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The boronic acid derivatization of carbohydrates is demonstrated as an ion mobility shift strategy to improve confidence in the identification and characterization of carbohydrate assignments using ion mobility-mass spectrometry. 相似文献
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Larissa S. Fenn Michal Kliman Ablatt Mahsut Sophie R. Zhao John A. McLean 《Analytical and bioanalytical chemistry》2009,394(1):235-244
The conformation space occupied by different classes of biomolecules measured by ion mobility-mass spectrometry (IM-MS) is
described for utility in the characterization of complex biological samples. Although the qualitative separation of different
classes of biomolecules on the basis of structure or collision cross section is known, there is relatively little quantitative
cross-section information available for species apart from peptides. In this report, collision cross sections are measured
for a large suite of biologically salient species, including oligonucleotides (n = 96), carbohydrates (n = 192), and lipids (n = 53), which are compared to reported values for peptides (n = 610). In general, signals for each class are highly correlated, and at a given mass, these correlations result in predicted
collision cross sections that increase in the order oligonucleotides < carbohydrates < peptides < lipids. The specific correlations
are described by logarithmic regressions, which best approximate the theoretical trend of increasing collision cross section
as a function of increasing mass. A statistical treatment of the signals observed within each molecular class suggests that
the breadth of conformation space occupied by each class increases in the order lipids < oligonucleotides < peptides < carbohydrates.
The utility of conformation space analysis in the direct analysis of complex biological samples is described, both in the
context of qualitative molecular class identification and in fine structure examination within a class. The latter is demonstrated
in IM-MS separations of isobaric oligonucleotides, which are interpreted by molecular dynamics simulations.
Figure Potential for performing simultaneous “omics” through the separation of biomolecular classes on the basis of structure and
mass using ion mobility-mass spectrometry
Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.
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John A. McLeanEmail: |