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Infrared laser multiphoton dissociation of proton-bound dimers of biomolecules: a new method to probe the acid-base properties of local sites in complex molecules

Campbell, Sherrie and Beauchamp, J. L. (1992) Infrared laser multiphoton dissociation of proton-bound dimers of biomolecules: a new method to probe the acid-base properties of local sites in complex molecules. In: Applied Spectroscopy in Materials Science II. Proceedings of SPIE. No.1636. Society of Photo-optical Instrumentation Engineers (SPIE) , Bellingham, WA, pp. 201-210. ISBN 9780819407825. https://resolver.caltech.edu/CaltechAUTHORS:20190221-110529822

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Abstract

New techniques such as matrix assisted laser desorption, electrospray ionization, and fast atom or ion bombardment make it possible to obtain quasimolecular (e.g. protonated) ions of thermally fragile biomolecules without significant decomposition or fragmentation. These ions can be studied using a variety of mass spectrometric techniques, most powerful among which is Fourier transform ion cyclotron resonance spectroscopy (FT-ICR). One of the important advantages of FT-ICR is the ability to store ions for long periods of time, facilitaüng studies of processes such as bimolecular reactions and laser photodissociation. One significant application of FT-ICR has been to study the acid-base properties of molecules in the gas phase. In this article we demonstrate a new method to probe the acid-base properties of local sites in biomolecules using a novel application of infrared multiphoton dissociation. The usual method of studying proton transfer reactions with appropriate reference bases does not work well with large molecules due to their propensity for radiative bimolecular cluster formation. The difficulty which this introduces can be circumvented by dissociating the proton bound dimer by infrared multiphoton excitation with a cw CO_2 laser. Infrared heating assists dissociation alongthe lowest energy pathway and fragments the dimer to leave the proton preferentially on the more basic site. We illustrate this technique by demonstrating that the proton affinity of N-acetyl glycine is intermediate between glycine and alanine.


Item Type:Book Section
Related URLs:
URLURL TypeDescription
https://doi.org/10.1117/12.59313DOIArticle
ORCID:
AuthorORCID
Beauchamp, J. L.0000-0001-8839-4822
Additional Information:© 1992 Society of Photo-Optical Instrumentation Engineers (SPIE). Contribution No. 8598 from the Arthur Amos Noyes Laboratory of Chemical Physics, California Institute of Technology. The authors wish to thank K. Irikura for his assistance in designing the sample volatilization source. We are indebted to Dr. Arnold Beckman and the Beckman Institute at Caltech for their support of our studies of biomolecule mass spectrometry. We gratefully acknowledge the financial support of Sherrie Campbell from a NIH-NRSA traineeship in Biotechnology. This work was supported in part by the National Science Foundation under grant CHE-9 108318.
Funders:
Funding AgencyGrant Number
Caltech Beckman InstituteUNSPECIFIED
NIH Predoctoral FellowshipUNSPECIFIED
NSFCHE-9108318
Other Numbering System:
Other Numbering System NameOther Numbering System ID
Arthur Amos Noyes Laboratory of Chemical Physics8598
Series Name:Proceedings of SPIE
Issue or Number:1636
DOI:10.1117/12.59313
Record Number:CaltechAUTHORS:20190221-110529822
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20190221-110529822
Official Citation:Sherrie Campbell and Jack L. Beauchamp "Infrared laser multiphoton dissociation of proton-bound dimers of biomolecules: a new method to probe the acid-base properties of local sites in complex molecules", Proc. SPIE 1636, Applied Spectroscopy in Materials Science II, (14 May 1992); doi: 10.1117/12.59313; https://doi.org/10.1117/12.59313
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:93159
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:22 Feb 2019 18:35
Last Modified:16 Nov 2021 16:55

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