悬浮液进样-火焰原子吸收光谱法测定茶叶中的微量铬

将茶叶悬浮于琼脂胶体中制成悬浮液 ,直接喷入空气 -乙炔火焰 ,用火焰原子吸收光谱法测定茶叶中的微量铬 ,方法简便、快速、灵敏度和精密度高、测定结果与用灰化法处理样品一致 ,检验表明 ,两种样品前处理方法之间无显著性差异。相对标准偏差为 3.4 %～ 6 .1% ,加标回收率为 95 .7%～ 10 3.8 %。     

Computer-aided thermodynamic study of solid Co---Pd alloys by Knudsen cell mass spectrometry, and calculation of the phase diagram

F.c.c. solid Co---Pd alloys have been investigated thermodynamically by means of computer-aided Knudsen cell mass spectrometry. Thermodynamic evaluation has been performed by applying the “digital intensity ratio” method. The thermodynamic excess properties can be described algebraically by means of thermodynamically adapted power series with two adjustable parameters, i.e. C₁^G (−20 810 + 9.608T) J mol⁻¹) and C₂^G (−30 720 + 6.78T) J mol⁻¹). At 1470 K, f.c.c. solid Co---Pd alloys are characterized by negative molar excess Gibbs energies G^E, exothermic molar heats of mixing (H^E) and small negative molar excess entropies S^E. At 1470 K, the minimum G^E value is −4600 J mol⁻¹ (61.9 at.% Pd), the minimum H^E value is −9400 J mol⁻¹ (59.5 at.% Pd) and the minimum S^E value is −3.3 J mol⁻¹ K⁻¹ (55.9 at.% Pd). The thermodynamic activities of Co show small positive deviations from the ideal case for the Co-rich alloys (x_Pd < 0.34), and negative deviations from Raoults' law for alloys with higher Pd contents. The Pd activities a_Pd show negative deviations from the ideal case for all compositions. The phase diagram has been computed by means of a generally applicable procedure for the calculation of the equilibrium compositions of coexisting phases. This was achieved using the results of this work, thermodynamic data from earlier mass spectrometric studies on the liquid phase, and literature data for the heat capacities and enthalpies of Co and Pd.     

原子吸收光谱法快速测定松香皂中几种金属元素

提出了用原子吸收光谱法快速测定松香皂中几种金属元素的方法。考察了元素干扰情况及灰化温度。该方法快速、简便、准确 ,RSD为 0 .95 %～ 2 .2 1% ,回收率为 95 .6 %～ 10 8.7%。     

聚丙烯餐盒复用过程中邻苯二甲酸酯类塑化剂和合成酚类抗氧化剂的检测及迁移规律研究

目的 建立气相色谱-质谱法(gas chromatography-mass spectrometry,GC-MS)同时测定聚丙烯(polypropylene,PP)餐盒中邻苯二甲酸酯类塑化剂和合成酚类抗氧化剂含量的分析方法,并研究其在复用过程中向酸性食品模拟物(4%乙酸)、非酸性食品模拟物(10%乙醇、水)以及油脂类食品模拟物(异辛烷、橄榄油)的迁移量。方法 PP餐盒经正己烷超声提取,食品模拟物根据其不同的性质选择不同萃取液,液液萃取辅以超声提取,经SH-Rxi-5MS (30 m×0.25 mm, 0.25 μm)石英毛细管柱分离,单离子监测(single ion monitoring, SIM)模式扫描,外标法定量。结果 20种化合物的线性关系在0.01~1.00 mg/L范围内表现良好,其相关系数均大于0.99,检出限和定量限分别是0.01~0.02 mg/L和0.03~0.06 mg/L。5种食品模拟物在0.05、0.10和0.50 mg/L 3个水平下加标回收率为80.4%~108.4%,相对标准偏差为1.3%~10.6% (n=6)。结论 该方法实验过程简便,灵敏度、精密度、回收率高,适用于PP餐盒中邻苯二甲酸酯类塑化剂和合成酚类抗氧化剂含量和迁移量的测定。实验结果可知,PP餐盒在热接触和微波加热的复用过程中均有一定程度的迁移,需要引起重视。     

基于气相离子迁移谱技术分析延安市不同县区的富士苹果挥发性成分的差异

目的 分析比较延安市不同区县富士苹果之间挥发性成分的差异。方法 采用气相离子迁移谱(gas chromatography-ion mobility spectrometry,GC-IMS)技术对延安市13个县区的晚熟富士苹果的挥发性成分进行分析,建立富士苹果的挥发性成分特征指纹图谱,并进行主成分法和聚类分析法分析。结果 在延安市13个县区富士苹果样品中共鉴别出的挥发性成分54种,主要有酯类、醇类、酮类、醛类和酸类等物质,各县区富士苹果的酯类和醇类物质占比较高,分别占总挥发性成分的48.98%~53.19%和13.04%~19.23%。13个县区富士苹果共有的挥发性成分有2-乙基呋喃、丙酸乙酯、甲酸异戊酯、乙酸己酯、乙酸异戊酯、2-甲基丁基乙酸酯等,这些物质共同奠定了延安富士苹果香气的总体基调,各县区富士苹果的挥发性成分的具体种类和含量各有不同。结论 本研究通过建立挥发性成分特征指纹图谱,明确了延安市不同区县富士苹果之间挥发性成分存在的差异。研究发现延安市宝塔区的富士苹果挥发性成分种类及含量较丰富,其特征性物质有巴豆酸乙酯、异丙醇、2,3-丁二酮、乙酸甲酯等。黄陵县富士苹果特有丁酸丙酯、丁酸甲酯等物质。宜川县富士苹果的特征性物质有反式-2-已烯醛、丁酸异戊酯、丁酸等。此外富县富士苹果中含量丰富的挥发性成与黄陵县富士苹果的部分挥发性成分一致。延川、洛川县、甘泉县、黄龙县和吴起县的富士苹果中含量丰富的挥发性成分较为相似;子长市、安塞区、志丹县、延长县的富士苹果中含量丰富的挥发性成分较为相似。结果表明GC-IMS技术在延安市富士苹果的挥发性成分的分析方面具有较好的应用价值,可用于不同县区富士苹果的风味识别和品质评价。     

Rapid and Sensitive Liquid Chromatography-Tandem Mass Spectrometry for Quantification of Glycyrrhetic Acid in Human Plasma

A simple, rapid and sensitive liquid chromatography-tandem mass spectrometry(LC-MS/MS) for the determination of glycyrrhetic acid in human plasma with ginsenoside Rh2 as internal standard was developed and validated. The plasma samples were prepared via liquid-liquid extraction with ethyl acetate. Chromatographic separation was accomplished on a Venusil MP-C18(50 mm×2.1 mm, 5μm i.d.) column at 25℃. The mobile phase consisted of acetonitrile/5 mmol·L-1 ammonium acetate(10:90, volume ratio) at a flow rate of 0.4 mL/min. Negative electrospray ionization was utilized as the ionization source. Glycyrrhetic acid and internal standard were determined via the mutiple reaction monitoring of precursor→production ion transitions at m/z 469→425, 409 and m/z 621→161,respectively. Each sample was chromatographed within 2.5 min. The lower limit of uantification was 0.50 ng/mL for 200 μL of plasma sample and the linear range was from 0.50 ng/mL to 800 ng/mL. The intra-and inter-day precisions were less than 8.76% in terms of relative standard deviation(RSD), and the accuracy was within a range of -3.25%-1.32% in terms of relative error(RE). The method was successfully applied to the pharmacokinetic studies of glycyrrhetic acid in healthy male Chinese volunteers after a single oral administration of 75 mg of glycyrrhizin.     

浓缩硼同位素的化学提纯与质谱分析

一、引言 在核燃料循环中,准确地测定硼同位素丰度及确定核燃料产品中硼含量具有重要意义。 关于硼的化学提纯方法有蒸馏法、萃取法,离子交换法,汞阴极电解法等,其中蒸馏法能使硼与其他杂质元素分离比较完全,而且,操作简便、重复性好、适应范围广。本工作用蒸馏法提纯浓缩硼元素获得了比较满意的结果。     

Identification of heavy metal-contaminated Tegillarca granosa using laser-induced breakdown spectroscopy and linear regression for classification

Tegillarca granosa (T. granosa) is susceptible to heavy metals, which may pose a threat to consumer health. Thus, healthy and polluted T. granosa should be distinguished quickly. This study aimed to rapidly identify heavy metal pollution by using laser-induced breakdown spectroscopy (LIBS) coupled with linear regression classification (LRC). Five types of T. granosa were studied, namely, Cd-, Zn-, Pb-contaminated, mixed contaminated, and control samples. Threshold method was applied to extract the significant variables from LIBS spectra. Then, LRC was used to classify the different types of T. granosa. Other classification models and feature selection methods were used for comparison. LRC was the best model, achieving an accuracy of 90.67%. Results indicated that LIBS combined with LRC is effective and feasible for T. granosa heavy metal detection.     

Orbitrap高分辨质谱法快速筛查上海市流通环节蔬菜的农药残留

摘 要：目的 建立蔬菜农药多残留的筛查方法。方法 使用国家标准方法规定的QuEChERS法净化蔬菜样品,结合静电场轨道阱高分辨质谱法(orbitrap high resolution mass spectrometry)开展809种农药的快速非靶向筛查。结果 62种阳性农药的筛查限(screening detection limit, SDL)为0.005~0.010 mg/kg,定量限(limits of quantitation, LOQ)为0.01 mg/kg,线性范围为0.01~0.20 mg/kg,线性相关系数(r2)为0.9917~0.9997,日内精密度为2.77%~6.98% (n=5),日间精密度为4.82%~10.8% (n=5)。200批次样品共检出62种农药,不合格样品28批次,不合格率为14.0%。豇豆的不合格情况比较突出,不合格样品22批次,主要的不合格项是灭蝇胺和噻虫胺。结论 方法快速、准确、分析通量高,在无标准品的情况下实现了蔬菜中809种农药的非靶向快速筛查,可为蔬菜农药残留风险监测和质量控制提供支撑。     

超高效液相色谱串联质谱法测定牛奶中三氮脒残留

目的 本研究旨在结合超高效液相色谱－串联质谱(ultra performance liquid chromatography-tandem mass spectrometry, UPLC-MS/MS)技术,建立简便、快速的样品前处理方法,对牛奶中的痕量三氮脒残留进行检测。方法 用1%乙酸乙腈溶液振荡提取后,在-4℃条件下高速离心,取上清液旋转蒸干后,用10%乙腈水溶液复溶,用超高效液相色谱-串联质谱仪在正离子扫描及多反应监测(multiple reaction monitoring, MRM)模式下分析,外标法定量。结果 牛奶中三氮脒的检出限(limit of detection, LOD)为5 μg/kg,定量限(limit of quantification, LOQ)为15 μg/kg,在20~1000 μg/L浓度范围内线性良好,相关系数(r)为0.9993。将所研究的方法应用于实际牛奶样本中,其加标回收率在81.65%至85.49%之间,日内精密度分别在4.5%~5.5%,日间精密度在5.9%~8.2%之间。结论 本方法采用振荡提取加低温高速离心净化的前处理方法,简单快速,结合UPLC-MS/MS,可实现痕量水平残留的高灵敏度检测,适用于快速、高灵敏检测牛奶及其他动物源性食品中的三氮脒残留。