全二维气相色谱/飞行时间质谱用于莪术挥发油分离分析特性的研究

用全二维气相色谱 /飞行时间质谱 (GC×GC/TOFMS)研究莪术挥发油。对GC×GC与GC的分离特性和GC×GC/TOFMS与GC/MS的定性能力进行了比较。在相同条件下 ,GC分离出 87个峰 ,GC×GC分出约 5 0 0个峰 ,GC/MS和GC×GC/TOFMS鉴定出匹配度大于 80 0的组分分别为 4 6种和 2 2 7种。除此之外 ,GC×GC/TOFMS对每一个组分可给出三维定性信息 ,定性可靠性大大提高。研究结果显示与传统的分析技术相比 ,GC×GC/TOFMS在中药挥发油成分分析领域有很大的优势     

过氧草酰类化学发光反应及其在分析化学中的应用

在化学发光试剂中，过氧草酰类试剂是发光量子产率最高的一类试剂，本文对这类试剂的合成、性质、发光机理及其在液相色谱、薄层色谱及流动注射分析等方面的应用进行了评述。引用文献９３篇。     

复杂生物体系中蛋白质高效分离分析技术的新进展

继人类基因组计划完成之后,作为一种新的研究策略,蛋白质组学在生命科学研究中发挥着愈来愈重要的作用。由于生物体系的复杂性和多样性,使得分离效率高、灵敏度高、通量高和动态范围宽的分离分析技术平台的研究和应用已成为蛋白质组学研究的重点和热点之一。着重介绍了近年来应用日益广泛的多维色谱预分离、毛细管液相色谱-质谱联用、毛细管电泳及其与质谱联用等高效分离分析技术在复杂生物体系的蛋白质分析中的最新进展。引用相关文献40篇。     

定量结构-性质关系在分析化学中的应用研究进展

定量结构-性质关系研究应用理论计算方法和各种统计分析工具相结合,研究系列化合物的结构与其生物学性质和各种物理化学性质之间的定量函数关系．它不仅可以建立预测化合物的各种物理化学性质以及生物活性的理论,而且还可以发现和确定对化合物的各种性质起决定作用的结构因素,从而在分子水平上了解物质的微观结构对各种宏观性质的影响,在很多领域得到了广泛的应用．主要介绍定量结构—性质关系在分析化学中的应用研究,主要包括在色谱分析、毛细管电泳分析中的应用两大部分．     

A history of mass spectrometry in Australia

An interest in mass spectrometry in Australia can be traced back to the 1920s with an early correspondence with Francis Aston who first visited these shores a decade earlier. The region has a rich tradition in both the development of the field and its application, from early measurements of ionization and appearance potentials by Jim Morrison at the Council for Scientific and Industrial Research (CSIR) around 1950 to the design and construction of instrumentation including the first use of a triple quadrupole mass spectrometer for tandem mass spectrometry, the first suite of programs to simulate ion optics (SIMION), the development of early TOF/TOF instruments and orthogonal acceleration and the local design and construction of several generations of a sensitive high-resolution ion microprobe (SHRIMP) instrument. Mass spectrometry has been exploited in the study and characterization of the constituents of this nation's unique flora and fauna from Australian apples, honey, tea plant and eucalyptus oil, snake, spider, fish and frog venoms, coal, oil, sediments and shale, environmental studies of groundwater to geochronological dating of limestone and granite, other terrestrial and meteoritic rocks and coral from the Great Barrier Reef. Peter Jeffery's establishment of geochronological dating techniques in Western Australia in the early 1950s led to the establishment of geochronology research both at the Australian National University and at what is now the Curtin Institute of Technology in the 1960s. This article traces the history of mass spectrometry in its many guises and applications in the island continent of Australia. An article such as this can never be complete. It instead focuses on contributions of scientists who played a major role in the early establishment of mass spectrometry in Australia. In general, those who are presently active in the field, and whose histories are incomplete, have been mentioned at best only briefly despite their important contributions to the field.     

3D打印在分析化学中的应用研究

3D打印是一种以计算机三维设计数字模型文件为基础,运用特殊可粘合材料,借助光固化和纸层叠等方式逐层打印的,一种快速成形构造物体的新技术.本文侧重从色谱仪器分析、电化学仪器分析、原子分子光谱和质谱仪器分析等方面评论了近年来3D打印在分析化学中的应用研究,为现代仪器分析研究提供借鉴参考,以使3D打印技术和分析化学学科交叉融合协同发展.     

Detection by Gas Phase Analytical Methods of Derivatives of Barbiturate Epoxides

Abstract

Reactive epoxides, formed as intermediates in the enzymic hydroxylation of olefinic compounds, can be trapped by their reaction with trimethylchlorosilane and detected by gas chromatography and combined gas chromatography-mass spectrometry as the trimethylsilyl derivatives of their chlorohydrin adducts. Mass spectrometric identification of the products is facilitated by the characteristic isotope ratio of chlorine. By using these derivatives, epoxides have been detected as intermediates in the metabolic conversion in the rat of allylic barbiturates to their corresponding glycols.     

Accelerating the development of phase-change random access memory with in-fab plasma profiling time-of-flight mass spectrometry

We demonstrate the potential of using plasma profiling time-of-flight mass spectrometry (PP-TOFMS) to accelerate process developments for phase-change random access memory (PCRAM) applications, which require advanced materials with composition-driven properties. We assess the performances of PP-TOFMS for the chemical depth-profiling of GeSbTe phase change materials, first after deposition steps to investigate the top surface layer and the incorporation of silicon into the amorphous matrix, then after the thermal annealing step to refine in situ capping strategies, and finally in close loop with etching process steps. Comparison of reference-free semiquantitative PP-TOFMS analysis based on ion beam ratio with Rutherford backscattering spectrometry shows remarkable agreement (~10% relative). PP-TOFMS proves to be a fast screening tool, which allows process monitoring and selection of samples that indeed need more complex analysis.     

Analysis of the Sulfonylurea Herbicide Metsulfuron-Methyl and Its Metabolites in the Soil of Cereal Crops. Comparative Analytical Chemistry of the Sulfonylureas

Abstract

For the analysis of metsulfuron-methyl in the crop soils with a sensitivity limit of 0.3 μg kg^?1 dry soil, in the soil extract metsulfuron-methyl was separated from its soil metabolites and the soil impurities by repeated thin-layer chromatographies (TLC). In the cleaned soil extract, diazomethane transformed metsulfuron-methyl 1 into N,N′ -dimethyl metsulfuron-methyl 2 (methyl 2-[[[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)methylamino]carbonyl]methylamino]sulfonyl]benzoate). In the gas-liquid chromatograph with detection by electron capture (GC-EC) and in the combined gas chromatograph-mass spectrometer (GC-MS), 2 was transformed into 1-dioxy-2-N-methyl-3-keto-1,2-benzisothiazole 3 which was measured by GC-EC with confirmation by GC-MS. The metsulfuron-methyl soil metabolites 2-sulfonamido-methylbenzoate 6, 1-dioxy-3-keto-1,2-benzisothiazole (saccharin) 7 and 2-sulfonamidobenzoic acid 8 were analyzed in the soil of winter wheat crops by a procedure similar to the one for metsulfuron-methyl. After their separation and purification in the soil extracts by TLC, 7 and 8 were methylated, and analyzed as 3 in the GC-EC and GC-MS apparatus where the generated 6 was quantitatively transformed into 3; 6 was analyzed as such with the GC and GC-MS apparatus wherein it was transformed into 3. The sensitivity limit for each metabolite was 0.3 μg of equivalents of metsulfuron-methyl kg^?1dry soil. The syntheses of the analysis standards of the metsulfuron-methyl derivatives 2 and 3, and of the metsulfuron-methyl metabolites 6, 7 and 8 are described. The transformation pathways of metsulfuron-methyl and of its derivatives are different from those of the pyridine-pyrimidine sulfonylurea herbicides flupyrsulfuron-methyl and rimsulfuron. The soil analysis of a sulfonylurea -by means of one of its transformation product- needs a previous study of the chemical reactivity of the sulfonylurea. This leads to the analysis procedures for the main soil metabolites of the sulfonylurea.     

毛细管气相色谱法分析虾蛄肉中的脂肪酸

以快速脂肪提取器分别提取雄、雌虾蛄肉中脂肪,利用５０ｍ×０．３５ｍｍｉ．ｄ．ＰＥＧ－２０Ｍ玻璃毛细管柱分离测定了雄、雌虾蛄肉中的脂肪酸,结合气相色谱／质谱法,鉴定出４５个峰,分别占脂肪酸总量的９９．２％和９８．０％,其中不饱和脂肪酸分别为７４．７％和７１．５％。     

染毒水样中神经性毒剂水解产物的分析

考察了对水中6种神经性毒剂水解产物固相萃取的萃取剂,洗脱剂等因素对萃取率的影响,以LC－CN小柱为萃取剂,1％冰醋 甲醇溶液为洗脱剂,测得萃取回收率为59．7％－100％,相对标准偏差为1．4％－7．2％,采用气相色谱和色质联用－选择离子检测法对水解产物三甲基硅烷（TMS）衍生物进行分析鉴定,水中水解产物最低检测浓度为0．002－0．02mg/L。为今后水中神经性毒剂未知样品分析提供了简便,快速的分析方法。     

大口径毛细管柱气相色谱法测定工业异丁基苯含量

采用大口径毛细管柱技术和色谱－质谱联用技术对工业异丁基苯进行了定性和定量分析,建立了一种测定工业异丁基苯的新方法。实验结果表明新方法操作简单、快速、精密度高、复现性好。     

Separation assay of histamine and its metabolites in biological specimens

This review summarizes the determination methods for histamine and the metabolites in biological specimens by separation techniques, such as gas chromatography, liquid chromatography and capillary electrophoresis. The typical applications using these methods are also described in this review together with the characteristics of the methods. Copyright (c) 2008 John Wiley & Sons, Ltd.     

砷形态分析方法进展

对光变分析法,高效液相色谱法,毛细管电泳法以及气相色谱法在砷形态分析中的应用进行了评述,比较了各种方法的优缺点,引用文献82篇。     

Direct determination of acrylamide in food by gas chromatography-high-resolution time-of-flight mass spectrometry

Simple and rapid gas chromatographic (GC) method employing a high-resolution time-of-flight mass analyzer that enables direct analysis (no derivatization) of acrylamide in various heat-processed foodstuffs has been developed and validated. Co-isolation of acrylamide precursors such as sugars and asparagine, constituting the risk of results overestimation due to additional formation of analyte in hot GC injector, is avoided by the extraction with n-propanol followed by solvent exchange to acetonitrile (MeCN). Introduction of a novel purification strategy, dispersive solid phase extraction, based on addition of primary-secondary amine (PSA) sorbent into deffated extract in MeCN, provides a significant reduction of some abundant matrix co-extracts (mainly free fatty acids). Isotope dilution technique (d₃-acrylamide as an internal standard) is employed for compensation of potential target analyte losses and/or matrix-inducted chromatographic response enhancement. Limits of quantifications (LOQs) ranged between 15 and 40 μg kg⁻¹ and recoveries were between 97 and 108% depending on the examined food matrix. The repeatability of measurements (expressed as relative standard deviation, R.S.D.) was as low as 1.9% for potato crisps containing acrylamide at a level of 1 mg kg⁻¹. Slightly higher values (R.S.D. < 4.0%) were achieved for breakfast cereals and crisp bread with approximately 10 times lower content of this processing contaminant. Trueness of results generated by this new method was demonstrated via FAPAS^® (Food Analysis Performance Assessment Scheme) interlaboratory proficiency tests.     

Chemistry in Court

Chromatographic separation techniques are now widely used to examine the material evidence associated with a crime. Four areas are considered. Analysis of drugs of abuse by GC, GC-MS and GC-FTIR; HPLC; chiral chromatography; capillary electrophoresis (CE) and capillary electrochromatography (CEC); solid-phase microextraction (SPME). The quantitative detection of adulterants and trace pesticides in foods using supercritical fluid extraction (SFE). DNA profiling by separation of fragments by gel and capillary electrophoresis and fluorescence detection. Future developments in automation and miniaturisation and the design of microchips and micro-electrode devices allowing complete analysis in 8 μL cells.     

基于全二维气相色谱-四极杆飞行时间质谱高通量检测独活挥发油化学成分

利用全二维气相色谱-四极杆飞行时间质谱(GC×GC-QTOF MS)建立了一种适用于独活挥发油化学成分的高通量检测方法,样品经水蒸气蒸馏提取后,直接采用全二维气相色谱进行分离,并根据谱库匹配、保留指数及精确质量数进行定性确认.结果表明,共分离鉴定了独活挥发油中207种化学成分,其中正向、反向匹配因子大于800的化合物占...     

Analytical strategies for chemical characterization of bio‐oil

Bio‐oils, produced by biomass pyrolysis, have become promising candidates for feedstocks of high value‐added chemicals and alternative sources for transportation fuels. Bio‐oil is such a complicated mixture that contains nonpolar hydrocarbons and polar components which cover almost all kinds of organic oxygenated compounds such as carboxylic acids, alcohols, aldehydes, ketones, esters, furfurals, phenolic compounds, sugar‐like material, and lignin‐derived compounds. Comprehensive characterization of bio‐oil and its subfractions could provide insight into the conversion process of biomass processing, as well as its further utilization as transportation fuels or chemical raw materials. This review focuses on advanced analytical strategies on in‐depth characterization of bio‐oil, which is concerned with gas chromatography, high‐resolution mass spectrometry, FTIR spectroscopy and NMR spectroscopy, offering complementary information for previous reviews.     

多种气相色谱联用技术分析陕西刺五加茎挥发油的化学成分

采用气相色谱/四极杆质谱(GC/qMS)、气相色谱/正交加速飞行时间质谱(GC/oaTOFMS)和气相色谱/傅里叶变换红外光谱(GC/FTIR)联用技术,对一种陕西产刺五加Acanthopanax senticosus (Rupr. et Maxim.) Harms茎挥发油的化学成分进行了分析。基于GC/qMS谱库的检索功能,结合GC/FTIR在结构鉴别上的优势和GC/oaTOFMS对质谱碎片离子精确的质量测定功能,成功地实现了对68个色谱组分的定性分析。与使用单一的联用技术(例如GC/qMS)相比,利用多种色谱联用技术在定性分析上的互补性,可以明显提高对组成复杂的挥发油类样品分析的可靠性。     

全二维气相色谱-飞行时间质谱法测定烟草的中性化学成分

建立了采用全二维气相色谱-飞行时间质谱(GC×GC-TOFMS)分析烟草的中性化学成分的方法。以DB-Petro(50 m×200 μm×0.5 μm) 为第一维色谱柱,DB-1701(2.3 m×100 μm×0.1 μm)为第二维色谱柱;调制周期为8 s;柱头压力为550 kPa;采用程序升温方式,初始温度分别为80 ℃和85 ℃。采用所建立的方法对不同部位的烟叶、不同品种烟草中的25种中性香味成分含量进行了测定和对比。结果表明：云南楚雄产云烟85的中性香味成分(不包括新植二烯)的总量以中部叶最高,其次是上部叶,下部叶最少;国内外不同品种的烤烟中中性香味成分的含量高低顺序为：巴西烤烟最高,其次是津巴布韦烤烟、云烟85、中烟101、NC89、K326;4类烟草中中性香味成分含量最高的是香料烟,其次是白肋烟、烤烟、马里兰烟。