Acyl and α-Ketoacyl Complexes of Pt(II) with Weak Donor Ligands

Treatment of trans-Pt(COCOPh)(Cl)(PPh₃)₂ (1a) with AgBF₄in THF led to the formation of a metastatic complex trans-[Pt(COCOPh)(THF)(PPh₃)₂](BF₄) (2) which readily underwent ligand substitution to give a cationic aqua complex trans-[Pt(COCOPh)(OH₂)(PPh₃)₂](BF₄) (5a). Complex 5a has been characterized spectroscopically and crystallographically. Analogous reaction of trans-Pt(COCOOMe)(Cl)(PPh₃)₂ (1b) with Ag(CF₃SO₃) in dried CH₂C1₂ was found first to yield a methoxyoxalyl triflato complextrans-Pt(COCOOMe)(OTf)(PPh₃)₂ (6). Attempts to crystallize the triflato product in CH₂-cl₂hexane under ambient conditions also afforded an aqua complex of the triflate salt f/wu-[Pt(COCOOMe)(OH₂)(PPhj)₂](CF₃SO₃) (5b). Complex 5a in a noncoordinating solvent such as CH₂C1₂ or CHCl₃ suffered spontaneous decarbonylation to form first cis-[Pt(COPh)(CO)(PPh₃)₂l(BF₄) (3a) then the thermodynamically stable isomer trans-[Pt(COPh)(CO)(PPh₃)₂](BF₄) (3b). Crystallization of complex 3b under ambient conditions resulted in an aqua benzoyl complex trans-[Pt(COPh)(OH₂)(PPh₃)₂](BF₄) (7). The replacement of the H_2O ligand in complex 7 by CO was done simply by bubbling CO into the solution of 7. The single crystal structures of 5b and 7 have been determined by X-ray diffraction. The distances of the Pt-O bonds in 5a, 5b, and 7 support that the aqua ligand is a weak donor in such cationic aquaorganoplatinum(lI) complexes, in agreement with their lability to the substitution reactions.     

Element determination in medieval soil samples by total reflection X-ray fluorescence analysis

An aqua regia extraction procedure for heavy metals in soils optimised for total reflection X-ray fluorescence analysis is presented. The procedure is applied to 92 soil samples of medieval layers from the city area of Dortmund. Sixteen elements (P, S, K, Ca, Ti, Cr, Mn, Fe, Ni, Cu, Zn, Rb, Sr, Ag, Sn, and Pb) were used to characterise 17 sample sites. The results are projected onto the medieval urban structure of Dortmund. Two sites loaded with non-ferrous heavy metal could be detected and correlated with archaeological data. The efficiency and repeatability of the proposed extraction procedure is discussed.     

Analysis of low Z elements on Si wafer surfaces with synchrotron radiation induced total reflection X-ray fluorescence at SSRL, Beamline 3-3: comparison of droplets with spin coated wafers

The unique properties of synchrotron radiation, such as high incident flux combined with low divergence, its linear polarization and energy tunability, make it an ideal excitation source for total reflection X-ray fluorescence (TXRF) spectroscopy in order to non-destructively detect trace impurities of transition metals on Si wafer surfaces. When used with a detector suitable for the determination of low energy radiation this technique can be extended to the detection of low-Z elements, such as Al, Na and Mg. Experiments have been performed at SSRL Beamline 3-3, a bending magnet beamline using monochromatic radiation from a double multilayer monochromator. The wafer was mounted vertically in front of the detector, which was aligned along the linear polarization vector of the incoming synchrotron radiation. This configuration allows the detector to accept a large solid angle as well as to take advantage of the reduced scattered X-ray intensity emitted in the direction of the linear polarization vector. A comparison between droplet samples and spin coated samples was done, in order to compare the capabilities of vapor phase decomposition (VPD-TXRF) with conventional SR-straight-TXRF. Detection limits in the range of 50 fg corresponding to 2E10 atoms/cm² have been obtained for Na. The spin coated samples, prepared from solutions containing an equal amount of Na, Mg and Al showed an unexpected result when performing a scan of the angle of incidence of the incoming X-rays suggesting a different adsorption behavior of the elements in a multielement solution on the wafer surface. The observation of this behavior is important because the spin coating technique is the standard method for the preparation of surface standards in semiconductor quality control. This effect could be characteristic of the Na, Mg, Al solution used, but the angle dependence of the fluorescence signal of a standard should always be investigated before using the standard for calibration of the apparatus and quantification.     

Immunosensor for estrone with an equal limit of detection as common analytical methods

Immunoanalytical methods at a very low limit of detection (LOD) and a low limit of quantification (LOQ) are becoming more and more important for environmental analysis and especially for monitoring drinking water quality. Biosensors have suitable characteristics such as efficiency in allowing very fast, sensitive, and cost-effective detection. Here we describe a fully automated immunoassay for estrone with a LOD below 0.20 ng L^–1 and a LOQ below 1.40 ng L^–1. In contrast to common analytical methods such as GC-MS or HPLC-MS, the biosensor used requires no sample pre-treatment and pre-concentration. The basis of our sensitive assay is the antibody with a high affinity constant towards estrone. The very low amount of antibody per sample results in low validation parameters (LOD, LOQ, and IC50), but this assay for estrone represents the current device-related limitation of the River Analyser (RIANA).     

双菱体λ/4消色差相位延迟器的设计

根据菲涅尔全内反射相变理论,给出了双菱体λ/4消色差器的结构设计、性能分析和测量方法.由有效通光孔径和光线追迹设计出BK7玻璃在波长532 nm时相位延迟λ/4的双菱体的结构,用作532 nm至1 064 nm波长范围的标准λ/4相位延迟器.理论分析了入射角变化和波长变化对双菱体相位延迟的影响,当入射角变化限制在±4.3°以内时,其影响得到补偿;波长从532 nm到1 064 nm产生的误差为－0.65°.采用椭偏法中的消光技术,分别实测了双菱体在532 nm和1 064 nm波长下的相位延迟为：90.08±0.14°和88.99±0.1°,可知两不同波长产生的相位延迟误差为－1.09°.     

基于IBIS5-A-1300 CMOS图像传感器的噪音抑制技术研究

为了提高图像质量,在分析APS CMOS图像传感器工作时序的基础上,对标准时序做了改进,并对改进后的时序进行了实验仿真.结果表明,改进后的时序可有效消除固定模式噪音,达到改进图像质量的目的.     

复合近红外光谱法在牛奶测定中的应用

研究了用于快速测定牛奶主要成分含量的近红外透射光谱法和漫反射光谱法,分析了两种方法在实际测量中的差异,并提出将两种方法结合形成复合光谱法用于牛奶成分含量的检测。结果表明:复合光谱法的应用有效地提高了多变量回归分析中牛奶成分含量的预测精度。     

Singular perturbation analysis of dynamic fields in a thermoelastic solid with a small surface-breaking crack

An asymptotic analysis is presented for a dynamic problem of a semi-infinite isotropic thermoelastic solid with a small surface breaking crack. The exterior surface of the solid is subjected to a series of short thermal pulses. The crack surface is traction free and an ideal thermal contact is assumed across the crack. The stress intensity factor is asymptotically evaluated as a function of the crack depth and time. The effect of a boundary layer associated with the diffusive term is identified. The theoretical model is supplied with numerical simulations.     

超声速大攻角旋成体迎风激波数值模拟

旋成弹体在大攻角超声速流动中其迎风面上有时会出现一种迎风激波．采用非定常雷诺平均的NavierStokes方程以及两方程kω—sst和代数B—L湍流模型成功地模拟了该现象,验证了该迎风激波是由于流场主旋涡导致超声速流动偏移造成的涡诱导激波的一部分的结论．     

考虑油膜力作用的船舶主推进系统冲击研究

舰船推进轴系是舰船动力装置的重要组成部分,它的稳定性是舰船生命力的基本保证.本文以舰船主推进轴系为研究对象,考虑了非线性油膜力的作用,在推进轴的非线性油膜力模型中,考虑了油膜涡动效应和挤压效应以及多个轴承油膜力的耦合影响,并考虑了轴承结构本身的刚度.文中采用弹性体动力学方法对推进轴建模,考虑了在外冲击作用下转速和轴承油膜力对于转轴冲击响应的影响,考虑横向运动与转动耦合作用,导出以非线性偏微分方程描述的舰船主推进轴的动力学方程,并用经典理论对其进行离散,最后采用龙格-库塔法进行数值仿真.实例分析指出转速对于转轴冲击响应的影响不可忽略.