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101.
Ming-juan Wang Murali Pendela Chang-qin Hu Shao-hong Jin Jos Hoogmartens Ann Van Schepdael Erwin Adams 《Journal of chromatography. A》2010,1217(42):6531-6544
Investigation of acetylspiramycin (ASPM) and its related substances was carried out using a reversed-phase liquid chromatography/tandem mass spectrometry method. The identification of impurities in the ASPM complex was performed with a quadrupole ion trap mass spectrometer, with an electrospray ionization (ESI) source in the positive ion mode which provides MSn capability. A total of 83 compounds were characterized in commercial samples, among which 31 impurities that had never been reported and 31 partially characterized impurities were deduced using the collision-induced dissociation (CID) spectra of major ASPM components as templates. Most of the major impurities arise from the starting materials and the synthesis process. This work provides very useful information for quality control of ASPM and evaluation of its synthesis process. 相似文献
102.
S. Dooley M. P. Burke M. Chaos Y. Stein F. L. Dryer V. P. Zhukov O. Finch J. M. Simmie H. J. Curran 《国际化学动力学杂志》2010,42(9):527-549
The oxidation of methyl formate (CH3OCHO) has been studied in three experimental environments over a range of applied combustion relevant conditions:
- 1. A variable‐pressure flow reactor has been used to quantify reactant, major intermediate and product species as a function of residence time at 3 atm and 0.5% fuel concentration for oxygen/fuel stoichiometries of 0.5, 1.0, and 1.5 at 900 K, and for pyrolysis at 975 K.
- 2. Shock tube ignition delays have been determined for CH3OCHO/O2/Ar mixtures at pressures of ≈ 2.7, 5.4, and 9.2 atm and temperatures of 1275–1935 K for mixture compositions of 0.5% fuel (at equivalence ratios of 1.0, 2.0, and 0.5) and 2.5% fuel (at an equivalence ratio of 1.0).
- 3. Laminar burning velocities of outwardly propagating spherical CH3OCHO/air flames have been determined for stoichiometries ranging from 0.8–1.6, at atmospheric pressure using a pressure‐release‐type high‐pressure chamber.
103.
Hai X Nauwelaers T Busson R Adams E Hoogmartens J Van Schepdael A 《Electrophoresis》2010,31(19):3352-3361
A rapid and sensitive electrophoretically mediated microanalysis method with field-enhanced sample injection (FESI) for in-capillary derivatization was developed to determine selenomethionine (SeMet) and selenomethionine selenoxide (SeOMet). Phthalic anhydride (PA) was selected as the derivatization reagent due to the fast reaction at room temperature and the stability of derivatives. The in-capillary derivatization was accomplished by electrophoretically mixing PA and sample plugs. PA reagent was introduced hydrodynamically into the capillary, whereas the sample solution was injected electrokinetically, thus allowing a selective preconcentration of the analytes by FESI. For FESI, the optimum sample solvent was 2 mM borate solution. The borate buffer was suitable for both in-capillary derivatization and separation of the derivatives. The combination of electrophoretically mediated microanalysis with FESI for in-capillary derivatization was successfully achieved with about 800-fold concentration sensitivity enhancement compared to direct CE-UV detection in the same setup. The present method is miniaturized and fully automated, which ensures the on-line derivatization, stacking, separation and detection in 10 min. Finally, the developed method was successfully applied to measure enzyme activities by analyzing the reaction mixtures of SeMet with human flavin-containing monooxygenases (FMO). The results showed that both FMO1 and FMO3, but not FMO5 could catalyze the Se-oxygenation of SeMet. 相似文献
104.
Bronstein LM Shtykova EV Malyutin A Dyke JC Gunn E Gao X Stein B Konarev PV Dragnea B Svergun DI 《The journal of physical chemistry. C, Nanomaterials and interfaces》2010,114(50):21900-21907
Iron oxide nanoparticles (NPs) with a diameter 21.6 nm were coated with poly(maleic acid-alt-1-octadecene) (PMAcOD) modified with grafted 5,000 Da poly(ethyelene glycol) (PEG) or short ethylene glycol (EG) tails. The coating procedure utilizes hydrophobic interactions of octadecene and oleic acid tails, while the hydrolysis of maleic anhydride moieties as well as the presence of hydrophilic PEG (EG) tails allows the NP hydrophilicity. The success of the NP coating was found to be independent of the degree of grafting which was varied between 20 and 80% of the -MacOD-units, but depended on the length of the grafted tail. The NP coating and hydrophilization did not occur when the modified copolymer contained 750 Da PEG tails independently of the grafting degree. To explain this phenomenon the micellization of the modified PMAcOD copolymers in water was analyzed by small angle x-ray scattering (SAXS). The PMAcOD molecules with the grafted 750 Da PEG tails form compact non-interacting disk-like micelles, whose stability apparently allows for no interactions with the NP hydrophobic shells. The PMAcOD containing the 5,000 Da PEG and EG tails form much larger aggregates capable of an efficient coating of the NPs. The coated NPs were characterized using transmission electron microscopy, dynamic light scattering, ζ-potential measurements, and thermal gravimetry analysis. The latter method demonstrated that the presence of long PEG tails in modified PMAcOD allows the attachment of fewer macromolecules (by a factor of ~20) compared to the case of non-modified or EG modified PMAcOD, emphasizing the importance of PEG tails in NP hydrophilization. The NPs coated with PMAcOD modified with 60% (towards all -MAcOD- units) of the 5,000 PEG tails bear a significant negative charge and display good stability in buffers. Such NPs can be useful as magnetic cores for virus-like particle formation. 相似文献
105.
Bhaskar Godugu Pedatsur Neta Yamil Simón-Manso Stephen E. Stein 《Journal of the American Society for Mass Spectrometry》2010,21(7):1169-1176
A prominent dissociation path for electrospray generated tryptic peptide ions is the dissociation of the peptide bond linking
the second and third residues from the ammo-terminus. The formation of the resulting b2 and y
n−2 fragments has been rationalized by specific facile mechanisms. An examination of spectral libraries shows that this path
predominates in diprotonated peptides composed of 12 or fewer residues, with the notable exception of peptides containing
glutamine or glutamic acid at the N-terminus. To elucidate the mechanism by which these amino acids affect peptide fragmentation,
we synthesized peptides of varying size and composition and examined their MS/MS spectra as a function of collision voltage
in a triple quadrupole mass spectrometer. Loss of water from N-terminal glutamic acid and glutamine is observed at a lower
voltage than any other fragmentation, leading to cyclization of the terminal residue. This cyclization results in the conversion
of the terminal amine group to an imide, which has a lower proton affinity. As a result, the second proton is not localized
at the N-terminus but is readily transferred to other sites, leading to fragmentation near the center of the peptide. Further
confirmation was obtained by examining peptides with N-terminal pyroglutamic acid and N-acetyl peptides. Peptides with N-terminal
proline maintain the trend of forming b2 and y
n−2 because their ring contains an imine rather than imide and has sufficient proton affinity to retain the proton at the N-terminus. 相似文献
106.
107.
A Poly(cobaloxime)/Carbon Nanotube Electrode: Freestanding Buckypaper with Polymer‐Enhanced H2‐Evolution Performance 下载免费PDF全文
Dr. Bertrand Reuillard Dr. Julien Warnan Jane J. Leung David W. Wakerley Dr. Erwin Reisner 《Angewandte Chemie (International ed. in English)》2016,55(12):3952-3957
A freestanding H2‐evolution electrode consisting of a copolymer‐embedded cobaloxime integrated into a multiwall carbon nanotube matrix by π–π interactions is reported. This electrode is straightforward to assemble and displays high activity towards hydrogen evolution in near‐neutral pH solution under inert and aerobic conditions, with a cobalt‐based turnover number (TONCo) of up to 420. An analogous electrode with a monomeric cobaloxime showed less activity with a TONCo of only 80. These results suggest that, in addition to the high surface area of the porous network of the buckypaper, the polymeric scaffold provides a stabilizing environment to the catalyst, leading to further enhancement in catalytic performance. We have therefore established that the use of a multifunctional copolymeric architecture is a viable strategy to enhance the performance of molecular electrocatalysts. 相似文献
108.
Clean Donor Oxidation Enhances the H2 Evolution Activity of a Carbon Quantum Dot–Molecular Catalyst Photosystem 下载免费PDF全文
Benjamin C. M. Martindale Evelyne Joliat Dr. Cyril Bachmann Prof. Dr. Roger Alberto Dr. Erwin Reisner 《Angewandte Chemie (International ed. in English)》2016,55(32):9402-9406
Carbon quantum dots (CQDs) are new‐generation light absorbers for photocatalytic H2 evolution in aqueous solution, but the performance of CQD‐molecular catalyst systems is currently limited by the decomposition of the molecular component. Clean oxidation of the electron donor by donor recycling prevents the formation of destructive radical species and non‐innocent oxidation products. This approach allowed a CQD‐molecular nickel bis(diphosphine) photocatalyst system to reach a benchmark lifetime of more than 5 days and a record turnover number of 1094±61 molH2 (molNi)?1 for a defined synthetic molecular nickel catalyst in purely aqueous solution under AM1.5G solar irradiation. 相似文献
109.
Jinbo Hu Prof. Andreas Stein Prof. Philippe Bühlmann 《Angewandte Chemie (International ed. in English)》2016,55(26):7544-7547
Ion‐selective electrodes (ISEs) are widely used tools for fast and accurate ion sensing. Herein their design is simplified by embedding a potentiometric cell into paper, complete with an ISE, a reference electrode, and a paper‐based microfluidic sample zone that offer the full function of a conventional ISE setup. The disposable planar paper‐based ion‐sensing platform is suitable for low‐cost point‐of‐care and in‐field testing applications. The design is symmetrical and each interfacial potential within the cell is well defined and reproducible, so that the response of the device can be theoretically predicted. For a demonstration of clinical applications, paper‐based Cl? and K+ sensors are fabricated with highly reproducible and linear responses towards different concentrations of analyte ions in aqueous and biological samples. The single‐use devices can be fabricated by a scalable method, do not need any pretreatment prior to use, and only require a sample volume of 20 μL. 相似文献
110.
Babushok VI Linstrom PJ Reed JJ Zenkevich IG Brown RL Mallard WG Stein SE 《Journal of chromatography. A》2007,1157(1-2):414-421
A comprehensive database of gas chromatographic retention properties of chemical compounds has been developed using multiple literature sources. The National Institute of Standards and Technology (NIST) database of retention data for non-polar and polar stationary phases currently contains 292,924 data records for 42,888 compounds. The database includes data for Kováts indices, linear indices, Lee indices, retention times and retention volumes. The first release of this database for non-polar stationary phases is available with NIST/US Environmental Protection Agency (EPA)/National Institutes of Health (NIH) Mass Spectral Database (June 2005) and through the internet (NIST Chemistry WebBook). The paper describes the database and the process by which it has been compiled. The format of data presentation and the quality control procedures are described. Data sources of gas chromatographic retention data are also discussed. 相似文献