水环境中溴化1-烷基-3-甲基咪唑类离子液体与胸腺嘧啶相互作用体系的计算研究

溴化咪唑类离子液体的生物小分子作用机制亟待探索.本文采用M06-2X/6-311++G（2d,p）/PCM/water理论方法计算了研究胸腺嘧啶（T）与溴化1-烷基-3-甲基咪唑类离子液体（[C_nmim]Br,n=2、4、6、8、10）相互作用形成的T-[C_nmim]⁺、T-Br^-、T-[C_nmim]Br和T-2[C_nmim]Br体系的结构和能量学特征.结果表明T与阴阳离子间形成典型构型的稳定顺序是：共面 < 垂直 < 堆积（T-[C_nmim]⁺）,top < front（T-Br^-）,T-[C_nmim]⁺ < T-Br^- < T-[C_nmim]Br < T-2[C_nmim]Br.T与Br^-之间的氢键作用与咪唑阳离子伴随弱氢键的堆积环境更有利,阳离子烷基链长影响不明显.在堆积构型中胸腺嘧啶与咪唑阳离子以π-π⁺色散吸引为主,并伴随C-H…O和C-H…π弱氢键作用,部分碱基电子转移至阳离子（π→π⁺）,其NBO分析显示稳定化能主要来自π→π^+*（ΣE_π→π+*²）轨道作用的贡献;T与Br^-之间以静电吸引为主,溴离子向胸腺嘧啶转移电子,稳定化能源于lp_Br→σ_N-H^*.     

咪唑类离子液体系列对卤虫的急性毒性研究

选取卤虫作为实验生物,研究了1-丁基,1-辛基,1-十二烷基-3甲基咪唑盐酸盐( [Cnmim][Cl](n = 4,8,12) ) 3种离子液体的暴露对卤虫个体存活率的影响.同时,选取了实验室常用的有机试剂甲醇和乙腈,无机化学品重铬酸钾作为阳性对照.根据剂量效应曲线的拟合结果发现,受试离子液体系列随着咪唑环上烃基侧链碳原子数的增加,对卤虫的毒性效应也相应增强,3种离子液体对卤虫的LC50-24h依次为171.1,133.6,17.76μg/mL.离子液体对卤虫的LC50-24h比甲醇(LC50-24h=84.83mg/mL)和乙腈(LC50-24h=52.84mg/mL)低了2~3个数量级,重铬酸钾对卤虫的(LC50-24h=16.87μg/mL)与离子液体对卤虫的LC50-24h处于同一水平.     

离子液体[C14mim]Br对大鼠亚慢性毒性的初步研究

研究了离子液体溴化-1-十四烷基-3-甲基咪唑盐([C_(14)mim]Br)对大鼠的亚慢性毒性.实验设立3个染毒组(2.5、5、10 mg·kg~(-1))和1个对照组,对大鼠经口染毒90 d后,分别考察大鼠的体重、血清生化指标、脏体指数、组织形态学的变化.结果表明,与对照组相比,染毒组大鼠的体重增长随着染毒剂量的增加而降低,肝脏/体重系数增大,其血清中碱性磷酸酶(ALP)、丙氨酸氨基转移酶(ALT)、天门冬氨酸转氨酶(AST)、直接胆红素(DBIL)和和球蛋白(GLB)水平均明显升高,A/G(ALB/GLB)、血清总蛋白(TP)值则明显下降.病理检查结果显示,染毒组大鼠的肝脏、肾脏及肺均有不同程度的损伤及病变.研究表明,[C_(14)mim]Br亚慢性染毒对大鼠的肝肾均有损伤,且其毒性呈一定的剂量依赖性.     

不同结构离子液体对含Pb~(2+)废水萃取性能的对比研究

通过比较3种不同结构的离子液体对含铅废水的萃取性能,探讨了萃取时间、温度、铅离子初始浓度、水相与有机相的体积比等对萃取过程的影响,结果表明,烯基取代的[AMIM][PF6]离子液体对含铅废水中铅离子的去除效果最好,同时,离子液体通过回收可再次利用,实现离子液体的绿色化。     

一种离子液体——溴化1-辛基—3-甲基咪唑对大型溞摄食强度的影响

用计数法研究了一种离子液体--溴化I-辛基-3-甲基咪唑对大型溞滤水率和摄食率的影响及恢复条件下子代大型溞摄食强度的变化,以初步探讨离子液体对水生生态系统可能的影响.实验结果表明:离子液体显著降低了母代大型溞的滤水率和摄食率,最低浓度(7μg·L-1)处理组二者分别比对照下降了26.5%和20.6%,最高浓度处理组(112μg·L-1)二者下降了84%和80%;子代的滤水率和摄食率也受到抑制,且抑制程度大于母代,在离子液体浓度为112μg·L-1时子代第3胎幼潘滤水率和摄食率的下降比率高达95.5%和94.3%.将母体暴露于不同浓度离子液体的大型溞的子代第1胎和第3胎幼溞转入恢复实验,较低浓度处理组其摄食行为得到一定的恢复,但高浓度处理组仍受到较强的抑制,约比对照下降了80%.因此,离子液体严重影响了大型溞的摄食强度,对水生生态系统安全具有潜在的威胁.     

2-溴乙烷磺酸钠对ABR反应器运行效果和微生物菌群结构的影响

针对厌氧反应器酸化问题,研究了2-溴乙烷磺酸钠(2-bromoethane sulfonate,BES)对厌氧折流板反应器(ABR)运行效果、中间代谢产物挥发性脂肪酸(VFA)及微生物群落结构的影响。结果表明,BES会导致ABR反应器处理效能降低,当BES投加量为0.27 mmol/L时,COD_Cr去除率由95%降到10%以下。BES的投加加剧了ABR反应器酸化风险,导致出水pH降到5.5以下,反应器内VFA明显积累,丁酸、戊酸和己酸等占VFA总量的36%以上,出水VFA浓度达到15.3 mmol/L左右;此外,BES的投加导致产甲烷菌的相对丰度降低25%左右,而产氢产乙酸菌及耗氢产乙酸菌的相对丰度分别增加了9%和7%。PCR-DGGE和多样性指数结果表明,BES的投加显著影响了ABR反应器内各隔室的微生物种群结构,导致反应器的细菌种群多样性及丰富度指数均有所减少,优势微生物种群由厚壁菌门、杆菌属变为拟杆菌门、螺旋菌门及δ-变形菌门。     

离子液体[TETAH]+[BF4]--乙二醇混合体系吸收CO2的实验研究

以三乙烯四胺(TETA)为阳离子前驱体、氟硼酸(HBF_4)为阴离子前驱体制备多胺基离子液体[TETAH]~+[BF_4]~-,并与助溶剂乙二醇(EG)按一定计量比组成[TETAH]~+[BF_4]~--EG混合体系.实验考察了离子液体的浓度、吸收温度和气体流量等对该混合体系吸收CO_2性能的影响.结果表明,当[TETAH]~+[BF_4]~-的浓度为20%,吸收温度为15℃,气体流量为200 mL·min~(-1)时,该混合体系对CO_2的吸收容量达到1.50 mol·mol~(-1)(以每mol离子液体吸收的CO_2量(mol)计,下同);离子液体的浓度、CO_2流量和温度均会影响该混合体系达到吸收平衡的时间.同时,该混合体系对CO_2的吸收容量均高于[TETAH]~+[BF_4]~-和EG单独吸收CO_2的容量,这表明离子液体[TETAH]~+[BF_4]~-与助溶剂EG之间存在某种协同作用.另外,该混合体系具有良好的再生性能,在80℃的条件下经过5次吸收-解吸循环实验后的吸收摩尔分率为1.00 mol·mol~(-1),性能下降仅为33.3%.     

以三乙烯四胺为前驱体合成的离子液体对CO2的吸收效果研究

以三乙烯四胺(TETA)为阳离子前驱体合成多胺基离子液体([TETAH]+[Cl]-、[TETAH]+[NO_3]~-、2[TETAH]+[SO_4]~(2-)和[TETAH]+[BF_4]~-),以CO_2摩尔吸收量和CO_2平均吸收速率为评价指标,优选出对CO_2吸收效果最优的2[TETAH]+[SO_4]~(2-)离子液体.进一步考察在不同含水率、气体流量和温度等因素下2[TETAH]+[SO_4]~(2-)离子液体对CO_2的吸收效果,结果表明:2[TETAH]+[SO_4]~(2-)吸收CO_2的最佳条件为含水率30%、气体流量50 m L·min~(-1)、温度10℃,此时CO_2饱和摩尔吸收量达到1.325 mol·mol~(-1),各因素对CO_2吸收量的影响大小顺序为含水率气体流量温度.     

The thermal transformation mechanism of chlorinated paraffins: An experimental and density functional theory study

The increasing production and usage of chlorinated paraffins(CPs) correspondently increase the amount of CPs that experience thermal processes. Our previous study revealed that a significant amount of medium-chain chlorinated paraffins(MCCPs), short-chain chlorinated paraffins(SCCPs) as well as aromatic and chlorinated polycyclic aromatic hydrocarbons(Cl-PAHs) were formed synergistically during the thermal decomposition of CP-52(a class of CP products).However, the transformation mechanisms of CP-52 to these compounds are still not very clear.This article presents a mechanistic analysis on the decomposition of CP-52 experimentally and theoretically. It was found that CP-52 initially undergoes dehydrochlorination and carbon chain cleavage and it transformed into chlorinated and unsaturated hydrocarbons. Cyclization and aromatization were the most accessible pathways at low temperatures(200–400°C), both of which produce mostly aromatic hydrocarbons. As the temperature exceeds 400°C, the hydrocarbons could decompose into small molecules, and the subsequent radical-induced reactions become the predominant pathways, leading to the formation of Cl-PAHs. The decomposition of CP-52 was investigated by using density functional theory and calculations demonstrating the feasibility and rationality of PCB and PCN formation from chlorobenzene. The results improve the understanding of the transformation processes from CP-52 to SCCPs and Cl-PAHs as well as provide data for reducing their emissions during thermal-related processes.     

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.     

聚离子液体修饰荷电超滤复合膜的构建及其抗污染性分析

以氯化-1-烯丙基-3-乙烯基咪唑离子液体为反应单体,偶氮二异丁腈(AIBN)为引发剂,通过自由基聚合先合成聚离子液体预聚物,并将其与聚偏氟乙烯(PVDF)、聚乙二醇(PEG)进一步共混反应,以制备聚离子液体/PVDF共混铸膜液.然后将该铸膜液在聚丙烯(PP)微孔膜表面进行涂覆成膜,以制备具有互穿网络结构的聚离子液体/PVDF荷电复合膜.采用红外光谱、扫描电镜、Zeta电位计等对复合膜表面的化学结构、形貌及荷电性能等进行分析,并采用水通量测定仪对复合膜的纯水通量及蛋白质和染料的分离性能等进行了研究.结果表明,该复合膜表面具有较好的荷电性能,且随聚离子液体的加入可以有效提高膜的亲水性和抗污染性,复合膜M2的纯水通量可达到101.7 L·m-2·h-1,该膜对溶菌酶和染料罗丹明6G的截留率分别为88.0%和94.1%,该分离膜经清水反冲洗后通量恢复率分别达到72.5%和91.8%.     

二噁英结构与正辛醇-水分配系数相关性的密度泛函理论

为精确描述二噁英分子的电子结构及其定量结构/性质相关关系(QSPRs),运用密度泛函理论,在B3LYP/6-311G**水平上,分别对多氯二苯并对二噁英(PCDDs)和多氯二苯并呋喃(PCDFs)进行了优化计算.相应量子化学参数,即平均分子极化率(α),熵(S),极化率和四极矩的张量分量(αxx,αyy,αzz和Qxx,Qyy,Qzz)用于该类化合物辛醇-水分配系数的QSPR研究,构建了2个单变量和1个双变量模型,其决定系数R2分别为0.962、0.950和0.951;其显著性检验因子F分别为509.759、379.498和186.234.PCDD/Fs在辛醇相-水相间的分配性质主要与分子体积因素有关,而电性因素的影响较小;不同模型预测值间的差异与模型中预测变量本身性质和实验值的有限性有关.经比较,本研究中所建立的3个QSPRs模型尽管只有1个或2个变量,但其结果与复杂的偏最小二乘分析(PLS)相近.     

Experimental and density functional theory study of the adsorption of N2O on ion-exchanged ZSM-5: Part II. The adsorption of N2O on main-group ion-exchanged ZSM-5

The adsorption and desorption of N2O on main-group ion-exchanged ZSM-5 was studied using temperature-programmed desorption (TPD) and density functional theory (DFT) calculations. TPD experiments were carried out to determine the desorbed temperature Tmax corresponding to the maximum mass intensity of N2O desorption peak and adsorption capacity of N2O on metal-ion-exchanged ZSM- 5s. The results indicated that Tmax followed a sequence of Ba2+ > Ca2+ > Cs+ > K+ > Na+ > Mg2+and the amount of adsorbed N2O on main-group metal cation followed a sequence of Ba2+ > Mg2+ > Ca2+ > Na+ > K+ > Cs+. The DFT calculations were performed to obtain the adsorption energy (Eads), which represents the strength of the interaction between metal cations and the N-end or O-end of N2O. The calculation results showed that the N-end of the N2O molecule was favorably adsorbed on ion-exchanged ZSM-5, except for Cs-ZSM-5. For alkali metal cations, the Eads of N2O on cations followed the order which was the same to that of Tmax: Cs+ > K+ > Na+. The calculated and experimental results consistently showed that the adsorption performances of alkaline-earth metal cations were better than those of alkali metal cations.     

Toxic effects of 1-methyl-3-octylimidazolium bromide on the wheat seedlings

The toxic effects of 1-methyl-3-octylimidazolium bromide ([C8mim]Br) on wheat seedlings were evaluated. Wheat seedlings were cultivated in aqueous solution with [C8mim]Br at di erent concentrations (0, 1, 2, 4, 6, 8 mg/L). The contents of photosynthetic pigment and proline, peroxidation of membrane lipid, and activities of antioxidation enzymes (superoxide dismutase, catalase, peroxidase and ascorbate peroxidase) in leaves were measured on day 7 after treatment with [C8mim]Br. The results showed that [C8mim]Br significantly decreased the contents of photosynthetic pigments, activities of antioxidant enzymes in the wheat leaves and in dry weight of seedlings, while increased the proline content and membrane lipid peroxidation. The results suggested that [C8mim]Br can inhibit photosynthesis and lead to oxidative stress to wheat seedlings.