新型绿色溶剂--室温离子液体

室温离子液体是一种具有特殊性质的液体,具有较低的熔点、良好的导电性和可以忽略的蒸气压等优点,已被应用到诸多领域。作为一种高效绿色溶剂,室温离子液体在化学分离、催化、电化学等方面发挥着重要的作用。对离子液体的种类、性质、制备方法及其在绿色化学中的应用进行了介绍。     

基于替代模型的地下水DNAPLs污染源反演识别

应用基于核极限学习机替代模型的模拟-优化理论和方法研究解决了地下水DNAPLs污染源及含水层参数的同步反演识别问题.结果表明：1）核极限学习机替代模型对模拟模型有较高的逼近精度,能够识别并模仿模拟模型的输入-输出关系,绝大部分相对误差小于5%,平均相对误差仅有2.98%;2）以替代模型代替模拟模型,大幅度地减小了模拟-优化过程的计算负荷,将反演识别时间由传统方法的83天减少到3小时,并能够保持较高的计算精度;3）应用基于模拟退火的粒子群优化算法求解优化模型,能够以较快的速度搜寻到全局最优,同时避免搜索过程陷于局部极小解.     

Field study of TCE diffusion profiles below DNAPL to assess aquitard integrity

An area where a free-product accumulation of trichloroethylene (TCE) dense non-aqueous phase liquid (DNAPL) occurs at the bottom of a 10-m-thick surficial sand aquifer was studied to determine the integrity of the underlying, 20-m-thick, clayey silt aquitard formed of glaciolacustrine sediment. TCE concentration-versus-depth profiles determined from aquitard cores collected at five locations indicated penetration of detectable TCE 2.5 to 3.0 m into the aquitard. Two of the profiles show persistent DNAPL at the aquitard interface, while two others indicate that DNAPL, present initially, was completely dissolved away producing concentration declines at the aquitard interface. The fifth profile suggests shallow DNAPL penetration (<0.5 m) into the aquitard, however, this penetration, which was likely caused by cross-contamination during core collection or cone penetrometry (CPT) of the aquitard interface, did not increase the maximum depth of TCE penetration. Combining the field profiles with one-dimensional model simulations, downward migration of the aqueous TCE front, defined as the EPA MCL of 5 microg/l, which was below the analytical detection limit, was projected to a distance between 4 and 5 m below the top of the aquitard. Using a single set of estimated aquitard parameter values, simulations of aqueous TCE migration into the aquitard provided a good fit to four of the field profiles with a migration time of 35 to 45 years, consistent with the history of TCE use at the site. These simulations indicate aqueous TCE migration is diffusion-dominated with only small advective influence by the downward groundwater velocity of 2 to 3 cm/year or less in the aquitard due to pumping of the underlying aquifer to supply water to the facility in the past 50 years. The applicability of the parameter values was confirmed by in situ diffusion experiments of 1-year duration, in which stainless steel cylinders containing DNAPL were inserted into the aquitard. The diffusion-dominated nature of the profiles indicates that the aquitard provides long-term protection of the underlying aquifer from contamination from this DNAPL zone. Simulations of long-term migration of the TCE solute front indicate breakthrough to the lower aquifer at 1200 years for the no advection scenario and at 500 years if the strong downward hydraulic gradient persists. However, even after breakthrough, the mass flux through the aquitard to the underlying aquifer remains relatively low, and when considered in terms of potential impacts to pumping wells, concentrations are not expected to increase significantly above present-day MCLs. The use of contaminant profiles of different time and distance scales, in addition to hydraulic data, dramatically improves the ability to assess aquitard integrity, and provides improved transport parameter values for estimating contaminant arrival times and fluxes. The apparent lack of deep preferential pathways for TCE migration, such as open fractures, is probably due to the softness of the silty aquitard deposit and minimal physical or chemical weathering of the aquitard provides long-term protection of the underlying aquifer from contamination from this DNAPL zone. Simulations of long-term migration of the TCE solute front indicate breakthrough to the lower aquifer at 1200 years for the no advection scenario and at 500 years if the strong downward hydraulic gradient persists. However, even after the breakthrough, the mass flux through the aquitard to the underlying aquifer remains relatively low, and when considered in terms of potential impacts to pumping wells , concentrations are not expected to increase significantly above present-day MCLs. The use of contaminant profiles of different time and distance scales, in addition to hydraulic data, dramatically improves the ability to assess aquitard integrity, and provides improved transport parameter values for estimating contaminant arrival times and fluxes. The apparent lack of deep preferential pathways for TCE migration, such as open fractures, is probably due to the softness of the silty aquitard deposit and minimal physical or chemical weathering of the aquitard.     

离子强度、pH值和Ca2+/Al3+对马尾松幼苗的铝毒影响

测定了在不同溶液酸度、不同离子强度和Ca²⁺/Al³⁺比下,铝对马尾松幼苗生长状况的影响。结果表明,溶液酸度增加,离子强度减小时,铝的毒害作用增大。钙对铝毒有明显缓解作用,当Ca²⁺/Al³⁺增大时,铝的毒性减小,但其缓解作用与铝浓度有关,当铝浓度增加,钙的缓解能力下降。     

植物吸收环境中金属元素的动力学模型

植物吸收金属元素的过程主要是一个主动吸收过程。目前用离子载体学说解释离子主动吸收过程已经得到了广泛的认同 ;而且各种各样的酶参与了植物主动吸收金属离子的过程。本文对利用酶促反应动力学描述植物吸收环境中金属元素这一现象的可行性及应用现状作了讨论。     

日本东京湾地区冬季飘尘污染研究

对东京湾地区冬季高浓度飘尘污染进行了分析，研究结果表明，日本某些特定地区也存在着与中国严重污染城市相当的飘尘污染；分析指出高浓度的飘尘污染主要来自于人为污染，其中废弃物焚烧和汽车排气的贡献占重要地位，这与中国大气煤烟型污染截然不同。     

不同种类表面活性剂联合离子液体预处理稻秆的物化特性研究

预处理是提高木质纤维材料酶解效果的关键步骤,更是木质纤维材料制造生物乙醇的重要环节.因此,对木质纤维材料进行预处理以促进酶解糖化过程具有重要意义.本研究以稻秆为原料,探讨不同类型表面活性剂(包括阳离子型、阴离子型、非离子型、生物)联合离子液体对木质纤维材料转化率及酶解初速度的影响,并通过稻秆成分分析、FTIR、XRD对处理前后稻秆的结构、结晶性进行了分析比较.结果表明,与单独离子液体处理相比,表面活性剂联合离子液体预处理稻秆可提升纤维转化率,效果为:生物表面活性剂-离子液体非离子型表面活性剂-离子液体阴离子型表面活性剂-离子液体阳离子型表面活性剂-离子液体.与未处理及单独离子液体处理稻秆相比,生物表面活性剂-离子液体预处理稻秆的纤维转化率分别提高55.38%和22.03%.     

功能化层状复合材料的制备及其电催化性能

目的制备一种新型功能化离子液体修饰层状复合材料,研究其对L-酪氨酸(L-Tyr)的电催化氧化行为。方法通过静电自组装方式将氮氧自由基功能化离子液体(TEMPO-IL)与钙铌酸钾(KCa_2Nb_3O_(10))进行复合,并运用XRD,FTIR,SEM,HRTEM等测试手段对所作材料的微观形貌和结构进行分析表征。另外,将其作为电极修饰剂修饰于电极表面通过电化学工作站测试其电化学性质。结果该修饰电极对于电催化氧化L-Tyr有着较高的电化学活性。同时实验还表明,当L-Tyr的浓度在1×10~(-4)~1.16×10~(-2) mol/L之间时,峰电流值与L-Tyr浓度呈良好的线性相关,检测下限为6.2×10~(-5) mol/L(信噪比为3)。结论静电自组装是一种能够快捷、高效的制备层状复合材料方法,且得到的复合材料显示出在生物传感器方面的应用前景。     

The use of ionic liquids based on choline chloride for metal deposition: A green alternative?

Ionic liquids are studied intensively for different applications. They tend to be denoted as “green solvents”, largely because of their low vapour pressure. In recent years toxicity and biotoxicity of ionic liquids have also been investigated, which proved that not all of these are “green”. In this paper the use of ionic liquids based on choline chloride and ethylene glycol in electrochemistry is discussed in the context of their use as green solvents. Due to their low toxicity and ready biodegradability, these deep eutectic solvents are promising for the electrodeposition of metals. The influence of the use of these liquids as metal deposition baths on the waste water is investigated. Drag-out was found to be the most influencing parameter on the environmental impact of the process, as it is three times higher compared to classical solutions due to the higher viscosity of the ionic liquid. There are no major changes needed in the rinsing configuration of classic electroplating plants, and ion exchange to remove the metal out of the waste water was not hindered by the presence of the ionic liquid. The formation of by-products during the deposition of metals has to be further investigated and evaluated in consideration of the environmental impact.     

Development of a novel mathematical model using a group contribution method for prediction of ionic liquid toxicities

A new mathematical model has been developed that expresses the toxicities (EC₅₀ values) of a wide variety of ionic liquids (ILs) towards the freshwater flea Daphnia magna by means of a quantitative structure-activity relationship (QSAR). The data were analyzed using summed contributions from the cations, their alkyl substituents and anions. The model employed multiple linear regression analysis with polynomial model using the MATLAB software. The model predicted IL toxicities with R² = 0.974 and standard error of estimate of 0.028. This model affords a practical, cost-effective and convenient alternative to experimental ecotoxicological assessment of many ILs.