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Cluster Phase Reactions: Alkylation of Triphosphate and DNA Anions with Alkylammonium Cations

Hodyss, Robert and Cox, Heather A. and Beauchamp, J. L. (2004) Cluster Phase Reactions: Alkylation of Triphosphate and DNA Anions with Alkylammonium Cations. Journal of Physical Chemistry A, 108 (45). pp. 10030-10034. ISSN 1089-5639. doi:10.1021/jp0475032. https://resolver.caltech.edu/CaltechAUTHORS:20170706-085554992

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Abstract

Electrospray ionization is used to create what are demonstrated to be highly reactive, metastable clusters of alkylammonium cations and triphosphate dianions. Collision-induced activation of the clusters leads to either S_N2 or E2 reactions, resulting in the formation of an alkyltriphosphate or triphosphate anion, respectively. The series of tetraalkylammonium ions from tetramethylammonium to tetraheptylammonium is studied. The S_N2 pathway is favored over the E2 pathway. The replacement of a proton in the triphosphate dianion with a sodium cation in these clusters leads to enhanced yields of the E2 product. PM5 calculations of the reaction energetics correlate well with the observed product distributions. The doubly deprotonated DNA oligomer CCGG can also be alkylated by CID of its cluster with a tetraalkylammonium cation. The cluster phase reactions described in this study serve to illustrate a general scheme which we propose for the rational design of ionic clusters where reactivity is ensured by inhibiting direct dissociation. The experimental methodology implied by the cluster design criteria expands the utility of small molecular clusters for structure−reactivity studies and directed chemical synthesis.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/jp0475032DOIArticle
http://pubs.acs.org/doi/abs/10.1021/jp0475032PublisherArticle
ORCID:
AuthorORCID
Hodyss, Robert0000-0002-6523-3660
Beauchamp, J. L.0000-0001-8839-4822
Additional Information:© 2004 American Chemical Society. Received 9 June 2004. Published online 21 August 2004. Published in print 1 November 2004. We thank Dr. Mona Shagoli for use of the Mass Spectrometry facility, as well as the Director's Research and Development Fund at the Jet Propulsion Laboratory and the Beckman Institute for funding. This material is based on work supported by the National Science Foundation under Grant No. CHE-0416381.
Funders:
Funding AgencyGrant Number
JPL Director’s Research and Development FundUNSPECIFIED
Caltech Beckman InstituteUNSPECIFIED
NSFCHE-0416381
Issue or Number:45
DOI:10.1021/jp0475032
Record Number:CaltechAUTHORS:20170706-085554992
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20170706-085554992
Official Citation:Cluster Phase Reactions:  Alkylation of Triphosphate and DNA Anions with Alkylammonium Cations Robert Hodyss, Heather A. Cox, and J. L. Beauchamp The Journal of Physical Chemistry A 2004 108 (45), 10030-10034 DOI: 10.1021/jp0475032
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:78795
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:06 Jul 2017 22:08
Last Modified:15 Nov 2021 17:43

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