title: Photodetachment of zwitterions: probing intramolecular Coulomb repulsion and attraction in the gas phase using mono-decarboxylated pyridinium dicarboxylates. Implications on the mechanism of orotidine 5'-monophosphate decarboxylase.
abstract: Negative ion photoelectron spectra resulting from the decarboxylation of nine zwitterionic pyridinium dicarboxylates (D(x,y)) are reported. Structural assignments are made on the basis of analogy to the spectra of related species, labeling experiments with (13)C- or (2)H-containing substrates, independent syntheses, and comparison to density functional theory and ab initio (B3LYP and CCSD(T), respectively) results. In some cases, an acid-catalyzed isomerization of the D(x,y)-CO(2) ions was found to take place. Adiabatic detachment energies of the resulting zwitterionic ions were measured and are well reproduced by theory. The relative stabilities of the D(x,y)-CO(2) decarboxylation products are largely determined by their intramolecular electrostatic interactions, which are directly probed by the photoelectron spectra and were analyzed in terms of the resulting Coulombic forces. Expulsion of carbon dioxide from the D(x,y) ions was also used as an electrostatic model to probe the mechanism of the enzyme-catalyzed conversion of orotidine 5'-monophosphate (OMP) to uridine 5'-monophosphate (UMP). It was found that the loss of CO(2) from these zwitterions and from oxygen-protonated OMP is retarded by the presence of an additional anionic group. This suggests that the formation of a zwitterion intermediate in the enzyme-catalyzed transformation of OMP to UMP may have less of an energetic impact than commonly thought and could be a "red herring". If so, the electrostatic stress mechanism proposed by Larsen et al. and Pai, Guo, and co-workers maybe followed.
authors.affiliation: Department of Physics, Washington State University, 2710 University Drive, Richland, WA 99352, USA.
authors.forename: Xue-Bin
authors.initials: XB
authors.lastname: Wang
authors.forename: Jelena E
authors.initials: JE
authors.lastname: Dacres
authors.forename: Xin
authors.initials: X
authors.lastname: Yang
authors.forename: Lev
authors.initials: L
authors.lastname: Lis
authors.forename: Victoria M
authors.initials: VM
authors.lastname: Bedell
authors.forename: Lai-Sheng
authors.initials: LS
authors.lastname: Wang
authors.forename: Steven R
authors.initials: SR
authors.lastname: Kass
mesh_terms: D003198:Computer Simulation; D003998:Dicarboxylic Acids / Q000737:chemistry; D007477:Ions / Q000737:chemistry; D008958:Models, Molecular; D009964:Orotidine-5'-Phosphate Decarboxylase / Q000737:chemistry*; D010777:Photochemistry; D011726:Pyridinium Compounds / Q000737:chemistry*; D013057:Spectrum Analysis; D055672:Static Electricity; D013816:Thermodynamics; D014542:Uridine Monophosphate / Q000031:analogs & derivatives* / Q000737:chemistry*
chemical_list: D003998:Dicarboxylic Acids; D007477:Ions; D011726:Pyridinium Compounds; C005417:orotidylic acid; D014542:Uridine Monophosphate; D009964:Orotidine-5'-Phosphate Decarboxylase