钌联吡啶络合物与脱氧核糖核酸分子相互作用的荧光光谱研究与分析应用

合成了2苯基(4溴)咪唑[f]邻菲咯啉(简称PIP(Ⅲ)新的配体及〔Ru(bpy)_2PIP(Ⅲ)]~(2+)新的络合物,用荧光光谱研究了络合物与小牛胸腺DNA分子的结合情况,在 pH7.4,络合物与DNA作用后,在587nm(λ_(ex)=471nm)产生很强的荧光峰,其发光强度与DNA浓度呈线性关系;线性范围0～1.2mg/L;检测限(3a(?))为2.8mg/L.该方法具有较高灵敏度和准确度,对合成样品测定,结果令人满意.     

Confinement effects on electromigration of long DNA molecules in an ordered cavity array

Confinement effects on the electromigration of long dsDNA molecules in an array of well-ordered, molecular sized cavities interconnected by nanopores are described. The array was prepared by replicating the structure of a colloidal crystal of microspheres in a polymer matrix. Both conformation and mobility studies show that the electrophoretic behavior of large DNA molecules is distinct from that in gels and other microfabricated sieves, showing a peak in mobility versus electric field, and an inversion in the separation order with field strength. A simple model was proposed to interpret this unexpected observation qualitatively. We conclude that the molecular behavior of DNA can be modified by the combination of entropic effect and electric trapping as a consequence of both unique geometry and conductivity of this cavity array material. This approach provides insights for design and optimization of on-chip molecular sieving structures for rapid separation of long DNA molecules. It may lead to a promising material for manipulation and size fractionation of other biological macromolecules.     

NMR and theoretical study on interactions between diperoxovanadate complex and 4-substituted pyridines

To understand the substituting group effects of organic ligands on the reaction equilibrium, the interactions between diperoxovanadate complex [OV(O2)2(D2O)]-/[OV(O2)2(HOD)](-) and a series of 4-substituted pyridines in solution were explored using multinuclear (1H, 13C, and 51V) magnetic resonance, DOSY, and variable temperature NMR in 0.15 mol/L NaCl ionic medium for mimicking the physiological condition. Some direct NMR data are given for the first time. The reactivity among the 4-substituted pyridines is pyridine > isonicotinate > N-methyl isonicotinamide > methyl isonicotinate. The competitive coordination results in the formation of a series of new six-coordinated peroxovanadate species [OV(O2)2L](n-) (L = 4-substituted pyridines, n = 1 or 2). The results of density functional calculations provide a reasonable explanation on the relative reactivity of the 4-substituted pyridines. Solvation effects play an important role in these reactions.     

Preparation and evaluation of a lysine-bonded silica monolith as polar stationary phase for hydrophilic interaction pressurized capillary electrochromatography

A silica-based monolith as polar stationary phase was described for hydrophilic interaction pressurized capillary electrochromatography (HI-pCEC). The polar monolithic column was prepared by on-column reaction of lysine with epoxy groups on a gamma-glycidoxypropyltrimethosysilane-modified silica monolith. The stationary phase yielded strong hydrophilic interaction due to the slightly polar hydroxyl groups, and the strong polar lysine ligand with amino groups and carboxylic groups contained on the surface of the monolith. In order to evaluate the hydrophilic character of lysine ligand, the chromatographic behaviors of epoxy monolith (before lysine bonded) and diol monolith (hydroxyl groups contained) were also investigated. Two groups of comparative experiment were developed in terms of the separation of typical neutral non-polar and polar compounds performed in a mobile phase of aqueous-acetonitrile solution. Results showed that the lysine monolith was much more hydrophilic than the diol monolith, which presented less hydrophobic than the epoxy monolith. For further study on its hydrophilic character, the lysine monolith was demonstrated in the HI-pCEC mode for the separations of various polar compounds such as phenols, nucleic acid bases and nucleosides.     

Analysis of fatty acids in sputum from patients with pulmonary tuberculosis using gas chromatography–mass spectrometry preceded by solid-phase microextraction and post-derivatization on the fiber

A method based on solid-phase microextraction (SPME) and post-derivatization on the fiber coupled to gas chromatography–mass spectrometry (GC–MS) was developed for the analysis of fatty acids in sputum from patients with pulmonary tuberculosis. The sputum specimens were digested, hydrolyzed, extracted, derivertized, injected and analyzed without cultivation or isolation of the microorganism. Under optimized conditions, the relative standard deviations (RSD, n = 5) for all analytes were below 17% and the limits of detection varied from 1.68 (C_24:0) to 150.4 μg L⁻¹ (C_12:0). Good linearity was observed for all the fatty acids studied except for C_12:0 within a wide concentration range of three orders of magnitudes with the correlation coefficients ranging from 0.91 (C_24:0) to 0.99 (C_14:0). Fatty acids in sputum specimens from 21 persons were directly analyzed using the proposed method. The results show that in all the sputum specimens from patients, who were clinically diagnosed with tuberculosis (TB), tuberculosis stearic acid (TBSA) was detected, while in all the sputum samples from persons without TB, TBSA was not found. The possibility of using the proposed method to detect mycobacterium tuberculosis (MTB) via the identification of TBSA in sputum was discussed. The comparison with other methods including sputum culture and microscopy of direct smears indicated that the proposed method is fast and sensitive for the analysis of fatty acids in sputum and offers an alternative for the detection of MTB in sputum.     

纵环加筋圆柱壳塑性屈曲分析

采用Mises屈服准则和塑性形变理论,基于能量原理对纵环加筋圆柱壳的塑性屈曲进行了分析,给出了简明的临界压力求解公式并讨论了壳板塑性屈曲、肋板局部塑性屈曲和环筋柱壳塑性屈曲等几种特殊情况.计算结果表明,本文方法具有较好的精度和通用性.     

基于SURE-LET和非张量积小波的遥感图像去噪

针对遥感图像中的高斯噪声,提出了基于SURE-LET和非张量积小波的去噪方法,主要包括图像在非张量积小波下的分解、各个子带在不同阈值函数下的处理以及它们最优的线性组合3个步骤．通过选择合适的非张量积小波滤波器参数,使无噪遥感图像和噪声在变换分解中得到的小波系数分离较好,去除噪声对应的小波系数时被去除的无噪图像对应的小波系数较少,从而取得更好的去噪效果．实验结果表明：此方法用于高斯噪声的遥感图像的去噪不仅速度很快,而且去噪效果优于传统基于张量积小波的SURE-LET方法．     

预蠕变—塑性的本构描述及其实验验证

基于热力学相容的本构模型并合理地定义广义时间标度，得到了描述蠕变，塑性及其交互作用的统一型本构方程。进而通过对蠕变、塑性及其交互作用过程中材料内部子结构及其变化的分析，将材料的强化分解为对应于累积非弹性变形的强化和由蠕变变形导致的附加强化。对对高温环境二维应力路径下３１６不锈钢的预蠕变－塑性变形过程进行了分析，取得了与Ｏｈａｓｈｉ等的实验数据相吻合的结果。     

Effects of truncated mutants of the ε subunit of chloroplast ATP synthase on the fast phase of millisecond delayed light emission of chloroplast and its ATP synthesis ability

The ε subunit of the chloroplast ATP synthase and the truncated ε mutants which lack some amino acid residues from the N-terminus or C-terminus were overexpressed in E. coil When the ε subunit or the truncated ε proteins was added to the spinach chloroplast suspension, both the intensity of the fast phase of millisecond delayed light emission (ms-DLE) and the cyclic and noncyclic photophosphorylation activity of chloroplast were enhanced. With an increase in the number of residues deleted from the N-terminus, the enhancement effect of the N-terminal truncated proteins decreased gradually. For the C-terminal truncated proteins, the enhancement effect increased gradually with an increase in the number of residues deleted from the C-terminus. Besides, the ATP synthesis activity of ε-deficient membrane reconstituted with the ε subunit or the truncated ε proteins was compared. The ATP synthesis activity of reconstituted membrane with the N-terminal truncated proteins decreased gradually as the number of residues deleted from the N-terminus increased. For the C-terminal truncated proteins, the ATP synthesis activity of reconstituted membrane increased gradually with an increase in the number of residues deleted from the C-terminus, but was still lower than that of the wild type ε protein. These results suggested that: (a) the N-terminal domain of the ε subunit of the chloroplast ATP synthase could affect the ATP synthesis activity of ATP synthase by regulating the efficiency of blocking proton leakage of ε subunit; and (b) the C-terminal domain of the ε subunit of the chloroplast ATP synthase had a subtle function in modulating the ATP synthesis ability of ATP synthase.     

激光位相调制的麦克尔逊干涉光外差探测

导出了激光经位相调制后的麦克尔逊干涉光外差探测的讯号特征表式。并讨论用该技术对激光进行稳频及用来测量反射镜的反射率的现实可能性。