Enantioseparation of dansyl amino acids and dipeptides by chiral ligand exchange capillary electrophoresis based on Zn(II)-l-hydroxyproline complexes coordinating with γ-cyclodextrins

A chiral ligand exchange capillary electrophoresis (CLE-CE) method using Zn(II) as the central ion and l-4-hydroxyproline as the chiral ligand coordinating with γ-cyclodextrin (γ-CD) was developed for the enantioseparation of amino acids (AAs) and dipeptides. The effects of various separation parameters, including the pH of the running buffer, the ratio of Zn(II) to l-4-hydroxyproline, the concentration of complexes and cyclodextrins (CDs) were systematically investigated. After optimization, it has been found that eight pairs of labeled AAs and six pairs of labeled dipeptides could be baseline-separated with a running electrolyte of 100.0 mM boric acid, 5.0 mM ammonium acetate, 3.0 mM Zn(II), 6.0 mM l-hydroxyproline and 4.0 mM γ-CD at pH 8.2. The quantitation of AAs and dipeptides was conducted and good linearity (r² ≥ 0.997) and favorable repeatability (RSD ≤ 3.6%) were obtained. Furthermore, the proposed method was applied in determining the enantiomeric purity of AAs and dipeptides. Meanwhile, the possible enantiorecognition mechanism based on the synergistic effect of chiral metal complexes and γ-CD was explored and discussed briefly.     

Broadband dielectric investigation on poly(vinyl pyrrolidone) and its water mixtures

Broadband dielectric spectroscopy and differential scanning calorimetry measurements have been performed to study the molecular dynamics poly (vinyl pyrrolidone) and its water solutions in a wide range of concentrations (0 wt %20 wt % suggesting that this dynamical process is dominated by water-water interactions. In addition, the temperature dependence of the water relaxation times exhibits a crossover from non-Arrhenius to Arrhenius behavior during cooling throughout the glass transition range, which has been interpreted as due to the constrains imposed by the rigid polymer matrix on the water molecules dynamics.     

Glycine enolates: the effect of formation of iminium ions to simple ketones on alpha-amino carbon acidity and a comparison with pyridoxal iminium ions

Equilibrium constants in D2O were determined by 1H NMR analyses for formation of imines/iminium ions from addition of glycine methyl ester to acetone and from addition of glycine to phenylglyoxylate. First-order rate constants, also determined by 1H NMR, are reported for deuterium exchange between solvent D2O and the alpha-amino carbon of glycine methyl ester and glycine in the presence of increasing concentrations of ketone and Br?nsted bases. These rate and equilibrium data were used to calculate second-order rate constants for deprotonation by DO- and by Br?nsted bases of the alpha-imino carbon of the ketone adducts. Formation of the iminium ion between acetone and glycine methyl ester and between phenylglyoxylate and glycine is estimated to cause 7 unit and 15 unit decreases, respectively, in the pKa's of 21 and 29 for deprotonation of the parent carbon acids. The effect of formation of iminium ions to phenylglyoxylate and to 5'-deoxypyridoxal (DPL) [Toth, K.; Richard, J. P. J. Am. Chem. Soc. 2007, 129, 3013-3021] on the carbon acidity of glycine is similar. However, DPL is a much better catalyst than phenylglyoxylate of deprotonation of glycine, because of the exceptionally large thermodynamic driving force for conversion of the amino acid and DPL to the reactive iminium ion.     

聚醚氨酯薄膜表面性质的反相色谱法研究

本文报道了用反相色谱法研究多嵌段聚醚氨酯与几种低分子化合物的相互作用,测定了表征相互作用的热力学参数。结果表明,由ESCA证明表面软段富集的聚醚氨酯的反相色谱行为主要决定于富集层与探针分子的相互作用;苯及几种烷烃和聚醚氨酯的偏摩尔混合热和它的溶度参数与软段组分的溶度参数差值有关。     

Pyrazino[2,3-c][1,2,6]thiadiazine 2,2-dioxides. Sulfur dioxide analogs of pteridines

Several pyrazino[2,3-c][1,2,6]thiadiazine 2,2-dioxide derivatives have been synthesized for the first time by condensation of suitable 4,5-diamino-1,2,6-thiadiazine 1,1-dioxides and symmetrical 1,2-dicarbonyl compounds. Structures of these compounds have been characterized by their elementary analyses, ¹H-nmr and uv spectra as well as their pK_a values. The most striking differences between this series and the corresponding pteridines are discussed.     

Determination of diastereoisomeric alkaloids in urine by capillary electrophoresis with electrochemiluminescence detection

A new and simple capillary electrophoresis with electrochemiluminescence detection was developed for the separation and the quantification of a pair of diastereoisomenc alkaloids（ephedrine and pseudoephedrine）.The limits of detection（S/N = 3） were 4.5×10^-8 mol/L for ephedrine and 5.2×10^-8 mol/L for pseudoephedrine,respectively.The RSDs of migration time and peak area were less than 1.3 and 2.5%（n = 5）,respectively.The applicability of the propose method was illustrated in the determination of ephedrine and pseudoephedrine in human urine,ephedrine in nasal drops,and the monitoring of pharmacokinetics for pseudoephedrine.     

基于样本熵的听觉神经锁相机理的实验分析

锁相是指系统的响应与周期性刺激的特定相位同步的物理现象. 听觉神经的锁相对揭示人的听觉认知基本的神经机理及改善听觉感知有重要意义. 然而, 现有研究主要集中于心理物理方法和幅度谱分析, 不能有效区分包络响应和时域细节结构响应, 不能直观反映神经锁相. 本文主要利用拔靴法和离散傅里叶变换, 提出了基于样本熵的时域细节结构频率跟随响应(temporal-fine-structure-related frequency following response, FFR_T)的神经锁相值(phase locking value, PLV)计算方法, 用于分析神经物理实验数据. 两个脑电实验结果表明: FFR_T的PLV样本熵显著大于包络相关频率跟随响应(envelope-related frequency following response, FFR_E)的PLV, 且二者正交独立, 新方法能有效地分别反映听觉系统对包络和时间细节结构的锁相机理; 基频处的响应主要来源于FFR_E的锁相; 基频处, 不可分辨谐波成分包络的锁相能力优于对可分辨谐波; 基频缺失时, 畸变产物是不同的听觉神经通路的FFR_E的混合; 谐波处, FFR_E 集中于低频, FFR_T则集中于中、高频; 听觉神经元锁相能力与声源的频率可分辨性相关. FFR_T的PLV方法克服了现有FFR分析的局限性, 可用于深入研究听觉神经机理.     

CeO2缓冲层热处理对Tl-2212薄膜超导特性的影响

本文采用原子力显微镜(AFM)和XRD研究了生长在蓝宝石(11-02)基片上的CeO_2缓冲层在不同的退火温度和退火时间下表面形貌和相结构的变化,以及对Tl-2212薄膜超导特性的影响.AFM和XRD研究表明,CeO_2薄膜在流动氧环境中退火,表面形貌发生显著的变化;CeO_2薄膜在最佳条件下退火后,可获得原子级光滑表面,结晶质量明显提高.实验结果表明,缓冲层的结晶质量和表面粗糙度与Tl-2212薄膜的超导特性密切相关.在经过最佳条件退火后的CeO_2缓冲层上制备了厚度为500 nm无裂纹的Tl-2212超导薄膜,其临界转变温度(T_c)达到107 K,液氮温度下临界电流密度(J_c)为3.9 MA/cm~2(77 K,0 T),微波表面电阻(R_s)约为281 μΩ(77 K,10 GHz).     

3‐[(E)‐(3‐tert‐Butyl‐1‐phenyl‐1H‐pyrazol‐5‐yl)iminomethyl]quinolin‐2(1H)‐one: chains built by π‐stacking of hydrogen‐bonded R22(8) dimers

In the title compound, C₂₃H₂₂N₄O, there is evidence for some bond fixation in the aryl component of the quinolinone unit. Pairs of molecules related by inversion are linked into R₂²(8) dimers by almost linear N—H...O hydrogen bonds, and dimers related by inversion are linked into chains by a single aromatic π–π stacking interaction.