基质辅助激光解吸与离子化时间飞行质谱在高分子研究中的应用

对基质辅助激光解吸与离子化时间飞行质谱的发展历程和基本原理作了简要介绍,对这一分析技术在高分子研究中的应用进行了全面的综述和展望。本文表明,ＭＡＬＤＩ－ＴＯＦ－ＭＳ能快速准确地测定窄分布高分子的分子量,可测分子是一达１５０００００,所得平均分子量值及分子量分布指数与ＧＰＣ等常规方法相符;能用于高分子末端基的检测,从而推断聚合反应机理;也能用于共聚反应与共聚物结构的分析;另外,还能从分子量分布理到自     

生物素-亲和素系统在压电免疫传感器中质量放大作用研究

生物素-亲和素系统(BiotinAvidinSystem,BAS)是70年代后期迅速发展起来的一种新型生物放大系统,具有高灵敏度、高特异性以及简便、经济、快速等优点,在现代生物免疫学领域中已得到广泛的应用^[1].     

多用途薄层光谱电化学池的设计和表征

设计并组装了一种简易薄层光谱电化学池.该池具有结构简单、操作方便、对工作电极无透光要求,且能适用于多种现场光谱电化学研究的特点.用该池记录了邻联甲苯胺高氯酸醋酸组成的氧化还原体系的荧光光谱电化学和紫外可见光谱电化学响应,并用吡啶氯化钾体系进行了喇曼光谱电化学表征.     

In cation interactions with some organics: ab initio molecular orbital and density functional theory

Ab initio molecular orbital and density functional theory studies were undertaken to investigate the structural and energetic characteristics of complexes of In⁺ with several different organic molecules for the first time. HF, MP2, QCISD, and CCD levels of theory in ab initio MO as well as B3LYP, B3PW91 hybrid functionals in density functional theory were used. A valence TZ+P basis set with relativistic effective core potentials was used for the In atom while the 6-311++G(3d, 2p) basis set was utilized for all other atoms. Both closed-shell (H₂O, CH₄, CH₃OH, and C₆H₆) and open-shell (CH₃ and C₂H₃) molecules were considered for complexation with In⁺. In⁺ affinities of 21.5, 24.8, 28.6, 18.4, and 23.0 kcal/mol were obtained with the B3PW91 hybrid functional for H₂O, CH₃OH, C₆H₆, CH₃, and C₂H₃, respectively. The large values for the calculated affinities indicate the validity of our recent experimental detection of In⁺ ion attachment to some organic molecules.     

Laser output power over 5 W at 1.06 μm for Nd:GdVO4 single crystal

In this paper, we report the polarization absorption spectra from 400 to 850 nm, polarization emission spectra from 1050 to 1100 nm and laser properties of an Nd:GdVO₄ crystal. An output power of up to 5.29 W at 1.06 μm has been achieved with a 3×3×3 mm Nd:GdVO₄ crystal sample when it is pumped by a cw laser diode.     

正交投影用于红外光谱图中光谱提取及背景扣除

利用正交投影方法以及原始信号及其投影与背景矢量之间的线性关系,确定背景光谱,从而将待测组分的红外光谱从混合物光谱中提取出来,达到扣除背景及分辨重叠光谱之目的。本方法用于二氯乙烷及丙酮中各组分红外光谱的提取,获得了满意的结果。     

肽—银（Ⅰ）相互作用的NMR研究

用ＮＭＲ谱研究了银（Ⅰ）离子与肽－Ｇｌｙ－Ｇｌｙ、Ｇｌｙ－Ｇｌｙ－Ｇｌｙ、Ｇｌｙ－Ｌｅｕ、Ｇｌｙ－Ｔｙｒ、Ｎ－Ａｃｅ－Ｇｌｙ的相互作用。在所研究和配合物中,肽是螯合配体,其配位原子包括羧基的Ｏ原子和氨基的Ｎ原子。结果表明,氨基和羧基和Ａｇ（Ⅰ）离子的相互作用是有利的,将决定肽的取向和构象。     

High-frequency sonoelectrochemical processes: mass transport, thermal and surface effects induced by cavitation in a 500 kHz reactor

The use of high frequency ultrasound in electrochemical systems is of major interest for the optimisation of electrosynthetic and electroanalytical procedures, especially when the strong mechanical effects of 20 kHz ultrasound are detrimental. The characterisation of a 500 kHz ultrasound reactor for sonoelectrochemical experiments by voltammetric and potentiometric measurements revealed the presence of considerable thermal, as well as mass transport, effects depending on geometric parameters and the material used for the construction of the working electrode. Micromixing and cavitation processes govern the mass transport to and from the electrode surface and are shown by atomic force microscopy (AFM) to cause erosion on the electrode surface. Electrochemically active films of Prussian blue are shown to be gradually removed by cavitation erosion. Degassing the solution prior to sonication increases the efficiency of cavitation processes.     

tBuN = VCl2 · 1,2-Dimethoxoethan,eine Schlüsselverbindung zur Darstellung von zweikernigen,diamagnetischen tert-Butylimidovanadium(IV)-Verbindungen

^tBuN = VCl₂ · 1,2-Dimethoxoethane, a Precursor in the Synthesis of Binuclear Diamagnetic tert -Butylimidovanadium(IV) Compounds Syntheses of the paramagnetic tert-butylimidovanadium(IV) complexes ^tBuN = VCl₂ · DME ( 7 ), ^tBuN = VCl₂ · 2 L (L = 1,4-dioxane, thf, PMe₃, PEt₃, pyridine) and ^tBuN = VBr₂ · DME are described; the free Lewis acids has been found by mass spectroscopy to be the binuclear compounds [(μ-N^tBu)₂V₂Cl₄] und [(μ-N^tBu)₂V₂Br₄]. 7 reacts with LiOR, LiOAr and LiNR₂ forming binuclear diamagnetic tert-butylimidovanadium(IV) compounds: [(μ-N^tBu)₂V₂Cl₂(OⁱPr)₂] ( 18 ), [(μ-N^tBu)₂V₂(OR)₄], [(μ-N^tBu)₂V₂Cl₂(OAr)₂], [(μ-N^tBu)₂V₂(OAr)₄] and [(μ-N^tBu)₂V₂Cl₂(NR₂)₂]. In additional experiments the complexes [(μ-N^tBu)₂V₂(CH₂CMe₃)₂(OAr)₂], [(μ-N^tBu)₂V₂Me₂(NR₂)₂], [(μ-N^tBu)₂V₂Cl₄] and ^tBuN = V(OAr)₃ has been prepared. All compounds obtained are characterized by spectroscopic methods (MS; ¹H, ¹³C, ⁵¹V NMR), [(μ-N^tBu)₂V₂Cl₂(N^tBuSiMe₃)₂] ( 21 ) by single crystal x-ray diffraction. For 18 the presence of cis/trans isomeres was shown by NMR spectroscopy. The ⁵¹V NMR spectra of the binuclear diamagnetic vanadium (IV) compounds are discussed.     

AlO自由基在辐射场中的物理和光谱特性

AlO自由基在金属有机化学、催化材料、燃烧化学及天体物理学等领域受到人们的广泛关注,研究外辐射场下对AlO自由基的物理特性和光谱特征的影响将有助于更深入理解和增强在相关领域的应用。采用密度泛函理论B3PW91方法,在6-311+G(3df,2p)基组水平上优化了不同辐射场(-0.04~0.04 a.u.)下AlO自由基的基态稳定构型,用同样方法计算了该构型的分子结构、总能量、能隙以及红外光谱、拉曼光谱、紫外可见吸收光谱受外辐射场的影响。结果表明,分子结构与辐射场有关。在外辐射场变化范围(-0.04~0.04 a.u.),自由基总能先小幅度增大(-0.03 a.u.达到最大值)后大幅度单调减小;分子键长在负辐射场(-0.04~0 a.u.)没有明显变化,但在(0~0.04 a.u.)正辐射场下单调变长;偶极矩先减小(-0.03 a.u.达到最小值)后增大;而能隙先不断增大(-0.04^-0.02 a.u.),在(-0.02~0.03 a.u.)辐射场能隙基本稳定,随后单调下降。正辐射场(0~0.04 a.u.)对AlO自由基的振动频率和红外强度的影响较大, AlO自由基在0.04 a.u.辐射场下的红外光谱红移74 cm^-1,其对应光谱强度是未加辐射场的80倍;正辐射场(0~0.04 a.u.)的拉曼光谱红移较明显,在0.04 a.u.红移78 cm^-1;负辐射场(0^-0.04 a.u.)对拉曼光谱影响也较大,在-0.03 a.u.辐射场下具有很强的拉曼活性是未加辐射场的688倍;正辐射场(0~0.04 a.u.)下AlO自由基的紫外可见吸收光谱中原来无辐射场下的最大吸收峰(170 nm)蓝移了22 nm且吸收幅度减至一半,在负辐射场范围内(0^-0.04 a.u.)该吸收峰也辐有蓝移其强度也有减弱趋势;AlO自由基的无辐射场下第二个最大紫外可见峰在正辐射场作用下,其波长从282 nm一直递减蓝移13 nm和吸收强度递增至2.2倍,负辐射场范围内(0^-0.04 a.u.)该吸收峰红移10 nm和吸收强度递增了6.2倍,超过了无辐射场下最大吸收波长强度。