加速溶剂提取-同位素稀释-高分辨气相色谱-高分辨质谱法测定生物样品中82种多氯联苯

我国水产品中多氯联苯(PCBs)的检测方法,主要以6种指示性PCBs和12种二噁英类共平面PCBs为主,仅涵盖有限的PCBs。为更全面地获得生物体中PCBs的浓度水平,深入探讨PCBs在生物体内的代谢和富集特征,进而准确评价PCBs对人类的暴露水平及风险,以鱼和贝类作为生物样品代表,建立了加速溶剂提取-同位素稀释-高分辨气相色谱-高分辨质谱(ASE-ID-HRGC-HRMS)测定生物样品中82种PCBs的方法。比较了振荡提取和加速溶剂提取两种提取方式的回收率和重复性,最终采用正己烷-二氯甲烷(1∶1, v/v)对PCBs进行加速溶剂提取。考察了各流分淋洗液对PCBs的回收率,确定了样品提取液经8 g 44%酸性硅胶层析柱(内径15 mm), 90 mL正己烷洗脱的净化方式。样品提取液净化浓缩后进行HRGC-HRMS分析,色谱柱采用DB-5MS超低流失石英毛细管柱(60 m×0.25 mm×0.25 μm)。通过优化后的升温程序对化合物进行分离,以保留时间和两个特征离子精准定性,采用同位素内标法定量。结果表明,在0.1~200 μg/L范围内,平均相对响应因子(RRF)的相对标准偏差值(RSD, n=7)均≤20%,相关系数(r²)>0.99。生物样品中PCBs的方法检出限为0.02~3 pg/g;鱼类中PCBs平均加标回收率为71.3%~141%, RSD(n=7)为2.1%~14%;贝类中PCBs平均加标回收率为76.9%~143%, RSD为1.4%~11%。该方法灵敏、准确、可靠,可以更加全面具体地分析鱼和贝类等水产品受PCBs的污染情况,为国内外开展生物监测提供有效的技术支持,从而服务于相关生态环境管理及履行《斯德哥尔摩公约》。     

Vapor deposition of ultrathin hydrophilic polymer coatings enabling candle soot composite for highly sensitive humidity sensors

Candle soot (CS) is a desirable carbon nanomaterial for sensors owing to its highly porous nanostructure and large specific surface area. CS is advantageous in its low-cost and facile preparation compared to graphene and carbon nanotubes, but its pristine nanostructure is susceptible to collapse, hampering its application in electronic devices. This article reports conformal coating of nanoscale crosslinked hydrophilic polymer on CS film using initiated chemical vapor deposition, which well preserved the CS nanostructure and obtained nanoporous CS@polymer composites. Tuning coating thickness enabled composites with different morphologies and specific surface areas. Surprisingly, the humidity sensor made from composite with the lowest filling degree, thus largest specific surface area, showed relatively low sensitivity, which is likely due to its discontinuous structure, thus insufficient conductive channels. Composite sensor with optimum filling degree shows excellent sensing response of more than 10³ with the linearity of R² = 0.9400 within a broad relative humidity range from 11% to 96%. The composite sensor also exhibits outstanding sensing performance compared to literature with low hysteresis (3.00%), a satisfactory response time (28.69 s), and a fast recovery time (0.19 s). The composite sensor is fairly stable and durable even after 24 h soaking in water. Furthermore, embedding a humidity sensor into a face mask realizes real-time monitoring of human breath and cough, suggesting promising applications in respiratory monitoring.     

Multiphase Flow Regime Characterization and Liquid Flow Measurement Using Low-Field Magnetic Resonance Imaging

Multiphase flow metering with operationally robust, low-cost real-time systems that provide accuracy across a broad range of produced volumes and fluid properties, is a requirement across a range of process industries, particularly those concerning petroleum. Especially the wide variety of multiphase flow profiles that can be encountered in the field provides challenges in terms of metering accuracy. Recently, low-field magnetic resonance (MR) measurement technology has been introduced as a feasible solution for the petroleum industry. In this work, we study two phase air-water horizontal flows using MR technology. We show that low-field MR technology applied to multiphase flow has the capability to measure the instantaneous liquid holdup and liquid flow velocity using a constant gradient low flip angle CPMG (LFA-CPMG) pulse sequence. LFA-CPMG allows representative sampling of the correlations between liquid holdup and liquid flow velocity, which allows multiphase flow profiles to be characterized. Flow measurements based on this method allow liquid flow rate determination with an accuracy that is independent of the multiphase flow profile observed in horizontal pipe flow for a wide dynamic range in terms of the average gas and liquid flow rates.     

General expression of the calibration curve for the CR-39 radon track detectors

The CR-39 detectors are widely used as passive radon dosimeters, as well as in physics laboratories or for industrial applications. For what concerns radon monitoring, the calibration curve which is usually adopted corresponds to a linear relation between the actual etched track density and the track density counted by an automatic acquisition system. This linear calibration provides very accurate radon exposure assessments in a restricted range of etched track density, however it neglects the effect of the tracks overlapping that becomes as relevant as the track density increases. In the present work the mathematical expression of the area covered by a set of uniformly distributed tracks is deduced. This result allows then to infer the probability that the system acquires the right track density, providing a general calibration curve for a solid state radon track detector. The process of track production and reading routine is also simulated adopting a Monte Carlo approach, showing that the obtained results are in agreement with the function proposed as calibration curve. Moreover, a linear dependence between the track average area and the rate parameter of the calibration curve has been observed. Finally a semi-empirical correlation based on the previous results is proposed.     

石化厂区有毒气体泄漏在线监测平台的构建

针对石化厂区在生产过程中可能发生有毒气体泄露带来的生产安全问题,构建了石化厂区有毒气体在线监测平台。该平台是由PC监控中心、网络监控中心、ARM便携式终端、安卓手机客户端组成。实现对石化厂区中有毒气体及环境参数的实时、在线监测和预警,使生产管理人员掌握石化厂区的有毒气体实时动态信息,对可能引发危险事故的因素及时排除,把危险控制在始发阶段,以实现化工生产的安全、持续、高效进行。测试结果表明该平台能实现所设计的各项功能,并具有良好的稳定性、安全性和实用性。     

基于扩展DALI总线的智能照明系统设计

针对大型商业照明场合存在的如组网不便、照明效果单一,能源利用率底的问题,设计了一套基于扩展DALI总线的商业智能照明系统,以实现系统的大面积组网和集中控制,获得丰富的照明效果,实现系统的绿色环保运行。测试系统搭建完成后,实现了管理人员对系统的集中管理和远程监控;系统可按照工作日程表、时间表自动运行;具有分区、分组、单灯、场景等多种控制方式,控制灵活,能达到较好的照明效果和节能要求,可满足多种商业照明需求。     

Optimized precursor ion selection for labile ions in a linear ion trap mass spectrometer and its impact on quantification using selected reaction monitoring

The fragmentation of fragile ions during the application of an isolation waveform for precursor ion selection and the resulting loss of isolated ion intensity is well‐known in ion trap mass spectrometry (ITMS). To obtain adequate ion intensity in the selected reaction monitoring (SRM) of fragile precursor ions, a wider ion isolation width is required. However, the increased isolation width significantly diminishes the selectivity of the channels chosen for SRM, which is a serious problem for samples with complex matrices. The sensitive and selective quantification of many lipid molecules, including ceramides from real biological samples, using a linear ion trap mass spectrometer is also hindered by the same problem because of the ease of water loss from protonated ceramide ions. In this study, a method for the reliable quantification of ceramides using SRM with near unity precursor ion isolation has been developed for ITMS by utilizing alternative precursor ions generated by in‐source dissociation. The selected precursor ions allow the isolation of ions with unit mass width and the selective analysis of ceramides using SRM with negligible loss of sensitivity. The quantification of C18:0‐, C24:0‐ and C24:1‐ceramides using the present method shows excellent linearity over the concentration ranges from 6 to 100, 25 to 1000 and 25 to 1000 nM, respectively. The limits of detection of C18:0‐, C24:0‐ and C24:1‐ceramides were 0.25, 0.25 and 5 fmol, respectively. The developed method was successfully applied to quantify ceramides in fetal bovine serum. Copyright © 2014 John Wiley & Sons, Ltd.     

On‐Line Monitoring of Chemical Reactions by using Bench‐Top Nuclear Magnetic Resonance Spectroscopy

Real‐time nuclear magnetic resonance (NMR) spectroscopy measurements carried out with a bench‐top system installed next to the reactor inside the fume hood of the chemistry laboratory are presented. To test the system for on‐line monitoring, a transfer hydrogenation reaction was studied by continuously pumping the reaction mixture from the reactor to the magnet and back in a closed loop. In addition to improving the time resolution provided by standard sampling methods, the use of such a flow setup eliminates the need for sample preparation. Owing to the progress in terms of field homogeneity and sensitivity now available with compact NMR spectrometers, small molecules dissolved at concentrations on the order of 1 mmol L^?1 can be characterized in single‐scan measurements with 1 Hz resolution. Owing to the reduced field strength of compact low‐field systems compared to that of conventional high‐field magnets, the overlap in the spectrum of different NMR signals is a typical situation. The data processing required to obtain concentrations in the presence of signal overlap are discussed in detail, methods such as plain integration and line‐fitting approaches are compared, and the accuracy of each method is determined. The kinetic rates measured for different catalytic concentrations show good agreement with those obtained with gas chromatography as a reference analytical method. Finally, as the measurements are performed under continuous flow conditions, the experimental setup and the flow parameters are optimized to maximize time resolution and signal‐to‐noise ratio.     

金属标记结合高效液相色谱-选择离子监测质谱的蛋白质绝对定量新方法

建立了金属标记结合高效液相色谱-选择性离子监测质谱(SIM)的蛋白质绝对定量新方法。实验考察了金属标记效率、金属标记的稳定性、标记后肽段的色谱保留和质谱行为、新定量方法的线性范围和准确度。实验结果表明金属标记具有标记效率高,稳定性好,色谱保留行为一致等优点。另外,金属标记-选择离子监测质谱绝对定量方法灵敏度高,其定量限低至1 fmol,线性范围为1~500 fmol,线性范围内R2值大于0.99,具有良好的线性关系;经过测量,标准肽段的回收率为117.01%,说明该方法具有较高的准确度。将该方法应用于腾冲嗜热菌中烯醇酶蛋白的定量分析,相对标准偏差为5.47%,表明该方法的精密度高。以上结果表明该方法可以用于生物样本中的蛋白质的绝对定量分析,为比较简单的生物样本中蛋白质的绝对定量方法提供了一种新的选择。     

Real-time in situ monitoring of manufacturing process and CFRP quality by relative resistance change measurement

In situ monitoring of resin flow, impregnation of carbon fiber fabrics, and curing during composite manufacturing are very important for determining the quality of composite parts. In conventional methods, sensors, such as optical fibers and strain gages, are bonded to or embedded in the composites for measuring the changes in mechanical and chemical properties. Although they can detect resin curing behavior and impregnation of carbon fibers, they may adversely affect the manufacturing process or structural integrity of the composites. In this study, carbon fiber itself was used as a sensor that minimizes the degradation of mechanical properties and increases the efficiency of monitoring the manufacturing process. The change in the electrical resistance of carbon fiber fabrics was monitored during the various manufacturing processes when the resin flowed through the carbon fiber fabric and curing progressed. The effectiveness of this monitoring method was confirmed, and it is expected to be applicable in monitoring the quality of the finished composite parts.