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Raman Microscopy and Imaging 拉曼显微镜与成像
Pub Date : 2018-06-14 DOI: 10.1002/9780470027318.A6404.PUB2
G. Steiner
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引用次数: 0
Gradient Elution Chromatography 梯度洗脱色谱法
Pub Date : 2012-06-15 DOI: 10.1002/9780470027318.A5907.PUB2
J. Dolan, L. Snyder
Elution chromatography can be carried out in either isocratic or gradient modes. In isocratic elution, the mobile-phase composition is held constant during separation of the sample, e.g. 60% v acetonitrile–water. In gradient elution, the mobile-phase composition will be varied during sample separation, e.g. changing from 0 to 100% v acetonitrile–water. Gradient elution requires special chromatographic equipment, as well as somewhat greater care on the part of the operator, but it has important advantages for many separations. Thus, in isocratic elution (Figure 1a), sample peaks tend to “bunch up” at the beginning of the chromatogram (often with decreased resolution) and to broaden at the end of the chromatogram (with reduced detection sensitivity). Gradient elution (Figure 1b), on the other hand, provides a more even spacing of peaks, similar widths throughout the chromatogram, and often a shorter run time. For these and other reasons, gradient elution is preferred for the separation of many samples.
洗脱色谱可以在等温或梯度模式下进行。在等温洗脱中,样品分离过程中流动相组成保持恒定,例如60% v乙腈-水。在梯度洗脱中,流动相组成在样品分离过程中会发生变化,例如从0到100% v乙腈-水。梯度洗脱需要特殊的色谱设备,也需要操作人员更加小心,但它对许多分离都有重要的优点。因此,在等密度洗脱中(图1a),样品峰在色谱开始时趋向于“聚集”(通常分辨率降低),并在色谱结束时变宽(检测灵敏度降低)。另一方面,梯度洗脱(图1b)提供了更均匀的峰间距,整个色谱图的宽度相似,并且通常运行时间更短。由于这些和其他原因,梯度洗脱是许多样品分离的首选方法。
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引用次数: 1
Infrared Spectroscopy of Biological Applications: An Overview 红外光谱学在生物领域的应用综述
Pub Date : 2012-06-15 DOI: 10.1002/9780470027318.A0208.PUB2
B. Stuart
Infrared spectroscopy has proved to be a powerful tool for the study of biological molecules, including proteins, lipids, carbohydrates, and nucleic acids. This spectroscopic approach enables such molecules to be identified and changes to their chemical structures to be characterized. The application of this technique to biological problems is continually expanding, particularly with the advent of increasingly sophisticated sampling techniques associated with Fourier transform infrared (FTIR) spectroscopy. Biological systems, including animal and plant tissues, microbial cells, clinical samples, and food, have all been successfully studied using infrared spectroscopy. In particular, recent decades have seen a rapid expansion in the number of studies of more complex systems, such as diseased tissues. This article reviews the sampling methods available for biological molecules. The interpretation of infrared data, both qualitatively and quantitatively, for such systems is covered. The specific information to be obtained from the main types of biological molecules is detailed, and the application of biological infrared spectroscopy is reviewed.
红外光谱已被证明是研究生物分子的有力工具,包括蛋白质、脂类、碳水化合物和核酸。这种光谱学方法可以识别这些分子,并对其化学结构的变化进行表征。该技术在生物问题上的应用正在不断扩大,特别是随着傅立叶变换红外光谱(FTIR)采样技术的日益成熟。生物系统,包括动植物组织、微生物细胞、临床样品和食品,都已经成功地使用红外光谱进行了研究。特别是近几十年来,对更复杂系统(如病变组织)的研究数量迅速增加。本文综述了生物分子的采样方法。介绍了这类系统的红外数据的定性和定量解释。详细介绍了从主要类型的生物分子中获得的具体信息,并对生物红外光谱的应用进行了综述。
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引用次数: 23
Verification of Chemicals Related to the Chemical Weapons Convention 核查与《化学武器公约》有关的化学品
Pub Date : 2011-12-15 DOI: 10.1002/9780470027318.A0401.PUB3
P. Vanninen
This article gives a short historical review of the Chemical Weapons Convention (CWC), discusses the tasks of the Organisation for the Prohibition of Chemical Weapons (OPCW) related to chemical analysis, and lists the chemicals scheduled in the CWC. The Recommended Operating Procedures (ROPs) proposed originally by Finland and subsequently developed further in international cooperation as well as the work instructions (WIs) of the OPCW are briefly discussed. Strategy for analysis of CWC-related chemicals in an off-site laboratory is presented. The international interlaboratory comparison (round-robin) and proficiency tests as well as future prospects are discussed.
本文简要回顾了《禁止化学武器公约》(CWC)的历史,讨论了禁止化学武器组织(OPCW)在化学分析方面的任务,并列出了《禁止化学武器公约》所列的化学品。本文简要讨论了最初由芬兰提出并随后在国际合作中进一步发展的建议作业程序以及禁化武组织的工作指示。提出了在非现场实验室分析化武相关化学品的策略。讨论了国际实验室间比较(循环)和能力测试以及未来的发展前景。
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引用次数: 1
Mass Spectrometry Applications in Forensic Science 质谱法在法医学中的应用
Pub Date : 2010-06-15 DOI: 10.1002/9780470027318.A9121
Darrin L. Smith
The role of mass spectrometry (MS) in forensic science can be characterized as either molecular or elemental analysis. Relatively small, volatile, nonpolar molecules found in a variety of forensic samples can be analyzed with electron and chemical ionization (CI) routinely coupled with single-stage mass analyzers that provide molecular weight and structural information. Nonvolatile and polar molecules including drugs, poisons, and/or their metabolites routinely found in biological matrices along with other analytes of forensic interest can be determined using electrospray or related soft ionization techniques coupled to tandem mass analyzer systems to identify a molecule through structure elucidation and provide excellent screening and quantitative results. New ambient ionization sources now allow the direct analysis of molecules from a forensic sample surface, with minimal prior preparation or separation. In addition, the sequencing of deoxyribonucleic acid (DNA) has also been difficult with most ionization sources until matrix-assisted laser desorption ionization (MALDI), which has the potential to provide quick and dependable results, was utilized. Elemental profiles also provide reliable methods for characterizing and distinguishing forensic samples. This article aims at providing information about MS and its uses in the field of forensic science. Keywords: forensic science; gas chromatography mass spectrometry (GC/MS); liquid chromatography mass spectrometry (LC/MS); ambient ionization; matrix-assisted laser desorption ionization (MALDI); elemental mass spectrometry
质谱法在法医学中的作用可分为分子分析和元素分析。在各种法医样品中发现的相对较小,易挥发的非极性分子可以通过电子和化学电离(CI)常规结合单级质量分析仪进行分析,该分析仪可以提供分子量和结构信息。非挥发性和极性分子,包括药物、毒药和/或其代谢物,通常在生物基质中发现,以及其他法医感兴趣的分析物,可以使用电喷雾或相关的软电离技术与串联质分析仪系统相结合,通过结构解析来识别分子,并提供出色的筛选和定量结果。新的环境电离源现在允许直接分析法医样品表面的分子,最小的事先准备或分离。此外,在使用基质辅助激光解吸电离(MALDI)之前,大多数电离源对脱氧核糖核酸(DNA)的测序也很困难,因为它有可能提供快速可靠的结果。元素剖面也为鉴定和区分法医样品提供了可靠的方法。本文旨在提供有关质谱的信息及其在法医学领域的应用。关键词:法医学;气相色谱-质谱法;液相色谱-质谱法;环境电离;基质辅助激光解吸电离;元素质谱法
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引用次数: 3
Noble Metals, Analytical Chemistry of 贵金属,分析化学
Pub Date : 2006-09-15 DOI: 10.1002/9780470027318.A2411
M. Balcerzak
Analytical methods for the determination of noble (precious) metals: ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os), iridium (Ir), platinum (Pt) and gold (Au) are presented in this article. Discovery, natural occurrence and main applications of the metals are described. Physical and chemical properties of noble metals are summarized. The nobility and catalytic activity of precious metals are the main properties that allow their use in a wide variety of applications, e.g. as catalysts in various chemical processes, as autocatalysts, in the electrical and electronic industry and in jewellery. Recent applications of some platinumcompounds (cisplatin and its derivatives) as anticancer drugs are important. The large variety of complex matrices, wide analytical concentration range (from sub-ppb to >99.99%), low reactivity towards single chemical reagents, great chemical similarities (especially between the pairs Ru and Os, Rh and Ir, Pt and Pd), complexity of platinum group metals (PGMs) species in solutions and rates of reaction make the accurate determination of noble metals a difficult analytical problem. The use of direct instrumental methods is restricted owing to interferences caused by matrix elements and low analyte concentrations. Sampling, sample decomposition, separation and preconcentration are critical steps in the majority of analytical procedures used. The choice of the digestion procedure used depends on the nature of the sample matrix and the analyte concentration. Fire assay (lead, iron, copper, nickel, tin or nickel sulfide as collectors), oxidizing fusion, acids treatment and chlorination are used to digest various materials. Precipitation, solvent extraction and chromatographic methods (ion-exchange and chelating resins, capillary electrophoresis) are applied to separate noble metals from associated base metals and to separate the individual precious metals. Preliminary isolation of ruthenium and osmium from the other noble and base metals, as well as from each other, by distillation or extraction in the form of RuO4 and OsO4, is often applied. Spectrophotometric methods using the complexes with inorganic and organic reagents can be applied to the determination of precious metals at ppm levels. Atomic absorption spectroscopy (AAS) (flame and graphite furnace) is well suited to the determination of Au, Pd, Rh and Pt (ppm and ppb levels, respectively). Ultratraces (ppb and sub-ppb levels) of noble metals can be determined in a large number of complex matrices by inductively coupled plasma mass spectrometry (ICPMS) with or without separation and preconcentration steps. A wide range of PGM concentrations, from percentage to ppm levels, can be determined by X-ray fluorescence (XRF) directly in solid samples or after pretreatment procedures (fire assay, coprecipitation, chromatographic preconcentration). Nuclear techniques (mainly neutron activation) are favored for the determination of low (ppb and
本文介绍了贵金属钌(Ru)、铑(Rh)、钯(Pd)、锇(Os)、铱(Ir)、铂(Pt)和金(Au)的分析方法。介绍了稀土金属的发现、自然赋存和主要应用。综述了贵金属的物理和化学性质。贵金属的高贵性和催化活性是其广泛应用的主要特性,例如在各种化学过程中作为催化剂,作为汽车催化剂,在电气和电子工业以及珠宝中。近年来一些铂类化合物(顺铂及其衍生物)作为抗癌药物的应用具有重要意义。复杂基体的种类繁多,分析浓度范围广(从亚ppb到>99.99%),对单一化学试剂的反应活性低,化学相似性大(特别是Ru和Os, Rh和Ir, Pt和Pd对),溶液中铂族金属(铂族金属)的种类和反应速率的复杂性使贵金属的准确测定成为一个难题。由于基质元素和低分析物浓度引起的干扰,直接仪器方法的使用受到限制。取样、样品分解、分离和预富集是大多数分析方法的关键步骤。所使用的消解程序的选择取决于样品基质的性质和分析物的浓度。火分析(铅、铁、铜、镍、锡或硫化镍作为收集剂)、氧化熔合、酸处理和氯化用于消化各种材料。沉淀法、溶剂萃取法和色谱法(离子交换和螯合树脂法、毛细管电泳法)被用于从伴生贱金属中分离贵金属和分离单个贵金属。通常采用以RuO4和OsO4形式蒸馏或萃取的方法,从其他贵金属和贱金属以及彼此之间初步分离钌和锇。使用无机和有机试剂配合物的分光光度法可用于测定ppm水平的贵金属。原子吸收光谱法(火焰和石墨炉)适用于Au、Pd、Rh和Pt(分别为ppm和ppb级)的测定。电感耦合等离子体质谱(ICPMS)可以在大量复杂基质中测定贵金属的超痕量(ppb和亚ppb水平),无论是否采用分离和富集步骤。可通过x射线荧光(XRF)直接在固体样品中或经过预处理程序(火焰测定、共沉淀、色谱预浓缩)确定从百分比到ppm水平的广泛范围的PGM浓度。核技术(主要是中子活化)被用于测定地质样品中低(ppb和亚ppb)水平的贵金属(对Au、Ir、Pd和Os具有高灵敏度)。伏安测量与样品制备相结合,包括将贵金属转化为电化学活性化合物,为测定提供高灵敏度(ppm和ppb水平)。标准标准物质的使用对于检查各种分析技术所得结果的准确性至关重要。
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引用次数: 4
Gas Chromatography in Analysis of Polymers and Rubbers 气相色谱法分析聚合物和橡胶
Pub Date : 2006-09-15 DOI: 10.1002/9780470027318.A2010
M. Hakkarainen, S. Karlsson
This chapter gives an overview of gas chromatography (with mass spectrometry) (GC/MS) of polymers and rubbers. Gas Chromatography (GC) analyzes volatile organic compounds, with an upper limit of 350°C, which means that the compounds to be analyzed must be volatile below this temperature. The technique is able to analyze small quantities of material, which means that it is applicable for example to residual monomers, initiators, catalysts, some additives and degradation products of polymers. It is generally not suitable for analysis of organic compounds at high molecular weight or of low volatility. Care must be taken not to analyze reactive species, which may ruin columns or other parts of the equipment. Proper sample preparation is necessary before GC/MS. Sensitive and selective techniques are used to separate and extract low-molecular-weight organic compounds from polymers. The sample preparation–extraction techniques may be grouped into (1) solvent extraction from solid matrices, (2) solvent extraction of organic compounds from aqueous solutions containing polymer (e.g. biomedical implants in physiological buffers) and (3) solvent-free extraction methods. An ideal extraction method is quantitative, selective, rapid and uses little or no solvent. Soxhlet is the old and traditional method for solvent extraction from solid sample matrices. Soxhlet is, however, time-consuming (two or three days is not uncommon), nonselective, uses large volumes of solvents and is often not quantitative. Ultrasonication and microwave-assisted extraction (MAE) are instead much more effective. Ultrasonication works by agitating the solution and producing cavitation in the liquid. The technique is useful for example to extract antioxidants from polyethylene (PE). MAE, extracts (semi)volatiles from solid matrices and has been successfully used to extract additives from polyolefins, aroma and flavor compounds from recycled polymers, and oligomers from poly(ethylene terephthalate) (PET). Solvent extractions from aqueous solutions are liquid–liquid extraction (LLE) and solid-phase extraction (SPE). LLE is rapid, but lacks in selectivity, is labor intensive and uses large volumes of organic solvents. SPE is instead suitable for separating volatile and semivolatile compounds and is a physical extraction process involving liquid and a solid phase (sorbent). Examples of separations are degradation products of PE and hydroxyacids in buffer solutions. Solvent-free extraction methods are headspace gas chromatography (HS/GC), solid-phase microextraction (SPME) and supercritical fluid extraction (SFE). HS/GC determines volatile compounds in liquids and solids. SPME is an inexpensive, rapid and solvent-free technique with applications reported for air samples, water and soil, based on 1-cm long, thin fused silica fiber coated with a polymeric stationary phase mounted in a modified syringe. The stationary phase is available in four different kinds. SFE uses a supercrit
本章概述了聚合物和橡胶的气相色谱(质谱)(GC/MS)。气相色谱(GC)分析挥发性有机化合物,其上限为350℃,这意味着要分析的化合物必须在此温度以下挥发。该技术能够分析少量的材料,这意味着它适用于残余单体、引发剂、催化剂、一些添加剂和聚合物的降解产物。它一般不适合分析高分子量或低挥发性的有机化合物。必须注意不要分析反应性物质,这可能会破坏色谱柱或设备的其他部分。在GC/MS之前,必须进行适当的样品制备。灵敏和选择性技术用于从聚合物中分离和提取低分子量有机化合物。样品制备-提取技术可分为(1)从固体基质中溶剂提取,(2)从含有聚合物的水溶液中溶剂提取有机化合物(例如,生理缓冲液中的生物医学植入物)和(3)无溶剂提取方法。一种理想的提取方法是定量、选择性、快速、少溶剂或不使用溶剂。索氏法是从固体样品基质中提取溶剂的古老而传统的方法。然而,索氏法耗时(两到三天并不罕见),无选择性,使用大量溶剂,而且通常不能定量。超声波和微波辅助提取(MAE)更有效。超声波的工作原理是搅动溶液并在液体中产生空化。该技术可用于从聚乙烯(PE)中提取抗氧化剂。MAE是从固体基质中提取(半)挥发物,并已成功地用于从聚烯烃中提取添加剂,从回收聚合物中提取香气和风味化合物,从聚对苯二甲酸乙酯(PET)中提取低聚物。水溶液的溶剂萃取分为液-液萃取(LLE)和固相萃取(SPE)。LLE快速,但缺乏选择性,是劳动密集型的,使用大量的有机溶剂。SPE适用于分离挥发性和半挥发性化合物,是一种涉及液体和固相(吸附剂)的物理萃取过程。分离的例子是PE和羟酸在缓冲溶液中的降解产物。无溶剂萃取方法有顶空气相色谱法(HS/GC)、固相微萃取法(SPME)和超临界流体萃取法(SFE)。HS/GC测定液体和固体中的挥发性化合物。SPME是一种廉价、快速、无溶剂的技术,据报道可用于空气样品、水和土壤,该技术基于1厘米长、薄的熔融二氧化硅纤维,表面涂有聚合物固定相,安装在改良的注射器中。固定相有四种不同的类型。SFE使用超临界流体穿透材料。应用于聚烯烃的抗氧化剂,PE和表面涂层及其原料中吸收的芳香蒸汽。本文报道了在聚合物合成相关化合物、室内环境下聚合物的顶空分析、聚合物在加工温度下的热降解产物、环境降解产物以及塑料和涂料添加剂体系中的应用。
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引用次数: 8
Photoacoustic Spectroscopy in Trace Gas Monitoring 光声光谱在微量气体监测中的应用
Pub Date : 2000-10-30 DOI: 10.1002/9780470027318.A0718
F. Harren, J. Mandon, S. Cristescu
Gas phase spectroscopy is nowadays very common in a wide variety of fields next to chemistry and physics. From research involving living organisms to air pollution monitoring, spectroscopic gas sensors have proven to be indispensable tools. There are various ways of utilizing gas sensors, and each application has different demands. Some applications require a very high sensitivity for one specific gas compound, while others benefit more from sensors able to measure a wide range of gases. A high time resolution is also desirable, as well as selectivity, robustness, and little or no need for sample preparation. This paper discusses photoacoustic spectroscopy as a sensitive, on-line and non-invasive tool to monitor the concentration of trace gases. After a short introduction and a historic overview, attention is focused onto the description of devices and equipment; they determine the detection limits and selectivity. Applications are discussed with emphasis on environmental monitoring, medical applications and biological applications (such as post-harvest physiology, plant physiology, microbiology, and entomology).
如今,气相光谱学在化学和物理之外的许多领域都很常见。从生物研究到空气污染监测,光谱气体传感器已被证明是不可或缺的工具。气体传感器的使用方法多种多样,每种应用都有不同的需求。一些应用要求对一种特定气体化合物具有非常高的灵敏度,而另一些应用则从能够测量广泛气体的传感器中获益更多。高时间分辨率也是理想的,以及选择性,鲁棒性,很少或不需要样品制备。本文讨论了光声光谱法作为一种灵敏、在线、无创的痕量气体浓度监测工具。在简短的介绍和历史概述之后,注意力集中在设备和设备的描述上;它们决定了检测限和选择性。重点讨论了环境监测、医学应用和生物学应用(如收获后生理学、植物生理学、微生物学和昆虫学)。
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引用次数: 110
Paper‐Based Microfluidic Devices 基于纸张的微流体装置
Pub Date : 1900-01-01 DOI: 10.1002/9780470027318.a9732
Bingbing Gao
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引用次数: 0
期刊
Encyclopedia of Analytical Chemistry
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