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1.
Solvent Influence on Cellulose 1,4‐β‐Glycosidic Bond Cleavage: A Molecular Dynamics and Metadynamics Study 下载免费PDF全文
Claudia Loerbroks Eliot Boulanger Prof. Dr. Walter Thiel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(14):5477-5487
We explore the influence of two solvents, namely water and the ionic liquid 1‐ethyl‐3‐methylimidazolium acetate (EmimAc), on the conformations of two cellulose models (cellobiose and a chain of 40 glucose units) and the solvent impact on glycosidic bond cleavage by acid hydrolysis by using molecular dynamics and metadynamics simulations. We investigate the rotation around the glycosidic bond and ring puckering, as well as the anomeric effect and hydrogen bonds, in order to gauge the effect on the hydrolysis mechanism. We find that EmimAc eases hydrolysis through stronger solvent–cellulose interactions, which break structural and electronic barriers to hydrolysis. Our results indicate that hydrolysis in cellulose chains should start from the ends and not in the centre of the chain, which is less accessible to solvent. 相似文献
2.
Timm Bergholz Dr. Benjamin Oelkers Dr. Benedikt Huber Prof. Bernhard Roling Prof. Dr. Jörg Sundermeyer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(6):2613-2620
New salts based on imidazolium, pyrrolidinium, phosphonium, guanidinium, and ammonium cations together with the 5‐cyanotetrazolide anion [C2N5]? are reported. Depending on the nature of cation–anion interactions, characterized by XRD, the ionic liquids (ILs) have a low viscosity and are liquid at room temperature or have higher melting temperatures. Thermogravimetric analysis, cyclic voltammetry, viscosimetry, and impedance spectroscopy display a thermal stability up to 230 °C, an electrochemical window of 4.5 V, a viscosity of 25 mPa s at 20 °C, and an ionic conductivity of 5.4 mS cm?1 at 20 °C for the IL 1‐butyl‐1‐methylpyrrolidinium 5‐cyanotetrazolide [BMPyr][C2N5]. On the basis of these results, the synthesized compounds are promising electrolytes for lithium‐ion batteries. 相似文献
3.
Eco‐friendly ionic liquid assisted capillary electrophoresis and α‐acid glycoprotein‐assisted liquid chromatography for simultaneous determination of anticancer drugs in human fluids 下载免费PDF全文
Deia Abd El‐Hady Hassan M. Albishri Rajesh Rengarajan 《Biomedical chromatography : BMC》2015,29(6):925-934
In the current work, two eco‐friendly analytical methods based on capillary electrophoresis (CE) and reversed phase liquid chromatography (RPLC) were developed for simultaneous determination of the most commonly used anticancer drugs for Hodgkin's disease: methotrexate (MTX), vinblastine, chlorambucil and dacarbazine. A background electrolyte (BGE) of 12.5 mmol/L phosphate buffer at pH 7.4 and 0.1 µmol/L 1‐butyl‐3‐methyl imidazolium bromide (BMImBr) ionic liquid (IL) was used for CE measurements at 250 nm detection wavelength, 20 kV applied voltage and 25 °C. The rinsing protocol was significantly improved to reduce the adsorption of IL on the interior surface of capillary. Moreover, RPLC method was developed on α‐1‐acid glycoprotein (AGP) column. Mobile phase was 10 mmol/L phosphate buffer at pH 6.0 (100% v/v) and flow rate at 0.1 mL/min. As AGP is a chiral column, it was successfully separated l ‐MTX from its enantiomer impurity d ‐MTX. Good linearity of quantitative analysis was achieved with coefficients of determinations (r2) >0.995. The stability of drugs measurements was investigated with adequate recoveries up to 24 h storage time under ambient temperature. The limits of detection were <50 and 90 ng/mL by CE and RPLC, respectively. The using of short‐chain IL as an additive in BGE achieved 600‐fold sensitivity enhancement compared with conventional Capillary Zone Electrophoresis (CZE). Therefore, for the first time, the proposed methods were successfully applied to determine simultaneously the analytes in human plasma and urine samples at clinically relevant concentrations with fast and simple pretreatments. Developed IL‐assisted CE and RPLC methods were also applied to measure MTX levels in patients’ samples over time. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
4.
Tuning the Basicity of Cyano‐Containing Ionic Liquids to Improve SO2 Capture through Cyano–Sulfur Interactions 下载免费PDF全文
Dr. Guokai Cui Fengtao Zhang Xiuyuan Zhou Prof. Haoran Li Prof. Jianji Wang Prof. Congmin Wang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(14):5632-5639
A new approach has been developed to improve SO2 sorption by cyano‐containing ionic liquids (ILs) through tuning the basicity of ILs and cyano–sulfur interaction. Several kinds of cyano‐containing ILs with different basicity were designed, prepared, and used for SO2 capture. The interaction between these cyano‐containing ILs and SO2 was investigated by FTIR and NMR methods. Spectroscopic investigations and quantum chemical calculations showed that dramatic effects on SO2 capacity originate from the basicity of the ILs and enhanced cyano–sulfur interaction. Furthermore, the captured SO2 was easy to release by heating or bubbling N2 through the ILs. This efficient and reversible process, achieved by tuning the basicity of ILs, is an excellent alternative to current technologies for SO2 capture. 相似文献
5.
We show that using ionic liquids as reagents in conjunction with microwave heating it is possible to prepare primary alkyl halides from the corresponding alcohols rapidly. Using ionic liquids as solvents in conjunction with microwave heating it is possible to prepare aryl nitriles from the corresponding aryl bromides or iodides. The scope and limitations of using microwave-promotion as a tool in these reactions is discussed. 相似文献
6.
You‐Liang Zhao Chuan‐Fu Chen Fu Xi 《Journal of polymer science. Part A, Polymer chemistry》2003,41(14):2156-2165
The atom transfer radical copolymerization of N‐substituted maleimides such as N‐phenylmaleimide (PhMI), N‐cyclohexylmaleimide (ChMI), and N‐butylmaleimide (NBMI) with styrene initiated with dendritic polyarylether 2‐bromoisobutyrates in an ionic liquid, 1‐butyl‐3‐methylimidazolium hexafluorophosphate ([bmim][PF6]), at room temperature and anisole at 110 °C was investigated. The dendritic‐linear block copolymers obtained in ionic liquid possessed well‐defined molecular weight and low polydispersity (1.05 < Mw/Mn < 1.32) and could be used as a macroinitiator for chain‐extension polymerization, suggesting the living nature of the reaction system. The ionic liquids containing catalyst could be recycled in the atom transfer radical polymerization systems without further treatment. Compared with polymerization conducted in anisole, the polymerization in ionic liquid had a stronger tendency for alternation. The tendency for alternation decreased in the order PhMI > NBMI > ChMI in [bmim][PF6] and PhMI > ChMI > NBMI in anisole. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2156–2165, 2003 相似文献
7.
Tadeusz Biedro Przemysaw Kubisa 《Journal of polymer science. Part A, Polymer chemistry》2004,42(13):3230-3235
The cationic polymerization of styrene in a neutral ionic liquid, 1‐butyl‐3‐methylimidazolium hexafluorophosphate, with a 1‐phenetyl chloride/TiCl4 initiating system is reported. The polymerization proceeds to a high conversion, but an analysis of the matrix‐assisted laser desorption/ionization time‐of‐flight spectra of the polymers indicates that chain transfer is significant, leading to a lack of control over the molecular weight and molecular weight distribution. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3230–3235, 2004 相似文献
8.
Jnos Szanyi Ja Hun Kwak Sarah Burton Jose A. Rodriguez Charles H.F. Peden 《Journal of Electron Spectroscopy and Related Phenomena》2006,150(2-3):164-170
Adsorbed ionic NOx species formed upon the interaction of NO2 with dehydrated or hydrated Na- and Ba-Y, FAU zeolites were characterized using FT-IR/TPD, solid state NMR, and XANES techniques. NO2 disproportionates on both dehydrated catalyst materials forming NO+ and NO3− species. These ionic species are stabilized by their interactions with the negatively charged zeolite framework and the charge compensating cations (Na+ and Ba2+), respectively. Although the nature of the adsorbed NOx species formed on the two catalysts is similar, their thermal stabilities are strongly dependent on the charge compensating cations. In the presence of water in the channels of these zeolite materials new paths open for reactions between NO+ and H2O, and NO2 and H2O, resulting in significant changes in the adsorbed ionic species observed. These combined spectroscopic investigations afforded the understanding of the interactions between water and NO2 on these zeolite catalysts. 相似文献
9.
Hydrogels of N‐vinylimidazole (VI) and sodium styrenesulfonate (SSS) were synthesized in aqueous solution by radical crosslinking copolymerization with N,N′‐methylene‐bis(acrylamide) as crosslinker. Swelling in several saline solutions was measured for hydrogel samples synthesized with different comonomer concentrations (CT = 10, 25, or 40%) and with SSS mole fractions covering a broad range (fSSS = 0–0.7), while the crosslinker ratio was 2 wt % in all cases. The degree of swelling in aqueous solution with a specific ionic strength (μ), plotted versus the SSS composition of the feed, shows a minimum for any set of samples synthesized with a fixed CT. The dependence of swelling on μ shows both polyelectrolyte (fSSS beyond the minimum) and antipolyelectrolyte behaviors (in the low fSSS limit). It was found that the nonGaussian factor of the crosslinking density and the polymer‐solvent interaction parameter increase with fSSS for any CT. Moreover, in the low fSSS limit, the osmotic swelling pressure is governed not only by the ionic contribution, but also by the polymer‐solvent mixing and, the concentration of mobile counterions inside the gel is not proportional to the net fixed charge but to the addition of cationic and anionic side groups, what discards the formation of ionic pairs. The antipolyelectrolyte effect is interpreted as due to the increasing protonation of VI as μ goes up. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1683–1693, 2007 相似文献
10.
Yangyang Jiang Chen Guo Huizhou Liu 《中国颗粒学报》2007,5(1):130-133
A magnetically rotational reactor (MRR) has been developed and used in absorbing benzene emissions. The MRR has a permanent magnet core and uses magnetic ionic liquid [bmim]FeCl4 as absorbent. Benzene emissions were carried by N2 into the MRR and were absorbed by the magnetic ionic liquid. The rotation of the permanent magnet core provided impetus for the agitation of the magnetic ionic liquid, enhancing mass transfer and making benzene better dispersed in the absorbent. 0.68 g benzene emissions could be absorbed by a gram of [bmim]FeCl4, 0.27 and 0.40 g/g higher than that by [bmim]PF6 and [bmim]BF4, respectively. The absorption rate increased with increasing rotation rate of the permanent magnet. 相似文献