Non-destructive and in situ identification of rice paper, seals and pigments by FT-IR and XRD spectroscopy

This paper studied the chemical characteristics of rice paper, pigments and seals on Chinese calligraphies and traditional Chinese paintings. The techniques used here were Fourier transform infrared (FT-IR) spectroscopy and X-ray diffraction (XRD). FT-IR allows good identification of the substances present in pigments and inkpads and differentiates each era of rice paper. This can be the base of estimating the age of rice paper. Different crystalline phases can be identified by XRD, which is further evidence to separate different kinds of pigments or inkpads. Both of these methods were non-destructive in situ analysis and can be used in the identification in calligraphies and traditional Chinese paintings. These results confirmed that the applied techniques are relatively quicker and more reliable than traditional approaches authenticated by years of experience.     

Characterization of Paint by Fourier-Transform Infrared Spectroscopy,Raman Microscopy,and Scanning Electron Microscopy-Energy Dispersive X-ray Spectroscopy

The identification of automotive coatings has become important for forensic scientists to trace suspects. Popular automotive coatings include acrylic, amino, alkyd, nitro, and polyurethane paints. Various pigments and additives are added to the coatings, which may create difficulty in characterization of paint evidence. In this study, Fourier-transform infrared spectroscopy, Raman spectroscopy and scanning electron microscopy-energy dispersive X-ray spectroscopy were used to characterize an eleven-layer paint sample. Most layers were only a few micrometers thick. Infrared spectroscopy has several advantages in identifying resins and additives, while Raman is more effective in characterizing additives and inorganic pigments. Scanning electron microscopy-energy dispersive X-ray spectroscopy provides elemental analysis information. The results reveal that the combination of these techniques provides more accurate paint identification than using them separately.     

Identification of low amount of irradiated spices (red pepper,garlic, ginger powder) with luminescence analysis

For the identification of irradiated food, current analysis methods have limitations regarding presence and stability of radiation-induced markers. In this study, different spice blends with small quantity of different irradiated (0, 1 and 10 kGy) spice powders, such as red pepper, garlic or ginger, were investigated using PSL and TL techniques. In PSL-based screening analysis, the spice blends containing 10% of irradiated materials (1 or 10 kGy) were determined as intermediate or positive. In TL results, the blends containing 1% of 1 or 10 kGy-irradiated spices showed the typical TL glow curves that could be interpreted as positive. The blends with irradiated garlic powder provided more good results where identification was possible at 0.5% mixing of irradiated sample. However, the TL ratios of all spice blends were <0.1 and only TL glow curve shape and intensity may be used to discriminate the samples having irradiated component.     

Separation and positive identification of compounds in complex sample mixtures using on-line,LC-UV/VIS and LC-MS,direct coupling techniques

Summary In many analytical separation problems the retention time is not sufficient to identify the compounds of interest. This is especially true with complex mixtures where additional analytical data are necessary to confirm positively the identity of the separated components. An analytical high-pressure liquid chromatograph has been coupled to a UV/Visible spectrophotometer and a mass spectrometer and used for the separation and subsequent identification of compounds in different plant extracts. The results show that the direct combination of HPLC with on-line detection techniques can be successfully used in the analysis of complex mixtures giving positive identification of components and an overall reduction in analysis time.     

A study on retention "projection" as a supplementary means for compound identification by liquid chromatography-mass spectrometry capable of predicting retention with different gradients, flow rates, and instruments

Using current data analysis techniques, even the most advanced LC-MS instrumentation can identify only a small fraction of compounds found in typical biological extracts. Augmenting MS information with HPLC retention information allows many more to be identified. In fact, our calculations indicate that a quadrupole MS is able to identify more compounds than an FTICR-MS when the quadrupole spectrum is augmented with retention information. Unfortunately, retention information is extremely difficult to harness for compound identification. Here, we demonstrate the first use of isocratic data measured on one LC-MS to "project" gradient retention on to different LC-MS systems. Using 35 chemically diverse solutes chosen to encompass the full range of reversed-phase alkylsilica interactions, and using experimental conditions typical of metabolomics experiments, gradient retention was projected from one instrument to another with only 1.2-2.6% error-enough accuracy to considerably improve compound identification. Besides accounting for nonlinear relationships of retention versus solvent composition as well as dead time versus solvent composition, accounting for the precise shape of the gradient profile (not just the dwell volume) improved projection accuracy on one instrument by up to 4 fold whereas flow rate non-idealities likely caused considerable error on the other instrument. Thus, these two factors must be taken into account to accurately project retention on diverse instrumentation.     

Computational methods for remote homolog identification

As more and more protein sequences are available, homolog identification becomes increasingly important for functional, structural, and evolutional studies of proteins. Many homologous proteins were separated a very long time ago in their evolutionary history and thus their sequences share low sequence identity. These remote homologs have become a research focus in bioinformatics over the past decade, and some significant advances have been achieved. In this paper, we provide a comprehensive review on computational techniques used in remote homolog identification based on different methods, including sequence-sequence comparison, and sequence-structure comparison, and structure-structure comparison. Other miscellaneous approaches are also summarized. Pointers to the online resources of these methods and their related databases are provided. Comparisons among different methods in terms of their technical approaches, their strengths, and limitations are followed. Studies on proteins in SARS-CoV are shown as an example for remote homolog identification application.     

Unique Possibilities Offered by Radio-Tracers for Speciation Analysis of Trace Elements in Biological Fluids and Tissues

Speciation analysis of trace elements is the identification and/or measurement of the quantities of one or more individual chemical species in a sample. The general procedure starts with the separation of the species followed by the measurement of trace elements in the different fractions. The identification of the species may be done by UV-detection, mass spectrometry or other techniques. For the development of the methodology, and for in-vivo and in-vitro studies radiotracers are ideally suited. In speciation analysis of trace elements in biological fluids and tissues the search goes on for small inorganic and organometallic compounds, and for metal-protein complexes.     

A comparison of liquid chromatography, capillary electrophoresis, and mass spectrometry methods to determine xyloglucan structures in black currants

Different separation (HPAEC, RP-HPLC, CE) and identification (MALDI-TOF-MS, ESI-MS(n)) techniques were compared to analyse oligosaccharides obtained after incubation of xyloglucan with endo-glucanase. It was possible to analyse xyloglucan oligosaccharides with each technique. Several techniques, including off line (HPAEC-MALDI-TOF-MS) or online (CE-ESI-MS(n), RP-HPLC-ESI-MS(n)) connection provided complementary information on xyloglucan structure. Online CE-MS and RP-HPLC-MS are described for the first time in xyloglucan analysis. Advantages and disadvantages of the techniques for different purposes such as structural characterisation of oligosaccharides or oligosaccharide profiling are discussed. Black currant xyloglucans had a rather simple XXXG-type structure with galactose and fucose containing side chains.     

Use,analysis, and regulation of pesticides in natural extracts,essential oils,concretes, and absolutes

Natural extracts used by the fragrance and cosmetics industries, namely essential oils, concretes, resinoids, and absolutes, are produced from natural raw materials. These are often cultivated by use of monoculture techniques that involve the use of different classes of xenobiotica, including pesticides. Because of these pesticides’ potential effect on public health and the environment, laws regarding permitted residual levels of pesticides used in cultivation of raw materials for fragrance and cosmetic products are expected to become stricter. The purpose of this review is to present and classify pesticides commonly used in the cultivation of these natural raw materials. We will summarize the most recent regulations, and discuss publications on detection of pesticides via chemical analysis of raw natural extracts. Advances in analytical chemistry for identification and quantification of pesticides will be presented, including both sample preparation and modern separation and detection techniques, and examples of the identification and quantification of individual pesticides present in natural extracts, for example essential oils, will be provided.

The identification of fibers by infrared and Raman microspectroscopy

The application of Raman and infrared microspectroscopy to fiber identification has been investigated. Natural and synthetic fibers, both organic and inorganic in nature, can be rapidly characterized by these techniques. In general, it has been found that infrared microspectroscopy offers a nonsubjective method of fiber identification that is quicker, easier, and occasionally, more selective than classical methods. Raman microspectroscopy has also been proven useful for these analyses. It provides low-frequency information, requires virtually no sample preparation, and supplies data complementary to that furnished by infrared microspectroscopy. In many cases one may use these methods for a quick differentiation of fibers of the same type which have undergone different chemical treatments.     

Extraction, separation, and detection methods for phenolic acids and flavonoids

The impetus for developing analytical methods for phenolic compounds in natural products has proved to be multifaceted. Hundreds of publications on the analysis of this category of compounds have appeared over the past two decades. Traditional and more advanced techniques have come to prominence for sample preparation, separation, detection, and identification. This review provides an updated and extensive overview of methods and their applications in natural product matrices and samples of biological origin. In addition, it critically appraises recent developments and trends, and provides selected representative bibliographic examples.     

Comparison of gas chromatography-pulsed flame photometric detection-mass spectrometry, automated mass spectral deconvolution and identification system and gas chromatography-tandem mass spectrometry as tools for trace level detection and identification

The complexity of a matrix is in many cases the major limiting factor in the detection and identification of trace level analytes. In this work, the ability to detect and identify trace level of pesticides in complex matrices was studied and compared in three, relatively new methods: (a) GC-PFPD-MS where simultaneous PFPD (pulsed flame photometric detection) and MS analysis is performed. The PFPD indicates the exact chromatographic time of suspected peaks for their MS identification and provides elemental information; (b) automatic GC-MS data analysis using the AMDIS ("Automated Mass Spectral Deconvolution and Identification System") software by the National Institute of Standards and Technology; (c) GC-MS-MS analysis. A pesticide mixture (MX-5), containing diazinon, methyl parathion, ethyl parathion, methyl trithion and ethion was spiked, in descending levels from 1 ppm to 10 ppb, into soil and sage (spice) extracts and the detection level and identification quality were evaluated in each experiment. PFPD-MS and AMDIS exhibited similar performance, both superior to standard GC-MS, revealing and identifying compounds that did not exhibit an observable GC peak (either buried under the chromatographic background baseline or co-eluting with other interfering GC peaks). GC-MS-MS featured improved detection limits (lower by a factor of 6-8) compared to AMDIS and PFPD-MS. The GC-PFPD-MS-MS combination was found useful in several cases, where no reconstructed ion chromatogram MS-MS peaks existed, but an MS-MS spectrum could still be extracted at the elution time indicated by PFPD. The level of identification and confirmation with MS-MS was inferior to that of the other two techniques. In comparison with the soil matrix, detection limits obtained with the loaded sage matrix were poorer by similar factors for all the techniques studied (factors of 5.8, >6.5 and 4.0 for AMDIS, PFPD-MS and MS-MS, respectively). Based on the above results, the paper discusses the trade-offs between detectivity and identification level with the compared three techniques as well as other more traditional techniques and approaches.     

Peptidomics: the integrated approach of MS, hyphenated techniques and bioinformatics for neuropeptide analysis

MS is currently one of the most important analytical techniques in biological and medical research. ESI and MALDI launched the field of MS into biology. The performance of mass spectrometers increased tremendously over the past decades. Other technological advances increased the analytical power of biological MS even more. First, the advent of the genome projects allowed an automated analysis of mass spectrometric data. Second, improved separation techniques, like nanoscale HPLC, are essential for MS analysis of biomolecules. The recent progress in bioinformatics is the third factor that accelerated the biochemical analysis of macromolecules. The first part of this review will introduce the basics of these techniques. The field that integrates all these techniques to identify endogenous peptides is called peptidomics and will be discussed in the last section. This integrated approach aims at identifying all the present peptides in a cell, organ or organism (the peptidome). Today, peptidomics is used by several fields of research. Special emphasis will be given to the identification of neuropeptides, a class of short proteins that fulfil several important intercellular signalling functions in every animal. MS imaging techniques and biomarker discovery will also be discussed briefly.     

Experiences with infrared microsampling for thin-layer and high-performance liquid chromatography

Summary IR-spectroscopy can assist in the reliable identification of chromatographic analytes. With the direct IR-measurement of TLC and HPLC fractions, the substrate or the eluent, respectively, can render difficulties in the detection of microsamples. After isolation of the analyte, the microsampling for the different separation techniques is the same. Experiences are reported using diffuse reflectance and transmittance measurements from micropellets and enriched solutions in microcells. The performances of the microsampling techniques are compared. For often varying samples, the sample handling presented is more flexible than the different existing interfaces for the coupling of chromatography with IR-spectroscopy.

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Erfahrungen mit der IR-Spektroskopie im Mikrobereich für die Analyse von DC- und HPLC-Fraktionen

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Dedicated to Prof. Dr. W. Fresenius on the occasion of his 75th birthday     

Comparative studies of the leachate of an industrial landfill by gas chromatography-mass spectrometry, liquid chromatography-nuclear magnetic resonance and liquid chromatography-mass spectrometry

Nowadays, the need to have a realistic characterization of industrial effluents in the environment has become more and more recognized. A palette of different analytical methods both for sample extraction and instrumental analysis are available today, some older, others introduced more recently. The aim of this research is to compare a number of these techniques. To do this we studied a real leachate from an industrial landfill and carried out chemical analyses for organic pollutants, using different extraction methods based on solid-phase extraction and solid-phase microextraction and different instrumental techniques such as GC-MS, LC-MS, NMR and LC-NMR. Results show the performances of the different techniques, which are complementary.     

Comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometric detection for the trace analysis of flavour compounds in food

The practicability and potential of comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GC x GC-TOF-MS) for the analysis of complex flavour mixtures in food were studied. With the determination of key flavour targets in dairy samples as an example, it was demonstrated that GC x GC dramatically improves the separation. As a consequence, identification and, more importantly, quantification down to the ng/g level can be performed more reliably: background interferences largely disappear. Next to the peak table generated from the GC-TOF-MS software after data processing, the additional use of well-ordered patterns in the 2D-plane and information from second-dimension retention times can substantially help the identification of unknowns. The technique was successfully used for an evaluation of extraction techniques and the characterisation of different types of samples.     

Use of matrix-assisted laser desorption/ionization time-of-flight mass mapping and nanospray liquid chromatography/electrospray ionization tandem mass spectrometry sequence tag analysis for high sensitivity identification of yeast proteins separated by two-dimensional gel electrophoresis

Current analytical techniques in protein identification by mass spectrometry are based on the generation of peptide mass maps or sequence tags that are idiotypic for the protein sequence. This work reports on the development of the use of mass spectrometric methods for protein identification in research on metabolic pathways of a genetically modified strain of the baker's yeast Saccharomyces cerevisiae. This study describes the use of matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass mapping and liquid chromatography/quadrupole time-of-flight electrospray ionization tandem mass spectrometry (LC/Q-TOF-ESI-MS/MS) sequence tag analysis in identification of yeast proteins separated by two-dimensional polyacrylamide gel electrophoresis (2D-PAGE). The spots were selected for analysis in order to collect information for future studies, to cover the whole pI range from 3 to 10, and to evaluate information from spots of different intensities. Mass mapping as a rapid, high-throughput method was in most cases sensitive enough for identification. LC/MS/MS was found to be more sensitive and to provide more accurate data, and was very useful when analyzing small amounts of sample. Even one sequence tag acquired by this method could be enough for unambiguous identification, and, in the present case, successfully identified a point mutation.     

Discriminating animal fats and their origins: assessing the potentials of Fourier transform infrared spectroscopy,gas chromatography,immunoassay and polymerase chain reaction techniques

The objective of the reported study was to assess the abilities of various methods to differentiate the sources of fats used in feedstuff formulations. The main target was the identification of tallow (ruminant fat) and its differentiation from non-ruminant fats. Four different techniques were compared in terms of their suitability for enforcing existing and upcoming legislation on animal by-products: (1) Fourier transform infrared spectroscopy (FT-IR) applied to fat samples, (2) gas chromatography coupled with mass spectrometry (GC–MS) to determine fatty acid profiles, (3) immunoassays focusing on the protein fraction included in the fat, and (4) polymerase chain reaction (PCR) for the detection of bovine-specific DNA. Samples of the different fats and oils as well as mixtures of these fats were probed using these analytical methods. FT-IR and GC–MS differentiated pure fat samples quite well but showed limited ability to identify the animal species or even the animal class the fat(s) belonged to; no single compound or spectral signal that could permit species identification could be found. However, immunoassays and PCR were both able to identify the species or groups of species that the fats originated from, and they were the only techniques able to identify low concentrations of tallow in a mixture of fats prepared by the rendering industry, even when the samples had been sterilised at temperatures >133 °C. Fats used in animal nutrition come mainly from the rendering industry, thereby confirming the suitability of PCR and immunoassays for their identification. However, neither of these latter techniques was able to detect premier jus tallow, representing the highest quality standard of fat with extremely low protein concentration.     

双原子催化剂:制备、表征和应用

发展可持续和清洁的电化学能源转化技术是应对能源短缺和环境污染挑战的关键一步,燃料电池、电解电池和金属空气电池作为清洁能源储存和转换装置目前得到广泛应用推广,这些装置依靠电催化反应以及电极材料上发生的电荷转移过程来转换电能和化学能.而电催化剂是该类装置电极材料的核心部件,电催化反应的热力学和动力学过程与电催化剂的物理性质和化学状态密切相关.因此探索和开发性能优良、成本低廉的新型电催化剂,将进一步促进这些能源转化技术的商业化应用.单原子催化剂(SACs)以其暴露的活性位点、高选择性和最大限度地原子利用率而受到人们的广泛关注.然而,随着单原子表面自由能的增加,粒子在制备和催化过程中的聚集,催化活性位点的降低和催化剂负荷的相对较低,严重制约了SACs的发展和应用.考虑到SACs的缺点,为了进一步增加单原子活性位点的数量和负载,双原子催化剂(DACs)作为SACs家族成员的扩展近年来逐渐兴起,且两种金属原子(同核/异核)在DACs中的协同作用显著提高了催化剂的催化活性.本文基于当前最新的研究工作对比了同核/异核DACs的不同优势,列举了一系列包括原子层沉积法、湿化学吸附法以及高温热处理法等方法用于制备性能优异的DACs,其中高温热处理法因应用广泛被重点强调.同时,本文也对DACs的表征和识别手段进行了重点概括,包含XANES, EXAFS, IR, DFT等;详细概括和对比了当前DACs在电化学方面的主要应用,如氧还原反应(ORR)和二氧化碳还原反应.目前, DACs作为一个新兴的研究领域,由于其金属原子负载量高、活性位点比SACs更为灵活,已经在电催化领域取得了快速的发展.相对于同核DACs,原则上不同的两个金属原子会组成更多的异核DACs,因此,对于性能优异的异核DACs还有更多的可能性值得深入探索.可以预见, DACs的发展将弥补SACs的不足,在电化学能源的转换和储存方面发挥全面的优势;借助于异核DACs中不同的两个金属原子的多样性,探索以过渡金属为主的DACs,将会为节约贵金属资源及环境保护带来巨大贡献,进一步设计和优化DACs,有利于燃料电池和金属-空气电池创造出更大的经济效益和社会效益.因此,我们相信DACs的发展将成为材料研究的一个新前沿,并为合成更多的高效应用催化剂开辟一条新的途径.     

Classification of coordination polygons and polyhedra according to their mode of self-assembly

This work extends techniques for the controlled formation of synthetic molecular containers by metal-mediated self-assembly. A new classification system based on the self-assembly of such species is proposed. The system: 1) allows a systematic identification of suitable acceptor-donor combinations, 2) widens the variety of design possibilities available, 3) allows a ready comparison of the self-assembly of different compounds, 4) reveals useful commonalities between different compounds, 5) aids in the development of novel architectures, and 6) permits identification of systems capable of being switched back-and-forth between architectures.