Rapid Methods in Analytical Chemistry

This article presents the most recent research in analytical chemistry concerning the development of rapid methodologies covering the period from 2009 up until today. In this context, different useful analytical methods have been developed based mainly on typical techniques such as gas chromatography, liquid chromatography, mass spectrometry, electrophoresis, electroanalytical chemistry, and biosensors. The analytical features of these methods have allowed the analysis of samples of different natures, such as environmental, food, pharmaceutical, and biological type, in which wide classes of analytes are promptly determined. The main advantages of these methods are included and discussed in this review regarding novelty, rapidity, sensitivity, selectivity, and costs. It is concluded that the development of rapid methods is still a growing trend in analytical chemistry and that gas- and liquid-chromatography mainly coupled to different modes of mass spectrometry are the most common analytical techniques applied today. Regarding the matrices analyzed, most of the methods have been developed for food analysis, followed by biological and environmental matrices.     

The application of electrospray ionization coupled to ultrahigh resolution mass spectrometry for the molecular characterization of natural organic matter

Mass spectrometry has recently played a key role in the understanding of natural organic matter (NOM) by providing molecular-level details about its composition. NOM, a complex assemblage of organic molecules present in natural waters and soils/sediments, has the ability to bind and transport anthropogenic materials. An improved understanding of its composition is crucial in order to understand how pollutants interact with NOM and how NOM cycles through global carbon cycles. In the past, low-resolution (>3000) mass analyzers have offered some insights into the structure of NOM, but emerging ultrahigh resolution (>200,000) techniques such as electrospray ionization (ESI) coupled to Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) have significantly advanced our knowledge of NOM chemistry. Here, a review of the recent literature on the advancements of NOM characterization and the applications of mass spectrometry to this central task is presented. Various methods for the analysis and display of the extremely complex mass spectra, such as the van Krevelen diagram and Kendrick mass defect analysis, are discussed. We also review tandem mass spectrometry techniques employed to gain structural information about NOM components. Finally, we show how ESI-FT-ICR-MS has been applied to examine specific issues that are important to the NOM scientific community, such as NOM reactivity, transport and fate, degradation, and existence of components, which are indicators of NOM origin. In general, ultrahigh resolution provided by FT-ICR-MS is essential for the complete separation of the thousands of peaks present in the complex NOM mixture and will clearly lead to additional future advancements in the areas of aquatic, soil, and analytical chemistry.     

On-line sample processing involving microextraction techniques as a front-end to atomic spectrometric detection for trace metal assays: A review

Within the last decade, liquid-phase microextraction (LPME) and micro-solid phase extraction (μSPE) approaches have emerged as substitutes for conventional sample processing procedures for trace metal assays within the framework of green chemistry. This review surveys the progress of the state of the art in simplification and automation of microextraction approaches by harnessing to the various generations of flow injection (FI) as a front end to atomic absorption spectrometry (AAS), atomic fluorescence spectrometry (AFS) or inductively coupled plasma atomic emission spectrometry or mass spectrometry (ICP-AES/MS). It highlights the evolution of flow injection analysis and related techniques as vehicles for appropriate sample presentation to the detector and expedient on-line matrix separation and pre-concentration of trace levels of metals in troublesome matrices. Rather than being comprehensive this review is aimed at outlining the pros and cons via representative examples of recent attempts in automating green sample preparation procedures in an FI or sequential injection (SI) mode capitalizing on single-drop microextraction, dispersive liquid-phase microextraction and advanced sorptive materials including carbon and metal oxide nanoparticles, ion imprinted polymers, superparamagnetic nanomaterials and biological/biomass sorbents. Current challenges in the field are identified and the synergetic combination of flow analysis, nanotechnology and metal-tagged biomolecule detection is envisaged.     

Applications of mass spectrometry in the trace element analysis of biological materials

The importance of mass spectrometry for the analysis of biological material is illustrated by reviewing the different mass spectrometric methods applied and describing some typical applications published recently. Though atomic absorption spectrometry is used in the majority of analyses of biological material, most mass spectrometric methods have been used to some extent for trace element determination in biomedical research. The relative importance of the different methods is estimated by reviewing recent research papers. It is striking that especially inductively coupled plasma mass spectrometry is increasingly being applied, partly because the method can be used on-line after chromatographic separation, in speciation studies. Mass spectrometric methods prove to offer unique possibilities in stable isotope tracer studies and for this purpose also experimentally demanding methods such as thermal ionization mass spectrometry and accelerator mass spectrometry are frequently used.     

A brief introduction to analytical methods in nuclear forensics

Nuclear forensic (NF) techniques are critical in responding to both environmental releases of nuclear materials and illicit trafficking activities involving both nuclear and counterfeit materials. Despite rising need, however, significant barriers exist to the future success of such research. This subset of analytical chemistry contains unique concerns (e.g. chronometry and impurity signatures), a wide variety of preparatory/instrumental approaches, and is in need of innovative solutions to current problems both in and out of the lab. The present work introduces existing NF research, development challenges and notes potential areas for advancement by highlighting several key analytical approaches. Examples of concerns and techniques discussed in this review include: chronometry, reference materials, separations, counting spectrometry, mass spectrometry and more.     

History of gas chromatography

Modern gas chromatography (GC) was invented by Martin and James in 1952 [1], and has become one of the most important and widely applied analytical techniques in modern chemistry. Major milestones in the development of GC, especially in column technology, detection and sample introduction are described in this historical review. Many trends in current progress can be seen to originate in the first two decades of the history of GC, but the invention of fused-silica capillary columns greatly increased the application of high-resolution GC across the field of organic analysis; the development of low-cost, bench-top mass spectrometers led to further advances. Progress continues to be rapid in comprehensive 2D GC, fast analysis, detection by atomic emission and time-of-flight mass spectrometry, and in applications to process analysis.     

Nanoparticles,Proteins, and Nucleic Acids: Biotechnology Meets Materials Science

Based on fundamental chemistry, biotechnology and materials science have developed over the past three decades into today's powerful disciplines which allow the engineering of advanced technical devices and the industrial production of active substances for pharmaceutical and biomedical applications. This review is focused on current approaches emerging at the intersection of materials research, nanosciences, and molecular biotechnology. This novel and highly interdisciplinary field of chemistry is closely associated with both the physical and chemical properties of organic and inorganic nanoparticles, as well as to the various aspects of molecular cloning, recombinant DNA and protein technology, and immunology. Evolutionary optimized biomolecules such as nucleic acids, proteins, and supramolecular complexes of these components, are utilized in the production of nanostructured and mesoscopic architectures from organic and inorganic materials. The highly developed instruments and techniques of today's materials research are used for basic and applied studies of fundamental biological processes.     

Direct, rapid quantitative analyses of BVOCs using SIFT-MS and PTR-MS obviating sample collection

The purpose of this short review is to describe the origins and the principles of operation of selected-ion flow-tube mass spectrometry (SIFT-MS) and proton-transfer-reaction mass spectrometry (PTR-MS), and their application to the analysis of biogenic volatile organic compounds (BVOCs) in ambient air, the humid air (headspace) above biological samples, and other samples. We briefly review the ion chemistry that underpins these analytical methods, which allows accurate analyses. We pay attention to the inherently uncomplicated sampling methodologies that allow on-line, real-time analyses, obviating sample collection into bags or onto traps, which can compromise samples.Whilst these techniques have been applied successfully to the analysis of a wide variety of media, we give just a few examples of data, including for the analysis of BVOCs that are present in tropospheric air and those emitted by plants, in exhaled breath and in the headspace above cell and bacterial cultures (which assist clinical diagnosis and therapeutic monitoring), and the products of combustion. The very wide dynamic ranges of real-time analyses of BVOCs in air achieved by SIFT-MS and PTR-MS - from sub-ppbv to tens of ppmv - ensure that these analytical methods will be applied to many other media, especially when combined with gas-chromatography methods, as recently trialed.     

单一稀土元素检测方法的新近进展

本文对1999～2004年间有关单一稀土元素检测方法的研究进展进行了综述,内容包括原子吸收/原子荧光光谱法,荧光光度法,X-射线荧光光谱法,中子活化分析,电感耦合等离子体原子发射光谱法、电感耦合等离子体质谱法以及其干扰效应、进样技术和分析应用.引用文献127篇.     

Determination of metals in biofluids and tissues: sample preparation methods for atomic spectroscopic techniques

Several sample preparation methods unique to each instrumental technique exist for the elemental analysis of biological specimens, but no review or book has dealt with them. The present review is an attempt to fill this void and focuses on sample preparation methods unique to atomic and X-ray spectroscopic techniques. The techniques covered are: flame and electrothermal AAS, inductively coupled plasma atomic emission spectrometry (ICP-AES), inductively coupled plasma mass spectrometry (ICP-MS) and X-ray fluorescence spectrometry (XRF) since these are most commonly used in trace element analysis of biological materials. The intent is not to present the procedural details for the various tissues or elements, but rather to highlight the methods which are unique to each instrument. The bibliography accompanying this review should aid the analytical chemist in his/her search for the detailed preparation protocols.     

模式识别在食品质量控制方面的应用进展

本文介绍了食品质量研究中常用的一些化学模式识别方法的基本原理,并介绍了模式识别结合红外、原子吸收、原子发射、气相色谱、液相色谱、质谱、电子鼻传感器等检测技术在食品质量控制中的应用.对化学计量学在食品质量控制中的应用前景作了展望.     

Novel analytical methods for characterising binding media and protective coatings in artworks

Since the first reported analytical studies and technical examinations of art and archaeological objects conducted in the late 18th century, analytical techniques and methods applied to the study of artworks have constantly grown. Among the materials composing the art object, organic compounds used as binding media or protective coatings have attracted the attention of the conservation profession given their noticeable ability for undergoing morphological and chemical changes on ageing. Thus, the aim of this paper is to review the most recent advances in the identification and determination of organic compounds present in art and art conservation materials. Immunofluorescence techniques have been proposed in recent decades as an alternative to the classical and simpler microchemical tests. Besides, a variety of instrumental techniques have also been improved in an attempt to enhance the sensitivity, repeatability and accuracy of the analytical results. Spectroscopic techniques, such as UV-vis, FTIR and Raman spectroscopy, have been coupled with light microscopes for these purposes. Synchrotron radiation FTIR microspectroscopy has also been successfully applied to the analysis of artworks. Mass spectrometry has also been increasingly used as a detector system coupled with a chromatographic device. Chromatographic methods have also improved in recent years. Paper and thin layer chromatographic techniques have been progressively replaced with gas chromatography (GC), pyrolysis-GC, high performance liquid chromatography and capillary electrophoresis. More complex proteomics hyphenated techniques, such as nano-liquid chromatography-nano-electrospray ionisation/collision quadrupole time-of-flight tandem mass spectrometry, have been recently applied to the identification and determination of proteinaceous binders. Microbeam analytical techniques have also been incorporated into the list of advanced instrumental techniques for art conservation purposes. Finally, a number of new instrumental techniques have been proposed as a suitable alternative to the conventional microscopy techniques for morphological studies.     

Recent developments in synchrotron vacuum ultraviolet photoionization coupled to mass spectrometry

In recent years, increasing attention has been paid to “soft” photoionization (PI), which will potentially become a standard, universal ionization method. Tunable synchrotron vacuum ultraviolet (SVUV) light, a quasi-continuous light with good energy resolution and high photon flux, has proved an ideal source for “soft” PI in various research fields (e.g., combustion chemistry and molecular imaging).This review focuses on combinations of SVUV light with commonly used techniques (e.g., molecular-beam sampling, laser desorption, ion desorption, and thermal vaporization). These couplings have successful applications in flame chemistry, organic analysis, chemical imaging and aerosol mass spectrometry.     

Characterisation and quantification of organic phosphorus and organic nitrogen components in aquatic systems: a review

This review provides a critical assessment of knowledge regarding the determination of organic phosphorus (OP) and organic nitrogen (ON) in aquatic systems, with an emphasis on biogeochemical considerations and analytical challenges. A general background on organic phosphorus and organic nitrogen precedes a discussion of sample collection, extraction, treatment/conditioning and preconcentration of organic phosphorus/nitrogen from sediments, including suspended particulate matter, and waters, including sediment porewaters. This is followed by sections on the determination of organic phosphorus/nitrogen components. Key techniques covered for organic phosphorus components are molecular spectrometry, atomic spectrometry and enzymatic methods. For nitrogen the focus is on the measurement of total organic nitrogen concentrations by carbon hydrogen nitrogen analysis and high temperature combustion, and organic nitrogen components by gas chromatography, high-performance liquid chromatography, gel electrophoresis, mass spectrometry, nuclear magnetic resonance spectrometry, X-ray techniques and enzymatic methods. Finally future trends and needs are discussed and recommendations made.     

Selenoproteins: the key factor in selenium essentiality. State of the art analytical techniques for selenoprotein studies

Selenium is an essential element for human health. The benefits of selenium are many including protection against cancer, heart diseases and other cardiovascular and muscle disorders. Selenium is also helpful in controlling gastrointestinal disorders, enhancing immunity of the human body and reducing age-related diseases. The health-promoting properties of Se are due to vital functions of selenoproteins in which selenium is present as selenocysteine, the 21st amino acid. To date, dozens of selenoprotein families have been described though many have roles that have not been fully elucidated. Selenoproteins research has attracted tremendous interest from different scientific areas. Analytical chemists have not remained indifferent to the attractive features of these unique proteins. Different analytical techniques, such as multidimensional chromatography–inductively coupled plasma mass spectrometry (ICPMS), electrospray (tandem) mass spectrometry (ESI-MS/MS), matrix-assisted laser desorption ionization time-of flight (MALDI-TOF) and sodium dodecyl sulphate polyacrylamide gel electrophoresis–laser ablation inductively coupled plasma mass spectrometry (SDS-PAGE-LA-ICPMS), have been applied to the determination of selenoproteins and selenium-containing proteins. This review describes the best-characterized selenoproteins to date in addition to the major contributions of analytical chemistry to the field of selenoproteins. The article also highlights the challenges of combining elemental and molecular mass spectrometry for the determination of selenoproteins and selenium-containing proteins.     

Tandem mass spectrometry of synthetic polymers

The detailed characterization of macromolecules plays an important role for synthetic chemists to define and specify the structure and properties of the successfully synthesized polymers. The search for new characterization techniques for polymers is essential for the continuation of the development of improved synthesis methods. The application of tandem mass spectrometry for the detailed characterization of synthetic polymers using the soft ionization techniques matrix‐assisted laser desorption/ionization mass spectrometry (MALDI‐MS) and electrospray ionization mass spectrometry (ESI‐MS), which became the basic tools in proteomics, has greatly been increased in recent years and is summarized in this perspective. Examples of a variety of homopolymers, such as poly(methyl methacrylate), poly(ethylene glycol), as well as copolymers, e.g. copolyesters, are given. The advanced mass spectrometric techniques described in this review will presumably become one of the basic tools in polymer chemistry in the near future. Copyright © 2009 John Wiley & Sons, Ltd.     

Metallomics: An integrated biometal science

Metallomics is an emerging scientific area integrating the research fields related to the understanding of the molecular mechanisms of metal-associated life processes and the entirety of metal and metalloid species within a cell or tissue type. In metallomics, metalloproteins, metalloenzymes and other metal-containing biomolecules in a biological system are referred to as metallomes, similar to genomes and proteomes in genomics and proteomics, respectively. This review discusses the concept of metallomics with a focus on analytical techniques and methods, particularly the so-called hyphenated techniques which combine a high-resolution separation technique (gel electrophoresis/laser ablation, chromatography or capillary electrophoresis) with a highly sensitive detection method such as elemental (inductively coupled plasma, ICP) or molecular (electron spray ionization (ESI) or matrix-assisted laser desorption/ionization (MALDI)) mass spectrometry, or nuclear X-ray fluorescence/absorption spectrometry. The applications of these advanced analytical methods in the identification of metallo-/phospho-/seleno-proteins, probing of relationships between structure and function of metalloproteins, and study of clinically used metallodrugs will be selectively outlined, along with their advantages and limitations.     

基础有机化学实验教学内容的改革探索

对基础有机化学实验的教学内容进行了全方位、系统化的改革探索。对传统有机化学实验内容,增加了新的知识和实验技术。将有机人名反应、优秀的科研成果改编成新的实验教学项目,同时增设了新的微型实验、绿色实验、原子经济反应实验、全英实验。该实验内容新体系经过多年的教学实践,教学效果有显著提高。     

Recent developments in detection for microfluidic systems

Microfluidic systems have become more and more important in the field of analytical chemistry. Detection methods on these microsystems are essential for the identification and quantification of chemical species that are being analyzed. This review concentrates on the latest developments of optical detection methods and mass spectrometry in conjunction with microfluidic systems. Electrochemical methods are discussed in another review in the same issue of this journal. Within the optical detection section, topics such as multiplexed detection and the use of waveguides are discussed. Within the discussion of mass spectrometry, the main focus is on electrospray emitters as interfaces between microsystem and spectrometer. Apart from optical detection and mass spectrometry, other techniques such as flame ionization and nuclear magnetic resonance are also mentioned.     

Solid-phase extraction in the determination of gold, palladium, and platinum

A simple classification of various sorbents and solid-phase extraction procedures used for preconcentration of trace levels of Au, Pd, and Pt from different sample types is proposed in this review article. The large variety of available sorbents/procedures has been organized according to expected mechanisms of sorption process (complex formation; ion exchange; adsorption; ion-imprinted or molecularly imprinted polymers); according to the kind of monomeric units of the polymer matrix as well as on the basis of the kind of functional group responsible for main performance characteristics (selectivity, capacity) of the sorbent. Advantages of chemically modified sorbents, sulfur-containing sorbent extractants, and ion-imprinted polymers, together with rational pretreatment by means of microwave treatments, scaling down of enrichment, and quantification by means of flow and flow injection approaches are given. Preferred instrumental techniques for quantification of ppb levels of Au, Pd, and Pt in prepared concentrates/column eluates are multielement instrumental techniques: inductively coupled plasma optical emission spectrometry (ICP-OES), and inductively coupled plasma mass spectrometry (ICPMS). Excellent limits of detection at picogram levels of these analytes are provided by electrothermal atomic absorption spectrometry (ETAAS), generally in single-element mode and the neutron activation analysis (NAA), while X-ray fluorescence spectrometry and flame AAS are rarely applied because of lack of sensitivity at sub-ppm levels of Au, Pd, and Pt. Some problems of atomic spectrometric quantification techniques and their representative limits of detection are given. Recent applications to geological, industrial, pharmaceutical, biological, and other materials are tabulated. References have been selected mostly from the period 1995 to 2010.