Journal ArticleDOI
Shattering of Peptide Ions on Self-Assembled Monolayer Surfaces
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TLDR
Modeling demonstrated that, for short reaction delays, dissociation of these peptides is solely determined by shattering, which results in much better sequence coverage for the singly protonated peptides than dissociation patterns obtained with any of the slow activation methods.Abstract:
Time- and collision energy-resolved surface-induced dissociation (SID) of des-Arg(1)- and des-Arg(9)-bradykinin on a fluorinated self-assembled monolayer (SAM) surface was studied by use of a novel Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS) specially equipped to perform SID experiments. Time-resolved fragmentation efficiency curves (TFECs) were modeled by an RRKM-based approach developed in our laboratory that utilizes a very flexible analytical expression for the internal energy deposition function capable of reproducing both single- and multiple-collision activation in the gas phase and excitation by collisions with a surface. Both experimental observations and modeling establish a very sharp transition in the dynamics of ion-surface interaction: the shattering transition. The experimental signature for this transition is the appearance of prompt (time-independent) fragmentation, which becomes dominant at high collision energies. Shattering opens a variety of dissociation pathways that are not accessible to slow collisional and thermal ion activation. This results in much better sequence coverage for the singly protonated peptides than dissociation patterns obtained with any of the slow activation methods. Modeling demonstrated that, for short reaction delays, dissociation of these peptides is solely determined by shattering. Internal energies required for shattering transition are approximately the same for des-Arg(1) and des-Arg(9)-bradykinin, resulting in the overlap of fragmentation efficiency curves obtained at short reaction delays. At longer delay times, parent ions depletion is mainly determined by a slow decay rate and fragmentation efficiency curves for des-Arg(1) and des-Arg(9)-bradykinin diverge. Dissociation thresholds of 1.17 and 1.09 eV and activation entropies of -22.2 and -23.3 cal/(mol K) were obtained for des-Arg(1) and des-Arg(9)-bradykinin from RRKM modeling of time-resolved data. Dissociation parameters for des-Arg(1)-bradykinin are in good agreement with parameters derived from thermal experiments. However, there is a significant discrepancy between the thermal data and dissociation parameters for des-Arg(9)-bradykinin obtained in this study. The difference is attributed to the differences in conformations that undergo thermal activation and activation by ion-surface collisions prior to dissociation.read more
Citations
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Journal ArticleDOI
Ion activation methods for tandem mass spectrometry.
Lekha Sleno,Dietrich A. Volmer +1 more
TL;DR: This tutorial presents the most common ion activation techniques employed in tandem mass spectrometry and individual methods are presented so as to facilitate the understanding of each mechanism of activation and their particular advantages and representative applications.
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Ultraviolet photofragmentation of biomolecular ions
TL;DR: This review discusses experimental results on various biological molecules that have been generated by several research groups using different light wavelengths and mass analyzers and examines the characteristics of photofragmentation.
Journal ArticleDOI
Collisional activation of peptide ions in FT-ICR mass spectrometry.
Julia Laskin,Jean H. Futrell +1 more
TL;DR: These studies provide the first quantitative comparison of gas-phase multiple-collision activation and SID of model peptides, and the combination of FT-ICR with SID was utilized to carry out the first time-resolved experiments that examine the kinetics of peptide fragmentation.
Journal ArticleDOI
Activation of large lons in FT-ICR mass spectrometry
Julia Laskin,Jean H. Futrell +1 more
TL;DR: This review emphasizes the most promising methods for activation and dissociation of complex ions and presents this discussion in the context of general knowledge of reaction kinetics and dynamics largely established for small ions.
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Direct Chemical Dynamics Simulations.
TL;DR: Direct dynamics simulation studies are described for bimolecular SN2 nucleophilic substitution, unimolecular decomposition, post-transition-state dynamics, mass spectrometry experiments, and semiclassical vibrational spectra.
References
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Journal ArticleDOI
Influence of Peptide Composition, Gas-Phase Basicity, and Chemical Modification on Fragmentation Efficiency: Evidence for the Mobile Proton Model
TL;DR: The relative positions of the ESI/SID fragmentation efficiency curves depend on several parameters which include peptide composition (e.g., presence/absence of a basic amino acid residue) and peptide size.
Journal ArticleDOI
Blackbody Infrared Radiative Dissociation of Bradykinin and Its Analogues: Energetics, Dynamics, and Evidence for Salt-Bridge Structures in the Gas Phase
TL;DR: Experimental evidence is provided that the most stable form of singly protonated bradykinin is a salt-bridge structure, and the presence of a second charge can dramatically influence the dissociation dynamics of these ions.
Journal ArticleDOI
Influence of Secondary Structure on the Fragmentation of Protonated Peptides
George Tsaprailis,Hari Nair,Árpád Somogyi,Vicki H. Wysocki,Wenqing Zhong,Jean H. Futrell,and Scott G. Summerfield,Simon J. Gaskell +7 more
TL;DR: The influence of acid−base interactions on the gas-phase dissociation of a series of protonated peptides was investigated and it was observed that the number of ionizing protons relative to the numberof basic residues in peptides containing acidic residues is a contributing factor in the fragmentation behavior.
Journal ArticleDOI
Surface-induced dissociation: an effective tool to probe structure, energetics and fragmentation mechanisms of protonated peptides.
TL;DR: The observed trends support the essential role of the mobile proton model in understanding peptide fragmentation by low-energy tandem mass spectrometry.
Journal ArticleDOI
A High‐performance Modular Data System for Fourier Transform Ion Cyclotron Resonance Mass Spectrometry
TL;DR: A high-performance data system based on a personal computer running user-friendly Windows software and readily available commercial components contained in a VXI chassis and a minimal complement of simple custom electronics is presented.
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