Smith－Hieftje背景校正法空心阴极灯供电条件的选择

本文提出在原子吸收光谱测定中，采用Ｓｍｉｔｈ－Ｈｉｅｆｔｊｅ法校正背景时，空心阴极灯供电条件（即最佳宽窄脉冲电流）的选择依据和选择方法；并给出２４个常见元素的宽窄脉冲电流的选定结果。     

多嵌段聚醚氨酯脲为基质的新型高分子固态离子导体

本文合成了一系列聚乙二醇型多嵌段聚醚氨酯脲，而且用这类聚醚氨酯甩与高氯酸锂制得了一种新型的高分子固态离子导体复合物。在室温和50℃之间，其电导率比聚环氧乙烷为基质的固体电解质的高一到二个数量级，它还具有优良的综合性能。因此，对于室温薄膜蓄电池来说，这种新型的固体电解质是一类良好的候选材料。     

基于小波变换的循环伏安弱信号特征信息提取

本研究采用连续小波变换(continuous wavelet transform，CWT)技术处理循环伏安弱信号，通过研究苯酚、对苯二酚和对硝基苯酚的共存体系循环伏安弱信号，表明CWT可以成功地识别出极弱信号中的指纹特征信息，并且经处理得到的对应的小波系数峰比原始信号更窄，更高，由此可以成功地确定弱峰的数目和位置。由循环伏安信号所得的结果，有力地证实CWT是循环伏安弱信号识别的有力工具，对于理解弱响应体系电化学机理具有重要作用。     

Correlation and response functions with non-Markovian dissipation: a reduced Liouville-space theory

Based on a recently developed quantum dissipation formulation [R. X. Xu and Y. J. Yan, J. Chem. Phys. 116, 9196 (2002)], we present a reduced Liouville-space approach to evaluate the response and correlation functions of dissipative systems. The weak system-bath interaction is treated properly for its effects on the initial state, the evolution, and the correlation between coherent driving and non-Markovian dissipation. Numerical demonstration shows this correlated effect cannot be neglected even in the calculation of linear response quantities that do not explicitly depend on external fields. Highlighted in this paper is also the proper choice of theory among various formulations in the weak system-bath interaction regime.     

聚全氟乙丙烯树脂中六氟丙烯分布问题的探讨

<正> 聚全氟乙丙烯树脂(以下简称FEP)是四氟乙烯与六氟丙烯的共聚物.目前对FEP尚无适当溶剂,所以不能用C~(3)高分辨NMR测定共聚单体在共聚物中的分布,故采用X射线衍射方法测量晶格常数和结晶度,以及密度与熔点的测定,对国产不同聚合体系FEP中的六氟丙烯分布问题进行探讨. 图1比较了聚四氟乙烯(PTFE)及FEP的X射线衍射谱(23℃)。在FEP共聚物中除了(100)晶面衍射峰外,尚有微弱的(110),(200)等晶面衍射峰,可以看出,FEP的行     

Characterization of phosphopeptides from protein digests using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry and nanoelectrospray quadrupole time-of-flight mass spectrometry

A two-step mass spectrometric method for characterization of phosphopeptides from peptide mixtures is presented. In the first step, phosphopeptide candidates were identified by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) based on their higher relative intensities in negative ion MALDI spectra than in positive ion MALDI spectra. The detection limit for this step was found to be 18 femtomoles or lower in the case of unfractionated in-solution digests of a model phosphoprotein, beta-casein. In the second step, nanoelectrospray tandem mass (nES-MS/MS) spectra of doubly or triply charged precursor ions of these candidate phosphopeptides were obtained using a quadrupole time-of-flight (Q-TOF) mass spectrometer. This step provided information about the phosphorylated residues, and ruled out nonphosphorylated candidates, for these peptides. After [(32)P] labeling and reverse-phase high-performance liquid chromatography (RP-HPLC) to simplify the mixtures and to monitor the efficiency of phosphopeptide identification, we used this method to identify multiple autophosphorylation sites on the PKR-like endoplasmic reticulum kinase (PERK), a recently discovered mammalian stress-response protein.     

Use of nitrocellulose films for affinity-directed mass spectrometry for the analysis of antibody/antigen interactions

Combination of affinity extraction procedures with mass spectrometric analyses is termed affinity-directed mass spectrometry, a technique that has gained broad interest in immunology and is extended here with several improvements from methods used in previous studies. A monoclonal antibody was immobilized on a nitrocellulose (NC) membrane, allowing the corresponding antigen to be selectively captured from a complex solution for analysis by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS). This method was also used to rapidly determine the approximate binding region responsible for the antibody/antigen interaction. The tryptic fragments of antigen protein in buffer were applied to the antibody immobilized on NC film and allowed to interact. The NC film was then washed to remove salts and other unbound components, and subjected to analysis by MALDI-TOFMS. Using interferon-alpha(2a) and anti-interferon-alpha(2a) monoclonal antibody IgG as a model system, we successfully extracted the antigen protein and determined the approximate binding region for the antigen/antibody interaction (i.e., the tryptic fragment responsible).     

Catalytic enantioselective synthesis of macrodiolides and their application in chiral recognition

New types of C₂-symmetric chiral macrodiolides are readily obtained via chiral N,N′-dioxide-scandium(iii) complex-promoted asymmetric tandem Friedel–Crafts alkylation/intermolecular macrolactonization of ortho-quinone methides with C3-substituted indoles. This protocol provides an array of enantioenriched macrodiolides with 16, 18 or 20-membered rings in moderate to good yields with high diastereoselectivities and excellent enantioselectivities through adjusting the length of the tether at the C3 position of indoles. Density functional theory calculations indicate that the formation of macrocycles is more favorable than that of 9-membered-ring lactones in terms of kinetics and thermodynamics. The potential utility of these intriguing chiral macrodiolide molecules is demonstrated in the enantiomeric recognition of aminols and chemical recognition of metal ions.

An asymmetric tandem Friedel–Crafts alkylation/intermolecular macrolactonization of ortho-quinone methides with C3-substituted indoles was achieved by using a chiral N,N′-dioxide-scandium(iii) complex.     

The absolute sign of J coupling constants determined using the order matrix calculation

A novel methodology using the order matrix calculation to determine the absolute sign of spin-spin couplings based on the structure of organic compounds is presented. The sign of the residual dipolar coupling (RDC) depends on the sign of corresponding scalar spin-spin coupling constant and the sign of the RDC has a dramatic influence on the order matrix calculation. Therefore, the sign of the spin-spin coupling constant can be obtained by an order matrix calculation through the corresponding RDC. Six types of spin-spin coupling constants, including 2J(H,H), 1J(C,F), 2J(C,F), 3J(C,F), 2J(F,H) and 3J(F,H), were obtained simultaneously. Except for 3J(C,F) where the measured RDCs have very small magnitudes, the signs were determined unambiguously.     

脂肪族酰胺二元醇的合成与表征

以ＤＬ－乳酸、ε己内酯及乙二胺和己二胺为原料合成了四种结构的脂肪族酰胺二元醇，并用ＩＲ，＾１ＨＮＭＲ，ＤＳＣ对酰胺二元醇的结构进行了表征。