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.
References
[1]
March, J. Advanced Organic Chemistry: Reactions, Mechanisms, and Structure, 3rd ed. ed.; John Wiley & Sons: New York, NY, USA, 1992; Volume 4.
Fleming, F.F.; Zhang, Z.; Wang, Q.; Steward, O.W. Alkenenitriles: Annulations with ω-Chloro grignard reagents. Org. Lett. 2002, 4, 2493–2495.
[6]
Duarte, L.T.; Jutten, C.; Temple-Boyer, P.; Benyahia, A.; Launay, J. A dataset for the design of smart ion-selective electrode arrays for quantitative analysis. IEEE Sens. J. 2010, 10, 1891–1892.
[7]
Duarte, L.; Jutten, C.; Moussaoui, S. Ion-Selective Electrode Array Based on a Bayesian Nonlinear Source Separation Method. In Independent Component Analysis and Signal Separation; Adali, T., Jutten, C., Romano, J., Barros, A., Eds.; Springer: Berlin/Heidelberg, Germany, 2009; Volume 5441, pp. 662–669.
Reinhoudt, D. Durable chemical sensors based on field-effect transistors. Sens. Actuators B Chem. 1995, 24, 197–200.
[14]
Zhu, X.; Gao, C.; Kai, J.; Do, J.; Choi, J.; Ahn, C. A Novel Dynamic Electrochemical Transduction Mechanism for Low Concentration Analyte Detection. Proceedings of the Seventh International Conference on Miniaturized Chemical and Biochemical Analysis System, Squaw Valley, CA, USA, 5–9 October 2003; pp. 801–804.
[15]
Umezawa, Y.; Umezawa, K.; Sato, H. Selectivity coefficients for ion-selective electrodes: Recommended methods for reporting Kpota,b values. Pure Appl. Chem. 1995, 67, 507–518.
[16]
National Recommended Water Quality Criteria: 2002; United States Environmental Protection Agency: Washington, DC, USA, 2002.
[17]
Duncan, D.M.; Cockayne, J. Application of calixarene ionophores in PVC based ISEs for uranium detection. Sens. Actuators B Chem. 2001, 73, 228–235.
[18]
Malinowska, E.; Gawart, L.; Parzuchowski, P.; Rokicki, G.; Brzózka, Z. Novel approach of immobilization of calix[4]arene type ionophore in “self-plasticized” polymeric membrane. Anal. Chim. Acta 2000, 421, 93–101.
[19]
Antonisse, M.M.G.; Snellink-Ruel, B.H.M.; Yigit, I.; Engbersen, J.F.J.; Reinhoudt, D.N. Neutral anion receptors: Synthesis and evaluation as sensing molecules in chemically modified field effect transistors. J. Org. Chem. 1997, 62, 9034–9038.
[20]
Zhang, Y.; Cremer, P.S. Interactions between macromolecules and ions: The Hofmeister series. Curr. Opin. Chem. Biol. 2006, 10, 658–663.
[21]
Boyd, J.W.; Cobb, G.P.; Southard, G.E.; Murray, G.M. Development of molecularly imprinted polymer sensors for chemical warfare agents. Johns Hopkins APL Tech. Dig. 2004, 25, 44–49.
[22]
Pernites, R.; Ponnapati, R.; Felipe, M.J.; Advincula, R. Electropolymerization molecularly imprinted polymer (E-MIP) SPR sensing of drug molecules: Pre-polymerization complexed terthiophene and carbazole electroactive monomers. Biosens. Bioelectron. 2011, 26, 2766–2771.
[23]
Data provided in supplementary document.
[24]
Keutsch, F.N.; Braly, L.B.; Brown, M.G.; Harker, H.A.; Petersen, P.B.; Leforestier, C.; Saykally, R.J. Water dimer hydrogen bond stretch, donor torsion overtone, and “in-plane bend” vibrations. J. Chem. Phys. 2003, 119, 8927–8937.
[25]
Xu, X.; Goddard, W.A., III. Bonding properties of the water dimer: A comparative study of density functional theories. J. Phys. Chem. A 2004, 108, 2305–2313.
[26]
Cramer, C.J.; Gladfelter, W.L. Ab Initio Characterization of [H3N-BH3]2,[H3N-AlH3]2, and [H3N-GaH3]2. Inorg. Chem. 1997, 36, 5358–5362.
Tomasi, J.; Mennucci, B.; Cances, E. The IEF version of the PCM solvation method: An overview of a new method addressed to study molecular solutes at the QM ab initio level. J. Mol. Struct. Theochem 1999, 464, 211–226.
[29]
Klooster, W.T.; Koetzle, T.F.; Siegbahn, P.E.M.; Richardson, T.B.; Crabtree, R.H. Study of the NH-HB dihydrogen bond including the crystal structure of BH3NH3 by neutron diffraction. J. Am. Chem. Soc. 1999, 121, 6337–6343.
[30]
Curtiss, L.A.; Raghavachari, K. Gaussian-3 and related methods for accurate thermochemistry. Theor. Chem. Account. 2002, 108, 61–70.
[31]
Curtiss, L.A.; Raghavachari, K.; Redfern, P.C.; Rassolov, V.; Pople, J.A. Gaussian-3 (G3) theory for molecules containing first and second-row atoms. J. Chem. Phys. 1998, 109, 7764–7776.
[32]
Pickard, F.C.; Griffith, D.R.; Ferrara, S.J.; Liptak, M.D.; Kirschner, K.N.; Shields, G.C. CCSD(T), W1, and other model chemistry predictions for gas-phase deprotonation reactions. Int. J. Quant. Chem. 2006, 106, 3122–3128.
[33]
Curtiss, L.A.; Redfern, P.C.; Raghavachari, K. Gaussian-4 theory. J. Chem. Phys. 2007, 126, 084108–084119.
[34]
Carey, F.A.; Sundberg, R.J. Advanced Organic Chemistry: Part A: Structure and Mechanisms; Springer: New York, NY, USA, 2007; pp. 54–59.
[35]
Rauk, A. Orbital Interaction Theory of Organic Chemistry; Wiley: New York, NY, USA, 1994; p. p. 104.
[36]
Yu, Z.-H. The Restricted Geometry Optimization - A New Procedure to Accurately evaluate the Aromatic Stabilization Energy. In Questioning the Fundamental Principles of Organic Chemistry; Chinese Academy of Sciences: Beijing, China, 2012.
[37]
Pauling, L. The Nature of the Chemical Bond and the Structure of Molecules and Crystals: An Introduction to Modern Structural Chemistry; Cornell University: Ithaca, NY, USA, 1960.
[38]
Lampman, G.M.; Pavia, D.L.; Krizz, G.S.; Vyvyan, J.R. Spectroscopy, 4th ed. ed.; Brooks/Cole: Pacific Grove, CA, USA, 2009; pp. 178–179.
[39]
Linstrom, P.J.; Mallard, W.G. NIST Chemistry WebBook. NIST Standard Reference Database Number 69; National Institute of Standards and Technology: Gaithersburg MD, 20899. Available online: http://webbook.nist.gov (accessed on 21 August 2013).
[40]
Weinhold, F. Discovering Chemistry with Natural Bond Orbitals; Wiley-VCH: Hoboken, NJ, USA, 2012.
[41]
Reed, A.E.; Curtiss, L.A.; Weinhold, F. Intermolecular interactions from a natural bond orbital, donor-acceptor viewpoint. Chem. Rev. 1988, 88, 899–926.
[42]
Müller, T.; Juhasz, M.; Reed, C.A. The X-ray structure of a vinyl cation. Angew. Chem. 2004, 116, 1569–1572.
[43]
Apeloig, Y.; Stanger, A. α-Silicon-substituted vinyl cations. A theoretical ab initio investigation. J. Org. Chem. 1982, 47, 1462–1468.
[44]
Winter, A.H.; Falvey, D.E. Vinyl cations substituted with β π-donors have triplet ground states. J. Am. Chem. Soc. 2009, 132, 215–222.
[45]
Kobayashi, S.; Matsumoto, T.; Taniguchi, H.; Mishima, M.; Fujio, M.; Tsuno, Y. Substituent effect on gas phase basicity of 1-phenylpropyne. Thermodynamic stability and resonance demand of 1-phenylpropenyl cations. Tetrahedron Lett. 1993, 34, 5903–5906.
[46]
Yates, K.; Schmid, G.H.; Regulski, T.W.; Garratt, D.G.; Leung, H.-W.; McDonald, R. Relative ease of formation of carbonium ions and vinyl cations in electrophilic additions. J. Am. Chem. Soc. 1973, 95, 160–165.
[47]
Scott, A.P.; Radom, L. Harmonic vibrational frequencies: An evaluation of Hartree-Fock, M？ller-Plesset, quadratic configuration interaction, density functional theory, and semiempirical scale factors. J. Phys. Chem 1996, 100, 16502–16513.
[48]
A.Bakar, M.A.; Rosli, A.N.; Meng, W.P.; Manan, N.S.A.; Lee, V.S.; Ahmad, M.R.; Zain, S.M.; Alias, Y. DFT study in vacuum and implicit water solvent model for acrylonitrile as ion pair receptors; 2013. unsubmitted.
[49]
Partin, D.E.; O'Keeffe, M. The structures and crystal chemistry of magnesium chloride and cadmium chloride. J. Solid State Chem. 1991, 95, 176–183.
[50]
Purcell, K.F.; Drago, R.S. Studies of the bonding in acetonitrile adducts. J. Am. Chem. Soc. 1966, 88, 919–924.
[51]
Daniel, C.H. Quantitative Chemical Analysis; W. H. Freeman and Company: New York, NY, USA, 1987.
[52]
Frisch, M.; Trucks, G.; Schlegel, H.; Scuseria, G.; Robb, M.; Cheeseman, J.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G.; et al. Fox Gaussian 09, Revision C. 01; Gaussian, Inc.: Wallingford, CT, USA, 2010.
[53]
Becke, A.D. Density-functional thermochemistry. III. The role of exact exchange. J. Chem. Phys. 1993, 98, 5648–5652.
[54]
Lee, C.; Yang, W.; Parr, R.G. Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. Phys. Rev. B: Condens. Matter 1988, 37, 785–789.
[55]
Cheeseman, J.R.; Trucks, G.W.; Keith, T.A.; Frisch, M.J. A comparison of models for calculating nuclear magnetic resonance shielding tensors. J. Chem. Phys. 1996, 104, 5497–5509.
[56]
Curtiss, L.A.; Raghavachari, K.; Trucks, G.W.; Pople, J.A. Gaussian-2 theory for molecular energies of first-and second-row compounds. J. Chem. Phys. 1991, 94, 7221–7230.
[57]
Namazian, M.; Zakery, M.; Noorbala, M.R.; Coote, M.L. Accurate calculation of the pKa of trifluoroacetic acid using high-level ab initio calculations. Chem. Phys. Lett. 2008, 451, 163–168.
[58]
Montgomery, J., Jr.; Frisch, M.; Ochterski, J.; Petersson, G. A complete basis set model chemistry. VI. Use of density functional geometries and frequencies. J. Chem. Phys. 1999, 110, 2822–2827.
[59]
Zhao, Y.; Truhlar, D.G. The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: Two new functionals and systematic testing of four M06-class functionals and 12 other functionals. Theor. Chem. Acc. 2008, 120, 215–241.
[60]
Zhao, Y.; Truhlar, D.G. Density functionals with broad applicability in chemistry. Acc. Chem. Res. 2008, 41, 157–167.
[61]
Weigend, F.; Furche, F.; Ahlrichs, R. Gaussian basis sets of quadruple zeta valence quality for atoms H–Kr. J. Chem. Phys. 2003, 119, 12753–12762.
[62]
Jensen, F. Atomic orbital basis sets. WIREs Comput. Mol. Sci. 2013, 3, 273–295.
[63]
Zhong, S.; Barnes, E.C.; Petersson, G.A. Uniformly convergent n-tuple-ζ augmented polarized (nZaP) basis sets for complete basis set extrapolations. I. Self-consistent field energies. J. Chem. Phys. 2008, 129, 184116–184127.
