Selective Analysis of Sulfur-Containing Species in a Heavy Crude Oil by Deuterium Labeling Reactions and Ultrahigh Resolution Mass Spectrometry

A heavy crude oil has been treated with deuterated alkylating reagents (CD₃I and C₂D₅I) and directly analyzed without any prior fractionation and chromatographic separation by high-field Orbitrap Fourier Transform Mass Spectrometry (FTMS) and Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR MS) using electrospray ionization (ESI). The reaction of a polycyclic aromatic sulfur heterocycles (PASHs) dibenzothiophene (DBT), in the presence of silver tetrafluoroborate (AgBF₄) with ethyl iodide (C₂H₅I) in anhydrous dichloroethane (DCE) was optimized as a sample reaction to study heavy crude oil mixtures, and the reaction yield was monitored and determined by proton nuclear magnetic resonance spectroscopy (¹H-NMR). The obtained conditions were then applied to a mixture of standard aromatic CH-, N-, O- and S-containing compounds and then a heavy crude oil, and only sulfur-containing compounds were selectively alkylated. The deuterium labeled alkylating reagents, iodomethane-d₃ (CD₃I) and iodoethane-d₅ (C₂D₅I), were employed to the alkylation of heavy crude oil to selectively differentiate the tagged sulfur species from the original crude oil.     

Simultaneous determination of mycotoxin in commercial coffee

Mycotoxins are secondary metabolites produced by filamentous fungi that usually contaminate food products. Coffee is a natural product susceptible to mycotoxin contamination. The present study evaluates the presence of nivalenol, deoxynivalenol, T-2 and HT-2 Toxin, diacetoxyscirpenol, aflatoxin B₁, aflatoxin B₂, aflatoxin G₁, aflatoxin G₂, fumonisin B₁, fumonisin B₂, ochratoxin A, zearalenone, enniatin A, enniatin A₁, enniatin B, enniatin B₁, and beauvericin in coffee samples, using liquid chromatography tandem mass spectrometry (LC-MS/MS). The results show that zearalenone was not present in any sample. In the positive samples the contents of fumonisins ranged from 58.62 to 537.45 μg/kg, emerging mycotoxins ranged from 0.10 to 3569.92 μg/kg, aflatoxins ranged from 0.25 to 13.12 μg/kg, and trichothecenes, excepting nivalenol, ranged from 5.70 to 325.68 μg/kg. Nivalenol presented the highest concentrations, from 0.40 to 25.86 mg/kg. Ochratoxin A ranged from 1.56 to 32.40 μg/kg, and five samples exceeded the maximum limit established by the European Commission.     

Synthesis,structure, stability and phase diagrams of selected bimetallic silver- and nickel-based nanoparticles

An overview of the research on silver-based (Ag-Sn, Ag-Cu, Ag-Ni) and nickel-based (Cu-Ni, Au-Ni, Ni-Pt) bimetallic nanoparticles is presented. The investigated nanoparticles in this review are formed by elements that represent an important group of metals revealing fcc lattice under macro-sized conditions (with the exception of Sn). The effects of surface stabilizing layer of the alloy nanoparticles are also described. Our experience with synthesis, characterization and stabilization of alloy nanoparticles is summarized. The development of the nanoparticle synthesis represents an important and mandatory part of the experimental nanoalloy research. Main synthetic routes under focus are the low temperature borohydride reduction method, the high temperature oleylamine synthesis, and the high pressure method in autoclave. The subsequent structural studies are focused on both nanoparticle core and outer stabilizing layer. The cores of the nanoparticles are studied mainly by electron microscopy techniques. The phase stability of the nanoparticle core is investigated by thermal analysis. The Knudsen effusion mass spectrometry was applied for studies of stabilizing organic molecules that can be found on the surface of the nanoparticles. The presented overview of the experimental results is complemented by thermodynamic calculations of phase diagrams by the CALPHAD method.     

氢化物原子荧光光谱法测定酱油中微量铅的方法研究

建立了一种快速、高效的QuEChERS-高效液相色谱-质谱联用法（QuEChERS-HPLC-MS/MS）测定谷类杂粮制品中脱氧雪腐镰刀菌烯醇（DON）、3-乙酰脱氧雪腐镰刀菌烯醇（3-ADON）、15-乙酰脱氧雪腐镰刀菌烯醇（15-ADON）和玉米赤霉烯酮（ZON）共4种真菌毒素。样品前处理采用乙腈-水溶剂提取，经Florisil+C18+无水硫酸镁净化后检测。以0.10%甲酸-乙腈作为流动相，在质谱检测器的多反应监测模式下进行分析。结果表明，4种真菌毒素在各自的线性范围内线性关系良好，相关系数R2均大于0.999，回收率在85.1%～102.0%，相对标准偏差（RSD）为2.11%～6.22%。该方法具有前处理简单、净化效果好、灵敏度高和检测速度快的优点，适用于谷类杂粮制品中DON、3-ADON、15-ADON 和ZON的分析和定量检测。     

便携式飞行时间质谱仪的研制及其在石化污水系统挥发性有机物监测中的应用

近年来，国内的大气污染问题越来越严重，挥发性有机物（VOCs）的排放是其中一个重要原因。VOCs是臭氧和气溶胶的前驱物之一，在大气化学反应过程中扮演着极其重要的角色。本实验自行研制了一台基于真空紫外（VUV）灯的高分辨光电离飞行时间质谱仪（TOF MS），建立了一种新的VOCs稀释采样方法，并将其应用于石化行业污水处理系统VOCs的采样与分析。结果表明：隔油系统的3个池子基本没有测到高浓度的挥发性有机物，其中溶气气浮甲苯物质的质量浓度最高，为50.41 mg/L，其余组分的质量浓度大多数在0.1~1.0 mg/L之间；1#加氢和2#加氢隔油池有着类似的组分浓度，以1#加氢隔油池为例，二甲苯物质的质量浓度为10.60 mg/L，乙苯为52.33 mg/L，苯为59.80 mg/L；由于罐区隔油池没有加盖，处于露天状态，挥发性有机物气体容易向大气中扩散，并没有检测出较高浓度组分。可以看出，新式采样方法可有效地稀释定量样品，操作简便，减少了样品因闪蒸过程造成的VOCs损失，检出物质更丰富；同时，使用自行研制的TOF MS仪器能够快速检测不同装置污水处理系统的VOCs种类，将该仪器用于实际样品检测，发现化工企业大多数密闭的池子都含有苯系物、醚类等，但不同工艺的污水处理系统VOCs存在明显差异。该质谱仪适用于石化企业污水系统VOCs监测。     

Real-time organic aerosol chemical speciation in the indoor environment using extractive electrospray ionization mass spectrometry

Understanding the sources and composition of organic aerosol (OA) in indoor environments requires rapid measurements, since many emissions and processes have short timescales. However, real-time molecular-level OA measurements have not been reported indoors. Here, we present quantitative measurements, at a time resolution of five seconds, of molecular ions corresponding to diverse aerosol-phase species, by applying extractive electrospray ionization mass spectrometry (EESI-MS) to indoor air analysis for the first time, as part of the highly instrumented HOMEChem field study. We demonstrate how the complex spectra of EESI-MS are screened in order to extract chemical information and investigate the possibility of interference from gas-phase semivolatile species. During experiments that simulated the Thanksgiving US holiday meal preparation, EESI-MS quantified multiple species, including fatty acids, carbohydrates, siloxanes, and phthalates. Intercomparisons with Aerosol Mass Spectrometer (AMS) and Scanning Mobility Particle Sizer suggest that EESI-MS quantified a large fraction of OA. Comparisons with FIGAERO-CIMS shows similar signal levels and good correlation, with a range of 100 for the relative sensitivities. Comparisons with SV-TAG for phthalates and with SV-TAG and AMS for total siloxanes also show strong correlation. EESI-MS observations can be used with gas-phase measurements to identify co-emitted gas- and aerosol-phase species, and this is demonstrated using complementary gas-phase PTR-MS observations.     

Zk线性码的对称形式的MacWilliams恒等式

该文定义了Zk线性码的码字的对称重量计数公式，利用离散的Hadamard变换，建立了线性码与其对偶码之间的对称形式的MacWilliams恒等式．     

多区双重介质复合气藏渗流数学模型及其压力动态

四川盆地大多数气藏属于裂缝孔隙型气藏,气藏非均质性强.经典的径向均质复合试井解释模型与气藏实际情况不相符,解释结果与实际地质情况出现抵触现象.针对这种情况,建立了多区双重孔隙介质复合地层模型,求得了该模型的拉氏空间解,分析了其典型的压力动态特征,并对影响因素可能对曲线产生的影响进行了分析.     

抵御已知/选择明文攻击的混沌图像加密算法

论文在对现有一类典型图像混沌加密算法的分析基础上,提出了一种改进的图像混沌加密算法。该算法引入小波变换,可以有效地克服一些混沌加密算法不能抵御已知/选择明文攻击的缺陷。