Optimization of headspace solid-phase microextraction for the determination of pesticide residues in vegetables and fruits.

A headspace solid-phase microextraction method has been developed for the determination of 8 pesticides in vegetables and fruits by using gas chromatography with an electron capture detector. Two types of fibers (polyacrylate, 85 microm and polydimethylsiloxane, 100 microm) have been assayed and compared. The main factors: extraction and desorption parameters, ionic strength, and the effects of dilution and organic solvents, were studied and optimized. The optimized procedures resulted in more than 80% recovery for all the investigated vegetable and fruit samples with RSD values below 10%.     

支付交易费的回望期权定价

以Black-Scholes模型为基础,通过对回望期权的研究,结合有交易费的欧式期权的定价公式,运用证券组合技术与无套利原理,建立了支付交易费的回望期权定价模型.通过对方程化简和分析,运到PDE相关方法化为Cauchy问题,得出定价公式.     

Electrochemiluminescence biosensor for the assay of small molecule and protein based on bifunctional aptamer and chemiluminescent functionalized gold nanoparticles

An electrochemiluminescence (ECL) biosensor for simultaneous detection of adenosine and thrombin in one sample based on bifunctional aptamer and N-(aminobutyl)-N-(ethylisoluminol) functionalized gold nanoparticles (ABEI-AuNPs) was developed. A streptavidin coated gold nanoparticles modified electrode was utilized to immobilize biotinylated bifunctional aptamer (ATA), which consisted of adenosine and thrombin aptamer. The ATA performed as recognition element of capture probe. For adenosine detection, ABEI-AuNPs labeled hybridization probe with a partial complementary sequence of ATA reacted with ATA, leading to a strong ECL response of N-(aminobutyl)-N-(ethylisoluminol) enriched on ABEI-AuNPs. After recognition of adenosine, the hybridization probe was displaced by adenosine and ECL signal declined. The decrease of ECL signal was in proportion to the concentration of adenosine over the range of 5.0 × 10⁻¹²–5.0 × 10⁻⁹ M with a detection limit of 2.2 × 10⁻¹² M. For thrombin detection, thrombin was assembled on ATA modified electrode via aptamer–target recognition, another aptamer of thrombin tagged with ABEI-AuNPs was bounded to another reactive site of thrombin, producing ECL signals. The ECL intensity was linearly with the concentration of thrombin from 5 × 10⁻¹⁴ M to 5 × 10⁻¹⁰ M with a detection limit of 1.2 × 10⁻¹⁴ M. In the ECL biosensor, adenosine and thrombin can be detected when they coexisted in one sample and a multi-analytes assay was established. The sensitivity of the present biosensor is superior to most available aptasensors for adenosine and thrombin. The biosensor also showed good selectivity towards the targets. Being challenged in real plasma sample, the biosensor was confirmed to be a good prospect for multi-analytes assay of small molecules and proteins in biological samples.     

Density functional theory with fractional orbital occupations

In contrast to the original Kohn-Sham (KS) formalism, we propose a density functional theory (DFT) with fractional orbital occupations for the study of ground states of many-electron systems, wherein strong static correlation is shown to be described. Even at the simplest level represented by the local density approximation (LDA), our resulting DFT-LDA is shown to improve upon KS-LDA for multi-reference systems, such as dissociation of H(2) and N(2), and twisted ethylene, while performing similar to KS-LDA for single-reference systems, such as reaction energies and equilibrium geometries. Because of its computational efficiency (similar to KS-LDA), this DFT-LDA is applied to the study of the singlet-triplet energy gaps (ST gaps) of acenes, which are "challenging problems" for conventional electronic structure methods due to the presence of strong static correlation effects. Our calculated ST gaps are in good agreement with the existing experimental and high-level ab initio data. The ST gaps are shown to decrease monotonically with the increase of chain length, and become vanishingly small (within 0.1 kcal/mol) in the limit of an infinitely large polyacene. In addition, based on our calculated active orbital occupation numbers, the ground states for large acenes are shown to be polyradical singlets.     

仿生捕光材料的研究进展

光合作用是地球上最重要的化学反应之一,而高等植物的光合作用发生在叶绿体的类囊体上,功能单元是类囊体上的蛋白质复合体.其中的捕光蛋白复合体是由天线色素和蛋白质组装而成的,协同组装在其中发挥了重要的作用,其结构的研究和模拟对充分利用太阳能具有重要的意义.本文综述了仿生捕光材料的最新研究进展,着重讨论了人们通过染料分子与无机有机材料、生物高分子、纳米胶束作为模板材料构成的人工捕光系统的研究.在此基础上,分析当前研究中存在的问题,评述了仿生捕光材料的发展趋势和方向.     

铒对铸态Mg-5Sn合金的变质作用研究

通过金相(OM)和扫描电镜(SEM)的显微组织分析、荧光成分分析(XRF),能谱微区成分分析(EDS)、X射线物相分析(XRD),显微硬度(HV)和差热分析(DSC)等测试手段和方法,对铸态Mg-5 Sn-xEr(x=0,0.5,1,1.5,2,2.5,4,6)合金的组织性能进行了全而研究研究结果表明,稀土Er对Mg-5 Sn合金的影响是多方而的,首先是稀土Er对晶粒有明显的细化作用;再就是稀土Er能抑制盘状Mg2 Sn第二相的形成,同时促进不规则ErMgSn稀土相的形成,最后就是提高了合金的相转变温度和显微硬度.因此稀土Er对铸态Mg-5Sn合金具有显著的变质效果.     

钇对Mg-Mn合金腐蚀性能的影响

采用熔盐保护技术制备Mg-Y-Mn合金,并对合金进行挤压处理,获得不同Y含量的镁合金。利用光学显微镜观察添加不同Y合金的挤压态显微组织,采用X射线衍射仪(XRD)对样品进行相结构分析,利用扫描电子显微镜(SEM)检测表面微观形貌,使用电化学测试系统对合金进行极化曲线及交流阻抗测试。结果表明:随着Y含量的增加,合金晶粒细化,平均晶粒尺寸在10,4,3μm。电化学测试结果显示,随Y含量的增加合金的自腐蚀电位正移,从-1.551 V增加到-1.505 V,增加了46 mV,合金显示较好的耐腐蚀倾向,具有较好的耐腐蚀性能。     

Gas‐phase Smiles Rearrangement of Sulfonylurea Herbicides in Electrospray Ionization Mass Spectrometry

In the negative ion mode of electrospray ionization tandem mass spectrometry (ESI‐MS/MS) of four sulfonylurea herbicides, Smiles rearrangements were observed in rimsulfuron and nicosulfuron. In the case of rimsulfuron, two competitive gas‐phase Smiles rearrangements initiated by nitrogen anion and oxygen anion respectively were witnessed. The ion‐neutral complex was proposed as the reactive intermediate in the course of this unimolecular dissociation reaction of the oxygen attack Smiles rearrangement route. The density functional theory (DFT) was carried out to elucidate the mechanism as well as to show the possible transition states and the intermediates.     

Weakening internal diffusion effect in selective hydrodesulfurization of FCC gasoline by novel designed eggshell CoMoS/Al2O3 catalysts

A simple method for preparation of presulfided eggshell CoMoS/γ-Al2O3 catalysts with sharp boundary is developed, through which the eggshell thicknesses of Co and Mo could be easily regulated by controlling the impregnation time. According to the results characterized by EDS, XRD, HRTEM and FT-IR of adsorbed CO, the active component structures, the nature and/or the amount of active sites on the eggshell catalyst are similar to these on the uniform catalyst. The evaluation results of the catalytic performance in selective hydrodesulfurization (HDS) of FCC gasoline show the presence of significant internal diffusion inhibition effect on HDS of S-compounds especially in the uniform catalyst. Compared with uniform catalyst, the eggshell catalyst could remarkably reduce such an internal diffusion inhibition effect due to a shortened diffusion path of the reactants, thus showing higher HDS activity and selectivity.