Chapter 10. Biomolecular Ions in a Solvent-Free Environment

  1. Igor A. Kaltashov and
  2. Stephen J. Eyles

Published Online: 27 JAN 2005

DOI: 10.1002/0471705179.ch10

Mass Spectrometry in Biophysics: Conformation and Dynamics of Biomolecules

Mass Spectrometry in Biophysics: Conformation and Dynamics of Biomolecules

How to Cite

Kaltashov, I. A. and Eyles, S. J. (2005) Biomolecular Ions in a Solvent-Free Environment, in Mass Spectrometry in Biophysics: Conformation and Dynamics of Biomolecules, John Wiley & Sons, Inc., Hoboken, NJ, USA. doi: 10.1002/0471705179.ch10

Author Information

  1. University of Massachusetts at Amherst, USA

Publication History

  1. Published Online: 27 JAN 2005
  2. Published Print: 6 APR 2005

Book Series:

  1. Wiley-Interscience Series in Mass Spectrometry

Book Series Editors:

  1. Dominic M. Desiderio2 and
  2. Nico M. M. Nibbering3

Series Editor Information

  1. 2

    Departments of Neurology and Biochemistry, University of Tennessee Health Science Center, USA

  2. 3

    Vrije Universiteit Amsterdam, The Netherlands

ISBN Information

Print ISBN: 9780471456025

Online ISBN: 9780471705178



  • gas phase protein ions;
  • solvent-free structure;
  • intrinsic properties;
  • ion mobility;
  • gas-phase hydrogen-deuterium exchange;
  • partially hydrated ions;
  • mesoscopics


One of the most intriguing features of biological mass spectrometry, which is also its major point of distinction from other biophysical techniques, is the environment in which the biopolymers are studied. Solvent removal from the macromolecular ion is usually a requirement for high-quality MS measurement; however, it certainly introduces rather dramatic changes in the behavior of the biopolymer. Such alteration of the protein environment and consequent changes of the macromolecular properties present a great challenge for biophysicists. At the same time, the ability to generate and manipulate solvent-free biopolymers also presents a unique opportunity to study intrinsic properties of biomolecules unaffected by the solvent. In this chapter we will briefly discuss the role played by the solvent molecules in determining the structural and dynamic characteristics of biopolymers and consider the consequences of solvent elimination from the biomolecular environment. This will be followed by a brief discussion of several MS-based techniques that are commonly used to study the behavior of biomolecular ions in a solvent-free environment. The chapter is not meant to be an exhaustive discussion of the current state of the field of the gas phase structure and dynamics of macromolecular ions. Instead, emphasis will be placed on the differences between the solution- and gas-phase structures of biopolymers and their implications for the studies of biomolecular properties in solution using MS-based methods.