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21.
Travelling‐wave ion mobility mass spectrometry and negative ion fragmentation of hybrid and complex N‐glycans 下载免费PDF全文
David J. Harvey Charlotte A. Scarff Matthew Edgeworth Kevin Pagel Konstantinos Thalassinos Weston B. Struwe Max Crispin James H. Scrivens 《Journal of mass spectrometry : JMS》2016,51(11):1064-1079
Nitrogen collisional cross sections (CCSs) of hybrid and complex glycans released from the glycoproteins IgG, gp120 (from human immunodeficiency virus), ovalbumin, α1‐acid glycoprotein and thyroglobulin were measured with a travelling‐wave ion mobility mass spectrometer using dextran as the calibrant. The utility of this instrument for isomer separation was also investigated. Some isomers, such as Man3GlcNAc3 from chicken ovalbumin and Man3GlcNAc3Fuc1 from thyroglobulin could be partially resolved and identified by their negative ion fragmentation spectra obtained by collision‐induced decomposition (CID). Several other larger glycans, however, although existing as isomers, produced only asymmetric rather than separated arrival time distributions (ATDs). Nevertheless, in these cases, isomers could often be detected by plotting extracted fragment ATDs of diagnostic fragment ions from the negative ion CID spectra obtained in the transfer cell of the Waters Synapt mass spectrometer. Coincidence in the drift times of all fragment ions with an asymmetric ATD profile in this work, and in the related earlier paper on high‐mannose glycans, usually suggested that separations were because of conformers or anomers, whereas symmetrical ATDs of fragments showing differences in drift times indicated isomer separation. Although some significant differences in CCSs were found for the smaller isomeric glycans, the differences found for the larger compounds were usually too small to be analytically useful. Possible correlations between CCSs and structural types were also investigated, and it was found that complex glycans tended to have slightly smaller CCSs than high‐mannose glycans of comparable molecular weight. In addition, biantennary glycans containing a core fucose and/or a bisecting GlcNAc residue fell on different mobility‐m/z trend lines to those glycans not so substituted with both of these substituents contributing to larger CCSs. Copyright © 2016 John Wiley & Sons, Ltd. 相似文献
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The crystal structure of the aluminosilicate MCM-68 was solved from synchrotron powder diffraction data by the program FOCUS. The unit cell framework contains Si100.6Al11.4O224. This material crystallizes in space group P42/mnm, where, after Rietveld refinement, a=18.286(1) A and c=20.208(2) A. A three-dimensional framework is found that contains continuous 12-ring channels and two orthogonal, intersecting, undulating 10-ring channels. Rietveld refinement of the model coordinates optimizes the framework geometry, to match the observed intensity profile by Rwp=0.1371, R(F2)=0.1411. It is not possible to determine the location of approximately 0.84 K+ cations remaining in the unit cell after the material is steamed and then dehydrated. The framework model also successfully predicts observed electron diffraction data in two projections, and the tetragonal projection can be determined independently from these data by direct methods. The calculated density of the framework structure is 1.66 g/cm3, and the T-site framework density is 16.6 T/1000 A3. 相似文献
23.
Lam WH Gaspar PP Hrovat DA Trieber DA Davidson ER Borden WT 《Journal of the American Chemical Society》2005,127(27):9886-9894
CASSCF, CASPT2, CCSD(T), and (U)B3LYP electronic structure calculations have been performed in order to investigate the thermal fragmentation of P-phenylphosphirane (1) to phenylphosphinidene (PhP) and ethylene. The calculations show that generation of triplet PhP via a stepwise pathway is 21 kcal mol(-1) less endothermic and has a 12 kcal mol(-1) lower barrier height than concerted fragmentation of 1 to give singlet PhP. The formation of singlet PhP via a concerted pathway is predicted to be stereospecific, whereas formation of triplet PhP is predicted to occur with complete loss of stereochemistry. However, calculations on fragmentation of anti-cis-2,3-dimethyl-P-mesitylphosphirane (cis-1Me) to triplet mesitylphosphinidene (MesP) indicate that this reaction should be more stereospecific, in agreement with the experimental results of Li and Gaspar. Nevertheless, with a predicted free energy of activation of 42 kcal mol(-1), the formation of MesP from cis-1Me is not likely to have occurred in an uncatalyzed reaction at the temperatures at which this phosphirane has been pyrolyzed. 相似文献
24.
J. D. Weston 《Mathematische Zeitschrift》1957,67(1):467-473
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Weston N.J. Baxter L.F. Simmons J.E.L. 《Engineering Management, IEEE Transactions on》1998,45(4):396-406
This paper examines the relationship between formal product development management tools and actual business processes in a world class company, NCR, Dundee, Scotland, UK, whose manufactured products include significant associated computer software written and designed in-house. After providing some background to the company and the research project which has led to this paper, a detailed case study of the software design and development processes in NCR is presented. This is contrasted with the formal management approach NCR is endeavoring to follow. The authors identify some key inconsistencies between the two processes and consider the implications for improving the management of the concept generation process 相似文献
28.
Weston H.T. Hofstatter E.A. Atwood D.K. Bayruns R.J. Michejda J.A. Procanik M.J. Stanik T.D. 《Electronics letters》1988,24(14):834-835
Reports on the development of an NMOS 2:1 frequency divider circuit that operates to over 5 GHz. It is powered from a 2.5 V supply and dissipates only 0.012 W. These results indicate that the use of silicon MOS technology may be extended to very-high-speed low-power applications 相似文献
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Weston I. Nathanson 《Journal of Optimization Theory and Applications》1971,8(4):256-270
Necessary conditions are obtained for the general control problem with the minimizing are required to pass through intermediate-constraint manifolds. It is shown that this includes cases where the integrand or the region of admissibility changes at the constraint points.This research was partly sponsored by the Office of Naval Research under contract NONR-233(76). 相似文献