Coinage Metal Complexes of Bis(quinoline-2-ylmethyl)phenylphosphine-Simple Reactions Can Lead to Unprecedented Results

The different coordination behavior of the flexible yet sterically demanding, hemilabile P,N ligand bis(quinoline-2-ylmethyl)phenylphosphine ( bqmpp ) towards selected Cu^I, Ag^I and Au^I species is described. The resulting X-ray crystal structures reveal interesting coordination geometries. With [Cu(MeCN)₄]BF₄, compound 1 [Cu₂(bqmpp)₂](BF₄)₂ is obtained, wherein the copper(I) atoms display a distorted square planar and square pyramidal geometry. The steric demand and π-stacking of the ligand allow for a short Cu⋅⋅⋅Cu distance (2.588(9) Å). Cu^I complex 2 [Cu₄Cl₃(bqmpp)₂]BF₄ contains a rarely observed Cu₄Cl₃ cluster, probably enabled by dichloromethane as the chloride source. In the cluster, even shorter Cu⋅⋅⋅Cu distances (2.447(1) Å) are present. The reaction of Ag[SbF₆] with the ligand leads to a dinuclear compound ( 3 ) in solution as confirmed by ³¹P{¹H} NMR spectroscopy. During crystallization, instead of the expected phosphine complex 3 , a tris(quinoline-2-ylmethyl)bisphenyl-phosphine ( tqmbp ) compound [Ag₂(tqmbp)₂](SbF₆)₂ 4 is formed by elimination of quinaldine. The Au(I) compound [Au₂(bqmpp)₂]PF₆ ( 5 ) is prepared as expected and shows a linear arrangement of two phosphine ligands around Au^I.     

新型低共熔溶剂的制备及其在分散液-液微萃取水样中臧红T和胭脂红的应用EI北大核心CSCD

建立了一种基于低共熔溶剂的旋涡辅助分散液-液微萃取和高效液相色谱连用检测水样中臧红T和胭脂红染料的方法。制备了一类分别由苄基三乙基溴化铵、苄基三丁基溴化铵、苄基三乙基氯化铵或苄基三丁基氯化铵(氢键受体)和正辛酸(氢键供体)组成的新型疏水性低共熔溶剂。最佳萃取条件为:选取苄基三丁基氯化铵和正辛酸(摩尔比为1∶2)制备的低共熔溶剂为萃取剂,萃取剂用量为75μL,萃取时间为1 min,溶液pH=7,NaCl浓度为3 mg/mL。在最优化条件下,检测臧红T和胭脂红的线性范围为4.8~1000 ng/mL;相关系数(R^(2))分别为0.9981和0.9987;检出限分别为1.5和1.8 ng/mL;定量限均为4.8 ng/mL。将该方法应用于实际水样中臧红T和胭脂红的测定,加标回收率为88.5%~113.6%,相对标准偏差均低于8.8%。     

岩石抽提物中极性化合物超高分辨质谱识别

采用具有超高分辨率的负离子电喷雾-傅立叶变换离子回旋共振质谱（ESI FT-ICR MS）分析了储层岩石抽提物中的石油酸及中性氮化物的分子组成,得到了抽提物中杂原子化合物类型分布、等效双键数（Double bonds equivalent,DBE）及碳数分布特征。研究结果表明,储层抽提物中含有多达16种不同杂原子类型的化合物,包括N1、N1O1、N1O2、N1O3、N1S1、N1S2、N2、N2S1、O1、O1S1、O2、O2S1、O1S2、O2S2、O3和O4,其中N1、N1S1、O2及O2S1类具有较高的相对丰度。抽提物中的N1类化合物以咔唑和苯并咔唑类化合物为主;N1S1类化合物以C2~C8烷基取代的咔唑并苯并噻吩类化合物为主;O2类化合物主要为1~2环环烷酸,其次还在抽提物中鉴别出具有较高相对丰度的DBE为5和6的O2类化合物;而O2S1类化合物中以DBE为7和8的O2S1具有最高的相对丰度。     

SiO2-Al2O3玻纤载体负载CuO-CeO2对挥发性有机化合物催化燃烧性能研究

采用等体积共浸渍法制备了CuO-CeO₂整体式催化剂,评价了催化剂对乙酸乙酯、异丙醇及甲苯的催化燃烧性能。采用N₂吸附-脱附、X射线衍射（XRD）、氢气程序升温还原（H₂-TPR）、氨气程序升温脱附（NH₃-TPD）以及挥发性有机化合物脱附等手段对催化剂进行了表征。表征数据显示,氧化铜以高分散态均匀分散存在于载体表面,氧化铈则是小的纳米颗粒,氧化铈颗粒粒径随着Cu/Ce物质的量比的减小而增大。添加铈氧化物会显著增加总酸量,特别是路易斯酸酸位的量,同时增强了乙酸乙酯和异丙醇的吸附量,吸附量的增加提高了催化剂对乙酸乙酯和异丙醇的催化燃烧性能。从甲苯的催化燃烧实验可以看出,大量添加CeO₂稍微增加了甲苯的吸附容量,减弱了催化剂的还原性、降低了活性氧的含量,最终导致甲苯的低转化率。催化行为由氧化铜、氧化铈以及载体三者之间的共同作用决定,这三者的协同作用不仅影响着表面氧的活性同时影响着催化剂对甲苯的吸附能力。     

适用小分子化合物MALDI分析的基质研究

基质辅助激光解吸电离技术（matrix assisted laser desorption/ionization,MALDI）是20世纪80年代发展起来的一种应用于质谱分析的电离化技术。MALDI技术在生物大分子的分析和检测方面获得了良好的应用。由于受有机基质分子的干扰,MALDI在小分子化合物分析方面的应用受到很大的限制。近年来为解决这一问题,一些用于MALDI分析的新型材料被设计和开发出来。这些新型材料主要包括：碳、硅、纳米金属等无机材料和新型有机分子等。除此之外,在传统基质中添加表面活性剂和对分析物衍生化等方法也被成功应用于小分子化合物的MALDI质谱分析中。本文对这些可应用于小分子化合物分析的新型MALDI基质进行了综述和展望。     

Molecular Salt Effects in the Gas Phase: Tuning the Kinetic Basicity of [HCCLiCl]− and [HCCMgCl2]− by LiCl and MgCl2

A combination of gas‐phase ion–molecule reaction experiments and theoretical kinetic modeling is used to examine how a salt can influence the kinetic basicity of organometallates reacting with water. [HC?CLiCl]^? reacts with water more rapidly than [HC?CMgCl₂]^?, consistent with the higher reactivity of organolithium versus organomagnesium reagents. Addition of LiCl to [HC?CLiCl]^? or [HC?CMgCl₂]^? enhances their reactivity towards water by a factor of about 2, while addition of MgCl₂ to [HC?CMgCl₂]^? enhances its reactivity by a factor of about 4. Ab initio calculations coupled with master equation/RRKM theory kinetic modeling show that these reactions proceed via a mechanism involving formation of a water adduct followed by rearrangement, proton transfer, and acetylene elimination as either discrete or concerted steps. Both the energy and entropy requirements for these elementary steps need to be considered in order to explain the observed kinetics.     

设计合成新型有机硒化合物用于金属阳离子识别性能研究

设计合成了有机硒化合物1,4-二(2-苄硒基)乙氧基蒽,利用1H NMR、13C NMR、红外光谱和质谱对化合物进行了结构表征,采用荧光光谱技术研究了其对金属阳离子的识别。结果表明,其对汞离子有较强的识别能力,且对汞离子表现出开关性能。最后,初步讨论了其的识别机理和应用。     

Emission of volatile sesquiterpenes and monoterpenes in grapevine genotypes following Plasmopara viticola inoculation in vitro

The grapevine (Vitis vinifera) is one of the most widely cultivated fruit crops globally, and one of its most important diseases in terms of economic losses is downy mildew, caused by Plasmopara viticola. Several wild Vitis species have been found to be resistant to this pathogen and have been used in breeding programs to introduce resistance traits to susceptible cultivars. Plant defense is based on different mechanisms, and volatile organic compounds (VOCs) play a major role in the response to insects and pathogens. Although grapevine resistance mechanisms and the production of secondary metabolites have been widely characterized in resistant genotypes, the emission of VOCs has not yet been investigated following P. viticola inoculation. A Proton Transfer Reaction‐Time of Flight‐Mass Spectrometer (PTR‐ToF‐MS) was used to analyze the VOCs emitted by in vitro‐grown plants of grapevine genotypes with different levels of resistance. Downy mildew inoculation significantly increased the emission of monoterpenes and sesquiterpenes by the resistant SO4 and Kober 5BB genotypes, but not by the susceptible V. vinifera Pinot noir. Volatile terpenes were implicated in plant defense responses against pathogens, suggesting that they could play a major role in the resistance against downy mildew by direct toxicity or by inducing grapevine resistance. The grapevine genotypes differed in terms of the VOC emission pattern of both inoculated and uninoculated plants, indicating that PTR‐ToF‐MS could be used to screen hybrids with different levels of downy mildew resistance. Copyright © 2015 John Wiley & Sons, Ltd.     

GPR40 受体苯丙酸类激动剂三维定量构效关系研究

苯丙酸类化合物是G蛋白偶联受体40(GPR40)潜在的生物活性药物。本文基于比较分子力场分析法(Co MFA)和比较分子相似性指数分析法(CoMSIA),分别建立了40个已知活性的GPR40受体苯丙酸类激动剂的三维定量构效关系(3D-QSAR)模型,研究该类激动剂与生物活性之间的关系。CoMFA和CoMSIA模型的交叉验证系数(q~2)分别为0. 527和0. 500,拟合验证系数(r~2)分别为0. 901和0. 860,两个3D-QSAR模型预测值与实验值基本一致,表明模型具有良好的可信度和预测能力。根据两个3D-QSAR模型提供的立体场、静电场、疏水场、氢键供体场和氢键受体场所提供的信息提出优化该类抑制剂结构的药物设计思路,为指导设计更高活性的GPR40激动剂以及GRR40新分子激动活性的预测提供理论依据。     

基于QSAR模型的有机磷化合物毒性预测

随着有机磷化合物(OPs)的广泛应用,其在越来越多的环境介质中被检测出来。大多数OPs具有毒性,但人们缺乏快速且有效的预测手段来对毒性进行评估。本文将结合E-Dragon软件计算的分子描述符,采用不同的QSAR模型对36个OPs的毒性进行预测。文中采用后退法作为描述符筛选方法,以均方根误差(RMSE)作为评价标准,共找到14个对线性核函数支持向量机(SVM)模型贡献较大的描述符;在最终得到的SVM模型交叉验证结果中,计算值与实际值的相关系数为0. 913,均方根误差为0. 388;外部测试验证结果中,平均相对误差为9. 10%。此外,采用多元线性回归(MLR)、人工神经网络(ANN)以及偏最小二乘回归(PLS)模型对OPs的毒性进行预测,交叉验证结果显示,三个模型的计算值与实际值的相关系数分别为0. 878、0. 686与0. 620,没有SVM模型的预测能力好。因此采用线性核函数的SVM模型对OPs进行毒性预测是一个行之有效的方法。