咪唑类离子液体毒性的QSAR/QSPR研究

离子液体因其独特的物化性质广受关注,被誉为"新一代绿色溶剂".用定量结构-性质/活性相关(QSAR/QSPR)方法建立了43种咪唑类离子液体毒性的多元线性回归预测模型,并用10种物质进行了外部测试.模型中包含了启发式算法筛选出的6个结构描述符,其统计数据分别为R2=0.921,R2CV=0.894,F=70.35,S2=0.098,外部测试集的R2=0.952.结果表明,该模型具有良好的可靠性,可用于咪唑类离子液体的毒性预测.     

A preliminary investigation on the use of organic ionic liquids as green solvents for acylation and oxidation reactions

Different organic ionic liquids (OILs) have been used as green solvents in Friedel–Crafts acylation and alcohol oxidation reactions. Specifically, three OILs were employed, 1-ethyl-3-methylimidazolium chloride, tetraethylammonium bromide, and 1-butyl-3-methylimidazolium chloride, and four reactions studied, acylation of toluene by acetyl chloride, acylation of benzene by propionyl chloride, oxidation of benzyl alcohol by N-methylmorpholine N-oxide, and oxidation of salicylic alcohol by o-iodoxybenzoic acid. The reactions were carried out, at room temperature, in a well-stirred lab-scale glass batch reactor, under inert atmosphere and for reaction times ranging from 5 to 90 min. Gas chromatography was employed to characterize the reaction products. First of all, the desired products yield as a function of the reaction time was investigated. Moreover, simple kinetic models were built for the interpretation of the experimental results. Additional tests were carried out to assess the possibility of recycling the OILs employed. The results of this preliminary study were satisfactory as the OILs investigated proved to be good media in which to carry out the reactions studied in this work (desired products yield greater than 90% were achieved). Moreover, the reaction rate expressions of the kinetic models were able to satisfactorily predict the experimental results. Finally, the possibility of recycling the OIL (in one of the reactions) was proved to be feasible and this suggests the use of recycled OIL together with a fresh make-up, to match high yield values with economical/ecological advantages.     

卤素离子对溶解性黑碳光化学活性的影响

溶解性黑碳(DBC)是天然有机质的重要组分,但其在河口水环境中的光化学活性尚不清楚.为解决这个问题,以大豆秸秆溶解性黑碳为目标物,使用山梨酸能量转移同分异构方法研究河口水卤素离子浓度条件下激发三重态DBC (³DBC^*)的生成速率(F_T)、淬灭速率(k_s')、稳态浓度([T]_ss)变化规律,并使用2,4,6-三甲基苯酚电子转移探针方法研究卤素离子对³DBC^*电子转移过程的影响.结果表明,卤素离子及其离子强度作用对F_T无显著影响,但k_s'因离子强度和Br^-重原子效应而减小,导致³DBC^*的[T]_ss增加.高浓度DBC光化学实验证实离子强度作用引起DBC分子聚集,导致³DBC^*的电荷转移过程减弱,从而抑制³DBC^*的淬灭.山梨酸探针实验表明,卤素离子及其离子强度作用对³DBC^*的能量转移无直接影响,主要是通过抑制³DBC^*的淬灭,增加[T]_ss.进一步研究发现卤素离子及其离子强度作用对低能态³DBC^*(E_T < 250kJ/mol)无显著影响,但抑制高能态³DBC^*(E_T > 250kJ/mol)的电子转移,且随卤素离子和离子强度的增加而愈发明显.     

地下水人工回灌水化学因素对生物堵塞的影响

通过室内砂柱实验及扫描电镜,红外光谱,光电子能谱等技术,研究回灌水中离子强度及回灌过程中水-岩作用对细菌在饱和多孔介质中迁移及滞留的影响,揭示回灌过程中离子强度对介质生物堵塞演化规律及其作用机理的影响.结果表明,适宜的离子强度刺激细菌的生长及胞外聚合物（EPS）的生成,导致介质渗透性下降幅度达到99%,离子强度过高或过低都会抑制微生物的生长;Na⁺可以中和介质与细菌表面的负电荷,通过压缩双电层及减少静电斥力,进而增强细菌在介质表面的附着能力;介质中的碳酸盐矿物水解可导致环境pH值升高,诱导介质中的微量SiO₂,Al₂O₃等矿物溶解,促使介质孔隙度增大,延缓生物堵塞的发生时间并缓解堵塞程度;外源Na⁺及内源介质溶解产生的Ca²⁺,Mg²⁺,Al （III）,刺激细菌产生更多的EPS,同时化学离子与EPS的官能团以新的官能团和化学键结合,形成新的物质,对堵塞的发生和演化起促进作用;溶解产生的Mg²⁺,Ca²⁺与细菌呼吸产生的CO₂,在微碱性条件下反应形成新的沉淀,也对堵塞产生促进作用.     

塔里木河上游绿洲土壤表层盐分特征及其影响因子分析

选择塔里木河上游阿拉尔垦区,以农田、新开农田、撂荒地、人工林、天然林、盐碱地及荒草地等不同土地利用类型的样地土壤为研究对象,结合通径分析,研究了土壤中w(全盐)与盐源分布、盐分化学特性、土壤理化特性、地下水等影响因子的分布规律及相互关系. 结果表明,该区域盐分表聚特征明显,土壤表土层w(全盐)远大于心土层和底土层,各土地利用类型表土层w(全盐)表现为盐碱地最高(平均值为52.93g/kg),盐碱地>天然林>人工林>荒草地>撂荒地>农田>新开农田. 由通径分析结果可知,S_20-50〔心土层w(全盐)〕、SAR(钠吸附比)、SDR(钠钙镁比)、D_g(地下水埋深)、c(Cl-)/c(SO₄2-)、c(HCO₃-)、pH、ρ(土壤容重)、S_50-80〔底土层w(全盐)〕、SSP(可溶性钠百分率)对表土层w(全盐)的直接通径系数依次为0.415、0.414、-0.344、-0.201、0.200、0.162、0.092、-0.086、0.080、0.071. 土壤盐源分布和土壤盐分化学特性对表土层w(全盐)影响较大,其次是D_g,土壤理化特性对表土层w(全盐)影响相对较小. 反映盐源分布的S_20-50和反映土壤盐分化学特性的SAR是表土层w(全盐)的主要控制因子.      

Groundwater quality in the major industrial area of Thessaloniki,Greece part 1: Chemical composition‐geochemical processes

Adsorption rates of Sb(V) ions on an activated alumina (AA) were analyzed by batchwise experiments, while the continuous adsorption, desorption, regeneration of AA, and multiple reuse cycles were studied by flow column tests. The adsorption rates increased quickly with the increases of shaking speed and operation temperature. The adsorbed Sb(V) ions were desorbed easily by a 50 mM NaOH solution, and a 41–90 times concentrated Sb(V) solution was yielded correspondingly. AA was effectively regenerated by desorption operation and ca. 93% of the initial adsorption capacity was retained after six times adsorption/desorption cycles.     

高效液相色谱和离子色谱在形态分析中的应用

本文综述了高效液相色谱（ＨＰＬＣ）和离子色谱（ＩＣ）在形态分析方面的应用，包含：元素的价态分析、有机金属化合物的形态确定、元素存在状态确定、对映体化合物的分离与鉴定。附参考文献１３３篇。     

[Bmim]PF_6溶剂浮选UV-Vis检测水中四环素类抗生素

建立了一种分离/富集的新体系——离子液体气浮溶剂浮选,该体系集离子液体萃取和气浮溶剂浮选优势于一体,以离子液体1-丁基-3-甲基咪唑六氟磷酸盐([Bmim]PF)6和乙酸乙酯(EA)混合溶剂为浮选溶剂,以稀土金属离子La(Ⅲ)或Ce(Ⅲ)为捕集剂,分离/富集了水中的四环素类抗生素,并用紫外-可见分光光度法测定其总含量,线性范围分别为0.0～34μg/L、0～23.0μg/L,表观摩尔吸光系数分别为ε390=1.92×105L/(mol·cm),ε380=1.15×105L/(mol·cm)。实测了鱼塘水样,加标回收率为84.06%～106.15%,RSD3.31%。研究结果表明:该方法灵敏度高、选择性好、富集倍数大、污染小,适用于环境水样中痕量四环素类抗生素的分离分析。     

Disruption of biofilms from sewage pipes under physical and chemical conditioning

Biofilms grown inside two sewage collecting pipes located in industrial and residential areas are studied. Bacterial biomass inside three layers of biofilms was evaluated. Biofilm cohesion under different mixing rate and ionic strength was also investigated. Effects of physical and chemical parameters in the biofilms were evaluated by monitoring turbidity, chemical and biochemical oxygen demands. Extracted organic matter from biofilms was partitioned to polar, aromatic and saturated fractions using activated silica column chromatography. Results revealed that bacterial biomass growth depending on biofilm thickness and stratification. The most loaded stratum in bacterial biomass was the sewage-biofilm interface stratum that represented 51% of the total bacterial biomass. Stirring rate and ionic strength of mono and bivalent salts showed a major influence in biofilm disruption. The stirring time enhanced the exchange dynamic and matter capture between biofilm fragments at the critical stirring rate 90 r/min. Sodium chloride showed the dispersing effect on biofilms in suspension, and decreased the BOD5 (biochemical oxygen demand) beyond the physiological salt concentration.     

离子液体支撑液膜萃取分离双酚A、辛基酚和壬基酚

本研究以离子液体1-甲基-3-丁基咪唑六氟磷酸盐([BM IM][PF6])作膜溶剂,利用支撑液膜分离技术,用0.1mol/L的氢氧化钠溶液作萃取溶液将三种环境内分泌干扰物壬基酚、辛基酚和双酚A进行分离。研究结果显示该支撑液膜分离技术对双酚A的萃取效果最好,其次是辛基酚,而壬基酚不被萃取。利用该技术能将三种混合物选择性地进行萃取分离,但萃取时间不宜超过46小时。