginic-Markovic, Milena,Johnston, Martin R.,Cooper, Peter D.,Petrovsky, Nikolai
, p. 117 - 125 (2012)
The hydrolysis of various carbohydrates was investigated under acidic conditions in real time by 1H NMR spectroscopy, with a focus on the polysaccharide inulin. Sucrose was used as a model compound to illustrate the applicability of this technique. The hydrolysis of sucrose was shown to follow pseudo first order kinetics and have an activation energy of 107.0 kJ mol -1 (SD 1.7 kJ mol-1). Inulin, pullulan and glycogen also all followed pseudo first order kinetics, but had an initiation phase at least partially generated by the protonation of the glycosidic bonds. It was also demonstrated that polysaccharide chain length has an effect on the hydrolysis of inulin. For short chain inulin (DPn 18, SD 0.70) the activation energy calculated for the hydrolytic cleavage of glucose was similar to sucrose at 108.5 kJ mol-1 (SD 0.60). For long chain inulin (DPn 30, SD 1.3) the activation energy for the hydrolytic cleavage of glucose was reduced to 80.5 kJ mol-1 (SD 2.3 kJ mol-1). This anomaly has been attributed to varied conformations for the two different lengths of inulin chain in solution.
Direct conversion of inulin to 5-hydroxymethylfurfural in biorenewable ionic liquids
Hu, Suqin,Zhang, Zhaofu,Zhou, Yinxi,Song, Jinliang,Fan, Honglei,Han, Buxing
, p. 873 - 877 (2009)
In this work, we found that inulin is soluble in ionic liquids (ILs) choline chloride (ChoCl)/oxalic acid and ChoCl/citric acid, which are prepared entirely from cheap and renewable materials. On the basis of this discovery, we conducted the one pot react
Exceptionally Efficient and Recyclable Heterogeneous Metal–Organic Framework Catalyst for Glucose Isomerization in Water
Oozeerally, Ryan,Burnett, David L.,Chamberlain, Thomas W.,Walton, Richard I.,Degirmenci, Volkan
, p. 706 - 709 (2018)
Heterogeneous catalysts are desired for the conversion of glucose, the most abundant sugar in renewable biomass, but presently their synthesis requires highly toxic chemicals with long synthesis times. We report the conversion of glucose into fructose and 5-hydroxymethylfurfural on a heterogeneous catalyst that is stable and selective and operates in the most environmentally benign solvent, water. We used a bifunctional solid with Lewis and Br?nsted acid sites by partially replacing the organic linker of the zirconium organic framework UiO-66 with 2-monosulfo-benzene-1,4-dicarboxylate. This catalyst showed high product selectivity (90 %) to 5-hydroxymethylfurfural and fructose at 140 °C in water after a reaction time of 3 h. It was recyclable and showed only a minor loss in activity after the third recycle, offering a realistic solution for the bottleneck glucose isomerization reaction for scale-up and industrial application of biomass utilization.
Cs-substituted tungstophosphate-supported ruthenium nanoparticles as efficient and robust bifunctional catalysts for the conversion of inulin and cellulose into hexitols in water in the presence of H2
Deng, Weiping,Zhu, Enze,Liu, Mi,Zhang, Qinghong,Wang, Ye
, p. 43131 - 43141 (2014)
Cellulose and inulin, two important biomasses, can be transformed to polyols using bifunctional catalysts combining acid sites for hydrolysis and metal nanoparticles for hydrogenation. Here, we report that Ru nanoparticles loaded on a Keggin-type polyoxometalate, i.e., Cs3PW12O40, without intrinsic Bronsted acidity exhibit superior catalytic performances for the transformation of inulin and cellulose into hexitols in water in the presence of H2. We demonstrated that new Bronsted acid sites were generated from H2 on the Ru/Cs3PW12O40 catalyst. The H2-originated reversible Bronsted acid sites were robust during the transformation of biomass under hydrothermal conditions. We further found that the mean size of Ru nanoparticles determined the product selectivity in the conversion of inulin under H2. The catalyst with larger Ru nanoparticles favoured the formation of fructose, the hydrolysis product, while the major products were hexitols over the catalyst with a smaller Ru particle size. We clarified that, as compared to that of inulin hydrolysis, the rate of fructose hydrogenation increased more rapidly upon decreasing the Ru particle size.
OSDA-Free Zeolite Beta with High Aluminum Content Efficiently Catalyzes a Tandem Reaction for Conversion of Glucose to 5-Hydroxymethylfurfural
Otomo, Ryoichi,Yokoi, Toshiyuki,Tatsumi, Takashi
, p. 4180 - 4187 (2015)
Organic structure-directing agent (OSDA)-free zeolite Beta with high Al content exhibit remarkably high catalytic performance in the conversion of glucose to 5-hydroxymethylfurfural (HMF) by virtue of their appropriate acid properties; specifically, a sufficient number of Lewis acid sites were generated by calcination of the NH4-form zeolite, while the original Bronsted acid sites were substantially maintained, with both acid sites being in close proximity. The OSDA-free Beta catalyst, having a large number of Bronsted acid sites and sufficient Lewis acid sites, showed superior catalytic performance to a physical mixture of each type of acid catalyst with a similar number of each acid site. This behavior could be ascribed to the high reactivity and slow intrazeolitic diffusion of fructose. The structure of the Al species active in the isomerization of glucose to fructose is discussed based on relationships between catalytic activities and changes in Al species by the calcination, changes that were observed by 27Al magic-angle spinning (MAS) NMR and IR spectroscopies. Lewis and Bronsted, working together: Organic structure-directing agent (OSDA)-free zeolite Beta with high Al content effectively promotes conversion of glucose to 5-hydroxymethylfurfural (HMF). The high aluminum content of the zeolite provides suitable acid properties; specifically, a large number of Bronsted acid sites with a sufficient number of Lewis acid sites in close proximity. The zeolite calcined at 773 K showed >70 % yield of HMF.
Effect of CO2 on conversion of inulin to 5-hydroxymethylfurfural and propylene oxide to 1,2-propanediol in water
Wu, Suxiang,Fan, Honglei,Xie, Ye,Cheng, Yan,Wang, Qian,Zhang, Zhaofu,Han, Buxing
, p. 1215 - 1219 (2010)
The CO2-water system has the potential to serve as a substitute for mineral acids for some reactions in acidic media. In this work, two reactions under hydrothermal conditions with and without CO2 were studied - the conversion of inulin to 5-hydroxymethylfurfural (5-HMF), and the hydrolysis of propylene oxide to 1,2-propanediol (1,2-PDO). The effects of CO2 pressure, reaction temperature and reactant concentration on the yield of 5-HMF and 1,2-PDO were examined. It was demonstrated that CO 2 could increase the yields of 5-HMF and 1,2-PDO considerably under optimized conditions. The methods to prepare 5-HMF and 1,2-PDO are greener, in that conventional acids are not required and the solution is neutralized automatically after depressurization. The Royal Society of Chemistry 2010.
Glucosylation of acetic acid by sucrose phosphorylase
Nomura, Koji,Sugimoto, Kazuhisa,Nishiura, Hiromi,Ohdan, Kohji,Nishimura, Takahisa,Hayashi, Hideo,Kuriki, Takashi
, p. 82 - 87 (2008)
Transglucosylation from sucrose to acetic acid by sucrose phosphorylase (EC 2.4.1.7) was studied. 1-O-Acetyl-α-D-glucopyranose was isolated as the main product of the enzyme reaction. We also compared the pH-dependence of transglycosylation catalyzed by sucrose phosphorylase toward carboxyl and hydroxyl groups. With hydroquinone as an acceptor molecule, the transfer ratio of glucose residue was higher at neutral pH. This pH-activity profile was similar to that of the phosphorolysis of sucrose by sucrose phosphorylase, but with acetic acid as an acceptor molecule, the transfer ratio of glucose residue was higher at low pH. These findings suggest that the undissociated carboxyl group is essential to the acceptor molecule for the transglycosylation reaction of sucrose phosphorylase. In a sensory test, the sour taste of acetic acid was markedly reduced by glucosylation. The threshold value of the sour taste of acetic acid glucosides was approximately 100 times greater than that of acetic acid.
NMR for direct determination of Km and Vmax of enzyme reactions based on the Lambert W function-analysis of progress curves
Exnowitz, Franziska,Meyer, Bernd,Hackl, Thomas
, p. 443 - 449 (2012)
1H NMR spectroscopy was used to follow the cleavage of sucrose by invertase. The parameters of the enzyme's kinetics, Km and V max, were directly determined from progress curves at only one concentration of the substrate. For comparison with the classical Michaelis-Menten analysis, the reaction progress was also monitored at various initial concentrations of 3.5 to 41.8 mM. Using the Lambert W function the parameters Km and Vmax were fitted to obtain the experimental progress curve and resulted in Km = 28 mM and V max = 13 μM/s. The result is almost identical to an initial rate analysis that, however, costs much more time and experimental effort. The effect of product inhibition was also investigated. Furthermore, we analyzed a much more complex reaction, the conversion of farnesyl diphosphate into (+)-germacrene D by the enzyme germacrene D synthase, yielding Km = 379 μM and kcat = 0.04 s- 1. The reaction involves an amphiphilic substrate forming micelles and a water insoluble product; using proper controls, the conversion can well be analyzed by the progress curve approach using the Lambert W function.
Bifunctional heterogeneous catalysts derived from the coordination of adenosine monophosphate to Sn(iv) for effective conversion of sucrose to 5-hydroxymethylfurfural
Ji, Peijun,Jiao, Lutong,Meng, Han,Wang, Chenyu
, p. 630 - 640 (2022/02/09)
Adenosine 5′-monophosphate (AMP) with multiple functional groups can bind to various metal ions. In this work, AMP has been used as a ligand to coordinate Sn(iv) for the synthesis of porous coordination polymers (Sn-AMPs). The Sn-AMPs have both Br?nsted acid (BA) and Lewis acid (LA) sites and have been used as bifunctional heterogeneous catalysts for catalyzing the conversion of sucrose to 5-hydroxymethylfurfural (HMF), involving hydrolysis of sucrose to glucose and fructose, isomerization of glucose to fructose, and dehydration of fructose to HMF. The protonated N1 and OH–P of the coordinated AMP can form hydrogen bonds with glucose and fructose. This can promote the conversion of the sugars. Sn-AMP has exhibited a superior capability for the conversion of biomass-derived sugars into HMF. The HMF yields of 76.1%, 67.5% and 62.9% were achieved from fructose, glucose, and sucrose, respectively.
