title: Guided-ion-beam scattering and direct dynamics trajectory study on the reaction of deprotonated cysteine with singlet molecular oxygen.
abstract: We present a study on the gas-phase reaction of deprotonated cysteine with the lowest electronically excited state of molecular oxygen O2[a(1)Δg], including the measurement of the effects of collision energy (E(col)) on reaction cross sections over a center-of-mass E(col) range from 0.1 to 1.0 eV. Deprotonated cysteine was generated using electrospray ionization, and has a carboxylate anionic structure (HSCH2CH(NH2)CO2(-)) in the gas phase. Three product ion channels were observed. The dissociation of HSCH2CH(NH2)CO2(-) to NH2CH2CO2(-) and neutral CH2S has the largest cross section over the entire E(col) range. This product channel is driven by the electronic excitation energy of (1)O2 (the so-called dissociative excitation transfer), and is strongly suppressed by E(col). Two minor channels correspond to the formation of HSCH2C(NH)CO2(-) + H2O2 via abstraction of two hydrogen atoms from HSCH2CH(NH2)CO2(-) by (1)O2, and the formation of OSCH2CH(NH2)CO2(-) radical via elimination of ·OH from an intermediate complex, respectively. Density functional theory calculations were used to locate various complexes, transition states, and products. Quasi-classical direct dynamics trajectory simulations were carried out at E(col) = 0.2 eV using the B3LYP/4-31G(d) level of theory. Trajectory results were used to guide the construction of a reaction coordinate, discriminate between different mechanisms, and provide additional mechanistic insights. Analysis of trajectories highlights the importance of complex mediation at the early stages of all reactions, and suggests a partially concerted mechanism for H2O2 elimination.
authors: Department of Chemistry and Biochemistry, Queens College and the Graduate Center of the City University of New York, 65-30 Kissena Boulevard, Queens, New York 11367, USA.
authors: Yigang
authors: Y
authors: Fang
authors: Fangwei
authors: F
authors: Liu
authors: Rifat
authors: R
authors: Emre
authors: Jianbo
authors: J
authors: Liu
mesh_terms: D003545:Cysteine / Q000737:chemistry*; D007477:Ions / Q000737:chemistry; D008958:Models, Molecular; D011522:Protons; D026082:Singlet Oxygen / Q000737:chemistry*
chemical_list: D007477:Ions; D011522:Protons; D026082:Singlet Oxygen; D003545:Cysteine