Infrared Multiple Photon Dissociation Action Spectroscopy and Theoretical Studies of Diethyl Phosphate Complexes: Effects of Protonation and Sodium Cationization on Structure

TitleInfrared Multiple Photon Dissociation Action Spectroscopy and Theoretical Studies of Diethyl Phosphate Complexes: Effects of Protonation and Sodium Cationization on Structure
Publication TypeJournal Article
Year of Publication2011
AuthorsB.S Fales, N.O Fujamade, Y.W Nei, J. Oomens, M.T Rodgers
JournalJournal of the American Society for Mass Spectrometry
Volume22
Number1
Pagination81-92
Date PublishedJan
Type of ArticleArticle
ISBN Number1044-0305
Accession NumberISI:000287696300010
KeywordsB-DNA DODECAMER, BINDING, COUNTERIONS, Diethyl phosphate, dissociation, free electron laser, GAS-PHASE, Infrared multiple photon, METAL-IONS, MINOR-GROOVE, MONOVALENT CATIONS, NUCLEIC-ACIDS, PHOSPHATE, Protons, Sodium cations, SPINE, TRIETHYL
Abstract

The gas-phase structures of deprotonated, protonated, and sodium-cationized complexes of diethyl phosphate (DEP) including [DEP - H](-), [DEP + H](+), [DEP + Na](+), and [DEP - H + 2Na](+) are examined via infrared multiple photon dissociation (IRMPD) action spectroscopy using tunable IR radiation generated by a free electron laser, a Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS) with an electrospray ionization (ESI) source, and theoretical electronic structure calculations. Measured IRMPD spectra are compared to linear IR spectra calculated at the B3LYP/6-31G(d,p) level of theory to identify the structures accessed in the experimental studies. For comparison, theoretical studies of neutral complexes are also performed. These experiments and calculations suggest that specific geometric changes occur upon the binding of protons and/or sodium cations, including changes correlating to nucleic acid backbone geometry, specifically P-O bond lengths and a OPO bond angles. Information from these observations may be used to gain insight into the structures of more complex systems, such as nucleotides and solvated nucleic acids.

URL<Go to ISI>://000287696300010
Division

GUTHz

Department

Molecular Dynamics

PID

3d447b10dcf3a5a1d6eaf5badbc11941

Alternate TitleJ. Am. Soc. Mass Spectrom.

Go back one page.