Improving the Alkaline Stability of Imidazolium Cations by Substitution

Imidazolium cations are promising candidates for preparing anion‐exchange membranes because of their good alkaline stability. Substitution of imidazolium cations is an efficient way to improve their alkaline stability. By combining density functional theory calculations with experimental results, it is found that the LUMO energy correlates with the alkaline stability of imidazolium cations. The results indicate that alkyl groups are the most suitable substituents for the N3 position of imidazolium cations, and the LUMO energies of alkyl‐substituted imidazolium cations depend on the electron‐donating effect and the hyperconjugation effect. Comparing 1,2‐dimethylimidazolium cations (1,2‐DMIm⁺) and 1,3‐dimethylimidazolium cations (1,3‐DMIm⁺) with the same substituents reveals that the hyperconjugation effect is more significant in influencing the LUMO energy of 1,3‐DMIms. This investigation reveals that LUMO energy is a helpful aid in predicting the alkaline stability of imidazolium cations.     

Optoelectronic and Self‐assembly Properties of Porphyrin Derivatives with Click Chemistry Modification

A series of functionalized porphyrin molecules containing electron‐rich alkynes, synthesized by means of the Sonogashira coupling reaction were further modified by reacting the ethynyl groups with click reagent through a formal [2+2] click reaction. The photophysical and electrochemical properties of the porphyrin derivatives were studied by UV/Vis spectroscopy and cyclic voltammetry. We show that the optoelectronic properties are affected by the click reagent groups and central metal ions. The functionalized porphyrin molecules show strong charge‐transfer (CT) bands in the visible region (near‐IR region) and potent redox activities. Through a phase‐exchange self‐assembly method, the highly organized morphologies were observed by scanning electron microscopy (SEM). The functionalized porphyrin molecules represent an interesting set of candidates for optoelectronic device components. The effect of the metal ions or click reagent groups on the self‐assembly properties were also studied by the UV/Vis spectroscopic titration experiments.     

流动注射-分光光度法测定药物中克林霉素磷酸酯的含量

试验表明:在pH 3.8的乙酸盐缓冲介质中,克林霉素磷酸酯(CLP)能将铁(Ⅲ)还原为铁(Ⅱ),而所生成的铁(Ⅱ)与邻菲啰啉反应生成有色络合物(λmax=508nm),且生成的铁(Ⅱ)量与CLP之间存在定量关系,经换算所测得吸光度与CLP的质量浓度在0.70~140mg·L-1之间呈线性关系。据此并结合流动注射技术(FI)提出了FI-分光光度法间接测定药物中CLP的新方法优化的分析条件如下:①乙酸盐缓冲溶液的加入量:2.5mL;②铁(Ⅲ)溶液质量浓度:10.0mg·L-1;③邻菲啰啉溶液浓度:1.5×10-3 mol·L-1;④反应温度:85℃。该方法的检出限为0.060mg·L-1。应用此方法测定了药物中CLP的含量,测定值与国家药品标准方法的测定值相符。     

Pollution characteristics of ambient PM2.5-bound PAHs and NPAHs in a typical winter time period in Taiyuan

The pollution characteristics of ambient fine particulate matter（PM2.5） containing polycyclic aromatic hydrocarbons（PAHs） and nitrated PAHs（NPAHs） in samples collected during a typical winter time period in Taiyuan of China were investigated.The obtained results revealed that the mean mass concentrations of PM2.5,SPAHs（sum of 16 PAHs） and SNPAHs（sum of 3 NPAHs） on PM2.5were161.4 mg/m3,119.8 ng/m3and 0.446 ng/m3,respectively.Diagnostic ratios of PAHs and NPAHs implied that coal consumption might be the main source of the PM2.5pollution.The measured PM2.5mass concentrations,BaP equivalent toxicity（28.632 ng/m3） and individual carcinogenicity index（3.14 10 5） were much higher than those of the recommended safety standards.     

Allyl phthalazinone synthesis,polymerization and polymer properties

A phthalazinone monomer with an allyl group, i.e. 4-（3-allyl-4-hydroxyphenyl）phthalazin-1（2H）-one, was synthesized and then copolymerized with 4-（4-hydroxylphenyl）（2H）-phthalazin-1-one and 2,6- diflurobenzonitrile by means of aromatic nucleophilic polycondensation to provide a series of crosslinkable poly（aryl ether nitrile）s. The virgin copolymers exhibited good solubility in polar organic solvents with relative high molecular weights （Mw： 45,130-58,403, inherent viscosities： 0.58-0.75 dL/ g）. After cross-linking, the thermal stability and solvent resistance of the polymer increased.     

Chemoselective hydrogenolysis of tetrahydrofurfuryl alcohol to 1,5-pentanediol over Ir-MoOx/Si02 catalyst

In this work, MoOx promoted Ir/SiO2 catalysts were prepared and used for the selective hydrogenolysis of tetrahydrofurfuryl alcohol （THFA） to 1,5-pentanediol in a continuous flow reactor. The effects of different noble metals （Ir, Pt, Pd, Ru, Rh）, supports and Ir contents were screened. Among the investigated catalysts, 4 wt%Ir-MoOx/SiO2 with a Mo/Ir atomic ratio of 0.13 exhibited the best catalytic performance. The synergy between Ix particles and the partially reduced isolated MoOx species attached on them is essential for the excellent catalytic performance of Ix-MoOx/SiO2. The catalyst exhibited a better hydrogenolysis efficiency of THFA with the selectivity of 1,5-pentanediol of 65%-74% at a conversion of THFA of 70%-75% when the initial THFA concentration is ranging from 20 wt% and 40 wt%. And higher system pressure was also in favor of the conversion of THFA. During a stability test, the conversion of THFA and 1,5-pentanediol yield over Ix-MoOz/SiO2 decreased with reaction time, which can be explained by the leaching of Mo species during the reaction.     

混合基质水处理膜:材料、制备与性能

以反渗透、纳滤为代表的膜技术已广泛应用于海水和苦咸水脱盐等水处理过程。通过将纳米颗粒添加到传统复合膜基质中,可以制备具有高分离性能和耐污染性的新型膜材料。混合基质膜结合了无机材料及有机聚合物各自的优点,是新型水处理膜材料的发展方向。本文综述了添加无机纳米颗粒的混合基质反渗透、纳滤及正渗透膜的研究进展,详细讨论了不同类型纳米材料的性质和功能,分析了表面有机改性对改善纳米材料分散性以及与聚合物基质相容性的作用,探讨了纳米材料添加方式和膜制备方法对膜结构和性能的影响。在此基础上,进一步探究了混合基质膜的成膜及分离机理,归纳了目前研究中存在的主要问题,并对未来水处理膜材料的研发方向提出了建议。     

以一种新型Gemini表面活性剂作为介孔模板剂通过转晶过程合成介孔ZSM-5分子筛

将一种新型Gemini表面活性剂,丙撑基双(十八烷基二甲基氯化铵)[C18H37(CH3)2–N+–(CH2)3–N+–(CH3)2C18H37]Cl2(C18-3-18),作为介孔模板剂用于水热法合成介孔ZSM-5分子筛.结果表明,在130 oC低温晶化即可高效合成介孔ZSM-5分子刷.C18-3-18的加入量可影响到所合成介孔ZSM-5分子筛的相对结晶度和织构性质,它的形成遵从一个转晶过程.在合成初期,凝胶中介孔模板剂C18-3-18的使用导向了介孔材料的生成;随后在TPABr的模板作用下,介孔材料慢慢转晶生成具有MFI结构的介孔ZSM-5;然后所合成的介孔ZSM-5晶粒进一步长大并聚集形成块状颗粒,同时产生晶间介孔.C18-3-18作为介孔导向剂不仅可用于合成介孔ZSM-5分子筛,也可用于其它介孔分子筛的合成中.     

哈茨木霉CGMCC 2979生物转化栀子中的京尼平苷制备京尼平

采用微生物直接转化药材的方法,将栀子中的京尼平苷转化为京尼平,无需糖苷酶和京尼平苷的制备. 在培养温度为30 ℃,pH 6.1以及栀子载量为80 g/L的条件下,48 h京尼平苷的转化率为97.8%. 转化后的京尼平通过XAD-16N大孔树脂偶联硅胶层析的方法,制备得到纯度大于95%的京尼平,收率为62.3%. 在催化、转化机制研究中,从哈茨木霉CGMCC2979的发酵液中分离得到了分子量为74.4 kDa的京尼平苷β-葡萄糖苷酶,该酶最优催化条件为50 ℃和pH 4.0-5.0. K_m和V_max分别为3.6 mmol/L和775 μmol/h/mg蛋白. 本文提供了一种简便、高效制备京尼平的新方法.     

改性ZSM-5分子筛催化裂解湛江等鞭金藻制取低碳烯烃(英)

研究了湛江等鞭金藻(Isochrysis zhanjiangensis)在改性ZSM-5分子筛上催化裂解制取低碳烯烃的过程.与热裂解过程相比,湛江等鞭金藻催化裂解可以得到更高的低碳烯烃选择性和收率.同时还研究了湛江等鞭金藻中不同油脂和藻渣的催化裂解.结果表明,微藻中的油脂能有效转化为烯烃,其中中性脂的烯烃收率最高,可达36.7%.不同溶剂抽提后得到的藻渣也可转化为低碳烯烃,但收率远低于微藻中的油脂.微藻中的油脂,特别是中性脂,是烯烃的主要贡献者,提高微藻中的中性脂含量能够得到更高的低碳烯烃收率.