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Complex Samples (complex + sample)
Selected AbstractsThe Impact of CHIP on Children's Insurance Coverage: An Analysis Using the National Survey of America's FamiliesHEALTH SERVICES RESEARCH, Issue 6 2009Lisa Dubay Objective. To assess the impact of the Children's Health Insurance Program (CHIP) on the distribution of health insurance coverage for low-income children. Data Source. The primary data for the study were from the 1997, 1999, and 2002 National Survey of America's Families (NSAF), which includes a total sample of 62,497 children across all 3 years, supplemented with data from other data sources. Study Design. The study uses quasi-experimental designs and tests the sensitivity of the results to using instrumental variable and difference-in-difference approaches. A detailed Medicaid and CHIP eligibility model was developed for this study. Balanced repeated replicate weights were used to account for the complex sample of the NSAF. Descriptive and multivariate analyses were conducted. Principle Findings. The results varied depending on the approach utilized but indicated that the CHIP program led to significant increases in public coverage (14,20 percentage points); and declines in employer-sponsored coverage (6,7 percentage points) and in uninsurance (7,12 percentage points). The estimated share of CHIP enrollment attributable to crowd-out ranged from 33 to 44 percent. Smaller crowd-out effects were found for Medicaid-eligible children. Conclusions. Implementation of the CHIP program resulted in large increases in public coverage with estimates of crowd-out consistent with initial projections made by the Congressional Budget Office. This paper demonstrates that public health insurance expansions can lead to substantial reductions in uninsurance without causing a large-scale erosion of employer coverage. [source] Modelling Overdispersion for Complex Survey DataINTERNATIONAL STATISTICAL REVIEW, Issue 3 2001E.A. Molina Summary The population characteristics observed by selecting a complex sample from a finite identified population are the result of at least two processes: the process which generates the values attached to the units in the finite population, and the process of selecting the sample of units from the population. In this paper we propose that the resulting observations by viewed as the joint realization of both processes. We overcome the inherent difflculty in modelling the joint processes of generation and selection by exploring second moment and other simplifying assumptions. We obtain general expressions for the mean and covariance function of the joint processes and show that several overdispersion models discussed in the literature for the analysis of complex surveys are a direct consequence of our formulation, undere particular sampling schemes and population structures. Résumé Les caracté d'une population sont observées grâce à un échantillon complexe sélectionnéâ partir d'une poplation finie. Ces caractéristiques sont le résultat de l'échantillon des unités de ette population. Dans cet article, nous considérons que l'observation globale peut être vue comme une réalisation simultanée de ces deux processus. Nous tentons de surmonter la difficulté intrinsèque liée à la modélisation du double processus de génération et de sélection par une étude du moment d'ordre deux et en considérant d'autres hypothèses simplificatrices. Nous obtenons une expression générale pour la moyenne et la covariance liée au sondage complexes, sont une conséquence directe de notre formulation, losque l'on considère un plan de sondage particulier et une population ayant une structure spécifique. [source] Fast GC analysis with a 50 ,m ID column: theory, practical aspects, and application to a highly complex sampleJOURNAL OF SEPARATION SCIENCE, JSS, Issue 14 2004Luigi Mondello Abstract This research focuses on the minimization of GC analysis times through the use of a 5 m×0.05 mm ID×0.05 ,m (film thickness) column. Experimental minimum plate height (Hmin) and optimum linear velocity values were derived from standard compound applications, under various analytical conditions, and then related to classical chromatographic theory. Deviations from the latter are measured and discussed. Practical aspects linked to the use of such capillaries, such as column sample capacity and detector acquisition rates, are also considered. Furthermore, a fast, and what can be considered a very fast method, were applied to the separation of a fuel sample. Coefficients of variation of elution times and relative peak areas were calculated in the very fast application. All analytical results are compared with those obtained by conventional 0.25 mm ID column applications. [source] Determination of organic acids in urine by solid-phase microextraction and gas chromatography,ion trap tandem mass spectrometry previous ,in sample' derivatization with trimethyloxonium tetrafluoroborateBIOMEDICAL CHROMATOGRAPHY, Issue 10 2008Marco Pacenti Abstract A method for the determination of the organic acids directly in the urine employing derivatization with trimethyloxonium tetrafluoroborate as a methylating agent and sequential extraction by head space and direct immersion/solid phase microextraction is reported. Furoic acid, hippuric acid, methylhippuric acid, mandelic acid, phenylglyoxylic acid and trans, trans muconic acid contained in urine and proposed by the American Conference of Governmental Industrial Hygienists as biological exposure indices were determined after a fast and economically convenient preparation step and sensitive gas chromatography,ion trap,mass spectrometry/tandem mass spectrometry analysis. Urine is rather a complex sample and hence the acquisition method required specific GC-MS instrumentation capable of supporting the changeover, fully automated during a single chromatographic separation, from mass to tandem mass spectrometry and both chemical and electron ionization modes. The automation of the analytical method provides a number of advantages, including reduced analysis time for both routine analysis and method development, and greater reproducibility. The equilibrium and kinetics of this substances vs head space/direct immersion-solid phase microextraction were investigated and evaluated theoretically. Copyright © 2008 John Wiley & Sons, Ltd. [source] Electroanalytical Determination of Promethazine Hydrochloride in Pharmaceutical Formulations on Highly Boron-Doped Diamond Electrodes Using Square-Wave Adsorptive VoltammetryELECTROANALYSIS, Issue 18 2008Francisco, Wirley Abstract The electrochemical oxidation of promethazine hydrochloride was made on highly boron-doped diamond electrodes. Cyclic voltammetry experiments showed that the oxidation mechanisms involved the formation of an adsorbed product that is more readily oxidized, producing a new peak with lower potential values whose intensity can be increased by applying the accumulation potential for given times. The parameters were optimized and the highest current intensities were obtained by applying +0.78,V for 30 seconds. The square-wave adsorptive voltammetry results obtained in BR buffer showed two well-defined peaks, dependent on the pH and on the voltammetric parameters. The best responses were obtained at pH,4.0, frequency of 50,s,1, step of 2,mV, and amplitude of 50,mV. Under these conditions, linear responses were obtained for concentrations from 5.96×10,7 to 4.76×10,6,mol L,1, and calculated detection limits of 2.66×10,8,mol L,1 (8.51,,g L,1) for peak 1 and of 4.61×10,8,mol L,1 (14.77,,g L,1) for peak 2. The precision and accuracy were evaluated by repeatability and reproducibility experiments, which yielded values of less than 5.00% for both voltammetric peaks. The applicability of this procedure was tested on commercial formulations of promethazine hydrochloride by observing the stability, specificity, recovery and precision of the procedure in complex samples. All results obtained were compared to recommended procedure by British Pharmacopeia. The voltammetric results indicate that the proposed procedure is stable and sensitive, with good reproducibility even when the accumulation steps involve short times. It is therefore very suitable for the development of the electroanalytical procedure, providing adequate sensitivity and a reliable method. [source] Cationic and anionic lipid-based nanoparticles in CEC for protein separationELECTROPHORESIS, Issue 11 2010Christian Nilsson Abstract The development of new separation techniques is an important task in protein science. Herein, we describe how anionic and cationic lipid-based liquid crystalline nanoparticles can be used for protein separation. The potential of the suggested separation methods is demonstrated on green fluorescent protein (GFP) samples for future use on more complex samples. Three different CEC-LIF approaches for protein separation are described. (i) GFP and GFP N212Y, which are equally charged, were separated with high resolution by using anionic nanoparticles suspended in the electrolyte and adsorbed to the capillary wall. (ii) High efficiency (800,000 plates/m) and peak capacity were demonstrated separating GFP samples from Escherichia coli with cationic nanoparticles suspended in the electrolyte and adsorbed to the capillary wall. (iii) Three single amino-acid-substituted GFP variants were separated with high resolution using an approach based on a physical attached double-layer coating of cationic and anionic nanoparticles combined with anionic lipid nanoparticles suspended in the electrolyte. The soft and porous lipid-based nanoparticles were synthesized by a one-step procedure based on the self-assembly of lipids, and were biocompatible with a large surface-to-volume ratio. The methodology is still under development and the optimization of the nanoparticle chemistry and separation conditions can further improve the separation system. In contrast to conventional LC, a new interaction phase is introduced for every analysis, which minimizes carry-over and time-consuming column regeneration. [source] CE coupled to MALDI with novel covalently coated capillariesELECTROPHORESIS, Issue 4 2010Stefan Bachmann Abstract CE offers the advantage of flexibility and method development options. It excels in the area of separation of ions, chiral, polar and biological compounds (especially proteins and peptides). Masking the active sites on the inner surface of a bare fused silica capillary wall is often necessary for CE separations of basic compounds, proteins and peptides. The use of capillary surface coating is one of the approaches to prevent the adsorption phenomena and improve the repeatability of migration times and peak areas of these analytes. In this study, new capillary coatings consisting of (i) derivatized polystyrene nanoparticles and (ii) derivatized fullerenes were investigated for the analysis of peptides and protein digest by CE. The coated capillaries showed excellent run-to-run and batch-to-batch reproducibility (RSD of migration time ,0.5% for run-to-run and ,9.5% for batch-to-batch experiments). Furthermore, the capillaries offer high stability from pH 2.0 to 10.0. The actual potential of the coated capillaries was tested by combining CE with MALDI-MS for analysing complex samples, such as peptides, whereas the overall performance of the CE-MALDI-MS system was investigated by analysing a five-protein digest mixture. Subsequently, the peak list (peptide mass fingerprint) generated from the mass spectra of each fraction was entered into the Swiss-Prot database in order to search for matching tryptic fragments using the MASCOT software. The sequence coverage of analysed proteins was between 36 and 68%. The established technology benefits from the synergism of high separation efficiency and the structure selective identification via MS. [source] Electrical field-assisted solid-phase extraction coupled on-line to capillary electrophoresis-mass spectrometryELECTROPHORESIS, Issue 10 2008Gabriel Morales-Cid Abstract A substantial demand currently exists for analytical methods affording the determination of very low concentrations of analytes in complex matrices, such as those of environmental and biological samples, as simply as possible. However, the pretreatment of complex samples, which is unavoidable prior to CE-MS analysis, is usually complicated and time-consuming. In this work, we used voltage-assisted SPE for the first time as an alternative to conventional treatments for preconcentrating and purifying analytes. To this end, we used a simple flow system coupled on-line to CE-MS equipment. The system is quite robust and provides reproducible peak areas (the precision ranges from 2.5 to 3.8%). Also, it provides increased sensitivity affording the determination of trace amounts (nanogram per liter levels) of analytes in only a few milliliters of sample. The proposed system was applied to the determination of members of two compound families (viz. tetracyclines and amines). [source] Rapid capillary electrophoresis time-of-flight mass spectrometry separations of peptides and proteins using a monoquaternarized piperazine compound (M7C4I) for capillary coatingsELECTROPHORESIS, Issue 8 2008Anisa Elhamili Abstract A monoquaternarized piperazine, 1-(4-iodobutyl) 4-aza-1-azoniabicyclo[2,2,2] octane iodide (M7C4I), has been evaluated as a surface derivatization reagent for CE in combination with TOF MS for the analysis of proteins, peptides, and protein digests. The M7C4I piperazine, at alkaline pH, forms a covalent bond via alkylation of the ionized silanols producing a cationic surface with a highly stable and reversed EOF. The obtained surface yields rapid separations (less than 5,min) of peptides and proteins at acidic pH with high separation efficiencies (up to 1.1×106 plates/m for peptides and up to 1.8×106 plates/m for proteins) and no observed bleeding of the coating reagent into the mass spectrometer. The simplicity of the coating procedure also enables fast (2,min) regeneration of the surface, if necessary. This is useful in the analysis of complex samples in order to prevent possible memory effects. The potential of using M7C4I-coated capillaries for MS analysis of complex samples is demonstrated by the separation of peptides, proteins, and protein digests. Even more, the spectacular thing in which large intact proteins with molecular masses over 0.5,MDa could be separated. The coating showed good ability to handle these large proteins with high efficiency and retained peak shape as demonstrated by separation of IgG1 (150,kDa) and thyroglobulin (669,kDa). [source] New supported liquid membrane-capillary electrophoresis in-line arrangement for direct selective analysis of complex samplesELECTROPHORESIS, Issue 15 2006Leonor Nozal Abstract An in-line coupling of a micro-membrane extraction unit, based on supported liquid membrane, with commercially available capillary electrophoresis equipment is described. A main characteristic of this micro-membrane device, made from a simple Eppendorf tube, is that it permits the application of voltage in the acceptor solution to be applied during the extraction process. This has been shown as an alternative to enhance sensitivity, as the analytical signal achieved by applying 10,kV for 20,min was similar to that obtained without the application of voltage and with extraction time of 60,min. In addition, the design has been made permitting both in-line hydrodynamic and electrokinetic sample introduction into the electrophoretic capillary. The analytical potential of the proposed system has been demonstrated by the direct determination of nitroimidazoles from pig liver tissue. The high efficiency of the proposed system allowed the extraction and the determination of the analytes to be performed from a simple tissue homogenate obtained in water. The precision of the analysis of spiked samples, expressed in terms of relative standard deviation, was better than 4.8%. [source] Rapid detection of Staphylococcus aureus by a combination of monoclonal antibody-coated latex and capillary electrophoresisELECTROPHORESIS, Issue 9 2006Peng Gao Abstract The rapid detection of pathogenic bacteria is extremely important in biotechnology and clinical diagnosis. CE has been utilized in the field of bacterial analysis for many years, but to some extent, simultaneous separation and identification of certain microbes from complex samples by CE coupled with UV detector is still a challenge. In this paper, we propose a new strategy for rapid separation and identification of Staphylococcus aureus (S.,aureus) in bacterial mixtures by means of specific mAb-coated latex coupled with CZE. An appropriate set of conditions that selectively isolated S.,aureus from the microorganisms Escherichia coli, Pseudomonas aeruginosa, and Klebsiella pneumoniae were established. S.,aureus could be differentiated from the others by unique peaks in the electropherograms. The validity was also confirmed by LIF with antibodies specific to both the latex and the microbial cells. The LOD is as low as 9.0×105 colony forming unit/mL. We have also utilized this technology to identify S.,aureus in a stool sample coming from a healthy volunteer spiked successfully with S.,aureus. This CZE-UV technique can be applied to rapid diagnosis of enteritis caused by S.,aureus or other bacterial control-related fields needing rapid identification of target pathogens from microbial mixtures. In theory, this method is suitable for the detection of any bacterium as long as corresponding bacterium-specific antibody-coated latex is available. [source] On-line sample preconcentration with chemical derivatization of bacterial biomarkers by capillary electrophoresis: A dual strategy for integrating sample pretreatment with chemical analysisELECTROPHORESIS, Issue 21 2005Adam S. Ptolemy Abstract Simple, selective yet sensitive methods to quantify low-abundance bacterial biomarkers derived from complex samples are required in clinical, biological, and environmental applications. In this report, a new strategy to integrate sample pretreatment with chemical analysis is investigated using on-line preconcentration with chemical derivatization by CE and UV detection. Single-step enantioselective analysis of muramic acid (MA) and diaminopimelic acid (DAP) was achieved by CE via sample enrichment by dynamic pH junction with ortho -phthalaldehyde/N -acetyl- L -cysteine labeling directly in-capillary. The optimized method resulted in up to a 100-fold enhancement in concentration sensitivity compared to conventional off-line derivatization procedures. The method was also applied toward the detection of micromolar levels of MA and DAP excreted in the extracellular medium of Escherichia coli bacterial cell cultures. On-line preconcentration with chemical derivatization by CE represents a unique approach for conducting rapid, sensitive, and high-throughput analyses of other classes of amino acid and amino sugar metabolites with reduced sample handling, where the capillary functions simultaneously as a concentrator, microreactor, and chiral selector. [source] Powder Metallurgical Near-Net-Shape Fabrication of Porous NiTi Shape Memory Alloys for Use as Long-Term Implants by the Combination of the Metal Injection Molding Process with the Space-Holder Technique,ADVANCED ENGINEERING MATERIALS, Issue 12 2009Manuel Köhl Abstract A new method was developed for producing highly porous NiTi for use as an implant material. The combination of the space-holder technique with the metal injection molding process allows a net-shape fabrication of geometrically complex samples and the possibility of mass production for porous NiTi. Further, the porosity can be easily adjusted with respect to pore size, pore shape, and total porosity. The influence of the surface properties of powder metallurgical NiTi on the biocompatibility was first examined using human mesenchymal stem cells (hMSCs). It was found that pre-alloyed NiTi powders with an average particle size smaller than 45,,m led to the surface properties most suitable for the adhesion and proliferation of hMSCs. For the production of highly porous NiTi, different space-holder materials were investigated regarding low C- and O-impurity contents and the reproducibility of the process. NaCl was the most promising space-holder material compared to PMMA and saccharose and was used in subsequent studies. In these studies, the influence of the total porosity on the mechanical properties of NiTi is investigated in detail. As a result, bone-like mechanical properties were achieved by the choice of Ni-rich NiTi powder and a space-holder content of 50,vol% with a particle size fraction of 355,500,,m. Pseudoelasticity of up to 6% was achieved in compression tests at 37,°C as well as a bone-like loading stiffness of 6.5,GPa, a sufficient plateau stress ,25 of 261,MPa and a value for ,50 of 415,MPa. The first biological tests of the porous NiTi samples produced by this method showed promising results regarding proliferation and ingrowth of mesenchymal stem cells, also in the pores of the implant material. [source] Iron K -edge anomalous small-angle X-ray scattering at 15-ID-D at the Advanced Photon SourceJOURNAL OF APPLIED CRYSTALLOGRAPHY, Issue 2007Nigel Kirby Small-angle X-ray scattering (SAXS) is an ideal technique for characterizing inorganic nanoparticles in biological specimens large enough to be representative of tissues. As tissues consist of complex mixtures of structures, identifying particular structural features from single-wavelength scattering data can be problematic. Synchrotron SAXS can supply element-specific structural information in complex samples, using anomalous scattering close to absorption edges. Anomalous dispersion is a secondary effect that produces relatively subtle changes in scattering patterns. In order to utilize this effect for anomalous SAXS analysis, stringent control of instrument performance is required. This work outlines the development of high-quality data collection and processing strategies for Fe K -edge anomalous SAXS on the ChemMatCARS beamline at the Advanced Photon Source (APS), Chicago, with an emphasis on intensity normalization. The methods reported here were developed during a study of iron-loaded mammal tissues, but could equally well be applied to other complex specimens. [source] Outcomes of the International Union of Crystallography Commission on Powder Diffraction Round Robin on Quantitative Phase Analysis: samples 2, 3, 4, synthetic bauxite, natural granodiorite and pharmaceuticalsJOURNAL OF APPLIED CRYSTALLOGRAPHY, Issue 4 2002Nicola V. Y. Scarlett The International Union of Crystallography (IUCr) Commission on Powder Diffraction (CPD) has sponsored a round robin on the determination of quantitative phase abundance from diffraction data. The aims of the round robin have been detailed by Madsen et al. [J. Appl. Cryst. (2001), 34, 409,426]. In summary, they were (i) to document the methods and strategies commonly employed in quantitative phases analysis (QPA), especially those involving powder diffraction, (ii) to assess levels of accuracy, precision and lower limits of detection, (iii) to identify specific problem areas and develop practical solutions, (iv) to formulate recommended procedures for QPA using diffraction data, and (v) to create a standard set of samples for future reference. The first paper (Madsen et al., 2001) covered the results of sample 1 (a simple three-phase mixture of corundum, fluorite and zincite). The remaining samples used in the round robin covered a wide range of analytical complexity, and presented a series of different problems to the analysts. These problems included preferred orientation (sample 2), the analysis of amorphous content (sample 3), microabsorption (sample 4), complex synthetic and natural mineral suites, along with pharmaceutical mixtures with and without an amorphous component. This paper forms the second part of the round-robin study and reports the results of samples 2 (corundum, fluorite, zincite, brucite), 3 (corundum, fluorite, zincite, silica flour) and 4 (corundum, magnetite, zircon), synthetic bauxite, natural granodiorite and the synthetic pharmaceutical mixtures (mannitol, nizatidine, valine, sucrose, starch). The outcomes of this second part of the round robin support the findings of the initial study. The presence of increased analytical problems within these samples has only served to exacerbate the difficulties experienced by many operators with the sample 1 suite. The major difficulties are caused by lack of operator expertise, which becomes more apparent with these more complex samples. Some of these samples also introduced the requirement for skill and judgement in sample preparation techniques. This second part of the round robin concluded that the greatest physical obstacle to accurate QPA for X-ray based methods is the presence of absorption contrast between phases (microabsorption), which may prove to be insurmountable in some circumstances. [source] High-sensitivity analysis of specific peptides in complex samples by selected MS/MS ion monitoring and linear ion trap mass spectrometry: Application to biological studiesJOURNAL OF MASS SPECTROMETRY (INCORP BIOLOGICAL MASS SPECTROMETRY), Issue 11 2007Inmaculada Jorge Abstract Mass spectrometry (MS) is a technique of paramount importance in Proteomics, and developments in this field have been possible owing to novel MS instrumentation, experimental strategies, and bioinformatics tools. Today it is possible to identify and determine relative expression levels of thousands of proteins in a biological system by MS analysis of peptides produced by proteolytic digestion. In some situations, however, the precise characterization of a particular peptide species in a very complex peptide mixture is needed. While single-fragment ion-based scanning modes such as selected ion reaction monitoring (SIRM) or consecutive reaction monitoring (CRM) may be highly sensitive, they do not produce MS/MS information and their actual specificity must be determined in advance, a prerequisite that is not usually met in a basic research context. In such cases, the MS detector may be programmed to perform continuous MS/MS spectra on the peptide ion of interest in order to obtain structural information. This selected MS/MS ion monitoring (SMIM) mode has a number of advantages that are fully exploited by MS detectors that, like the linear ion trap, are characterized by high scanning speeds. In this work, we show some applications of this technique in the context of biological studies. These results were obtained by selecting an appropriate combination of scans according to the purpose of each one of these research scenarios. They include highly specific identification of proteins present in low amounts, characterization and relative quantification of post-translational modifications such as phosphorylation and S -nitrosylation and species-specific peptide identification. Copyright © 2007 John Wiley & Sons, Ltd. [source] Time of flight versus ion trap MS coupled to CE to analyse intact proteinsJOURNAL OF SEPARATION SCIENCE, JSS, Issue 10 2008Guillaume L. Erny Abstract In this work, two different CE-MS instruments, namely, CE-ESI-IT-MS and CE-ESI-TOF-MS, applied to analyse intact proteins from complex samples are investigated. The aim of this work was to compare both instruments in terms of LOD, number of proteins detected, and precision and repeatability in the determination of the protein relative molecular mass. Results show that although CE-ESI-IT-MS provides cleaner MS spectra of intact proteins, CE-ESI-TOF-MS allows the identification of a higher number of proteins from complex matrices in an easier way. Performance in terms of peak area reproducibility, LOD and precision in the determination of the molecular mass were similar for both instruments. The usefulness of the optimised CE-ESI-IT-MS and CE-ESI-TOF-MS conditions was demonstrated by studying the zein-proteins composition of three natural maize lines and their corresponding transgenic lines, showing no significant differences. [source] Continuous mode of operation for large volume dosing in analytical carrier ampholyte-free isoelectric focusing of proteins applied to off-line detection of fractionsJOURNAL OF SEPARATION SCIENCE, JSS, Issue 11 2006Jana Budilová Abstract Mass spectrometry is being increasingly used for analysis of proteome complex samples. Sample preparation is often necessary to remove matrix interferences and to concentrate analytes prior to MS measurement. A useful method for this purpose is Carrier Ampholyte Free-Isoelectric Focusing (CAF-IEF). In this paper CAF-IEF of ampholytes was performed on a commercial apparatus EA101 (Villa Labeco, Slovakia) equipped with a specially made column for samples of large volume (up to 0.5 mL). A new continuous mode without voltage interruption or electrolyte replacement was developed. In this mode, a low molecular mass pI marker (PIM 7.4) and low concentrations of myoglobin and insulin (16 mg/L), respectively, were concentrated, and then 5-,L fractions collected for off-line analyses. The total time of focusing was 66 minutes. The concentration of PIM 7.4 in the fractions was increased up to 75 times (determined by UV-VIS spectrometry). The concentration in the fractions was increased up to 30 times for myoglobin and 10 times for insulin. [source] Chemometrics in capillary electrophoresis.JOURNAL OF SEPARATION SCIENCE, JSS, Issue 15-16 2003Part B: Methods for data analysis Abstract Methods for data analysis in CE are addressed to extract relevant information contained in the electrophoretic responses. The main objectives of chemometrics in this field are the characterization of complex samples, the study of peak purity and deconvolution of comigrations, and the quantification of the analytes in poorly resolved peaks. In this paper, the application of chemometric techniques to data analysis is reviewed. The chemometric methods for the optimization of CE separations have been reviewed in Part A (see Sentellas and J. Saurina, Chemometrics in capillary electrophoresis. Part A: Methods for optimization). [source] Phosphorus L2,3 -edge XANES: overview of reference compoundsJOURNAL OF SYNCHROTRON RADIATION, Issue 2 2009Jens Kruse Synchrotron-based X-ray absorption near-edge structure (XANES) spectroscopy is becoming an increasingly used tool for the element speciation in complex samples. For phosphorus (P) almost all XANES measurements have been carried out at the K -edge. The small number of distinctive features at the P K -edge makes in some cases the identification of different P forms difficult or impossible. As indicated by a few previous studies, the P L2,3 -edge spectra were richer in spectral features than those of the P K -edge. However, experimentally consistent spectra of a wide range of reference compounds have not been published so far. In this study a library of spectral features is presented for a number of mineral P, organic P and P-bearing minerals for fingerprinting identification. Furthermore, the effect of radiation damage is shown for three compounds and measures are proposed to reduce it. The spectra library provided lays a basis for the identification of individual P forms in samples of unknown composition for a variety of scientific areas. [source] Real-life applications of the MULVADO software package for processing DOSY NMR dataMAGNETIC RESONANCE IN CHEMISTRY, Issue 2 2006R. Huo Abstract MULVADO is a newly developed software package for DOSY NMR data processing, based on multivariate curve resolution (MCR), one of the principal multivariate methods for processing DOSY data. This paper will evaluate this software package by using real-life data of materials used in the printing industry: two data sets from the same ink sample but of different quality. Also a sample of an organic photoconductor and a toner sample are analysed. Compared with the routine DOSY output from monoexponential fitting, one of the single channel algorithms in the commercial Bruker software, MULVADO provides several advantages. The key advantage of MCR is that it overcomes the fluctuation problem (non-consistent diffusion coefficient of the same component). The combination of non-linear regression (NLR) and MCR can yield more accurate resolution of a complex mixture. In addition, the data pre-processing techniques in MULVADO minimise the negative effects of experimental artefacts on the results of the data. In this paper, the challenges for analysing polymer samples and other more complex samples will also be discussed. Copyright © 2005 John Wiley & Sons, Ltd. [source] Techniques for phosphopeptide enrichment prior to analysis by mass spectrometryMASS SPECTROMETRY REVIEWS, Issue 1 2010Jamie D. Dunn Abstract Mass spectrometry is the tool of choice to investigate protein phosphorylation, which plays a vital role in cell regulation and diseases such as cancer. However, low abundances of phosphopeptides and low degrees of phosphorylation typically necessitate isolation and concentration of phosphopeptides prior to MS analysis. This review discusses the enrichment of phosphopeptides with immobilized metal affinity chromatography, reversible covalent binding, and metal oxide affinity chromatography. Capture of phosphopeptides on TiO2 seems especially promising in terms of selectivity and recovery, but the success of all methods depends on careful selection of binding, washing, and elution solutions. Enrichment techniques are complementary, such that a combination of methods greatly enhances the number of phosphopeptides isolated from complex samples. Development of a standard series of phosphopeptides in a highly complex mixture of digested proteins would greatly aid the comparison of different enrichment methods. Phosphopeptide binding to magnetic beads and on-plate isolation prior to MALDI-MS are emerging as convenient methods for purification of small (µL) samples. On-plate enrichment can yield >70% recoveries of phosphopeptides in mixtures of a few digested proteins and can avoid sample-handling steps, but this technique is likely limited to relatively simple samples such as immunoprecipitates. With recent advances in enrichment techniques in hand, MS analysis should provide important insights into phosphorylation pathways. © 2009 Wiley Periodicals, Inc., Mass Spec Rev 29:29,54, 2010 [source] Analysis of volatile fractions of Schisandra chinensis (Turcz.) Baill. using GC-MS and chemometric resolutionPHYTOCHEMICAL ANALYSIS, Issue 1 2003Xiao-Ning Li Abstract The two-dimensional data obtained from GC-MS has been used qualitatively and quantitatively to determine the components of the volatile fractions of Schisandra chinensis obtained by six different extraction methods. Sub-window factor analysis (SFA) was employed to confirm the identities of components determined in different samples. With the help of SFA, and other chemometric techniques, peak purity in the chromatograms was determined, and overlapping peaks were resolved to yield a pure chromatographic profile and mass spectrum for each component. It is demonstrated that the accuracy of qualitative and quantitative analysis may be greatly enhanced using chemometric resolution methods, such methods being particularly valuable with respect to the analysis of complex samples such as traditional Chinese medicines. It is further demonstrated that different extraction methods give rise to volatile fractions of S. chinensis which differ qualitatively and quantitatively in their composition. Copyright © 2003 John Wiley & Sons, Ltd. [source] Molecular mass ranges of coal tar pitch fractions by mass spectrometry and size-exclusion chromatographyRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 13 2009F. Karaca A coal tar pitch was fractionated by solvent solubility into heptane-solubles, heptane-insoluble/toluene-solubles (asphaltenes), and toluene-insolubles (preasphaltenes). The aim of the work was to compare the mass ranges of the different fractions by several different techniques. Thermogravimetric analysis, size-exclusion chromatography (SEC) and UV-fluorescence spectroscopy showed distinct differences between the three fractions in terms of volatility, molecular size ranges and the aromatic chromophore sizes present. The mass spectrometric methods used were gas chromatography/mass spectrometry (GC/MS), pyrolysis/GC/MS, electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICRMS) and laser desorption time-of-flight mass spectrometry (LD-TOFMS). The first three techniques gave good mass spectra only for the heptane-soluble fraction. Only LDMS gave signals from the toluene-insolubles, indicating that the molecules were too involatile for GC and too complex to pyrolyze into small molecules during pyrolysis/GC/MS. ESI-FTICRMS gave no signal for toluene-insolubles probably because the fraction was insoluble in the methanol or acetonitrile, water and formic acid mixture used as solvent to the ESI source. LDMS was able to generate ions from each of the fractions. Fractionation of complex samples is necessary to separate smaller molecules to allow the use of higher laser fluences for the larger molecules and suppress the formation of ionized molecular clusters. The upper mass limit of the pitch was determined as between 5000 and 10,000,u. The pitch asphaltenes showed a peak of maximum intensity in the LDMS spectra at around m/z 400, in broad agreement with the estimate from SEC. The mass ranges of the toluene-insoluble fraction found by LDMS and SEC (400,10,000,u with maximum intensity around 2000,u by LDMS and 100,9320,u with maximum intensity around 740,u by SEC) are higher than those for the asphaltene fraction (200,4000,u with maximum intensity around 400,u by LDMS and 100,2680,u with maximum intensity around 286,u by SEC) and greater than values considered appropriate for petroleum asphaltenes (300,1200,u with maximum intensity near 700,u). Copyright © 2009 John Wiley & Sons, Ltd. [source] Improving peptide identification using an empirical peptide retention time databaseRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 1 2009Wei Sun Peptide retention time (RT) is independent of tandem mass spectrometry (MS/MS) parameters and can be combined with MS/MS information to enhance peptide identification. In this paper, we utilized peptide empirical RT and MS/MS for peptide identification. This new approach resulted in the construction of an Empirical Peptide Retention Time Database (EPRTD) based on peptides showing a false-positive rate (FPR) ,1%, detected in several liquid chromatography (LC)/MS/MS analyses. In subsequent experiments, the RT of peptides with FPR >1% was compared with empirical data derived from the EPRTD. If the experimental RT was within a specified time range of the empirical value, the corresponding MS/MS spectra were accepted as positive. Application of the EPRTD approach to simple samples (known protein mixtures) and complex samples (human urinary proteome) revealed that this method could significantly enhance peptide identification without compromising the associated confidence levels. Further analysis indicated that the EPRTD approach could improve low-abundance peptides and with the expansion of the EPRTD the number of peptide identifications will be increased. This approach is suitable for large-scale clinical proteomics research, in which tens of LC/MS/MS analyses are run for different samples with similar components. Copyright © 2008 John Wiley & Sons, Ltd. [source] Atmospheric pressure chemical ionisation reversed-phase liquid chromatography/ion trap mass spectrometry of intact bacteriohopanepolyolsRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 7 2003Helen M. Talbot Atmospheric pressure chemical ionisation liquid chromatography/multi-stage ion trap mass spectrometry (APCI-LC/MSn) has been applied to the study of intact bacteriohopanepolyols. Spectral characterisation of bacteriohopanepolyols of known structure present in bacterial extracts (Zymomonas mobilis and a fermenter containing methanotrophs including Methylococcus capsulatus) has revealed greater structural detail than previous liquid chromatography/mass spectrometry (LC/MS) methods and identified characteristic fragmentations indicative of numerous biohopanoid structures. Analysis of a Recent sedimentary extract from Lake Druzhby (Antarctica) has demonstrated the power of this technique to detect biohopanoids in complex samples including at least partial characterisation of previously unknown composite structures. Copyright © 2003 John Wiley & Sons, Ltd. [source] Gene expression in arcuate nucleus-median eminence of rats treated with leptin or ciliary neurotrophic factorBIOFACTORS, Issue 2 2007Suresh Ambati Abstract Ciliary neurotrophic factor (CNTF) and leptin are cytokine-like hormones and act on their corresponding receptors in the hypothalamic arcuate nucleus (ARC). The present study was designed to assess effects of intracerebroventricular (ICV) injection of leptin and CNTF on gene expression in micropunched hypothalamic arcuate nucleus-median eminence (ARCME) complex samples from rats. Male Sprague Dawley rats were implanted with lateral cerebroventricular cannulas for administration of control, 10 ,g/d leptin or 5 ,g/d CNTF for four days. Real-time Taqman RT-PCR was used to quantitatively compare the mRNA levels of selected genes in the ARC-ME complex. Leptin and CNTF increased ARC-ME mRNA levels of signal transducer and activator of transcription 3 (STAT3) by 64.5 and 124.7% (p < 0.01), suppressor of cytokine signaling 3 (SOCS3) by 258.9 and 1063.9% (p < 0.01), cocaine and amphetamine regulated transcript (CART) by 102.7 and 123.1% (p < 0.01), and proopiomelanocortin (POMC2) by 374.1 and 264.9% (p < 0.01), respectively. Leptin increased growth hormone releasing hormone (GHRH) by 309.9% (p < 0.01), while CNTF increased janus kinase 2 (JAK2) mRNA by 31.7% (p < 0.01) and decreased gonadotropin releasing hormone 1 (GNRH1) by 59.7% (p < 0.01), mitogen activated protein kinase 1 (MAPK1) by 19.4% (p < 0.05) and tyrosine hydroxylase (TH) by 74.5% (p < 0.05). Significant reduction in daily food intake and body weights by both the treatments was observed. Also, decrease in weights of fat pads was concomitant with lowered serum insulin and leptin levels. Our findings show that leptin and CNTF engage both convergent and divergent pathways involved in feeding, cellular signaling, inflammation, and other related regulatory systems. [source] Analysis of the Volatile Components in the Leaves of Cinnamomum camphora by Static Headspace Gas Chromatography Mass Spectrometry Combined with Accurate Weight MeasurementCHINESE JOURNAL OF CHEMISTRY, Issue 8 2010Fengjun Zhu Abstract The volatile components in the leaves of C. camphora were analyzed by static headspace-gas chromatography/mass spectrometry (HS-GC-MS) combined with accurate weight measurement. Accurate weight measurement obtained by Time-of-Flight mass spectrometry (TOF-MS) helped to confirm the identification of volatiles in the analysis. 59 volatile components in the leaves of C. camphora were identified, which mainly included cis -3-hexen-1-ol (5.6%), 3-hexen-1-ol, acetate (Z) (11.1%), , -caryophyllene (15.4%), bicyclogermarene (8.4%), trans -nerolidol (19.5%) and 9-oxofarnesol (7.7%). The results show that method using HS-GC-MS combined with accurate weight measurement achieves reliable identification and has extensive application in the analysis of volatile components present in complex samples. [source] | |||||||||||||||||||||||||||||||