综合设计性专业实验:离子液体[BMIM]Br的制备及在柴油脱硫中的应用

在微波辅助下合成、纯化了离子液体溴化1-甲基-3-丁基咪唑[BMIM]Br，测定了产率和纯度，并使用FTIR和1HNMR进行了产物结构表征；以[BMIM]Br为萃取剂对催化裂化和加氢裂化柴油进行超声辅助萃取脱硫，并测定了脱硫率；在反应条件优化、测试方法优化、脱硫选择性等方面设置了多个开放性设计实验。该实验项目融合精细化工和石油化工方向，在促进学生知识体系跨界，全面训练综合实验技能，培养学生解决实际问题能力以及科研能力形成等方面作用明显；实验项目以模块化设置，符合"绿色实验"原则。     

Permeation liquid membrane for trace metal speciation in natural waters. Transport of liposoluble Cu(II) complexes

In this paper, the transport of Cu(II) in the presence of lipophilic Cu(II) organic complexes through permeation liquid membranes (PLMs) have been investigated. In natural waters, small organic compounds, which form liposoluble neutral complexes with Cu(II), are potentially toxic and bioavailable. Hence, to understand the role of liposoluble Cu(II) complexes in natural waters, four organic ligands: phthalic acid, bipyridyl, pyrocatechol and hydroxyquinoline, which form uncharged or lipophilic Cu(II) complexes, were tested. The results showed that the transport of lipophilic Cu(II) complexes through PLM depends on the lipophilicity of the complex. Applications of PLMs in natural waters are presented.     

DFT法研究离子液中EMIM+催化丁烯双键异构反应机理(II)

用密度泛函理论(DFT)在B3LYP/6-31G(d, p)的计算水平上研究了离子液中1-乙基-3-甲基咪唑阳离子(EMIM⁺)的4-H和5-H原子催化丁烯双键异构反应的可能途径，优化了反应体系的平衡态和过渡态的几何构型，分析了反应过程中键参数的变化，通过振动分析对平衡态和过渡态进行了验证. 计算结果表明, 离子液中的EMIM⁺首先通过4-H和5-H原子吸附丁烯, 进而催化丁烯的双键异构反应, EMIM⁺的4-H和5-H催化1-丁烯异构为2-丁烯的正反应活化能分别为204.2和207.3 kJ•mol^-1，逆反应活化能约为220.9和223.8 kJ•mol^-1， 反应为基元反应.     

高效阳离子交换法分离纯化蛋清中的溶菌酶

 建立了用高效阳离子交换分离纯化蛋清中溶菌酶的新方法 ,讨论了纯化的工艺条件。蛋清样品匀浆后 ,用氯化钠初步纯化 ,然后用弱阳离子交换柱XIDACE WCX分离。结果表明 ,被纯化的溶菌酶和杂蛋白得到很好分离。经活性检测 ,溶菌酶过柱后的活性回收率为 10 7% ,蛋白的比活为 15 4 6 7U/mg ,纯化倍数提高了 5 6倍。用尺寸排阻 (SEC)鉴定 ,得到的溶菌酶呈均一性。该法较传统软基质低压离子交换分离速度快 ,纯化效率高。     

鞘磷脂和神经节苷脂对磷脂酰乙醇胺混合脂超分子体系液晶态立方相Im3m和Pn3m结构影响的研究

用磷脂酰乙醇胺(DEPE)、鞘磷脂(Sphingomyeline, Sph)、神经节苷脂(Gm1)和胆固醇(Chol)模拟了生物膜超分子体系液晶态结构, 通过用小角X射线衍射(SAXD)对混合脂体系液晶态结构进行了研究, 鉴定出了两种立方相: 即Im3m(Q²²⁹)和Pn3m(Q²²⁴)结构. 实验发现, 鞘磷脂的含量对DEPE膜的结构有一定的影响, 随着鞘磷脂浓度的增加, 混合脂体系的液晶态结构发生了由Im3m(Q²²⁹)到Pn3m(Q²²⁴)的变化. 神经节苷脂(Gm1)的含量对混合脂体系的液晶态结构也有一定的影响, 当神经节苷脂(Gm1)含量达到某一临界值时, 混合脂体系的液晶态结构发生了从Im3m(Q²²⁹)到Pn3m(Q²²⁴) 的变化. 当DEPE-Shp-Gm1超分子聚集体中含有胆固醇时, 胆固醇的极性头部(—OH)与磷脂酰乙醇胺(DEPE)、鞘磷脂(Shp)、神经节苷脂(Gm1)的极性头部通过氢键相互作用形成液晶态立方相Im3m(Q²²⁹)结构, 再通过疏水/亲水相互作用形成稳定的Pn3m (Q²²⁴)结构.     

无烟煤结构的高分辨电镜研究

镜质组不仅是煤结构变化最具规律性，也是影响煤质的主要微成分。用点分辨率为２．１Ａ的高分辨电镜对几种不同煤化程度的无烟煤大分子结构进行了研究。结果表明：电镜图像直接表征了无烟煤分子的非均匀性孔隙结构。京西煤分子方向化程度强，主要以芳层平行堆或有序化前结构为主；晋城煤方向化程度弱，主要以粒状嵌晶结构为主。高分辨电镜技术是研究煤分子结构和煤化作用实质的有效方法。     

Studies on bulk polymerization of methyl methacrylate. I. Thermal polymerization

The thermal bulk polymerization of methyl methacrylate (MMA) in a wide range of temperatures has been studied using a dilatometric reactor. It is shown that, irrespective of the care taken to purify the MMA, the evolution of the time-conversion curve can be explained only if we account for the presence of an impurity associated with the monomer acting as a free radical initiator. The activation energy for the decomposition of this impurity has been estimated as 98 kJ/mol. Having accounted for this impurity, the activation energy for the real thermal polymerization of the MMA has been estimated to be 75 kJ/mol. © 1993 John Wiley & Sons, Inc.     

Chiral resolution of diphenylalanine by high-performance liquid chromatography on a crown-ether-based chiral stationary phase and by NMR spectroscopy

Summary The enantiomers of diphenylalanine (DPA) were well separated by chiral HPLC and NMR spectroscopy on the chiral stationary phase (CSP) derived from (18-crown-6)-2,3,11,12-tetracarboxylic acid (18-C-6-TA). The chromatographic parameters such as separation factors and retention times were greatly influenced by the mobile phase conditions. The (+)-18-C-6-TA used in the CSP was also employed as a chiral solvating agent for the enantiodiscrimination of the DPA enantiomers by NMR spectroscopy. The proton of the DPA analyte showing the chemical shift nonequivalences was used in determining the enantiomeric composition of the analyte.     

Proton-ionizable crown compounds. 17. Transport studies of alkali metal ions in a H2O-CH2Cl2-H2O liquid membrane system by macrocycles containing two sulfonamide groups derived fromo- andm-phenylene diamine

The transport of alkali metal cations by several macrocycles possessing two sulfonamide groups as a part of an 18-, 20-, or 21-membered macroring has been studied. Some of these compounds were found to be more effective transport agents than the proton-ionizable pyridone- and triazole-containing crown ethers reported previously. The factors affecting transport, such as ring size, source and receiving phase pH, and the nature of the groups attached to the sulfonamide nitrogen atoms were examined. Also, extraction experiments by some of the ligands were performed. The behavior of sulfonamide type crowns in single and competitive transport of the alkali metal cations is explained. The mechanism of transport appears to be complex. Transport of one or two cations per molecule of the disulfonamide carriers occurs. Complexation of these cations appears to occur both within and outside the macrocycle cavity. Our results also suggest that kinetic factors may play a significant role in transport rates and selectivities.Deceased: September 5, 1987.     

Effects of ion-pairing reagents on the electrospray signal suppression of sulphonated dyes and intermediates

High-performance liquid chromatography/mass spectrometry (HPLC/MS) analysis of anionic species such as sulphonic acid dyes and intermediates requires volatile ion-pairing mobile phase additives. Six di- and trialkylammonium acetates were compared with tetraalkylammonium salts and ammonium acetate in the concentration range 0-20 mmol l(-1) as mobile phase additives for HPLC/MS of polysulphonated compounds. The effects of the structure and concentration of the ion-pairing reagents on the electrospray response of mono-, di- and tetrasulphonic aromatic acids and acid dyes were studied in detail. Further, five different mass analysers and instrument geometries were compared. A higher signal decrease is observed with linear geometry instruments in comparison to orthogonal or even Z-spray geometry mass spectrometers. The concentration of mobile phase additives has a significant influence on the abundance ratios of multiply charged ions in the mass spectra of polysulphonated compounds. The competing ions of sulphonic acids may also cause significant signal suppression.