高效液相色谱二氮杂冠醚键合相的合成及性能研究

本文报道在硅胶表面进行固－液相反应，合成硅胶键合二氮杂冠醚高效液相色谱固定相。采用有机元素分析、热分析、红外光谱、金属离子的络合容量测定等对键合材料进行鉴定和表征，并对其色谱性能进行了研究。     

The electrochemical oxidation of carbon monoxide adsorbed on Pt(111) in aqueous electrolytes as monitored by in situ potential step-second harmonic generation

The dynamics of electrooxidation of adsorbed CO on Pt(111) microfacets was examined in CO-saturated 0.1 M HClO4 aqueous solutions by in situ time resolved second harmonic generation (SHG). Analysis of the temporal dependence of the intensity of the SHG signals recorded for experiments in which the potential was stepped to values high enough for adsorbed CO oxidation to ensue, was found to be consistent with the mean field theory model, yielding rate constants somewhat higher than those reported by Lebedeva et al. (N. P. Lebedeva, M. T. M. Koper, J. M. Feliu and R. A. v. Santen, J. Electroanal. Chem., 2002, 524-525, 242-251) in sulfuric acid solutions. The smaller rates observed by these authors may be ascribed to the presence of anions, ie. in all likelihood bisulfate, which are capable of competing effectively for Pt sites thereby blocking formation of oxygenated species on the surface. Also discussed in this work are the virtues and limitations of in situ SHG for monitoring fast surface processes.     

In situ, time-resolved normal incidence reflectance spectroscopy of polycrystalline platinum microelectrodes in aqueous electrolytes

In situ normal incidence reflectance spectra of polycrystalline Pt microelectrodes have been monitored as a function of the applied potential in aqueous 0.5 M H(2)SO(4) using a He-Ne laser source (633 nm) and a beam splitter/microscope objective arrangement. Data recorded during voltammetric cycles in Ar-purged solutions revealed a linear correlation between the normalized change in reflectance, DeltaR/R = (R(s) - R(ref))/R(ref) (where R(s) and R(ref) are the light intensities measured by the detector at the sampling, s, and reference potentials, ref, respectively), and the extent of oxidation of the Pt surface over a wide coverage range. Reflectance spectra were also collected in CO-saturated 0.5 M H(2)SO(4) during chronocoulometric measurements involving judiciously selected limits for both the potential step and duty cycle parameters. Analysis of these results made it possible to extract contributions to the current derived from oxide formation during oxidation of adsorbed and bulk CO, based strictly on the optical response.     

UH和UH_2分子的结构与势能函数

用相对论有效原子实势 (RECP)和密度泛函 (B3LYP SDD)方法研究了UH ,UH2 基态和低激发态的结构和势能函数 ,导出了分子的光谱数据 .结果表明 ,UH和UH2 的基电子状态分别为X4 Π和X3A2 ,离解能分别为 2 .886eV和5 .2 4 9eV ,UH2 具有C2v对称性 ,得到了UH和UH2 的几个不同的低激发态的结构与光谱数据 .应用多体项展式理论以及数字拟合方法 ,计算得到了UH分子和基态UH2 三原子分子的分析势能函数 ,该函数正确反映了UH和UH2分子的结构特征 ,可用于研究UHH的微观反应动力学 .     

2,4,6-三硝基苯酚改性锆镁复合氧化物固定相分离富勒烯的色谱性能研究

制备了用于分离C60和C70的2,4,6-三硝基苯酚改性锆镁复合氧化物高效液相色谱固定相,并用元素分析仪、红外光谱仪和比表面积分析仪等对其进行了表征。考察了流动相中甲苯含量和柱温对C60和C70分离的影响。同时考察了以甲苯为流动相,在348 K的柱温下,该固定相分离富勒烯混合物(含3%高富勒烯)的情况。结果表明,2,4,6-三硝基苯酚改性锆镁复合氧化物固定相对富勒烯有较强的保留,并表现出较强的温度关系,提高柱温能提高固定相对富勒烯的分离能力,并具有用于富勒烯制备分离的潜力。     

芘基丁酸改性锆-镁复合氧化物HPLC固定相的制备及其在分离富勒烯中的应用

制备了用于分离C₆₀和C₇₀的芘基丁酸改性锆-镁复合氧化物高效液相色谱固定相,并对其进行了表征;考察了流动相中甲苯含量、柱温和进样量对C₆₀和C₇₀分离的影响.结果表明,芘基丁酸改性锆-镁复合氧化物固定相对富勒烯有较强的保留,并对富勒烯表现出较强的分离能力,具有制备分离富勒烯的潜力.     

声场干涉结构相似度匹配的目标运动参数估计

针对水中运动声源定位问题,建立了一种基于声场干涉结构谱向量相似度匹配的目标运动参数估计方法。结合声场干涉结构水平纵向相关特性,利用目标辐射噪声LOFAR谱图中不同频率的谱值序列,基于两方位-两距离目标运动要素计算方法获取的目标距离解向量,构造声场干涉结构谱向量相似度匹配代价因子,实现目标运动参数估计。仿真数据与试验数据验证结果表明:在绘制的目标运动要素解算结果可视化分布图中可清晰呈现出目标初距、航向和速度结果。该算法实现过程简单、解算效率高,对目标方位误差有较好的鲁棒性。     

单矢量水听器稀疏近似最小方差方位估计算法

针对单矢量水听器海上目标探测问题,利用稀疏近似最小方差(Sparse Asymptotic Minimum Variance,SAMV)算法进行目标方位估计,该算法利用单矢量水听器自身具有阵列流形的特点,将整个扫描空间离散化,目标方位分布于某一离散方向位置上,利用空间信号的稀疏性可提高目标方位估计性能。仿真结果表明,SAMV算法在各信噪比条件下方位估计噪声背景级明显优于常规波束形成(Conventional Beam Forming,CBF)算法和最小方差无失真响应(Minimum Variance Distortionless Response,MVDR)算法,当信噪比大于0dB时,该算法测向结果均方根误差小于2°,且SAMV算法具有更好的空间方位分辨能力。消声水池和海上声学浮标海上试验数据处理结果表明,SAMV算法给出了噪声背景级更低的目标方位历程图,有效验证了SAMV算法对海上目标的探测性能及其有效性。