1917-64-2Relevant academic research and scientific papers
5-Hydroxymethyl-2-vinylfuran: A biomass-based solvent-free adhesive
Han, Miaomiao,Liu, Xiao,Zhang, Xiaosa,Pang, Yuanyuan,Xu, Peng,Guo, Jianwei,Liu, Yadong,Zhang, Shuangyan,Ji, Shengxiang
, p. 722 - 728 (2017)
5-Hydroxymethylfurfural (HMF) is an important platform chemical derived from biomass. Tremendous efforts have been made to transform HMF into valuable chemicals for applications in biofuels, materials science, and pharmaceuticals. Here we report the conversion of HMF into 5-hydroxymethyl-2-vinylfuran (HMVF), a versatile adhesive. HMVF can bond to a variety of substrates, e.g. metal, glass, plastics and rubber, under heating or acid treatment at room temperature. Mechanistic studies show that the vinyl group undergoes free radical polymerization and the hydroxyl group dehydrates to form an ether linkage to crosslink HMVF under either heating or acid treatment. The bonding strength (τ) of HMVF cured by heating (h-HMVF) is close to that of Krazy Glue (Loctite 401, cyanoacrylate) and higher than that of white glue (Pattex No. 710, PVA) and Pattex PKME15C epoxy glue. The outstanding adhesive performance of HMVF is attributed both to the interaction of hydroxyl groups with substrates and crosslinking by etherification between hydroxyl groups. Similar to Krazy Glue, HMVF is also used in its monomer form, which eliminates the use of solvents. Cells show good adhesion on crosslinked HMVF, which makes HMVF a potential bio-adhesive.
An efficient catalyst for the conversion of fructose into methyl levulinate
Liu, Yan,Liu, Chun-Ling,Wu, Hai-Zhen,Dong, Wen-Sheng
, p. 1346 - 1353 (2013)
The catalytic alcoholysis of fructose in methanol to methyl levulinate was performed by using phosphotungstic acid iron catalysts. The catalysts were characterized by powder X-ray diffraction, infrared spectroscopy, and X-ray fluorescence spectroscopy. The results showed that the exchanging of H + with Fe3+ ions could modify the acidity of H 3PW12O40 and introduce some Lewis acidity into the molecules. The highest yield of methyl levulinate was obtained over the Fe-HPW-1 catalyst. This catalyst showed 100 % fructose conversion with 73.7 % yield of methyl levulinate at 130 °C, 2 MPa for 2 h, and it could be reused at least five times without obvious loss of activity. The results suggest that the combination of Bronsted acidity with some Lewis acidity could effectively promote the conversion of fructose in methanol to methyl levulinate.
Facile and high-yield synthesis of methyl levulinate from cellulose
Huang, Yao-Bing,Yang, Tao,Lin, Yu-Ting,Zhu, Ying-Zhi,Li, Li-Cheng,Pan, Hui
, p. 1323 - 1334 (2018)
Efficient production of chemicals from cellulose provides sustainable routes for the utilization of natural renewable resources to meet the requirements of human society. Herein, we reported a highly efficient and simple metal salt catalyst, Al2(SO4)3, for cellulose conversion to methyl levulinate (ML) under microwave conditions. A highest ML yield of 70.6% was obtained at 180 °C within a very short time of 40 min. The introduction of water could reduce humin/coke formation and solvent consumption, and could also switch the reaction pathway via the more reactive intermediate glucose. Kinetic and mechanistic studies of the subreactions showed that both cellulose hydrolysis and alcoholysis pathways were involved in the cellulose conversion to ML, with the former as the main route in the presence of water. The Lewis acid species [Al(OH)x(H2O)y]n+ and the Br?nsted acid species H+, generated by in situ hydrolysis of Al2(SO4)3, were responsible for the reaction conversions. The reaction with microwave heating showed accelerated reaction rates of 25 times the reaction with conventional oil heating, and even more times for the rates of glucose and methyl glucoside (MG) dehydration, resulting in higher reaction selectivity toward ML production. The catalyst was also successfully recycled and applied to the conversion of cellulose to other alkyl levulinates, as well as the conversion of raw biomass to ML with high yields. The homogeneous nature of Al2(SO4)3, together with its high efficiency and excellent recyclability, make it a potential catalyst for the large-scale production of ML in industry.
Preparation of potential biofuel 5-ethoxymethylfurfural and other 5-alkoxymethylfurfurals in the presence of oil shale ash
Viil, Indrek,Bredihhin, Aleksei,Maeeorg, Uno,Vares, Lauri
, p. 5689 - 5693 (2014)
5-Ethoxymethylfurfural (EMF) can be prepared from the corresponding halomethylfurfural and absolute ethanol in good yield. The use of significantly more affordable 96% ethanol results in formation of levulinic acid or its ester in considerable amount (up to 16%), which is difficult to separate from the desired EMF. In the present study we report that the addition of oil shale ash prevents the hydrolysis of the furan ring and enables the use of 96% ethanol with great success. The developed procedure is applicable to a wide range of aqueous alcohols, is operationally simple and utilizes an inexpensive basic ash, which is deposited in millions of tons per year. Notably, the basicity of the ash is decreased during the process, making its deposits less hazardous to the environment.
Synergistic Production of Methyl Lactate from Carbohydrates Using an Ionic Liquid Functionalized Sn-Containing Catalyst
Wang, Fenfen,Wen, Yi,Fang, Yanxiong,Ji, Hongbing
, p. 4154 - 4161 (2018)
Considerable progress has been made recently in the catalytic conversion of renewable biomass resources to methyl lactate (MLA). However, conceiving eco-friendly and effective catalytic systems for the production of MLA from biomass carbohydrates remains a key challenge. Herein, we report a multifunctional catalyst Sn(salen)/IL, consisting of a Sn(salen) complex and an imidazolium-based ionic liquid (IL), which acts via an intramolecular synergistic effect to convert carbohydrates to MLA in methanol. The versatile properties of the resultant catalyst were revealed to be responsible for the conversion of fructose to MLA and the efficient suppression of undesired side reactions. This catalyst displayed outstanding catalytic activity, high selectivity, and excellent recyclability, giving an MLA yield of up to 68.9 % at 160 °C after 2 h. The results of this study will contribute to new approaches for designing synergistic catalysts for producing liquid fuels and chemicals from biomass resources.
Acidic resin-catalysed conversion of fructose into furan derivatives in low boiling point solvents
Zhu, Hong,Cao, Quan,Li, Chunhu,Mua, Xindong
, p. 2016 - 2018 (2011)
Conversion of fructose into furan derivatives 5-hydroxymethylfurfural (HMF) and 5-methoxymethylfurfural (MMF) is performed in tetrahydrofuran (THF) and methanol-organic solvent systems, catalysed by an acidic resin Amberlyst-15. The melted fructose can be converted into HMF on the surface of the solid resin catalyst in the presence of THF as an extracting phase, which is a good solvent for HMF and other by-products. The solid resin catalyst can be reused eleven times without losing its catalytic ability, with an average HMF yield of approximately 50%. Upon the addition of methanol, the generated HMF can further react with methanol to form MMF, and the total yield of HMF and MMF could be promoted to 65%. GC-MS analysis confirms the formation of a small amount of methyl levulinate in methanolorganic solvent system.
Efficient synthesis of 5-ethoxymethylfurfural from biomass-derived 5-hydroxymethylfurfural over sulfonated organic polymer catalyst
Xiang, Yanping,Wen, Sha,Tian, Yi,Zhao, Kangyu,Guo, Dongwen,Cheng, Feng,Xu, Qiong,Liu, Xianxiang,Yin, Dulin
, p. 3585 - 3595 (2021)
Herein, we investigated catalytic potential of a functionalized porous organic polymer bearing sulfonic acid groups (PDVTA-SO3H) to the etherification of 5-hydroxymethylfurfural (HMF) to 5-ethoxymethylfurfural (EMF) under solvent-free conditions. The PDVTA-SO3H material was synthesized via post-synthetic sulfonation of the porous co-polymer poly-divinylbenzene-co-triallylamine by chlorosulfonic acid. The physicochemical properties of the PDVTA-SO3H were characterized by FT-IR, SEM, TG-DTG, and N2 adsorption isotherm techniques. PDVTA-SO3H had high specific surface area (591 m2 g-1) and high density of -SO3H group (2.1 mmol g-1). The reaction conditions were optimized via Box-Behnken response surface methodology. Under the optimized conditions, the PDVTA-SO3H catalyst exhibited efficient catalytic activity with 99.8% HMF conversion and 87.5% EMF yield within 30 min at 110 °C. The used PDVTA-SO3H catalyst was readily recovered by filtration and remained active in recycle runs.
Structure-based design and synthesis of novel furan-diketopiperazine-type derivatives as potent microtubule inhibitors for treating cancer
Ding, Zhongpeng,Li, Feifei,Li, Feng,Li, Wenbao,Liu, Yuqian,Wang, Shixiao,Zhao, Jianchun,Zhong, Changjiang
, (2020/04/15)
Plinabulin, a synthetic analog of the marine natural product “diketopiperazine phenylahistin,” displayed depolymerization effects on microtubules and targeted the colchicine site, which has been moved into phase III clinical trials for the treatment of non-small cell lung cancer (NSCLC) and the prevention of chemotherapy-induced neutropenia (CIN). To develop more potent anti-microtubule and cytotoxic derivatives, the co-crystal complexes of plinabulin derivatives were summarized and analyzed. We performed further modifications of the tert-butyl moiety or C-ring of imidazole-type derivatives to build a library of molecules through the introduction of different groups for novel skeletons. Our structure–activity relationship study indicated that compounds 17o (IC50 = 14.0 nM, NCI-H460) and 17p (IC50 = 2.9 nM, NCI-H460) with furan groups exhibited potent cytotoxic activities at the nanomolar level against various human cancer cell lines. In particular, the 5-methyl or methoxymethyl substituent of furan group could replace the alkyl group of imidazole at the 5-position to maintain cytotoxic activity, contradicting previous reports that the tert-butyl moiety at the 5-position of imidazole was essential for the activity of such compounds. Immunofluorescence assay indicated that compounds 17o and 17p could efficiently inhibit microtubule polymerization. Overall, the novel furan-diketopiperazine-type derivatives could be considered as a potential scaffold for the development of anti-cancer drugs.
Etherification of 5-hydroxymethylfurfural using a heteropolyacid supported on a silica matrix
Casella, Mónica,Lick, Daniela I.,Luque, Rafael,Martínez, José J.,Portilla-Zu?iga, Omar M.,Romanelli, Gustavo P.,Sathicq, ángel G.
, (2020/08/06)
In this work, Preyssler-type heteropolyacids and their silica-included counterparts were employed in the etherification reaction of HMF and n-BuOH. Materials were synthesized with a Preyssler acid load of 12.5percent w/w using the sol-gel technique, which improved surface areas and modulated their acid strength. Prepared materials were used as heterogeneous solid acid catalysts in the selective etherification of 5-hydroxymethylfurfural (HMF) to 5-butoxymethylfurfural (5BMF). The high catalytic performance of the bulk Preyssler acids is related to their high acid strength, while selectivity related to the decrease in acidity by the inclusion effects. Different reaction parameters were optimized, with PWMo(12.5percent)&at;SiO2 exhibited the highest catalytic activity with 89percent of HMF conversion and 73percent of 5BMF selectivity. The catalyst is reusable up to five cycles without noticeable decrease in selectivity.
Importance of the synergistic effects between cobalt sulfate and tetrahydrofuran for selective production of 5-hydroxymethylfurfural from carbohydrates
Dong, Dehua,Hu, Xun,Li, Qingyin,Li, Xueli,Shao, Yuewen,Sun, Kai,Wang, Yi,Ye, Zhengmao,Zhang, Lijun,Zhang, Shu
, p. 2293 - 2302 (2020/04/20)
In this study, an effective catalytic system (CoSO4·7H2O/THF) for selective conversion of fructose to 5-hydroxymethylfurfural (HMF; yield: 88%) was developed. The synergistic effects among Co2+, SO42-, crystal water and tetrahydrofuran (THF) were crucial for achieving selective dehydration of fructose to HMF. Co2+ worked as a Lewis acid for catalyzing mainly dehydration of fructose to HMF but not the further decomposition of HMF to levulinic acid. THF could help to retain HMF while CoSO4 could coordinate with HMF, enhancing the thermal stability of HMF in THF. The crystal water in cobalt sulfate could help to coordinate with fructose, which facilitated the conversion of fructose via dehydration reactions. The CoSO4·7H2O/THF catalytic system could also catalyze the conversion of inulin and cellulose into HMF. The main advantages of the CoSO4·7H2O/THF catalytic system are the low cost, the easy recycling of the CoSO4·7H2O catalyst and the easy separation of HMF from volatile THF.
