41847-06-7Relevant academic research and scientific papers
Efficient isomerization of glucose to fructose over zeolites in consecutive reactions in alcohol and aqueous media
Saravanamurugan, Shunmugavel,Paniagua, Marta,Melero, Juan A.,Riisager, Anders
, p. 5246 - 5249 (2013)
Isomerization reactions of glucose were catalyzed by different types of commercial zeolites in methanol and water in two reaction steps. The most active catalyst was zeolite Y, which was found to be more active than the zeolites beta, ZSM-5, and mordenite. The novel reaction pathway involves glucose isomerization to fructose and subsequent reaction with methanol to form methyl fructoside (step 1), followed by hydrolysis to re-form fructose after water addition (step 2). NMR analysis with 13C-labeled sugars confirmed this reaction pathway. Conversion of glucose for 1 h at 120 C with H-USY (Si/Al = 6) gave a remarkable 55% yield of fructose after the second reaction step. A main advantage of applying alcohol media and a catalyst that combines Bronsted and Lewis acid sites is that glucose is isomerized to fructose at low temperatures, while direct conversion to industrially important chemicals like alkyl levulinates is viable at higher temperatures.
Microwave-assisted catalytic conversion of glucose to 5-hydroxymethylfurfural using "three dimensional" graphene oxide hybrid catalysts
Beltramini, Jorge N.,Hayami, Shinya,Hirano, Yui,Karim, Mohammad Razaul,Kim, Yang,Mori, Atsushi,Nakamura, Manami,Nakamura, Masaaki
, p. 11727 - 11736 (2020)
Hybrids of reduced graphene oxide (rGO) and metal/metal oxide (Pt, NiO/Ni(OH)2, CoO, Fe3O4) nano particle were prepared by reduction of graphene oxide (GO) and metal ion (Pt2+, Ni2+, Co2+, Fe2+) hybrids. The M-rGO hybrids (M = Pt, Ni-, Co and Fe) were justified for the transformation of glucose to 5-hydroxymethylfurfural (5-HMF). High glucose → 5-HMF conversion was yielded depending on the nature of the M-rGO catalyst. The Ni-rGO showed the highest 5-HMF yield. The conversion reaction tuned to the optimized state under a microwave-assisted reaction accomplished by using Ni-rGO. In such case, the conversion rate was 99% with a 5-HMF yield of 75%. In order to improve both the conversion and yield, NiGO-FD was prepared by a freeze-dry method. The NiGO-FD remarkably showed the highest conversion of 99% and 5-HMF yield of 95%. Beside the biomass transformation process, the physico-chemical strategy employed herein for multiplying the catalytic efficiency might be justified for catalyzing similar reactions.
Two-step biosynthesis of D-allulose via a multienzyme cascade for the bioconversion of fruit juices
Li, Chao,Li, Lei,Feng, Zhiyuan,Guan, Lijun,Lu, Fuping,Qin, Hui-Min
, (2021/04/27)
D-Allulose, a low-calorie rare sugar with potential as sucrose substitute for diabetics, can be produced using D-allulose 3-epimerase (DAE). Here, we characterized a putative thermostable DAE from Pirellula sp. SH-Sr6A (PsDAE), with a half-life of 6 h at 60 °C. Bioconversion of 500 g/L D-fructose using immobilized PsDAE on epoxy support yielded 152.7 g/L D-allulose, which maintained 80% of the initial activity after 11 reuse cycles. A multienzyme cascade system was developed to convert sucrose to D-allulose comprising sucrose invertase, D-glucose isomerase and PsDAE. Fruit juices were treated using this system to convert the high-calorie sugars, such as sucrose, D-glucose, and D-fructose, into D-allulose. The content of D-allulose among total monosaccharides in the treated fruit juice remained between 16 and 19% during 15 reaction cycles. This study provides an efficient strategy for the development of functional fruit juices containing D-allulose for diabetics and other special consumer categories.
Tunable acidity in mesoporous carbons for hydrolysis reactions
Ferri,Campisi,Carniti,Gervasini,Shen
supporting information, p. 5873 - 5883 (2020/04/29)
A mesoporous carbon (CMC) has been treated under acidic conditions (32.5 wt% HNO3 at 10 °C or 40 °C) to prepare two new carbon samples (HCMC10 and HCMC40), which developed higher acidity in terms of quantity of sites and surface acid strength. The properties of the three carbons have been studied by using various techniques (N2 adsorption/desorption, TEM, XRPD, Raman spectroscopy, 13C NMR, 2D 1H-13C NMR, and XPS). Aromatic -COOH and -OH groups were identified as the main surface acid sites. Acid site density has been determined by pulse liquid-solid phase adsorption experiments carried out in different liquids. The samples retained acidity features in water, due to hydrophobicity of the surfaces, while acidity dropped when measured in methanol. From NH3-TPD analysis, a ranking of acid strength could be obtained: HCMC40 > HCMC10 > CMC. The good acidity of the carbon samples allowed them to act as catalysts in the hydrolysis reaction of sucrose to glucose and fructose. The catalytic activity of the carbon samples was compared to that of Amberlite, a commercial sulfated acid resin; the observed kinetic constant of HCMC40 was similar to that of Amberlite.
Hydrogenation of crude and purified d-glucosone generated by enzymatic oxidation of d-glucose
Aho, Atte,Lassfolk, Robert,Leino, Reko,Murzin, Dmitry Yu.
, p. 30476 - 30480 (2020/09/11)
D-Fructose is an important starting material for producing furfurals and other industrially important chemicals. While the base-catalyzed and enzymatic conversion of d-glucose to d-fructose is well known, the employed methods typically provide limited conversion. d-Glucosone can be obtained from d-glucose by enzymatic oxidation at the C2 position and, subsequently, selectively hydrogenated at C1 to form d-fructose. This work describes an investigation on the hydrogenation of d-glucosone, using both chromatographically purified and crude material obtained directly from the enzymatic oxidation, subjected to filtration and lyophilization only. High selectivities towards d-fructose were observed for both starting materials over a Ru/C catalyst. Hydrogenation of the crude d-glucosone was, however, inhibited by the impurities resulting from the enzymatic oxidation process. Catalyst deactivation was observed in the case of both starting materials.
FeVO4 decorated –SO3H functionalized polyaniline for direct conversion of sucrose to 2,5-diformylfuran & 5-ethoxymethylfurfural and selective oxidation reaction
Kumar, Abhinav,Srivastava, Rajendra
, p. 68 - 79 (2019/01/08)
In this study, a multi-functional catalyst, FeVO4 supported –SO3H functionalized polyaniline is prepared. First FeVO4 supported polyaniline is prepared. Then the resultant material is sulfonated using chlorosulphonic acid to obtain FeVO4 supported –SO3H functionalized polyaniline. This multi-functional catalyst exhibits excellent activity in the synthesis of 5-hydroxymethylfurfural from sucrose and oxidation of a wide range of aromatic and aliphatic alcohols. Further, the catalyst exhibits very good activity in the one-pot direct conversion of sucrose/fructose to 2,5-diformylfuran (DFF) and 5-ethoxymethylfurfural (EMF). This catalytic process involves the economical sucrose as a reactant and economical multi-functional catalyst based on polyaniline. In this one-pot, two-step process, -SO3H functionalized polyaniline is used in the first step for the conversion of sucrose to 5-hydroxymethylfurfural (HMF) followed by selective oxidation of HMF to DFF using FeVO4 sites present in the multi-functional catalyst. Moreover, acidic sites present in the multi-functional catalyst are suitable for the conversion of sucrose/fructose/HMF to EMF. Furthermore, molecular oxygen (1 atmosphere, 10 ml/min) is used as an eco-friendly and economical oxidant for the selective oxidation of a wide range of aromatic and aliphatic alcohols to aldehydes. The multi-functional catalyst presented here has been easily separated and recycled that make the process sustainable and economical for commercial perspectives.
One-pot sol-gel synthesis of a phosphated TiO2 catalyst for conversion of monosaccharide, disaccharides, and polysaccharides to 5-hydroxymethylfurfural
Rao, Kasanneni Tirumala Venkateswara,Souzanchi, Sadra,Yuan, Zhongshun,Xu, Chunbao
supporting information, p. 12483 - 12493 (2019/08/12)
Catalytic conversion of biomass or biomass-derived carbohydrates into 5-hydroxymethylfurfural (HMF) is an important reaction for the synthesis of bio-based polymers, fuels, and other industrially useful products. In this study, phosphated titania (P-TiO2) catalysts with different phosphoric acid content were prepared through a simple one-pot sol-gel method and characterized by BET, XRD, FT-IR, NH3-TPD, py-FT-IR, and XPS techniques. The catalyst characterization results revealed the incorporation of phosphorus into the TiO2 framework in the form of a Ti-O-P bond. The P-TiO2 catalysts were applied to the conversion of glucose (≥10 wt%) into HMF in a biphasic water/THF reaction medium at 175 °C. Under optimized reaction conditions, 98% glucose conversion and 53% HMF yield were obtained over a 15P-TiO2 catalyst, and the catalyst was reused for several cycles with consistent activity and selectivity. The presence of both Br?nsted and Lewis acid sites, high BET surface area and pore volume, and high acidity could account for the high catalytic activity and selectivity. Besides, the 15P-TiO2 catalyst was also demonstrated to be active for the conversion of disaccharides (sucrose and cellobiose), polysaccharides (starch and microcrystalline cellulose) and industrial grade sugar syrups into HMF with reasonable yield.
Tin Grafted on Modified Alumina-Catalyzed Isomerisation of Glucose to Fructose
Yatoo, Muhamad Aadil,Saravanamurugan, Shunmugavel
, (2019/06/28)
The present study focuses on designing a catalyst based on hot water treated alumina (Al2O3-HWT) for the conversion of glucose to fructose. The glucose isomerisation reactions are performed with tin incorporated on parent Al2O3 and Al2O3-HWT in methanol. 0.5 wt% Sn/Al2O3-HWT affords a combined yield of fructose and methylfructoside (30.4%) which is two-fold higher than that obtained with 0.5wt% Sn/Al2O3 (15.1%), implying the importance of hot water treatment of Al2O3. Al2O3-HWT shows a very broad peak centred around 3440 cm-1, which could be assigned to OH stretching band of gibbsite, γ-Al(OH)3 which significantly diminished after solid state ion-exchange with SnCl4.5H2O (0.5 wt% Sn/Al2O3-HWT). UV-Vis diffused reflectance spectrum of 0.5 wt% Sn/Al2O3-HWT displays a peak centered at 241 nm, which can be ascribed to the incorporation of tin into the alumina network. XRD patterns of 0.5, 3 and 5 wt% Sn/Al2O3-HWT show that no peak corresponding to SnO2 is formed. Importantly, 0.5wt% SnO2/Al2O3-HWT exhibits a low activity, giving 13.2% of the total yield of fructose and methylfructoside, respectively, compared to 0.5wt% Sn/Al2O3-HWT (30.4% fructose), signifying the role of incorporated tin into the alumina network.
Phenolic compounds from Belamcanda chinensis seeds
Song, Ying-Ying,Liu, Ying,Yan, Yong-Ming,Lu, Xi-Feng,Cheng, Yong-Xian
, (2018/03/21)
Two new sucrose derivatives, namely, belamcanosides A (1) and B (2), together with five other known compounds (3-7), were isolated from the seeds of Belamcanda chinensis (L.) DC. Their structures were identified based on spectroscopic data. Especially, the absolute configurations of fructose and glucose residues in 1 and 2 were assigned by acid hydrolysis, followed by derivatization and gas chromatography (GC) analysis. Among the known compounds, (-)-hopeaphenol (3), (+)-syringaresinol (4), and quercetin (5), were isolated from B. chinensis for the first time. In addition, biological evaluation of 1 and 2 against cholesterol synthesis and metabolism at the gene level was carried out. The results showed that compounds 1 and 2 could regulate the expression of cholesterol synthesis and metabolism-associated genes, including 3-hydroxy-3-methylglutaryl-coenzyme A reductase (HMGCR), squalene epoxidase (SQLE), low density lipoprotein receptor (LDLR), and sortilin (SORT1) genes in HepG2 cells.
Effect of Tetrahydrofuran on the Solubilization and Depolymerization of Cellulose in a Biphasic System
Jiang, Zhicheng,Zhao, Pingping,Li, Jianmei,Liu, Xudong,Hu, Changwei
, p. 397 - 405 (2018/01/03)
The dissolution of cellulose from biomass is a crucial but complicated issue for maximizing the utilization of biomass resources to produce valuable chemicals, because of the extreme insolubility of cellulose. A biphasic NaCl–H2O–tetrahydrofuran (THF) system was studied, in which most of the pure microcrystalline cellulose (M-cellulose, 96.6 % conversion at 220 °C) and that contained in actual biomass were converted. Nearly half of the O6?H???O3 intermolecular hydrogen bonds could be broken by THF in the H2O–THF co-solvent system, whereas the cleavage of O2?H???O6 intramolecular hydrogen bonds by H2O was significantly inhibited. In the NaCl–H2O–THF system, THF could significantly promote the effects of both H2O and NaCl on the disruption of O2?H???O6 and O3?H???O5 intramolecular hydrogen bonds, respectively. In addition, THF could protect and transfer the cellulose-derived products to the organic phase by forming hydrogen bonds between the oxygen atom in THF and the hydrogen atom of C4?OH in the glucose or aldehyde group in 5-hydroxymethylfurfural (HMF), which can lead more NaCl to combine with the -OH of M-cellulose and further disrupt hydrogen bonding in M-cellulose, thereby improving the yield of small molecular weight products (especially HMF) and further promoting the dissolution of cellulose. As a cheap and reusable system, NaCl–H2O–THF system may be a promising approach for the dissolution and further conversion of cellulose in lignocellulosic biomass without any enzymes, ionic liquids, or conventional catalysts.
