title: G3 assisted rational design of chemical sensor array using carbonitrile neutral receptors.
abstract: Combined computational and experimental strategies for the systematic design of chemical sensor arrays using carbonitrile neutral receptors are presented. Binding energies of acetonitrile, n-pentylcarbonitrile and malononitrile with Ca(II), Mg(II), Be(II) and H⁺ have been investigated with the B3LYP, G3, CBS-QB3, G4 and MQZVP methods, showing a general trend H⁺ > Be(II) > Mg(II) > Ca(II). Hydrogen bonding, donor-acceptor and cation-lone pair electron simple models were employed in evaluating the performance of computational methods. Mg(II) is bound to acetonitrile in water by 12.5 kcal/mol, and in the gas phase the receptor is more strongly bound by 33.3 kcal/mol to Mg(II) compared to Ca(II). Interaction of bound cations with carbonitrile reduces the energies of the MOs involved in the proposed σ-p conjugated network. The planar malononitrile-Be(II) complex possibly involves a π-network with a cationic methylene carbon. Fabricated potentiometric chemical sensors show distinct signal patterns that can be exploited in sensor array applications.
authors.affiliation: Department of Chemistry, Faculty of Science Building, University of Malaya, Kuala Lumpur 50603, Malaysia. nazmi86@siswa.um.edu.my.
authors.forename: Ahmad Nazmi
authors.initials: AN
authors.lastname: Rosli
authors.forename: Maizathul Akmam Abu
authors.initials: MA
authors.lastname: Bakar
authors.forename: Ninie Suhana Abdul
authors.initials: NS
authors.lastname: Manan
authors.forename: Pei Meng
authors.initials: PM
authors.lastname: Woi
authors.forename: Vannajan Sanghiran
authors.initials: VS
authors.lastname: Lee
authors.forename: Sharifuddin Md
authors.initials: SM
authors.lastname: Zain
authors.forename: Mohd Rais
authors.initials: MR
authors.lastname: Ahmad
authors.forename: Yatimah
authors.initials: Y
authors.lastname: Alias
mesh_terms: D002623:Chemistry Techniques, Analytical / Q000295:instrumentation*; D003198:Computer Simulation; D017076:Computer-Aided Design; D004867:Equipment Design; D019544:Equipment Failure Analysis; D008670:Metals / Q000032:analysis*; D046228:Microarray Analysis / Q000295:instrumentation*; D008956:Models, Chemical; D009570:Nitriles / Q000032:analysis* / Q000737:chemistry*; D014159:Transducers
chemical_list: D008670:Metals; D009570:Nitriles