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.
Keywords: sensor array design; carbonitrile neutral receptor; G3 theory; cation binding energies; hyperconjugation
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Rosli, A.N.; Bakar, M.A.A.; Manan, N.S.A.; Woi, P.M.; Lee, V.S.; Zain, S.M.; Ahmad, M.R.; Alias, Y. G3 Assisted Rational Design of Chemical Sensor Array Using Carbonitrile Neutral Receptors. Sensors 2013, 13, 13835-13860.
Rosli AN, Bakar MAA, Manan NSA, Woi PM, Lee VS, Zain SM, Ahmad MR, Alias Y. G3 Assisted Rational Design of Chemical Sensor Array Using Carbonitrile Neutral Receptors. Sensors. 2013; 13(10):13835-13860.
Rosli, Ahmad N.; Bakar, Maizathul A.A.; Manan, Ninie S.A.; Woi, Pei M.; Lee, Vannajan S.; Zain, Sharifuddin M.; Ahmad, Mohd R.; Alias, Yatimah. 2013. "G3 Assisted Rational Design of Chemical Sensor Array Using Carbonitrile Neutral Receptors." Sensors 13, no. 10: 13835-13860.