title: Single hydration of the peptide bond: the case of the Vince lactam.
abstract: 2-Azabicyclo[2.2.1]hept-5-en-3-one (ABH or Vince lactam) and its monohydrated complex (ABH···H(2)O) have been observed in a supersonic jet by Fourier transform microwave spectroscopy. ABH is broadly used in the synthesis of therapeutic drugs, whereas the ABH···H(2)O system offers a simple model to explain the conformational preferences of water linked to a constrained peptidic bond. A single predominant form of the Vince lactam and its singly hydrated complex have been detected, determining the rotational constants, centrifugal distortion constants, and nuclear quadrupole coupling tensor. The monohydrated complex is stabilized by two hydrogen bonds (C═O···H-O and N-H···O) closing a six-membered ring. The complexation energy has been estimated to be ∼10 kJ mol(-1) from experimental results. In addition, the observed structure in the gas phase has been compared with solid-phase diffraction data. The structural parameters and binding energies of ABH···H(2)O have also been compared with similar molecules containing peptide bonds. Ab initio (MP2) and density functional (M06-2X and B3LYP) methods have supported the experimental work, describing the rotational parameters and conformational landscape of the title compound and its singly hydrated complex.
authors.affiliation: Departamento de Química Física, Facultad de Ciencia y Tecnología, Universidad del País Vasco (UPV/EHU), Campus de Leioa, Ap. 644, E-48080 Bilbao, Spain.
authors.forename: Patricia
authors.initials: P
authors.lastname: Écija
authors.forename: Francisco J
authors.initials: FJ
authors.lastname: Basterretxea
authors.forename: Alberto
authors.initials: A
authors.lastname: Lesarri
authors.forename: Judith
authors.initials: J
authors.lastname: Millán
authors.forename: Fernando
authors.initials: F
authors.lastname: Castaño
authors.forename: Emilio J
authors.initials: EJ
authors.lastname: Cocinero
mesh_terms: D006860:Hydrogen Bonding; D007769:Lactams / Q000737:chemistry*; D008872:Microwaves; D010455:Peptides / Q000737:chemistry*; D011789:Quantum Theory; D012399:Rotation; D014867:Water / Q000737:chemistry*
chemical_list: D007769:Lactams; D010455:Peptides; D014867:Water; C062350:2-azabicyclo(2.2.1)hept-5-en-3-one