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Peak Widths (peak + width)
Selected AbstractsEnhanced pH-mediated stacking of anions for CE incorporating a dynamic pH junctionELECTROPHORESIS, Issue 20 2007Stacy D. Arnett Abstract A technique has been developed to enhance analyte focusing for CE for the analysis of physiological samples. High-ionic-strength samples are titrated to low-ionic-strength on-line using pH-mediated sample stacking in conjunction with a dynamic pH junction. This method concentrates analytes by reducing their electrophoretic mobility during field-amplification. Parameters responsible for enhanced focusing were investigated, and an enhanced pH-mediated stacking method was optimized for anionic nucleosides. The process results in ultra-narrow peak widths, for example, 0.28,s for thymidine with a 10,min analysis time. Peak width and resolution with the enhanced stacking method were also compared to normal base stacking and electrokinetic injection. With this technique, mass-loading capacity can be increased without degradation in peak shape and resolution is dramatically improved. [source] Microchip electrophoresis with wall-jet electrochemical detector: Influence of detection potential upon resolution of solutesELECTROPHORESIS, Issue 24 2006Martin Pumera Dr. Abstract This report studies the electrochemical response of wall-jet detector for microchip electrophoresis (µCE). It shows that in wall-jet configuration, the electrochemical detector operates in coulometric mode and that there is an influence of detection potential upon peak width and therefore upon the resolution of solutes. Upon raising the detection potential from +0.3 to +0.9,V, the resolution between model analytes, dopamine and catechol, increases from 0.63 to 2.90. The reasons for this behavior originate in wall-jet detector design and in its typically significant higher detector volume than the volume of injected sample. The conversion efficiency of the wall-jet electrochemical detection cell was found to be 97.4% for dopamine and 98.0% for catechol. The paper brings deeper understanding of operations of wall-jet electrochemical detectors for microchip devices, and it explains previously reported significantly sharper peaks when electrocatalytic electrodes (i.e., palladium and carbon nanotube) were used in µCE-electrochemistry wall-jet detector. [source] Miniaturized movable contactless conductivity detection cell for capillary electrophoresisELECTROPHORESIS, Issue 12-13 2003Miroslav Macka Abstract A miniaturized capacitively coupled contactless conductivity detector (mini-C4D) cell has been designed which is small enough to allow it to slide along the effective capillary length inside the capillary cassette of an Agilent capiillary electrophoresis system (CE) (or other CE brand of similar construction), including the possibility of positioning it close to the point of optical detection (4 cm), or even putting two such detector cells in one cassette. The cell was tested and the performance characteristics (noise, sensitivity, and peak width) were compared with those obtained with the previously used large C4D cell. No significant differences were observed. The mini-C4D was used in simultaneous separations of common cations and anions where its advantage over a larger C4D cell is the ability to vary the point of detection with the mini-C4D cell continuously at any point along the capillary length, so that the optimum apparent selectivity can be chosen. Other applications include providing a convenient second point of detection in addition to photometric detection, such as to measure accurately the linear velocity of a zone, or to allow placement of two mini-C4D cells in one capillary cassette simultaneously. [source] Preparation and Tribological Properties of Inorganic Fullerene-like MoS2,ADVANCED ENGINEERING MATERIALS, Issue 4 2006Z. Zou The decomposition temperature had little effect on the particle size with the addition of surface agent. It was just the crystallization that different from each other. With increasing the temperature, the peak width of XRD patterns sharpened, indicating that the crystallization of MoS2 particles went better. [source] Thermally Stimulated Currents of SiO2/Low-density Polyethylene Micro- and NanocompositesIEEJ TRANSACTIONS ON ELECTRICAL AND ELECTRONIC ENGINEERING, Issue 4 2010Yi Yin Non-member Abstract Composite samples of low-density polyethylene (LDPE)/nano-SiO2 and LDPE/micro-SiO2 were prepared with the method of double-solution mixture. Depolarization currents of all samples were investigated with thermally stimulated depolarization current (TSDC). It was found that the currents of both composites increased with the loading level of nano-SiO2 and/or micro-SiO2, and that the peak width of each composite is greater than that of pure LDPE. In addition, the peak position of the nanocomposite shifts as the loading level increases, while that of the microcomposite does not shift significantly. In order to understand activation energy of both composites and pure LDPE, the initial-rise method was used to analyze the depolarization current. It was found that LDPE has the greatest activation energy among all samples and the activation energy of both composites decreases with increasing loading levels. Moreover, the activation energy of the nanocomposite is less than that of the microcomposite at each of the same loading level. As the nano-SiO2 loading level reaches 5.0%wt, the composite has the lowest activation energy of 0.25 eV. In addition, dielectric spectra of all samples were investigated in the range of 10,4 to 107 Hz, and it was found that the peak position of loss tangent varied consistently with the TSDC curves as the loading levels of nano-SiO2 and/or micro-SiO2 were increased. Copyright © 2010 Institute of Electrical Engineers of Japan. Published by John Wiley & Sons, Inc. [source] Microstrain and grain-size analysis from diffraction peak width and graphical derivation of high-pressure thermomechanicsJOURNAL OF APPLIED CRYSTALLOGRAPHY, Issue 6 2008Yusheng Zhao An analytical method is presented for deriving the thermomechanical properties of polycrystalline materials under high-pressure (P) and high-temperature (T) conditions. This method deals with non-uniform stress among heterogeneous crystal grains and surface strain in nanocrystalline materials by examining peak-width variation under different P,T conditions. Because the method deals directly with lattice d spacing and local deformation caused by stress, it can be applied to process any diffraction profile, independent of detection mode. In addition, a correction routine is developed using diffraction elastic ratios to deal with severe surface strain and/or strain anisotropy effects related to nano-scale grain sizes, so that significant data scatter can be reduced in a physically meaningful way. Graphical illustration of the resultant microstrain analysis can identify micro/local yields at the grain-to-grain interactions resulting from high stress concentration, and macro/bulk yield of the plastic deformation over the entire sample. This simple and straightforward approach is capable of revealing the corresponding micro and/or macro yield stresses, grain crushing or growth, work hardening or softening, and thermal relaxation under high- P,T conditions, as well as the intrinsic residual strain and/or surface strain in the polycrystalline bulk. In addition, this approach allows the instrumental contribution to be illustrated and subtracted in a straightforward manner, thus avoiding the potential complexities and errors resulting from instrument correction. Applications of the method are demonstrated by studies of ,-SiC (6H, moissanite) and of micro- and nanocrystalline nickel by synchrotron X-ray and time-of-flight neutron diffraction. [source] Molecular mass determination of plasma-derived glycoproteins by ultraviolet matrix-assisted laser desorption/ionization time-of-flight mass spectrometry with internal calibrationJOURNAL OF MASS SPECTROMETRY (INCORP BIOLOGICAL MASS SPECTROMETRY), Issue 11 2002Omar Belgacem Abstract Human plasma-derived antithrombin III (AT-III), factor IX (FIX) and vitronectin (VN) were characterized as native glycoproteins and in their de- N -glycosylated form by means of MALDI mass spectrometry. The average molecular masses of the three complex glycoproteins were determined applying internal calibration with high-mass, well-defined protein calibrants. Internal calibration generated for the 47 kDa yeast protein enolase a mass precision in the continuous and delayed extraction mode of ±0.12 and ±0.022%, respectively. The achievable mass accuracy for such a high-mass, unmodified protein was in the range of 0.02% in the continuous mode, which turned out to be better than in the delayed extraction mode. Purification of all (glyco) proteins (even the calibration proteins) by means of ZipTip® technology and direct elution with a solvent system containing the appropriate MALDI matrix turned out to be a prerequisite to measure the exact molecular masses with an internal calibration. The average molecular masses of the two different forms of AT-III, namely AT-III, and AT-III,, were shown to be 57.26 and 55.04 kDa, respectively. The 2.22 kDa mass difference is attributed to the known difference in carbohydrate content at one specific site (Asn-135). After exhaustive de- N -glycosylation (by means of PNGase F) of the ,- and ,-form and subsequent MALDI-MS analysis, average molecular masses of 48.96 and 48.97 kDa, respectively, were obtained. These values are in good agreement (,0.15%) with the calculated molecular mass (49.039 kDa) of the protein part based on SwissProt data. The molecular mass of the heavily post-translational modified glycoprotein FIX was found to be 53.75 kDa with a peak width at 10% peak height of 4.5 kDa, because of the presence of many different posttranslational modifications (N - and O -glycosylation at multiple sites, sulfation, phosphorylation, hydroxylation and numerous ,-carboxyglutamic acids). MALDI-MS molecular mass determination of the native, size-exclusion chromatography-purified, VN sample revealed that the glycoprotein was present as dimer with molecular mass of 117.74 kDa, which could be corroborated by non-reducing SDS-PAGE. After sample treatment with guanidine hydrochloride and mass spectrometric analysis, a single, new main component was detected. The molecular mass turned out to be 59.45 kDa, representing the monomeric form of VN, known as V75. The determined molecular mass value was shown to be on one hand lower than from SDS-PAGE and on the other higher than the calculated amino acid sequence molecular mass (52 277 Da), pointing to the well-known SDS-PAGE bias and to considerable post-translational modifications. Further treatment of the sample with a reducing agent and subsequent MALDI-MS revealed two new components with molecular masses of 49.85 and 9.41 kDa, corresponding to V65 and V10 subunits of VN. PNGase F digest of the V75 and V65 units and MS analysis, exhibiting a molecular mass reduction of 6.37 kDa in both cases, verified the presence of a considerable amount of N -glycans. Copyright © 2002 John Wiley & Sons, Ltd. [source] Accuracy of orientation distribution function determination based on EBSD data-A case study of a recrystallized low alloyed Zr sheetJOURNAL OF MICROSCOPY, Issue 3 2007N. BOZZOLO Summary The question of the statistical accuracy of EBSD data for global texture calculation was re-explored on the basis of a very large grain population (83 000 grains measured on a recrystallized low-alloyed Zr sheet). Previous works aimed mainly at identifying and quantifying the main texture components and were based on much smaller data sets. The present work attempts to quantify the accuracy of the complete texture, including low-density regions of the orientation space. For that purpose, a new statistical parameter, V,, based on the calculation of texture difference functions is proposed. This parameter has two main advantages: it is equally sensitive to both high and low peaks of the orientation density function (ODF), and it has a physical interpretation because it is the material volume fraction corresponding to the difference between a given ODF and a reference ODF (considered, or known to be close to the truth). Two main variables were studied: the number of grains taken into account and the peak width ,0 of Bunge's ,Gaussian' model density used as kernel for the actual analysis. The orientation distribution functions were computed by nonparametric kernel density estimation with harmonics up to the order of 34. Minimizing the value of V, serves as the objective function for optimizing the peak width ,0 as a function of the number of grains. The properties of the V, parameter also allows for the definition of a method for estimating the accuracy of a given texture that has been obtained from a limited number of grains, without knowing the true texture of the investigated material. [source] Detectability enhancement of spectrophotometric detectors by the use of multidimensional gas chromatographyJOURNAL OF SEPARATION SCIENCE, JSS, Issue 18 2002Juan Carlos Medina Abstract Multidimensional gas chromatography (2D GC) is demonstrated as a way to improve limits of detectability of spectrophotometric detectors. UV and IR detectors are generally less sensitive than mass spectrometers or other GC detectors. This has placed some limitations on the useful capabilities provided by spectrophotometric detectors, such as the ability to provide structure-related information for a particular analyte. In this paper, we report results from interfacing a 2D GC instrument to a UV detector. Symmetry factor and the ratio of retention time divided by peak width did not show deterioration of the quality of chromatography when a megabore column was used with this detector. Furthermore, an increase in the limits of detectability over that attainable in a single-column system was realized by using the 2D GC system. However, the low flow (1 mL/min) imposed by the use of a microbore column (250 ,m ID) caused significant tailing when the UV detector was used. [source] Grain-Boundary Viscosity of BaO-Doped SiCJOURNAL OF THE AMERICAN CERAMIC SOCIETY, Issue 3 2000Giuseppe Pezzotti Internal friction characterization of the viscosity of a residual SiO2/BaO glass, segregated to grain boundaries of polycrystalline SiC, is presented. The anelastic relaxation peak of internal friction, arising from viscous slip along grain boundaries wetted by a glass phase, is analyzed. Two SiC polycrystals, containing SiO2/BaO glasses with different compositions, are studied and compared with a SiC polycrystal containing only pure SiO2. The internal friction peak is first analyzed with respect to its shift upon frequency change. This analysis allows quantitative assessment of both the intrinsic viscosity and the activation energy for viscous flow of the grain-boundary phase. Both parameters markedly decrease with increasing amounts of BaO dopant, which is consistent with data reported in the literature on SiO2 and SiO2/BaO bulk glasses with the same nominal composition. Analysis of the peak morphology is also attempted, considering the evolution of peak width while varying the grain-boundary glass composition. Moreover, the role of microstructural parameters, such as the distributions of grain size and grain-boundary angles, on the broadening of the internal friction peak is addressed, and a procedure is proposed that allows quantitative evaluation of the activation energy for viscous flow of intergranular glass merely from the width of the internal friction peak. [source] Thermoluminescence sensitivity and thermal history of type 3 ordinary chondrites: Eleven new type 3.0,3.1 chondrites and possible explanations for differences among H, L, and LL chondritesMETEORITICS & PLANETARY SCIENCE, Issue 6 2002P. H. Benoit We have identified 11 UOCs of petrologic types 3.0,3.1: Adrar 003, Elephant Moraine (EET) 90066, EET 90161, Grosvenor Mountains (GRO) 95502, Lewis Cliff (LEW) 88477, Meteorite Hills (MET) 96503, Yamato (Y)-790787, Y-791324, Y-791558, Y-793565, and Y-793596. These samples represent an important new resource for researchers interested in the nature of primitive solar system materials. Previously reported trends in which TL sensitivity increases with TL peak temperature and TL peak width, which we interpret in terms of crystallization of feldspar in the ordered or disordered forms during metamorphism, are confirmed by the new data. Importantly, the present data strengthen the trend described earlier in which the mean level of metamorphism experienced by UOCs increases along the series LL, L and H. This suggests either different burial depths for the UOCs from each class, or formation at similar depths in regoliths of different thickness. [source] Photoluminescence spectroscopy and transport electrical measurements reveal the quantized features of Si nanocrystals embedded in an ultra thin SiO2 layerPHYSICA STATUS SOLIDI (C) - CURRENT TOPICS IN SOLID STATE PHYSICS, Issue 2 2007C. Dumas Abstract In this paper, we have investigated the quantized charging features revealed by nanometer scale devices containing a 2D array of Si nanoparticles (nps) embedded into a SiO2 layer. The Si nps were synthesized by ultra low energy ion implantation and annealing under slightly oxidizing ambient. The structural characteristics of the material (oxide thicknesses, nps size and density) have been studied by Transmission Electron Microscopy (TEM) and Energy Filtered TEM (EFTEM). Moreover, photoluminescence (PL) spectroscopy and electrical I(V) measurements using a MOS capacitor addressing only a few nps have been performed at room temperature. It is observed that, as the oxidizing annealing temperature increases, the nps size decreases and the oxide quality is restored. These features appear on the PL spectra as a blue shift of the PL red band linked to quantum confinement into nps and on the I(V) characteristics as an increase of the voltage peak width and a decrease of the main current background. (© 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Evaluation of detection methods for the reversed-phase HPLC determination of 3,,4,,5,-trimethoxyflavone in different phytopharmaceutical products and in human serumPHYTOCHEMICAL ANALYSIS, Issue 2 2001Christian W. Huck Abstract Quantitative determination of the major compound, 3,,4,,5,-trimethoxyflavone (1), in plant extracts, in tablets of Flos and of Radix Primulae veris and in human serum has been accomplished using reversed-phase HPLC with UV, fluorescence and mass spectrometric (MS) detection. Compared to UV detection, fluorescence detection showed greater selectivity, was 10-fold more sensitive and allowed the determination of 1 in human serum after sample pre-treatment by solid-phase extraction. MS detection of 1 using electrospray ionisation (ESI) interface could be improved by substituting trifluoroacetic acid with the more polar and less conductive additive acetic acid, giving rise to a 230-fold improvement in analyte detectability at the cost of an increase of only 45% in the peak width of the eluting peak at its half height. Further optimisation of the acetic acid concentration showed the highest signal intensity at 1.25% for HPLC-atmospheric pressure chemical ionisation (APCI)-MS and at 0.75% for HPLC-ESI-MS. The optimised MS method proved to be extremely selective, 50 times more sensitive than UV detection and 5 times more sensitive than fluorescence detection. Furthermore, fragment-ion spectra produced by collision induced dissociation-MS have been used as "fingerprints" for identifying compounds in the highly complex mixtures examine. Copyright © 2001 John Wiley & Sons, Ltd. [source] The detection, correlation, and comparison of peptide precursor and product ions from data independent LC-MS with data dependant LC-MS/MSPROTEINS: STRUCTURE, FUNCTION AND BIOINFORMATICS, Issue 6 2009Scott J. Geromanos Abstract The detection, correlation, and comparison of peptide and product ions from a data independent LC-MS acquisition strategy with data dependent LC-MS/MS is described. The data independent mode of acquisition differs from an LC-MS/MS data acquisition since no ion transmission window is applied with the first mass analyzer prior to collision induced disassociation. Alternating the energy applied to the collision cell, between low and elevated energy, on a scan-to-scan basis, provides accurate mass precursor and associated product ion spectra from every ion above the LOD of the mass spectrometer. The method therefore provides a near 100% duty cycle, with an inherent increase in signal intensity due to the fact that both precursor and product ion data are collected on all isotopes of every charge-state across the entire chromatographic peak width. The correlation of product to precursor ions, after deconvolution, is achieved by using reconstructed retention time apices and chromatographic peak shapes. Presented are the results from the comparison of a simple four protein mixture, in the presence and absence of an enzymatically digested protein extract from Escherichia coli. The samples were run in triplicate by both data dependant analysis (DDA) LC-MS/MS and data-independent, alternate scanning LC-MS. The detection and identification of precursor and product ions from the combined DDA search results of the four protein mixture were used for comparison to all other data. Each individual set of data-independent LC-MS data provides a more comprehensive set of detected ions than the combined peptide identifications from the DDA LC-MS/MS experiments. In the presence of the complex E. coli background, over 90% of the monoisotopic masses from the combined LC-MS/MS identifications were detected at the appropriate retention time. Moreover, the fragmentation pattern and number of associated elevated energy product ions in each replicate experiment was found to be very similar to the DDA identifications. In the case of the corresponding individual DDA LC-MS/MS experiment, 43% of the possible detectable peptides of interest were identified. The presented data illustrates that the time-aligned data from data-independent alternate scanning LC-MS experiments is highly comparable to the data obtained via DDA. The obtained information can therefore be effectively and correctly deconvolved to correlate product ions with parent precursor ions. The ability to generate precursor-product ion tables from this information and subsequently identify the correct parent precursor peptide will be illustrated in a companion manuscript. [source] The use of acetone as a substitute for acetonitrile in analysis of peptides by liquid chromatography/electrospray ionization mass spectrometryRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 1 2010Theodore R. Keppel The recent worldwide shortage of acetonitrile has prompted interest in alternative solvents for liquid chromatography/mass spectrometry (LC/MS). In this work, acetone was substituted for acetonitrile in the separation of a peptide mixture by reversed-phase high-performance liquid chromatography (RP-HPLC) and in the positive electrospray ionization mass spectrometry (ESI-MS) of individual peptides. On both C12 and C18 stationary phases, the substitution of acetone for acetonitrile as the organic component of the mobile phase did not alter the gradient elution order of a five-peptide retention standard, but did increase peak width, shorten retention times, and increase peak tailing. Positive ESI mass spectra were obtained for angiotensin I, bradykinin, [Leu5]-enkephalin, and somatostatin 14 dissolved in both acetonitrile/water/formic acid (25%/75%/0.1%) and acetone/water/formic acid (25%/75%/0.1%). Under optimized ESI-MS conditions, the mass spectral response of [Leu5]-enkephalin was increased two-fold when the solvent contained acetone. The substitution of acetone for acetonitrile resulted in only slight changes in the responses of the remaining peptides. A higher capillary voltage was required for optimum response when acetone was used. Compared with acetonitrile/water/formic acid (50/50/0.1%), more interfering species below m/z,=,140 were found in the ESI-MS spectra of acetone/water/formic acid (50/50/0.1%). Copyright © 2009 John Wiley & Sons, Ltd. [source] Enhanced pH-mediated stacking of anions for CE incorporating a dynamic pH junctionELECTROPHORESIS, Issue 20 2007Stacy D. Arnett Abstract A technique has been developed to enhance analyte focusing for CE for the analysis of physiological samples. High-ionic-strength samples are titrated to low-ionic-strength on-line using pH-mediated sample stacking in conjunction with a dynamic pH junction. This method concentrates analytes by reducing their electrophoretic mobility during field-amplification. Parameters responsible for enhanced focusing were investigated, and an enhanced pH-mediated stacking method was optimized for anionic nucleosides. The process results in ultra-narrow peak widths, for example, 0.28,s for thymidine with a 10,min analysis time. Peak width and resolution with the enhanced stacking method were also compared to normal base stacking and electrokinetic injection. With this technique, mass-loading capacity can be increased without degradation in peak shape and resolution is dramatically improved. [source] Ammonium perfluorooctanoate as a volatile surfactant for the analysis of N -methylcarbamates by MEKC-ESI-MSELECTROPHORESIS, Issue 22 2006Geert Van Biesen Abstract Ammonium perfluorooctanoate (APFOA) was investigated as an MS-friendly surfactant for the analysis of a mixture of ten N -methylcarbamates with MEKC-ESI-MS. Because of the relatively low boiling point of perfluorooctanoic acid (,190°C), APFOA can be introduced into a mass spectrometer without the adverse effects of less volatile surfactants such as SDS. With a BGE consisting of 50,mM APFOA/isopropanol (IPA) 98:2 and with 30,kV applied, a very fast separation (,6,min) was possible with only one pair of analytes comigrating. Using an experimental design with four factors (voltage, nebulizer pressure, concentration of APFOA, and concentration of IPA) we were able to resolve all analytes in just over 11,min. Sheath liquid composition and flow rate, drying gas temperature and flow rate, and fragmentor voltage were then optimized for maximum signal intensity and S/N. It was found that the faster method gave better S/N because of narrower peak widths, and detection limits in SIM mode were between 0.01 (aldicarb) and 0.08,mg/L (methomyl). Calibration curves were prepared with standards of 0.50, 1.00, and 2.00,mg/L for the analysis of samples obtained after SPE of tap water spiked with the ten N -methylcarbamates at a level of 10,µg/L. All analytes showed very good recoveries (>86%), except for the most polar analyte aldicarb sulfone (recovery of 73%), testifying for the potential use of APFOA for this kind of analyses. [source] Determination of the cis-trans isomerization barrier of enalaprilat by dynamic capillary electrophoresis and computer simulationELECTROPHORESIS, Issue 2 2004Oliver Trapp Abstract Dynamic capillary electrophoresis (DCE) and computer simulation of the elution profiles with the stochastic model has been applied to determine the isomerization barriers of the angiotensin converting enzyme inhibitor enalaprilat. The separation of the rotational cis-trans isomeric drug has been performed in an aqueous 20 mM borate buffer at pH 9.3. Interconversion profiles featuring plateau formation and peak broadening were observed. To evaluate the rate constants kcis,trans and ktrans,cis of the cis-trans isomerization from the experimental electropherograms obtained by dynamic capillary electrophoresis, elution profiles were analyzed by a simulation with iterative convergence to the experimental data using the ChromWin software which requires the total migration times of the individual isomers tR, the electroosmotic break-through time t0, the plateau height hplateau, the peak widths at half height of the individual isomers wh, as well as the peak ratio of the isomers as experimental data input. From temperature-dependent measurements between 0° and 15°C the thermodynamic parameters ,G, ,H and ,S, the rate constants kcis,trans and ktrans,cis and the kinetic activation parameters ,G,, ,H,, and ,S, of the cis-trans isomerization of enalaprilat were obtained. From the activation parameters the isomerization barriers at 37°C were calculated to be ,G,trans,cis = 87.2 kJ·mol,1 and ,G,cis,trans = 91.9 kJ·mol,1. [source] Pair distribution functions calculated from interatomic potential models using the General Utility Lattice ProgramJOURNAL OF APPLIED CRYSTALLOGRAPHY, Issue 3 2007Elizabeth R. Cope A new module has been developed for the widely used General Utility Lattice Program (GULP). The phonon-based theory developed by Chung & Thorpe [Phys. Rev. B (1999), 59, 4807,4812] to calculate pair distribution function (PDF) peak widths has been utilized to give a selection of commonly used correlation functions. A numerical library of neutron scattering information is now available within GULP, and is used to produce results that can be compared with neutron scattering experimental data. The influence of different phonon modes on the PDF can be assessed by excluding modes above or below a cut-off frequency. Results are presented for sample crystallographic systems, MgO, SrTiO3 and ,-cristobalite, as well as CaxSr1,xTiO3 at x = 0.5, which makes use of the capability to handle partial occupancies to compare different Ca/Sr ordering arrangements with a disordered model in which every Ca/Sr site has 50% occupancy of both species. [source] Hyperspectral NIR image regression part II: dataset preprocessing diagnosticsJOURNAL OF CHEMOMETRICS, Issue 3-4 2006James Burger Abstract When known reference values such as concentrations are available, the spectra from near infrared (NIR) hyperspectral images can be used for building regression models. The sets of spectra must be corrected for errors, transformed to reflectance or absorbance values, and trimmed of bad pixel outliers in order to build robust models and minimize prediction errors. Calibration models can be computed from small (<100) sets of spectra, where each spectrum summarizes an individual image or spatial region of interest (ROI), and used to predict large (>20,000) test sets of spectra. When the distributions of these large populations of predicted values are viewed as histograms they provide mean sample concentrations (peak centers) as well as uniformity (peak widths) and purity (peak shape) information. The same predicted values can also be viewed as concentration maps or images adding spatial information to the uniformity or purity presentations. Estimates of large population statistics enable a new metric for determining the optimal number of model components, based on a combination of global bias and pooled standard deviation values computed from multiple test images or ROIs. Two example datasets are presented: an artificial mixture design of three chemicals with distinct NIR spectra and samples of different cheeses. In some cases it was found that baseline correction by taking first derivatives gave more useful prediction results by reducing optical problems. Other data pretreatments resulted in negligible changes in prediction errors, overshadowed by the variance associated with sample preparation or presentation and other physical phenomena. Copyright © 2007 John Wiley & Sons, Ltd. [source] Peak width-mass correlation in CID MS/MS of isomeric oligosaccharides using traveling-wave ion mobility mass spectrometryJOURNAL OF MASS SPECTROMETRY (INCORP BIOLOGICAL MASS SPECTROMETRY), Issue 10 2009Tohru Yamagaki Abstract Isomeric oligosaccharides ,-cyclodextrin (,-CD), glucosyl-,CD (Glc1 -,CD) and maltosyl-,CD (Glc2 -,CD) were analyzed by traveling-wave ion mobility (twIM) mass spectrometry (MS). Their formation of multicharged multimers differed from each other. The ion mobility-mass spectrometry was useful in the self-assembling and complex formation analyses of CD isomers. The drift times of the isomers and their product ions with the same mass were almost the same in collision-induced dissociation (CID) MS/MS. In contrast, the ion mobility peak widths were sensitive to structural differences of the isomeric product ions. The twIM peak width (ms - µs) of the product ions [M , Glcn + H]+ (n = 0 , 6) of ,-CD correlated linearly with their masses (Da); the large and/or long chain product ions had wider peak widths, which were much wider than those from the general diffusion effect. This was a novel and useful ,trend line' to discriminate between the three isomers. Plots of [M , Glc2 , 6 + H]+ of Glc1 -,CD and [M , Glc3 , 6 + H]+ of Glc2 -,CD product ions' plots were on the same trend line as ,-CD. The plots of [M , Glc1 + H]+ of Glc1 -,CD and [M , Glc1, 2 + H]+ of Glc2 -,CD strayed from the ,-CD line; their peak widths were narrower than those of ,-CD. These results indicated that product ions from the chemical species of Glc1 -, CD and Glc2 -,CD retained their CD structure. Analyses of the IM peak widths enable us to elucidate the structures of the product ions. Copyright © 2009 John Wiley & Sons, Ltd. [source] The application of small porous particles, high temperatures, and high pressures to generate very high resolution LC and LC/MS separationsJOURNAL OF SEPARATION SCIENCE, JSS, Issue 8 2007Robert Plumb Abstract The effect of combining sub-2 ,m porous particles with elevated operating temperatures on chromatographic performance has been investigated in terms of chromatographic efficiency, productivity, peak elution order, and observed operating pressure. The use of elevated temperature in LC does not increase the obtainable performance but allows the same performance to be obtained in less time. Increasing the column temperature did allow the use of longer columns, generating column efficiencies in excess of 100 000 plates and gradient peak capacities approaching 1000. Raising the temperature increased the optimal mobile phase linear velocity, negating somewhat the pressure benefits observed by reducing the solvent viscosity. When operating at higher temperature the analyte retention is not only reduced, but the order of elution will also often change. High temperature separations allowed exotic organic modifiers such as isopropanol to be exploited for alternative selectivity and faster analysis. Finally, care must be taken when using high temperature separations to ensure that the narrow peak widths produced do not compromise the quality of data obtained from detectors such as high resolution mass spectrometers. [source] The Quenched Instationary Polymerization Systems (QUIPS)MACROMOLECULAR THEORY AND SIMULATIONS, Issue 2-3 2003Irene Schnöll-Bitai Abstract The common element of quenched instationary polymerization systems is that at a given time all radicals present are deactivated by an efficient and fast quench reaction. Quenched instationary polymerizations can be carried out in a variety of ways distinguished by the way periods differing in their initiation characteristics are combined. The total chain length distribution of the resulting polymer is always the sum of the quenched radical and polymer chain length distribution. This distribution is either completely or at least partially dominated by the contribution of the quenched radical spectrum. Depending on the experimental conditions monomodal or multimodal distributions are obtained which can be characterized by their extrema (maximum, points of inflection) and peak widths (absolute, relative). The location of the extrema are related to the experimental parameters and can be used in an unambiguous way for the direct determination of the rate constant of propagation. Absolute peak widths (defined as the difference between two succeeding points of inflection) are invariant quantities with respect to the number, molar mass and hyper distribution which is only true for Poisson (and narrow Gauss) distributions. Relative peak widths are a valuable tool for the direct determination of axial dispersion which occurs in size exclusion chromatography. Comparison of experimental and ideal relative peak widths can be used for the direct determination of the axial dispersion. The influence of the type of termination and [R0] (termination by combination) on the total (number) chain length distribution for single , -pulse initiation. [source] The fine-grained matrix of the Semarkona LL3.0 ordinary chondrite: An induced thermoluminescence studyMETEORITICS & PLANETARY SCIENCE, Issue 5 2009Jonathan P. CRAIG The samples had TL sensitivities comparable with 4 mg of bulk samples of type 3.2,3.4 ordinary chondrites, which is very high relative to bulk Semarkona. The other induced TL properties of these samples, TL peak temperatures, and TL peak widths distinguish them from other ordinary chondrite samples where the TL is caused by feldspar. Cathodoluminescence images and other data suggest that the cause of the luminescence in the Semarkona fine-grained matrix is forsterite. In some respects the matrix TL data resemble that of Semarkona chondrules, in which the phosphor is forsterite and terrestrial forsterites from a variety of igneous and metamorphic environments. However, differences in the TL peak temperature versus TL peak width relationship between the matrix samples and the other forsterites suggest a fundamentally different formation mechanism. We also note that forsterite appears to be a major component in many primitive materials, such as nebulae, cometary dust, and Stardust particles. [source] Characterization of Antarctic micrometeorites by thermoluminescenceMETEORITICS & PLANETARY SCIENCE, Issue 5 2009F. SEDAGHATPOUR These micrometeorites have TL sensitivities ranging from 0.017 ± 0.002 to 0.087 ± 0.009 (on a scale normalized to 4 mg of the H3.9 chondrite Dhajala). The four micrometeorites have very similar TL peak temperatures and TL peak widths, and these distinguish them from CI, most CM, CV, CO, and ordinary chondrites. However, the TL properties of these micrometeorites closely resemble those of the unusual CM chondrite MacAlpine Hills (MAC) 87300 and terrestrial forsterites. Heating experiments on submillimeter chips of a CM chondrite and a H5 chondrite suggest that these TL properties are have not been significantly affected by atmospheric passage. Thus we suggest that there is no simple linkage between these micrometeorites and the established meteorite classes, and that forsterite is an important component of these micrometeorites, as it is in many primitive solar system materials. [source] Powder crystallography on macromoleculesACTA CRYSTALLOGRAPHICA SECTION A, Issue 1 2008I. Margiolaki Following the seminal work of Von Dreele, powder X-ray diffraction studies on proteins are being established as a valuable complementary technique to single-crystal measurements. A wide range of small proteins have been found to give synchrotron powder diffraction profiles where the peak widths are essentially limited only by the instrumental resolution. The rich information contained in these profiles, combined with developments in data analysis, has stimulated research and development to apply the powder technique to microcrystalline protein samples. In the present work, progress in using powder diffraction for macromolecular crystallography is reported. [source] High-throughput metabolic stability studies in drug discovery by orthogonal acceleration time-of-flight (OATOF) with analogue-to-digital signal capture (ADC)RAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 12 2010David G. Temesi Screening assays capable of performing quantitative analysis on hundreds of compounds per week are used to measure metabolic stability during early drug discovery. Modern orthogonal acceleration time-of-flight (OATOF) mass spectrometers equipped with analogue-to-digital signal capture (ADC) now offer performance levels suitable for many applications normally supported by triple quadruple instruments operated in multiple reaction monitoring (MRM) mode. Herein the merits of MRM and OATOF with ADC detection are compared for more than 1000 compounds screened in rat and/or cryopreserved human hepatocytes over a period of 3 months. Statistical comparison of a structurally diverse subset indicated good agreement for the two detection methods. The overall success rate was higher using OATOF detection and data acquisition time was reduced by around 20%. Targeted metabolites of diazepam were detected in samples from a CLint determination performed at 1,µM. Data acquisition by positive and negative ion mode switching can be achieved on high-performance liquid chromatography (HPLC) peak widths as narrow as 0.2,min (at base), thus enabling a more comprehensive first pass analysis with fast HPLC gradients. Unfortunately, most existing OATOF instruments lack the software tools necessary to rapidly convert the huge amounts of raw data into quantified results. Software with functionality similar to open access triple quadrupole systems is needed for OATOF to truly compete in a high-throughput screening environment. Copyright © 2010 John Wiley & Sons, Ltd. [source] The detection of phenotypic differences in the metabolic plasma profile of three strains of Zucker rats at 20 weeks of age using ultra-performance liquid chromatography/orthogonal acceleration time-of-flight mass spectrometryRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 19 2006Robert S. Plumb Analysis of biological fluids using ultra-performance liquid chromatography/mass spectrometry (UPLC/MS) (metabonomics) can allow new insights to be gained into disease processes, with advances in chromatographic techniques enabling the detection of thousands of metabolites. In this work metabonomics has been used to investigate the metabolic processes involved in type II diabetes in the Zucker obese rat. Plasma was analyzed from three different strains, the Zucker (fa/fa) obese, Zucker lean and the lean/(fa) obese cross. Using UPLC/MS, ca. 10,000 ions were detected due to the narrow peak widths and excellent peak shapes achieved with this technology. Confidence in the chromatographic performance was demonstrated by the use of quality control standards. The positive and negative ion total ion chromatograms obtained from the three strains were readily distinguishable using multivariate statistical analysis. The greatest difference was observed between the Zucker lean and Zucker lean/(fa) rats compared to the Zucker (fa/fa) obese rats. Positive ions m/z 220 (4.36,min), 282(3.78,min), 359 (5.33,min) and 405 (7.77,min) were elevated in the plasma derived from Zucker lean rats whilst ions m/z 385 (6.80,min) and 646 (4.36,min) were at a lower concentration compared to the plasma from the Zucker (fa/fa) obese animals. Negative ions elevated in the Zucker lean rats included m/z 212 (2.30,min), 514 (2.85,min), 295 (4.39,min), 329 (3.11,min), 343 (2.86,min) and 512 (2.86,min) with ions m/z 538 (4.18,min), 568 (4.18,min), 568 (5.09,min) and 612 (4.30,min) being raised in the samples derived from Zucker (fa/fa) obese animals. The ion m/z 514 (3.85,min) was found to correspond to taurocholate, providing further support for an involvement of taurine metabolism in diabetes. Copyright © 2006 John Wiley & Sons, Ltd. [source] Ultra-performance liquid chromatography coupled to linear ion trap mass spectrometry for the identification of drug metabolites in biological samplesRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 8 2006G. J. Dear The coupling of ultra-performance liquid chromatography, operating at elevated pressures, to a linear ion trap mass spectrometer provides a high-performance system suitable for drug metabolite characterisation. This system demonstrates improved chromatographic efficiency and sensitivity and at the same time provides diagnostic MSn data often critical for metabolite structural assignment. The linear ion trap was capable of dealing with the high chromatographic efficiencies and hence narrow peak widths associated with 1.7,µm particle-packed column separations. Polarity switching and data-dependent MSn data were generated with ease, and applied to the identification of metabolites found in human plasma. Copyright © 2006 John Wiley & Sons, Ltd. 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