APCI as an innovative ionization mode compared with EI and CI for the analysis of a large range of organophosphate esters using GC‐MS/MS

Organophosphate esters (OPEs) are chemical compounds incorporated into materials as flame‐proof and/or plasticizing agents. In this work, 13 non‐halogenated and 5 halogenated OPEs were studied. Their mass spectra were interpreted and compared in terms of fragmentation patterns and dominant ions via various ionization techniques [electron ionization (EI) and chemical ionization (CI) under vacuum and corona discharge atmospheric pressure chemical ionization (APCI)] on gas chromatography coupled to mass spectrometry (GC‐MS). The novelty of this paper relies on the investigation of APCI technique for the analysis of OPEs via favored protonation mechanism, where the mass spectra were mostly dominated by the quasi‐molecular ion [M + H]⁺. The EI mass spectra were dominated by ions such as [H₄PO₄]⁺, [M–R]⁺, [M–Cl]⁺, and [M–Br]⁺, and for some non‐halogenated aryl OPEs, [M]^+● was also observed. The CI mass spectra in positive mode were dominated by [M + H]⁺ and sometimes by [M–R]⁺, while in negative mode, [M–R]⁻ and more particularly [X]^‐ and [X₂]^‐● were mainly observed for the halogenated OPEs. Both EI and APCI techniques showed promising results for further development of instrumental method operating in selective reaction monitoring mode. Instrumental detection limits by using APCI mode were 2.5 to 25 times lower than using EI mode for the non‐brominated OPEs, while they were determined at 50‐100 times lower by the APCI mode than by the EI mode, for the two brominated OPEs. The method was applied to fish samples, and monitored transitions by using APCI mode showed higher specificity but lower stability compared with EI mode. The sensitivity in terms of signal‐to‐noise ratio varying from one compound to another. Copyright © 2016 John Wiley & Sons, Ltd.     

A REVIEW OF POLAR STRATOSPHERIC CLOUD FORMATION

Liquid and solid particles in polar stratospheric clouds （PSCs） have been known to play a crucial role in the chemical loss of stratospheric ozone over the Antarctic and Arctic regions in late winter and early spring. The stratospheric aerosol and cloud particles provide the sites where fast heterogeneous chemical reactions convert inactive halogen reservoir species into potential ozone destroying radicals. The sedimentation of nitric acid-containing PSC particles irreversibly removes HNO3 gas （denitrification） from the lower stratosphere, which slows the return of chlorine to its inactive forms, resulting in more severe stratospheric ozone destruction. Although these clouds have been investigated extensively during the past decade using in situ field observation, laboratory experiment and modeling studies, the detailed microphysics processes under cold stratospheric conditions are still uncertain. This paper reviews the recent advances in our understanding of PSCs.     

Exchange of Chemical Species between the Atmospheric Boundary Layer and the Reservoir Layer: An Analytical Interpretation

The exchange of chemical species between the atmospheric boundary layer and the reservoir layer is investigated by means of an analytical solution of the conservation equation of a decaying chemical species. The exchange mechanism is governed by two parameters: the Damköhler number (the ratio of the turbulence time scale to the chemical time scale) and the ratio of a concentration scale in the atmospheric boundary layer to the concentration in the reservoir layer. Depending on the value of these two parameters, the exchange flux between the two layers can vary in sign and by several orders of magnitude. The study demonstrates to what extent chemical transformation determines the transfer of chemical species between the atmospheric boundary layer and the reservoir layer.     

Analysis of Wind Fluctuations Using the Orthogonal Wavelet Transform

This paper presents a study of velocity fluctuations occurring in the stably stratified atmospheric boundary layer over an Antarctic ice shelf. The approach is based on wavelet analysis which has advantages over conventional Fourier analysis. Two case studies are presented, comprising: pure turbulent flow and a large amplitude solitary wave.     

Investigations of Droplet‐Plasma Interaction using Multi‐Dimensional Coupled Model

Recently developed multi‐dimensional coupled fluid‐droplet model is used to investigate the behavior of complex interaction between the liquid precursor droplets and atmospheric pressure plasma (APP). The significance of this droplet‐plasma interaction is not well understood under diverse realm of working conditions in two‐phase flow. In this study, we explain the implication of vaporization of liquid droplets in APP which are subsequently responsible to control major characteristics of surface coating depositions. Coalescence of water droplets is more dominant than Hexamethyldisiloxane (HMDSO) droplets because of its sluggish rate of evaporation. A disparity in the performance of evaporation is identified in two independent mediums, such as gas mixture and discharge plasma using HMDSO precursor. The length of evaporation of droplets is amplified by an increment of gas flow rate indicating with a reduction in the gas temperature and electron mean energy. In particular, the spatio‐temporal density distributions of charged particles show a clear pattern in which the typical nitrogen impurity ions are primarily effective as compared to other helium ionic species along the pulse of droplets in APP. Finally, we contrast the behavior of discharge species in the pure helium and He‐N2 gas mixtures revealing the importance of stepwise and Penning ionization processes. (© 2015 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Electron Temperatures and Electron Densities in Microwave Helium Discharges with Pressures Higher than 0.1 MPa

We adopted laser Thomson scattering for measuring the electron density and the electron temperature of microwave plasmas produced in helium at the pressures higher than the atmospheric pressure. The electron density decreased while we observed the increase in the electron temperature with the pressure. These are reasonable results by considering the decrease in the reduced electric field, the dominant loss of electrons via three‐body recombination with helium as the third body, and the production of electrons with medium energy via heavy particle collisions at the high gas pressure. The temporal variation of the electron temperature had the rise and the fall time constants of approximately 10 ns. The rapid heating and cooling of the electron temperature are due to the fast energy transfer from electrons to helium because of the high collision frequency in the high‐pressure discharge. (© 2015 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

基于MoO3/Ag/MoO3透明阳极的顶发射OLED的模拟计算与制备

运用传输矩阵法和正交分析法模拟计算出MoO₃/Ag/MoO₃透明电极的最佳厚度,采用镀膜实验验证模拟计算的准确性,制备了一系列不同MoO₃膜厚度和Ag膜厚度的透明电极。然后,制备了一系列顶发射有机电致发光器件:铝/氟化锂(LiF)/三(8-羟基喹啉)铝(Alq₃)/N,N'-二苯基-N,N'-(1-萘基)-1,1'-联苯-4,4'-二胺/三氧化钼(MoO₃)/银(Ag)/三氧化钼(MoO₃),来进一步验证模拟计算运用在器件制备中的准确性。MoO₃(10 nm)/Ag(10 nm)/MoO₃(25 nm)在532 nm处的透射率达到最大值88.256%,以该透明电极制备的器件与参考器件相比,性能有了明显提高,最大亮度和最大效率分别为20 076 cd/m²和4.03 cd/A,提高了18.5%和56%。器件性能的提高归因于顶发射OLED器件透射率的提高和MoO₃对空穴注入能力的提升。     

基于空间模型测量点的照度比值的CIE标准一般天空类型选择

为了计算自然光照度,需要从CIE定义的15种天空类型中正确选择一种对应当前实际天空。首先根据朝向太阳与背向太阳的垂直天空照度的比值将15种天空类型划分为6组,然后根据天空光透过窗口在空间模型两个不同测量点形成的照度的比值对6组天空类型做进一步划分,最终实现对CIE定义的15种天空类型的选择。将天空类型的选择结果与实际天空类型相比较,结果表明,这种天空类型选择方法所得结果可以准确地对应当前实际天空类型。     

大气折射对可见光波段辐射传输特性的影响

折射是影响辐射传输的重要因素. 为分析大气折射对辐射传输的影响, 基于Monte Carlo方法, 给出了考虑大气折射的矢量辐射传输模型, 实现了均匀气层和耦合面处光子随机运动过程的模拟, 实现了直射光及漫射光Stokes矢量、偏振度和辐射通量等参数的计算. 在考虑和不考虑大气折射两种条件下, 验证了模型的准确性; 在纯瑞利散射条件下, 讨论了大气折射对不同方向漫射光Stokes矢量的影响; 在不同太阳天顶角、大气廓线、气溶胶及含云大气条件下, 分析了大气折射对辐射传输过程的影响. 结果表明: 大气折射对漫射光Stokes矢量的影响主要体现在天顶角70°–110°区间, 且随着太阳入射角增大, 其影响更为显著; 不同大气廓线情形下, 大气折射对Stokes矢量的影响不一致, 其原因是不同大气廓线对应的折射率廓线存在差异. 含云及含气溶胶大气条件下, 大气折射对辐射传输的影响变弱, 沙尘型及海盐型气溶胶条件下, 折射对辐射传输的影响强于可溶型气溶胶情形; 不同形状气溶胶条件下, 大气折射对辐射传输的影响也存在显著差异; 不同云高条件下, 大气折射对漫射光Stokes矢量的影响无显著差异, 但随着云光学厚度增大, 大气折射的影响减弱.     

部分相干平顶光束在非Kolmogorov湍流中的湍流距离

给出了部分相干平顶光束通过非Kolmogorov湍流传输的湍流距离解析表达式,并研究了非Kolmogorov湍流的湍流广义指数、内尺度、外尺度和光束参数对部分相干平顶光束湍流距离的影响。研究表明:湍流距离随相干参数、束腰、外尺度(当湍流广义指数的取值为3.6~4.0时)的增大而减小;随光束阶数、内尺度的增大而增大;随湍流广义指数先减小后增大,且在湍流广义指数取3.11时存在极小值,即光束扩展的极大值。同时利用湍流广义指数及光束参数,具体比较了湍流距离与瑞利区间的大小,并指出光束参数及湍流广义指数决定了湍流是否在瑞利区间内就能对光束扩展构成明显的影响。