title: Preferred conformers and photochemical (lambda > 200 nm) reactivity of serine and 3,3-dideutero-serine in the neutral form.
abstract: A systematic investigation of the conformational potential energy surface of neutral serine [HOCH2CHNH2COOH] and 3,3-dideutero-serine [HOCD2CHNH2COOH] was undertaken, revealing the existence of 61 different minima. The structures and vibrational spectra of the most stable conformers, which were estimated to have relative energies within 7 kJ mol(-1) and account for ca. 93% of the total conformational population at room temperature, were calculated at both the MP2 and DFT/BLYP levels of theory with the 6-311++G(d,p) basis-set and used to interpret the spectroscopic data obtained for the compounds isolated in low-temperature inert matrixes. The assignment of the main spectral infrared features observed in the range 4000-400 cm(-1) to the most stable conformers of serine was undertaken. In addition, UV irradiation (lambda > 200 nm) of the matrix-isolated compounds was also performed, leading to decarboxylation, which was found to be strongly dependent on the conformation assumed by the reactant molecule.
authors.affiliation: Department of Chemistry, University of Coimbra, 3004-535 Coimbra, Portugal.
authors.forename: S
authors.initials: S
authors.lastname: Jarmelo
authors.forename: L
authors.initials: L
authors.lastname: Lapinski
authors.forename: M J
authors.initials: MJ
authors.lastname: Nowak
authors.forename: P R
authors.initials: PR
authors.lastname: Carey
authors.forename: R
authors.initials: R
authors.lastname: Fausto
mesh_terms: D000465:Algorithms; D003653:Decarboxylation; D003903:Deuterium / Q000737:chemistry*; D006860:Hydrogen Bonding; D008968:Molecular Conformation; D010777:Photochemistry; D012694:Serine / Q000031:analogs & derivatives* / Q000378:metabolism; D013057:Spectrum Analysis; D013816:Thermodynamics; D014466:Ultraviolet Rays
chemical_list: D012694:Serine; D003903:Deuterium