Comparison of the performance of three ion mobility spectrometers for measurement of biogenic amines

The performance of three different types of ion mobility spectrometer (IMS) devices: GDA2 with a radioactive ion source (Airsense, Germany), UV-IMS with a photo-ionization source (G.A.S. Germany) and VG-Test with a corona discharge source (3QBD, Israel) was studied. The gas-phase ion chemistry in the IMS devices affected the species formed and their measured reduced mobility values. The sensitivity and limit of detection for trimethylamine (TMA), putrescine and cadaverine were compared by continuous monitoring of a stream of air with a given concentration of the analyte and by measurement of headspace vapors of TMA in a sealed vial. Preprocessing of the mobility spectra and the effectiveness of multivariate curve resolution techniques (MCR-LASSO) improved the accuracy of the measurements by correcting baseline effects and adjusting for variations in drift time as well as enhancing the signal to noise ratio and deconvolution of the complex data matrix to their pure components. The limit of detection for measurement of the biogenic amines by the three IMS devices was between 0.1 and 1.2 ppm (for TMA with the VG-Test and GDA, respectively) and between 0.2 and 0.7 ppm for putrescine and cadaverine with all three devices. Considering the uncertainty in the LOD determination there is almost no statistically significant difference between the three devices although they differ in their operating temperature, ionization method, drift tube design and dopant chemistry. This finding may have general implications on the achievable performance of classic IMS devices.     

三维无溶剂含能Ag-MOF的制备、热分解动力学及爆炸性能

Solvent molecules can significantly reduce the heat of detonation and stability of energetic metal-organic framework (EMOF) materials, and the development of solvent-free EMOFs has become an effective strategy to prepare high-energy density materials. In this study, a solvent-free EMOF, [Ag₂(DTPZ)]_n (1) (N% = 32.58%), was synthesized by reacting a high-energy ligand, 2, 3-di(1H-tetrazol-5-yl)pyrazine (H₂DTPZ), with silver ions under hydrothermal conditions, and it was structurally characterized by elemental analysis, infrared spectroscopy, X-ray diffraction, and thermal analysis. In 1, the DTPZ²⁻ ligands that adopted a highly torsional configuration bridged the Ag⁺ ions in an octadentate coordination mode to form a three-dimensional framework (ρ = 2.812 g∙cm⁻³). The large steric effect and strong coordination ability of DTPZ²⁻ effectively prevented the solvent molecules from binding with the metal centers or occupying the voids of 1. Moreover, the strong π-π stacking interactions [centroid-centroid distance = 0.34461(1) nm] between the tetrazole rings in different DTPZ²⁻ ligands provided a high thermal stability to the framework (T_e = 619.1 K, T_p = 658.7 K). Thermal analysis showed that a one-step rapid weight loss with intense heat release primarily occurred during the decomposition of 1, suggesting potential energetic characteristics. Non-isothermal thermokinetic analyses (based on the Kissinger and Ozawa-Doyle methods) were performed using differential scanning calorimetry to obtain the thermoanalysis kinetic parameters of the thermodecomposition of 1 (E_a = 272.1 kJ·mol⁻¹, E_o = 268.9 kJ·mol⁻¹; lgA =19.67 s⁻¹). The related thermodynamic parameters [enthalpy of activation (ΔH^≠ = 266.9 kJ·mol⁻¹), entropy of activation (ΔS^≠ = 125.4 J·mol⁻¹·K⁻¹), free energy of activation (ΔG^≠ = 188.3 kJ·mol⁻¹)], critical temperature of thermal explosion (T_b = 607.1 K), and self-accelerating decomposition temperature (T_SADT = 595.8 K) of the decomposition reaction were also calculated based on the decomposition peak temperature and extrapolated onset temperature when the heating rate approached zero. The results revealed that 1 featured good thermal safety, and its decomposition was a non-spontaneous entropy-driven process. The standard molar enthalpy for the formation of 1 was calculated to be (2165.99 ± 0.81) kJ·mol⁻¹ based on its constant volume combustion energy determined using a precise rotating oxygen bomb calorimeter. Detonation and safety performance tests revealed that 1 was insensitive to impact and friction, and its heat of detonation (10.15 kJ·g⁻¹) was higher than that of common ammonium nitrate explosives, such as octogen (HMX), hexogene (RDX), and 2, 4, 6-trinitrotoluene (TNT), indicating that 1 is a promising high-energy and insensitive material.     

Studies on thermionic ionisation detection in comprehensive two-dimensional gas chromatography

This study explores the application of specific thermionic ionisation detection in comprehensive 2-D GC (GC x GC) and represents the first report of GC x GC with nitrogen phosphorus detection (GC x GC-NPD). Of particular interest is the performance of the NPD with respect to peak parameters of asymmetry and sensitivity. Since GC x GC produces much narrower peaks than obtained with fast GC (e.g. 100 ms vs. <1 s) the effect of detector response time and any lack of symmetry arising from the detection step is important if peak separation (resolution) is to be maintained. It was observed that detector gas flows had a significant impact on peak asymmetry and peak magnitude, and that optimisation of the detector was critical, particularly for complex sample analysis by GC x GC-NPD. Peak asymmetries ranging from As = 1.8 to 8.0 were observed under different conditions of detector gas flows. Comparison of GC x GC-NPD with GC x GC-flame ionisation detection (FID) showed the former to be approximately 20 times more sensitive for the detection of nitrogen-containing methoxypyrazines analytes, and GC x GC-NPD had a larger linear detection range compared to GC x GC-FID. Furthermore, comparison of GC x GC-NPD and GC x GC-TOFMS chromatograms for the analysis of coffee head-space demonstrated the benefits of selective detection, ultimately realised in a comparatively simplified contour plot.     

Estimation of the degree of asphericity of a glass sphere using a vectorial shearing interferometer

The degree of asphericity is estimated by determining the average radius of curvature in different sections, at various points on the surface of a sphere, and the deviation from it. We employ the vectorial shearing interferometer (VSI) as the instrument to determine the radius of curvature from two subapertures of the transparent glass sphere. We incorporate the sphere as a thick lens into the interferometric setup, illuminating it with an expanded beam. The spherical aberration, introduced by the sphere in the wave front, depends on the local sphere radius, on the refraction index of the glass, and on the cone angle of the source. The wave front aberrated by the sphere impinges on the VSI. Here, the wave front is divided in two in amplitude, it is sheared vectorially, and it is superimposed with itself. The fringe pattern is formed in the intersection of the wave fronts. The shape of the resulting fringe pattern is directly related to spherical aberration. We estimate qualitatively the degree of asphericity, comparing the phase gradients in different sections of the sphere. Here, we report on the experimental setup to test the asphericity, the results with different vectorial shearing (magnitude and direction). Finally, we perform a comparison with the theoretical predictions.     

资产组合的CVaR风险的敏感度分析

基于CVaR风险计量技术，分别给出了正态和t分布情形下资产组合的CVaR值，对一般情形下风险资产组合的CVaR风险关于头寸的敏感度进行了分析，研究了其经济意义。     

煤矿粉尘影响三种典型荒漠植被生长的高光谱指数研究

以新疆典型露天煤矿准东五彩湾开采区为研究区,选定并测定干旱煤矿区三种典型植物： 梭梭、假木贼和琵琶柴的冠层光谱,分析植被对煤炭粉尘的波谱响应,旨在研究露天煤炭开采引起的煤炭粉尘扩散对植被生长的影响.研究基于植被冠层实测光谱,提取19种常用的植物色素指数和水分指数,通过不同指数同煤炭粉尘降尘量的相关性的研究,探讨植被生长受损的关键参数及对煤炭粉尘影响敏感的指示性植被,为干旱煤矿区植被受损监测提供评价依据。结果表明： 在干旱露天煤矿区植被受到煤炭粉尘污染的过程中,从植被指数的角度可以间接确定,随着煤炭粉尘量的增加,叶绿素以及水分的含量会减少,而类胡萝卜素的含量会增加;植被体内的水分和叶绿素含量对煤炭粉尘量的响应较为敏感;在指示叶绿素(包括叶绿素a、叶绿素b和叶绿素)的指数中色素归一化指数b(PSNDb)敏感性较强;在指示类胡萝卜素的指数中结构不敏感色素指数(SIPI)敏感性较强;在指示水分的指数中植被水分指数(PWI)敏感性较强;三种植物中梭梭对煤炭粉尘量的增加较为敏感。     

用于原子吸收光谱仪的高灵敏度燃烧器

本文介绍了一种用于原子吸收光谱仪的气－样分进、双通道燃烧器，经过实际检测比较，该坷提高原子吸收灵敏度１￣５倍，且稳定性好。     

光纤光栅弹簧管压力传感器的压力和温度特性

本文利用弹簧管对于压力的机械放大作用,将弹簧管与光纤光栅悬臂梁调谐技术相结合,研制了一种新颖的光纤光栅弹簧管压力传感器,大大提高了光纤布喇格光栅对压力测量的灵敏度,压力灵敏度系数可达-1.79×10^-4/MPa,比裸光栅提高了两个数量级,在0～12MPa的压力范围内,光纤布喇格光栅中心反射波长的改变与压力成良好的线性关系.同时由于悬臂梁热膨胀效应的影响,光纤光栅的温度灵敏度提高为裸光栅的7倍.     

Sensitivity-enhanced IPAP experiments for measuring one-bond C–C and C–H residual dipolar couplings in proteins

Sensitivity-enhanced 2D IPAP experiments using the accordion principle for measuring one-bond 13C'-13Calpha and 1Halpha-13Calpha dipolar couplings in proteins are presented. The resolution of the resulting spectra is identical to that of the decoupled HSQC spectra and the sensitivity of the corresponding 1D acquisitions are only slightly lower than those obtained with 3D HNCO and 3D HN(COCA)HA pulse sequences due to an additional delay 2Delta. For cases of limited resolution in the 2D 15N-1HN HSQC spectrum the current pulse sequences can easily be modified into 3D versions by introducing a poorly digitized third dimension, if so desired. The experiments described here are a valuable addition to the suites available for determination of residual dipolar couplings in biological systems.