Ion Pairing Kinetics Does not Necessarily Follow the Eigen-Tamm Mechanism

The most recognized and employed model of the solvation equilibration in the ionic solutions was proposed by Eigen and Tamm, in which there are four major states for an ion pair in the solution： the completely solvated state, 2SIP （double solvent separate ion pair）, SIP （single solvent separate ion pair）, and CIP （contact ion pair）. Eigen and Tamm suggested that the transition from SIP to CIP is always the slowest step during the whole pairing process, due to a high free energy barrier between these two states. We carried out a series of potential of mean force calculations to study the pairing free energy profiles of two sets of model mono- atomic 1：1 ion pairs 2.0：x and x：2.0. For 2.0：x pairs the free energy barrier between the SIP and CIP states is largely reduced due to the salvation shell water structure. For these pairs the SIP to CIP transition is thus not the slowest step in the ion pair formation course. This is a deviation from the Eigen-Tamm model.     

Theoretical Insights into Intermolecular Hydrogen-Bonding Strengthening in Fluorenone-Methanol Complexes Induced by Electronic Excitation and Bulk Solvent Effect

This work presents a theoretical insight into the variation of the site-specific intermolecular hydrogen-bonding （HB）, formed between C=O group of fluorenone （FN） and O-H groups of methanol （MeOL） molecules, induced by both the electronic excitation and the bulk solvent effect. Through the calculation of molecular ground- and excited-state properties, we not only demonstrate the characters of HB strengthening induced by electronic excitation and the bulk solvent effect but also reveal the underlying physical mechanism which leads to the HB variation. The strengthening of the intermolecular HB in electronically excited states and in liquid solution is characterized by the reduced HB bond-lengths and the red-shift IR spectra accompanied by the increasing intensities of IR absorption corresponding to the characteristic vibrational modes of the O-H and C--O stretching. The HB strengthening in the excited electronic states and in solution mainly arises from the charge redistribution of the FN molecule induced by the electronic excitation and bulk solvent instead of the intermolecular charge transfer. The charge redistribution of the solute molecule increases the partial dipole moment of FN molecule and the FN-MeOL intermolecular interaction, which subsequently leads to the HB strengthening. With the bulk solvent effect getting involved, the theoretical IR spectra of HBed FN-MeOL complexes agree much better with the experiments than those of gas-phase FN-MeOL dimer. All the calculations are carried out based on our developed analytical approaches for the first and second energy derivatives of excited electronic state within the time-dependent density functional theory.     

A New Coordination Polymer Containing 4-[（8-Hydroxy-5-quinolinyl）azo]-benzenesulfonic Acid： Synthesis,Structure and Fluorescent Property

A new coordination polymer, {[CdL（en）]＇DMF}n （1, H2L = 4-[（8-hydroxy-5- quinolinyl）azo]-benzenesulfonic acid, en = ethylenediamine, DMF = N,N-dimethylformamide）, has been solvothermally synthesized and structurally characterized by single-crystal X-ray diffrac- tion, infrared （IR） spectra, elemental analysis, powder X-ray diffractions （PXRD） and thermo- gravimetric analysis （TGA）. Compound 1 crystallizes in monoclinic, space group P2Jc with a = 14.6525（9）, b = 13.3917（9）, c = 11.8838（8） A, β = 101.2290（10）°, V = 2287.2（3） A3, Z = 4, C20H24CdN6OsS, Mr = 572.91, Dc. = 1.664 mg-mm-3, F（000） = 1160, p = 1.091 mm-1, R = 0.0232 and wR = 0.0587 for 3597 observed reflections （I 〉 2σ（I））. Compound 1 exhibits a one-dimensional （1D） double-chain structure which is further connected through hydrogen bonding and π-π interactions into a three-dimensional （3D） supramolecular network. In addition, it exhibits blue fluorescence at room temperature in the solid state.     

CuInS2纳米纸阵列薄膜的制备及生长机理

采用溶剂热合成技术,以氯化铜、硝酸铟和硫脲为反应物,十六烷基三甲基溴化铵(CTAB)为阳离子表面活性剂,草酸为还原剂,无水乙醇为溶剂,直接在掺氟的SnO2透明导电玻璃(FTO)衬底上合成CuInS2(CIS)薄膜.采用扫描电子显微镜(SEM)、高分辨率透射电子显微镜(HRTEM)、X射线衍射(XRD)、拉曼光谱、能量色散谱(EDS)、紫外-可见(UV-Vis)反射光谱和透射光谱对样品的形貌、结构、成分和光学性能进行分析.结果表明,在适当的反应物浓度下,在FTO衬底上形成了垂直衬底生长的、具有良好结晶性能的黄铜矿结构的CIS纳米纸阵列薄膜.CIS薄膜中Cu,In,S的原子比为1.1∶1∶2.09,在紫外-可见和近红外波段具有良好的光吸收特性,禁带宽度约1.51 eV.结合不同反应时间制备的CIS薄膜的形貌、结构和成分分析,讨论了CIS纳米纸阵列薄膜的生长机理.     

低共熔溶剂用于高效可逆捕集二氧化碳的研究

本文通过一步合成法合成了四种不同摩尔比的四乙基氯化胺-乙醇胺低共熔溶剂（TEAC-MEA DES）。红外光谱表征分析表明该DES是依靠氢键作用而形成的;DES的热稳定性高于MEA,且随着MEA的比例的增加而降低;对不同比例的DES进行了四次循环CO₂吸收-解吸实验,发现其吸收容量几乎不变,重复使用性能较好。在不同温度下计算了化学平衡常数,lnK对1/T线性拟合结果表明DES吸收CO₂的反应焓是负值,即吸收CO₂的反应是放热过程。该DES在吸收CO₂方面具有很大的潜力。     

加速溶剂提取-同位素稀释-高分辨气相色谱-高分辨质谱法测定生物样品中82种多氯联苯

我国水产品中多氯联苯(PCBs)的检测方法,主要以6种指示性PCBs和12种二噁英类共平面PCBs为主,仅涵盖有限的PCBs。为更全面地获得生物体中PCBs的浓度水平,深入探讨PCBs在生物体内的代谢和富集特征,进而准确评价PCBs对人类的暴露水平及风险,以鱼和贝类作为生物样品代表,建立了加速溶剂提取-同位素稀释-高分辨气相色谱-高分辨质谱(ASE-ID-HRGC-HRMS)测定生物样品中82种PCBs的方法。比较了振荡提取和加速溶剂提取两种提取方式的回收率和重复性,最终采用正己烷-二氯甲烷(1∶1, v/v)对PCBs进行加速溶剂提取。考察了各流分淋洗液对PCBs的回收率,确定了样品提取液经8 g 44%酸性硅胶层析柱(内径15 mm), 90 mL正己烷洗脱的净化方式。样品提取液净化浓缩后进行HRGC-HRMS分析,色谱柱采用DB-5MS超低流失石英毛细管柱(60 m×0.25 mm×0.25 μm)。通过优化后的升温程序对化合物进行分离,以保留时间和两个特征离子精准定性,采用同位素内标法定量。结果表明,在0.1~200 μg/L范围内,平均相对响应因子(RRF)的相对标准偏差值(RSD, n=7)均≤20%,相关系数(r²)>0.99。生物样品中PCBs的方法检出限为0.02~3 pg/g;鱼类中PCBs平均加标回收率为71.3%~141%, RSD(n=7)为2.1%~14%;贝类中PCBs平均加标回收率为76.9%~143%, RSD为1.4%~11%。该方法灵敏、准确、可靠,可以更加全面具体地分析鱼和贝类等水产品受PCBs的污染情况,为国内外开展生物监测提供有效的技术支持,从而服务于相关生态环境管理及履行《斯德哥尔摩公约》。     

低共熔溶剂分散液液微萃取-悬浮固化-高效液相色谱法测定水产品中3种内分泌干扰物的含量北大核心CSCD

将癸酸和香叶醇在10 mL玻璃管中以2∶1的物质的量之比混合,然后将混合物在80℃水浴锅中加热,直至形成稳定的低共熔溶剂(DES)。该溶剂易合成、低成本、低毒性且具有高生物降解性,是一种新型的疏水性DES,可用于水产品中内分泌干扰物的微萃取。取已粉碎的水产品样品1 g和乙腈2 mL置于5 mL离心管中,以转速2 000 r·min^(-1)涡旋振荡3 min。取上清液400μL,经0.45μm滤膜过滤,滤液与100μL DES混合,并迅速注入装有5 mL 80 g·L^(-1)氯化钠溶液的10 mL离心管中,以完成DES的分散。将上述离心管以转速3 500 r·min^(-1)离心5 min,然后置于冰浴中进行固化。将固化后所得样品溶解于150μL甲醇中,以Eclipse Plus C;色谱柱为分离柱,以体积比90∶10的甲醇-水的混合液为流动相,在激发波长228 nm,发射波长305 nm处测定双酚A、4-叔辛基苯酚和壬基酚等3种内分泌干扰物的含量。结果表明,DES在冰浴中固化,可促进其从水溶液中分离,简单且快速,利于萃取剂的收集。3种内分泌干扰物的质量分数均在0.25~10μg·g^(-1)内与其对应的峰面积呈线性关系,检出限(3S/N)均为0.075μg·g^(-1)。用此法对空白加标样品进行测定,测定值的日内和日间相对标准偏差(n=5)均小于4.0%。以空白样品为基体进行加标回收试验,所得回收率为78.7%~91.6%。     

Yb^(3+)/Er^(3+)双掺杂的NaYF_(4)上转换纳米功能材料的制备与设计优化北大核心CSCD

为合成单分散、形貌尺寸均一、高上转换发光的稀土上转换纳米功能材料,本文以稀土氯化物为反应前驱体,采用溶剂热法合成Yb^(3+)/Er^(3+)双掺杂的NaYF_(4)上转换发光纳米材料,并对稀土元素掺杂比例、反应时间、反应温度、油酸体积分数等影响材料结构、形貌和发光性能的条件进行了优化。结果表明,最佳稀土元素掺杂比例为78%Y^(3+)∶20%Yb^(3+)∶2%Er^(3+),反应时间90 min,反应温度300℃,油酸体积分数15.5%。在最佳条件下,本研究合成的NaYF_(4)∶Yb^(3+),Er^(3+)纳米材料形貌呈六方晶型,直径约为30 nm,与标准卡片匹配良好;在980 nm近红外光激发下,该纳米材料在529 nm、542 nm以及657 nm处均可以观察到Er^(3+)的特征发射峰,且发射出明亮的绿色荧光。本研究为后续制备修饰有不同功能基团的NaYF_(4)∶Yb^(3+),Er^(3+)纳米材料及其应用奠定了基础。     

疏水性低共熔溶剂液液微萃取/高效液相色谱法测定豆奶中三嗪类和苯脲类除草剂

该文建立了一种简单、高效的新型疏水性低共熔溶剂液液微萃取法,用于提取和富集市售包装豆奶中的三嗪类（阿特拉津、去草净）和苯脲类（灭草隆、绿麦隆）除草剂,并结合高效液相色谱对目标分析物进行分离和测定。以六氟异丙醇为氢键供体,四丁基氯化铵为氢键受体,按照不同摩尔比制备了一系列疏水性低共熔溶剂,并对影响萃取效果的实验条件进行了优化,包括低共熔溶剂的种类及用量、氯化钠用量、涡旋时间、pH值和温度。结果表明,在最佳实验条件下,4种目标物在1.00～500.00 μg/L范围内具有良好的线性关系（r ≥ 0.998 4）,检出限和定量下限分别为0.56～0.95 μg/L和1.87～3.16 μg/L,日内和日间相对标准偏差（RSD）分别为0.28%～2.0%和2.1%～7.5%,加标回收率为86.4%～117%。该方法具有操作简单快速、萃取时间短、试剂用量少和实验成本低等优点,可用于市售包装豆奶中三嗪类和苯脲类除草剂的分析检测。     

金属性二维过渡金属硫化物的溶剂热合成及电催化析氢性能

采用溶剂热法制备了多种二维过渡金属硫化物(TMDCs), 在合成过程中通过调控反应前驱体的滴加速率来控制所得TMDCs的形貌和结构. 然后采用高温热处理来提高TMDCs的结晶性, 从而提升了其电催化活性. 在酸性电解液中进行电催化析氢性能测试. 结果表明, “花状”结构的金属性二维二硫化铌(NbS₂)具有最佳的催化活性和稳定性, 在电流密度为10 mA/cm²时, 其过电位仅为146 mV, 持续工作24 h后电流密度几乎不衰减. 研究发现, 可充分暴露面内活性位点的“花状”结构以及高温处理后材料导电性的提高是二维NbS₂具有优异电催化性能的主要因素.