超高效液相色谱串联质谱法测定烟草中的噁霉灵残留

为降低烟草中噁霉灵检测中的基质干扰，提高检测灵敏度和和稳定性，通过试验建立了以QuEChERS为样品前处理方法、液相色谱串联质谱仪为检测仪器的烟草中噁霉灵残留检测方法。样品加水浸润后，经丙酮提取、盐析试剂包除水、石墨化炭黑除杂后，采用Agilent ZORBAX 300SB-C8液相色谱柱（2.1 mm×100 mm，1.8 μm）分离，甲醇-水程序洗脱，ESI雾化，串联质谱MRM检测。结果发现，该方法在0.0025~0.0500 mg/L范围内线性良好，决定系数r²=0.9996，定量检测限1.06 μg/L，回收率在90.8%~92.0%之间，相对标准偏差为5.1%。运用该方法测定烟草中的噁霉灵，操作简单，检测精度高，满足CORESTA对烟草农残检测的要求。     

Headspace fingerprinting approach to identify the major pathway influencing volatile patterns of vinasse-cured duck processed by high pressure,as well as its impact on physicochemical and sensory attributes

As a decisive attribute, flavour could be influenced by HP treatments through multiple physical and chemical pathways within the high pressure (HP)-assisted meat curing process. This investigation aimed to identify the major pathway influencing volatile flavour patterns of two representative vinasse-cured duck (VCD) products with HP treatments (150–300 MPa/15 min), including wet and dry types, by employing headspace fingerprinting as an untargeted approach. Results suggested that HP treatments greatly lowered moisture contents and increased Warner-Bratzler shear force and thiobarbituric acid reactive substances of the cured samples. According to multivariate models, the volatile flavour patterns of the HP-processed VCD could be clearly separated from the unprocessed samples, but the VCD pressurised at different intensities represented similar volatile fingerprinting, which was validated by e-nose analysis. The discriminant analysis (OPLS-DA) model outlined vinasse-derived ethanol, acetic acid, 3-methyl-1-butanol, 2-methyl-1-butanol, phenethyl alcohol and 2-methyl-3-octanone as the major discriminant aromas across the unpressurised and pressurised samples.     

PAN纤维共聚单体作用机理的光电离质谱研究

本工作以丙烯腈/衣康酸（IA）二元共聚原丝以及丙烯腈/IA/丙烯酸甲酯（MA）三元共聚原丝为研究对象，利用热重分析仪（TG）和热解-同步辐射真空紫外光电离质谱（Py-SVUV-PIMS）对其热稳定化过程进行研究。TG结果表明，氮气气氛下，二元共聚原丝（PAN/IA）和三元共聚原丝（PAN/IA/MA）分别呈现三阶段和两阶段的热分解过程，其中PAN/IA的第一和第二阶段均对应PAN线型分子链的断裂，但前者是由自由基环化反应放热引发的，后者则是由正常温度下的热分解所致，而单体MA的加入显著抑制了自由基环化反应，使得PAN原丝的热稳定化能够以单体IA诱导的离子型环化反应为主较平缓地进行，相应的热失重过程也由两阶段转变为了单阶段。Py-SVUV-MS的实验结果表明，两种共聚PAN原丝在程序升温过程中会生成包括含氮小分子、丙烯腈单体及低聚物、成环化合物在内的三类主要热解产物，对比各类产物的生成趋势和产量，推断单体MA通过降低PAN结构的规整度，使其无定形化，从而增加环化反应的引发点，促进PAN原丝向稳定的预氧丝转变，同时由典型热解产物——甲基丙烯腈的生成路径可知，MA本身并不参与PAN大分子的环化反应，属于中性共聚单体。空气气氛下，CO₂的产量差异也间接证明了MA单体能够有效提升PAN纤维的固碳能力，采用三元共聚方法制得的PAN纤维热稳定性能更佳。     

Methodology for optimization of pouring variables using bottom pour for low masses of SS304 (<300 kg) in investment casting process (case study)

Bottom pour ladles with stopper rod systems are commonly used in the metal casting industry. However, stopper rod bottom-pouring systems have not yet been developed for the lower thermal masses of alloys typically used in the investment casting industry. Large thermal masses used with bottom pour systems are typically limited for ladles larger than 700 kg and to certain alloys with higher fluidity and longer solidification time like cast iron, aluminum alloys etc. In this study, bottom pour ladle designs and low thermal mass refractory systems have been developed and evaluated in production investment foundry trials with 300 kg pouring ladle. The ladles system and pouring practices used will be described along with the results from the pouring trials for SS304 that represents typical alloys used in Investment casting industries. Optimization of the variables used in an experimentation using Genetic algorithm is also explained.     

Development of mobile miniature natural gas liquefiers

With increasing consumption of natural gas (NG), small NG reservoirs, such as coalbed methane and oil field associated gas, have recently drawn significant attention. Owing to their special characteristics (e.g., scattered distribution and small output), small-scale NG liquefiers are highly required. Similarly, the mixed refrigerant cycle (MRC) is suitable for small-scale liquefaction systems due to its moderate complexity and power consumption. In consideration of the above, this paper reviews the development of mobile miniature NG liquefiers in Technical Institute of Physics and Chemistry (TIPC), China. To effectively liquefy the scattered NG and overcome the drawbacks of existing technologies, three main improvements, i.e., low-pressure MRC process driven by oil-lubricated screw compressor, compact cold box with the new designed heat exchangers, and standardized equipment manufacturing and integrated process technology have been made. The development pattern of “rapid cluster application and flexible liquefaction center” has been eventually proposed. The small-scale NG liquefier developed by TIPC has reached a minimum liquefaction power consumption of about 0.35 kW·h/Nm³. It is suitable to exploit small remote gas reserves which can also be used in boil-off gas reliquefaction and distributed peak-shaving of pipe networks.     

燃气热水器在无回水管水路中实现零冷水的方案研究

本文分析了燃气热水器行业针对无回水管水路系统实现零冷水功能的现有技术方案,指出现有技术方案存在的一些缺陷,并结合试验研究,对无回水管水路系统提出了一套全新的实现零冷水功能的技术解决方案。     

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.     

含煤盆地深层“超饱和”煤层气形成条件

中国深层煤层气资源丰富，但总体勘探和认识程度较低，尚未形成较为系统的深层煤层气地质理论。通过解剖分析准噶尔盆地白家海凸起和鄂尔多斯盆地临兴区块深层"超饱和"煤层气井的试气/生产动态，估算原地游离气的含气量，分析了深层"超饱和"煤层气的形成条件。研究表明：①深层"超饱和"煤层气储层中除吸附气外，还含有原地游离气，用常规试气方法可直接获得气流，煤层气的产出不明显依赖于排水降压；②埋藏超过一定深度，在煤阶和温度的综合作用下，煤的吸附能力将随埋深的继续增加而降低，煤层中吸附气的饱和度有增加的趋势，在达到吸附饱和后，出现原地游离气并形成"超饱和"煤层气，盆地深层具有"超饱和"煤层气形成的优势条件；③由于地温梯度和压力梯度的不同，不同盆地"超饱和"煤层气出现的临界深度不同，异常高压和异常高热流可以降低深层"超饱和"煤层气形成的临界深度；④深层"超饱和"煤层气开发具有大大缩短见气时间、充分利用地层能量和累积产水量低等优势，有望成为未来煤层气勘探开发的一个重要领域。