title: Computational study on a HS- sensing reaction utilizing a pyrylium derivative.
abstract: In this paper, we present a comprehensive computational study on the hydrogen sulfide sensing mechanism in aqueous solution using a pyrylium derivative. The possible sensing mechanisms were investigated under the neutral condition and acidic condition in the gas phase and in aqueous solution. The pyrylium-thiopyrylium transformation under the neutral condition is thermodynamically unfavorable, while it is greatly facilitated in the acidic condition catalyzed by a hydronium cation. In addition, the UV-vis absorption maxima of pyryliums and thiopyryliums were investigated at the TDDFT/B3LYP/6-31G+(d,p) level. The red shift of absorption maximum from unsubstituted pyrylium and thiopyrylium to dimethylamino-substituted pyrylium and thiopyrylium as well as the red shift seen in the pyrylium-thiopyrylium transformation is interpreted in terms of the molecular orbital theory.
authors.affiliation: Department of Chemistry & Mathematics, College of Arts & Sciences, Florida Gulf Coast University, 10501 FGCU Boulevard, South, Fort Myers, Florida 33965, USA. ysheng@fgcu.edu
authors.forename: Yinghong
authors.initials: Y
authors.lastname: Sheng
authors.forename: Yi
authors.initials: Y
authors.lastname: Ren
mesh_terms: D000042:Absorption; D004396:Coloring Agents / Q000737:chemistry; D003198:Computer Simulation; D005740:Gases / Q000737:chemistry; D006575:Heterocyclic Compounds, 3-Ring / Q000737:chemistry*; D006862:Hydrogen Sulfide / Q000737:chemistry*; D006863:Hydrogen-Ion Concentration; D008958:Models, Molecular; D008968:Molecular Conformation; D011789:Quantum Theory; D012997:Solvents / Q000737:chemistry; D013816:Thermodynamics; D013876:Thiophenes / Q000737:chemistry*; D014867:Water / Q000737:chemistry
chemical_list: D004396:Coloring Agents; D005740:Gases; D006575:Heterocyclic Compounds, 3-Ring; D012997:Solvents; D013876:Thiophenes; C505939:pyrylium 1; C521680:thiopyrylium; D014867:Water; D006862:Hydrogen Sulfide