On-line solid phase extraction-liquid chromatography–mass spectrometry for trace determination of nerve agent degradation products in water samples

Three primary nerve agent degradation products (ethyl-, isopropyl- and pinacolyl methylphosphonic acid) have been determined in water samples using on-line solid phase extraction-liquid chromatography and mass spectrometry (SPE-LC–MS) with electrospray ionisation. Porous graphitic carbon was employed for analyte enrichment followed by hydrophilic interaction chromatography. Diethylphosphate was applied as internal standard for quantitative determination of the alkyl methylphosphonic acids (AMPAs). By treating the samples with strong cation-exhange columns on Ba, Ag and H form, the major inorganic anions in water were removed by precipitation prior to the SPE-LC–MS determination. The AMPAs could be determined in tap water with limits of detection of 0.01–0.07 μg L⁻¹ with the [M−H]⁻ ions extracted at an accuracy of ±5 mDa. The within and between assay precisions at analyte concentrations of 5 μg L⁻¹ were 2–3%, and 5–9% relative standard deviation, respectively. The developed method was employed for determination of the AMPAs in three natural waters and a simulated waste water sample, spiked at 5 μg L⁻¹. Recoveries of ethyl-, isopropyl- and pinacolyl methylphosphonic acid were 80–91%, 92–103% and 99–106%, respectively, proving the applicability of the technique for natural waters of various origins.     

基于非对称场流分离技术分离表征小米淀粉

基于非对称场流分离技术耦合多角度激光光散射检测器和示差折光检测器,建立了分离表征小米淀粉的方法。研究了进样量、交叉流流速、半衰期（t_1/2）、载液离子强度和pH值对小米淀粉分离效果的影响;考察了该方法的重现性;探究了小米淀粉分子结构。结果表明,在进样体积为50 μL、进样质量浓度为0.50 g/L、交叉流流速为1.2 mL/min、t_1/2=3 min、载液为10 mmol/L pH 7.00 NaNO₃（含3 mmol/L NaN₃）的条件下,小米淀粉分离效果最佳。该方法具有良好的重现性,得到的小米淀粉的回转半径相对标准偏差为3.4%、摩尔质量相对标准偏差为7.0%。     

空间太阳望远镜在轨自动调焦的最小图像熵判据

由于复杂的发射状态和动态在轨空间环境以及高达0 1″的角分辨率,所以自动调焦技术已成为太阳空间望远镜在轨图像处理中的关键技术。在分析图像离焦时的状态特性的基础上,提出了一种新的更适用于空间相机的离焦判据———最小图像熵判据。最小图像熵合焦判据更适合于低对比度的天体目标。利用计算机仿真程序演示了给定目标经系统成像的过程,计算了不同离焦状态下的图像熵。这一技术将应用于2005年发射的太阳空间望远镜中。     

Study of the impact of penetrant characteristics upon diffusion into Teflon membranes to further assess the performance of an ATR/FTIR sensor

In order to critically assess the performance and measuring dynamics of an attenuated total reflectance (ATR)/Fourier transform infrared (FTIR) sensor based on polymer preconcentration the impact of penetrant properties upon diffusion into the enrichment membrane must be characterised. Teflon AF2400, a highly amorphous and robust polymer not previously used in this role, was chosen as the enrichment membrane and various environmentally significant chlorinated hydrocarbon and alcohol species selected as analytes. Analyses were performed on aqueous solutions running in continuous flow configuration. Diffusion coefficients, calculated through regression of experimental data with simulated Fickian diffusion curves, were employed as the primary indicator of diffusion behaviour. Penetrant size and shape were both demonstrated to exhibit a substantial impact upon diffusion behaviour. Significant multi-component effects were observed for the simultaneous detection of two analytes. The results presented highlight the necessity for full characterisation of the observed effects prior to the development of a sensing technology for real applications.     

Gas and vapor transport properties of amorphous perfluorinated copolymer membranes based on 2,2-bistrifluoromethyl-4,5-difluoro-1,3-dioxole/tetrafluoroethylene

Teflon AF 2400 (Du Pont) is an amorphous, glassy perfluorinated copolymer containing 87 mol% 2,2-bistrifluoromethyl-4,5-difluoro-1,3-dioxole and 13 mol% tetrafluoroethylene. The polymer has an extremely high fractional free volume of 0.327. Permeability coefficients for helium, hydrogen, carbon dioxide, oxygen, nitrogen, methane, ethane, propane, and chlorodifluoromethane (Freon 22) were determined at temperatures from 25 to 60°C and pressures from 20 to 120 psig. Permeation properties were also determined at a feed pressure of 200 psig at 25°C with a 2 mol% n-butane/98 mol% methane mixture. Permeabilities of permanent gases in Teflon AF 2400 are among the highest of all known polymers; the oxygen permeability coefficient at 25°C is 1600 × 10⁻¹⁰ cm³ (STP) cm/cm² s cmHg and the nitrogen permeability coefficient is 780 × 10⁻¹⁰ cm³ (STP) cm/cm² s cmHg. The permeabilities of organic vapors increase up to 20-fold as the vapor activity increases from 0.1 to unity, indicating that Teflon AF 2400 is easily plasticized. Although Teflon AF 2400 is an ultrahigh-free-volume polymer like poly(1-trimethylsilyl-1-propyne) [PTMSP], their gas permeation properties differ significantly. Teflon AF 2400 shows gas transport behavior similar to that of conventional, low-free-volume glassy polymers. PTMSP, on the other hand, acts more like a nanoporous carbon than a conventional glassy polymer.     

The nearest-neighbor resonating-valence bond state in a Grassmannian form

The nearest-neighbor resonating-valence bond (NNRVB) state is studied using classical anticommuting (Grassmann) variables. The classical partition function corresponding to the self-overlap of the NNRVB wavefunction is generated from a local (bond) Hamiltonian expressed in terms of four anticommuting variables. It is shown that the one-particle-per-site constraint introduces an interaction term which is a local product of all four variables. Two approaches are applied to study this Hamiltonian: (i) a self-consistent field decoupling scheme and (ii) a systematic perturbation expansion around the unconstrained soluble point. Bounds on the norm of the wavefunction are derived. Extensions to the presence of holes, long-range valence bonds, and the introduction of phase fluctuations [which violate the Marshall sign rule and yield aU(1) gauge theory] are discussed.     

Study of the quasi two-dimensional CoxNi1-xTa2O6 compounds by X-ray diffraction and magnetic susceptibility measurements

We report results on the structural and magnetic properties of the Co_xNi_1−xTa₂O₆ series of compounds by X-ray powder diffraction, magnetic susceptibility and magnetization measurements. X-ray refinements carried out by the Rietveld method show that these compounds crystallize in a P4₂/mnm tetragonal structure. Magnetic susceptibility curves show a broadened maximum witnessing that these compounds exhibit two-dimensional antiferromagnetic behaviors. All the Co_xNi_1−xTa₂O₆ compounds order below 10 K and present a large ion anisotropy. The magnetic properties have been determined in both the paramagnetic and antiferromagnetic state. In the hypothesis of two dimensional AF ordering, the near neighbor exchange constants (J₁) and the next near neighbor exchange constants for two different paths (J₂ and J'₂) were determined. The composition dependence of the magnetic properties including ordering temperature, exchange constants and anisotropy factors are discussed. The drastic reduction of the ordering temperature for x=0.20 for Co_xNi_1−xTa₂O₆, suggest the hypothesis of a peculiar magnetic behavior for this composition.