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81.
Xiaoyan Li Zixuan Li Boer Xie Joshua S. Sharp 《Journal of the American Society for Mass Spectrometry》2013,24(11):1767-1776
Protein oxidation is typically associated with oxidative stress and aging and affects protein function in normal and pathological processes. Additionally, deliberate oxidative labeling is used to probe protein structure and protein–ligand interactions in hydroxyl radical protein footprinting (HRPF). Oxidation often occurs at multiple sites, leading to mixtures of oxidation isomers that differ only by the site of modification. We utilized sets of synthetic, isomeric “oxidized” peptides to test and compare the ability of electron-transfer dissociation (ETD) and collision-induced dissociation (CID), as well as nano-ultra high performance liquid chromatography (nanoUPLC) separation, to quantitate oxidation isomers with one oxidation at multiple adjacent sites in mixtures of peptides. Tandem mass spectrometry by ETD generates fragment ion ratios that accurately report on relative oxidative modification extent on specific sites, regardless of the charge state of the precursor ion. Conversely, CID was found to generate quantitative MS/MS product ions only at the higher precursor charge state. Oxidized isomers having multiple sites of oxidation in each of two peptide sequences in HRPF product of protein Robo-1 Ig1-2, a protein involved in nervous system axon guidance, were also identified and the oxidation extent at each residue was quantified by ETD without prior liquid chromatography (LC) separation. ETD has proven to be a reliable technique for simultaneous identification and relative quantification of a variety of functionally different oxidation isomers, and is a valuable tool for the study of oxidative stress, as well as for improving spatial resolution for HRPF studies. Figure
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82.
A modified glassy carbon (GC) electrode was developed for the amperometric detection of biogenic amines, particularly histamine. The electrode was modified with the co‐enzyme pyrroloquinoline quinone (PQQ) by entrapment during electropolymerziation of pyrrole to form polypyrrole (PPy). This method formed a thin film on the electrode surface possessing very good stability with a shelf‐life exceeding one month without loss of signal. Optimal conditions for the PQQ/PPy electrode were determined and a linear response was found for histamine in phosphate buffer (pH 6) at +550 mV from 40 to 170 mg L?1 with a limit of detection (S/N≥3) of 38 mg L?1. The practical linear range offered by this method suggests ideal use for spoilage detection in fermented foods. 相似文献
83.
Eric D. Merkley Erin S. Baker Kevin L. Crowell Daniel J. Orton Thomas Taverner Charles Ansong Yehia M. Ibrahim Meagan C. Burnet John R. Cort Gordon A. Anderson Richard D. Smith Joshua N. Adkins 《Journal of the American Society for Mass Spectrometry》2013,24(3):444-449
Chemical cross-linking of proteins followed by proteolysis and mass spectrometric analysis of the resulting cross-linked peptides provides powerful insight into the quaternary structure of protein complexes. Mixed-isotope cross-linking (a method for distinguishing intermolecular cross-links) was coupled with liquid chromatography, ion mobility spectrometry and mass spectrometry (LC-IMS-MS) to provide an additional separation dimension to the traditional cross-linking approach. This method produced multiplet m/z peaks that are aligned in the IMS drift time dimension and serve as signatures of intermolecular cross-linked peptides. We developed an informatics tool to use the amino acid sequence information inherent in the multiplet spacing for accurate identification of the cross-linked peptides. Because of the separation of cross-linked and non-cross-linked peptides in drift time, our LC-IMS-MS approach was able to confidently detect more intermolecular cross-linked peptides than LC-MS alone. 相似文献
84.
Rosie Le Joshua E. Young Joseph J. Pesek Maria T. Matyska 《Journal of separation science》2013,36(16):2578-2583
Five ingredients (caffeine, l ‐arginine, creatine, β‐alanine, and 1,3‐dimethylamylamine) from a workout supplement were separated by HPLC with UV detection and LC–MS using an analytical column based on silica hydride operating in aqueous normal phase mode. While RP methods were observed to be inadequate for the analysis due to low retention, aqueous normal phase chromatography was able to readily retain and resolve the analytes. After method development on the HPLC–UV system, the conditions were successfully transferred to an LC–MS system for analysis. Based on calibration curve data, estimates of 63.5, 380.3, and 13.1 mg/serving (5.50 g) were obtained for creatine, l ‐arginine, and 1,3‐dimethylamylamine, respectively. Standard addition data results were compared to those of the calibration curve study, and the two values differed by less than 1% in the case of creatine. The conditions are suitable for further development as a reliable means of quantitating the analytes in workout supplement formulations. 相似文献
85.
Jimmy Yuk Kristina L. McIntyre Christian Fischer Joshua Hicks Kimberly L. Colson Ed Lui Dan Brown John T. Arnason 《Analytical and bioanalytical chemistry》2013,405(13):4499-4509
The use of 1H-NMR-based metabolomics to distinguish and identify unique markers of five Ontario ginseng (Panax quinquefolius L.) landraces and two ginseng species (P. quinquefolius and P. ginseng) was evaluated. Three landraces (2, 3, and 5) were distinguished from one another in the principal component analysis (PCA) scores plot. Further analysis was conducted and specific discriminating metabolites from the PCA loadings were determined. Landraces 3 and 5 were distinguishable on the basis of a decreased NMR intensity in the methyl ginsenoside region, indicating decreased overall ginsenoside levels. In addition, landrace 5 was separated by an increased amount of sucrose relative to the rest of the landraces. Landrace 2 was separated from the rest of the landraces by the increased level of ginsenoside Rb1. The Ontario P. quinquefolius was also compared with Asian P. ginseng by PCA, and clear separation between the two groups was detected in the PCA scores plot. The PCA loadings plot and a t-test NMR difference plot were able to identify an increased level of maltose and a decreased level of sucrose in the Asian ginseng compared with the Ontario ginseng. An overall decrease of ginsenoside content, especially ginsenoside Rb1, was also detected in the Asian ginseng’s metabolic profile. This study demonstrates the potential of NMR-based metabolomics as a powerful high-throughput technique in distinguishing various closely related ginseng landraces and its ability to identify metabolic differences from Ontario and Asian ginseng. The results from this study will allow better understanding for quality assessment, species authentication, and the potential for developing a fully automated method for quality control. Figure
Principal component analysis scores and loadings plot for differentiating between closely-related ginseng landraces in Ontario, Canada 相似文献
86.
Bismuth chloride was used to catalyze the [2 + 3] cycloaddition between sodium azide with aryl nitriles, aliphatic nitriles, and vinyl nitriles. A number of 5-substituted 1H-tetrazoles were synthesized in water or isopropanol/water mixtures using microwave heating. Good yields were obtained for these reactions when heated for 1 h at 120–160 °C in a 3:1 isopropanol/water mixture. A few of the less reactive nitriles required longer reaction times for good yields. 相似文献
87.
88.
Vipul Gupta Joshua A. Tuscano Naomi R. Romriell Robert C. Davis Matthew R. Linford 《Surface and interface analysis : SIA》2014,46(2):106-108
An important aspect of the robustness of an electronic device is its ability to resist water, fingerprints, dirt, and smudges that may compromise its ability to function and/or the information within it. Here, we report a chemical analysis by ToF‐SIMS, wetting, and XPS of the surfaces in a commercially available Apple iPod nano (8GB, MC525LL/A), which showed good resistance to its environment. This analysis reveals that the front panel (touchscreen) of the device is coated with a low free energy fluorinated polymer that may consist of short segments of a fluorinated hydrocarbon connected through ether linkages. No other part of the device appears to have this hydrophobic coating. A plasma treatment of the device leads to a deterioration of its performance. This work demonstrates how different analytical techniques can complement each other and contribute to a better understanding of a surface or a material. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
89.
Oscar B. Torres Rashmi Jalah Kenner C. Rice Fuying Li Joshua F. G. Antoline Malliga R. Iyer Arthur E. Jacobson Mohamed Nazim Boutaghou Carl R. Alving Gary R. Matyas 《Analytical and bioanalytical chemistry》2014,406(24):5927-5937
A potential new treatment for drug addiction is immunization with vaccines that induce antibodies that can abrogate the addictive effects of the drug of abuse. One of the challenges in the development of a vaccine against drugs of abuse is the availability of an optimum procedure that gives reproducible and high yielding hapten-protein conjugates. In this study, a heroin/morphine surrogate hapten (MorHap) was coupled to bovine serum albumin (BSA) using maleimide-thiol chemistry. MorHap-BSA conjugates with 3, 5, 10, 15, 22, 28, and 34 haptens were obtained using different linker and hapten ratios. Using this optimized procedure, MorHap-BSA conjugates were synthesized with highly reproducible results and in high yields. The number of haptens attached to BSA was compared by 2,4,6-trinitrobenzenesulfonic acid (TNBS) assay, modified Ellman’s test and matrix assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF MS). Among the three methods, MALDI-TOF MS discriminated subtle differences in hapten density. The effect of hapten density on enzyme-linked immunosorbent assay (ELISA) performance was evaluated with seven MorHap-BSA conjugates of varying hapten densities, which were used as coating antigens. The highest antibody binding was obtained with MorHap-BSA conjugates containing 3–5 haptens. This is the first report that rigorously analyzes, optimizes and characterizes the conjugation of haptens to proteins that can be used for vaccines against drugs of abuse. The effect of hapten density on the ELISA detection of antibodies against haptens demonstrates the importance of careful characterization of the hapten density by the analytical techniques described. 相似文献
90.
Stanislav S. Stoyko Andrew J. Craig Joshua W. Kotchey Jennifer A. Aitken 《Acta Crystallographica. Section C, Structural Chemistry》2021,77(1):1-10
The new quaternary thiosilicate, Li2PbSiS4 (dilithium lead silicon tetrasulfide), was prepared in an evacuated fused‐silica tube via high‐temperature, solid‐state synthesis at 800 °C, followed by slow cooling. The crystal structure was solved and refined using single‐crystal X‐ray diffraction data. By strict definition, the title compound crystallizes in the stannite structure type; however, this type of structure can also be described as a compressed chalcopyrite‐like structure. The Li+ cation lies on a crystallographic fourfold rotoinversion axis, while the Pb2+ and Si4+ cations reside at the intersection of the fourfold rotoinversion axis with a twofold axis and a mirror plane. The Li+ and Si4+ cations in this structure are tetrahedrally coordinated, while the larger Pb2+ cation adopts a distorted eight‐coordinate dodecahedral coordination. These units join together via corner‐ and edge‐sharing to create a dense, three‐dimensional structure. Powder X‐ray diffraction indicates that the title compound is the major phase of the reaction product. Electronic structure calculations, performed using the full potential linearized augmented plane wave method within density functional theory (DFT), indicate that Li2PbSiS4 is a semiconductor with an indirect bandgap of 2.22 eV, which compares well with the measured optical bandgap of 2.51 eV. The noncentrosymmetric crystal structure and relatively wide bandgap designate this compound to be of interest for IR nonlinear optics. 相似文献