scholarly journals Biomolecule structure characterization in the gas phase using mass spectrometry

2002 ◽  
Vol 16 (2) ◽  
pp. 71-79 ◽  
Author(s):  
Brian Bothner ◽  
Laurie Carmitchel ◽  
Kristin Staniszewski ◽  
Martin Sonderegger ◽  
Gary Siuzdak
Keyword(s):  
Mass Spectrometry ◽  
Gas Phase ◽  
Cation Binding ◽  
Structure Characterization ◽  
Alkali Cation ◽  
Desorption Ionization ◽  
Fab Mass Spectrometry ◽  
Deuterated Analog ◽  
Bidentate Complex ◽  
Cation Complexes

Carbohydrate/cation interactions were examined in the gas phase using mass spectrometry and the results were compared with computer generated models of the complexes. Monosaccharide/alkali cation complexes of five carbohydrates, D-fructose, D-glucose, D-galactose, D-mannose, and a deuterated analog of D-glucose, 6,6-D-glucose-d2, were studied. Among the technuques used in this effort were electrospray ionization (ESI), desorption/ionization on silicon (DIOS), matrix-assisted laser desorption/ionization (MALDI) and fast atom/ion bombardment (FAB) mass spectrometry. A series of ESI, DIOS, MALDI and FAB-MS experiments were used to obtain relative cation binding preferences of each monosaccharide. Heterodimers of 6,6-D-glucose-d2formed with each of the monosaccharides show that Na+binding for D-fructose, D-mannose and D-galactose is similar, while D-glucose was 25% weaker. Modeling studies and energy minimization calculations on the alpha and beta forms of the monosaccharide alkali cation complexes are consistent with the experimental data and indicate that D-fructose, D-galactose, and D-mannose undergo tridentate and tetradentate binding with Na+and Li+while D-glucose would only form a bidentate complex.

Halide Size-Selective Binding by Cucurbit[5]uril–Alkali Cation Complexes in the Gas Phase

2021 ◽  
Author(s):  
Tina Heravi ◽  
Jiewen Shen ◽  
Spencer Johnson ◽  
Matthew C. Asplund ◽  
David V. Dearden
Keyword(s):  
Gas Phase ◽  
Alkali Cation ◽  
Selective Binding ◽  
Cation Complexes

Matrix-Assisted Laser Desorption/Ionization Time-of-Flight Mass Spectrometry of Dextran and Dextrin Derivatives

2003 ◽  
Vol 9 (1) ◽  
pp. 61-70 ◽  
Author(s):  
Sajid Bashir ◽  
Peter J. Derrick ◽  
Peter Critchley ◽  
Paul J. Gates ◽  
James Staunton
Keyword(s):  
Mass Spectrometry ◽  
Gas Phase ◽  
Time Of Flight ◽  
Laser Desorption ◽  
Laser Desorption Ionization ◽  
Ionization Time ◽  
Desorption Ionization ◽  
Flight Mass Spectrometry ◽  
Matrix Assisted Laser ◽  
Matrix Assisted Laser Desorption

Application of matrix-assisted laser desorption/ionization (MALDI) to the analysis of dextran and dextrin derivatives, specifically glucose saccharides, by time-of-flight (TOF) mass spectrometry is reported. MALDI-TOF analysis was carried out on alpha-, beta-and gamma-cyclodextrin, two O-methylated beta-cyclodextrins of differing degrees of substitution (DS) and dextrans (a linear glucose saccharide), as pure and doped solutions and as mixtures of two or more of these analytes. Doping was carried out with trace amounts of inorganic salts. The purpose of the analysis of the cyclodextrins was to determine whether they would form inclusion complexes with the various added cations, or whether less specific cation addition/exchange was occurring either prior to desorption or in the gas phase.

scholarly journals DNA and RNA Telomeric G-Quadruplexes: What Topology Features Can be Inferred from Ion Mobility Mass Spectrometry?

2019 ◽  
Author(s):  
Valentina D’Atri ◽  
Valerie Gabelica
Keyword(s):  
Mass Spectrometry ◽  
Gas Phase ◽  
Ion Mobility Spectrometry ◽  
Ion Mobility ◽  
Native Mass Spectrometry ◽  
Cation Binding ◽  
Telomeric Dna ◽  
Dna And Rna ◽  
G Quadruplex ◽  
Multiple Structures

Maintenance of the telomeres is key to chromosome integrity and cell proliferation. The G-quadruplex structures formed by telomeric DNA and RNA (TTAGGG and UUAGGG repeats, respectively) are key to this process. However, because these sequences are particularly polymorphic, solving high-resolution structures is not always possible, and there is a need for new methodologies to characterize the multiple structures coexisting in solution. In this context, we evaluated whether ion mobility spectrometry coupled to native mass spectrometry could help separate and assign the G-quadruplex topologies. We explored the circular dichroism spectra, multimer formation, cation binding, and ion mobility spectra of several 4-repeat and 8-repeat telomeric DNA and RNA sequences, both in NH<sub>4</sub><sup>+</sup> and in K<sup>+</sup>. In 1 mM K<sup>+</sup> and 100 mM trimethylammonium acetate, all RNAs fold intramolecularly (no multimer). In 8-repeat sequences, the subunits are not independent: in DNA the first subunit disfavors the folding of the second one, whereas in RNA the two subunits fold cooperatively via cation-mediated stacking. Ion mobility spectrometry shows that gas-phase structures keep a memory of the solution ones, but not identical. At the native charge states, the loops can rearrange in a variety of ways (unless they are constrained by pre-formed hydrogen bonds), thereby wrapping the core and masking the strand arrangements. Our study highlights that, to progress towards structural assignment from IM-MS experiments, deeper understanding of the solution-to-gas-phase rearrangement mechanisms is warranted. <br>

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