FT-IR and Raman spectra of methacrylamidoantipyrine (MAAP) have been reported in the region of 4000–10 cm？1 and 4000–100 cm？1, respectively. The optimized geometric parameters, conformational analysis, normal mode frequencies, and corresponding vibrational assignments of MAAP (C15H17N3O2) have been examined by means of density functional theory (DFT) method using the Becke-3-Lee-Yang-Parr (B3LYP) exchange-correlation functional and the 6-31G++(d,p) basis sets. Vibrational assignments have been made on the basis of potential energy distribution (PED) and the thermodynamics functions, and the highest occupied and the lowest unoccupied molecular orbitals (HOMO and LUMO) of MAAP have been predicted. Calculations are carried out with the possible seven (amide-1–5 and imide-1-2) conformational isomers of MAAP. Comparison between the experimental and theoretical results indicates that the B3LYP method provides satisfactory evidence for the prediction of vibrational wavenumbers, and the amide-1 conformational isomer is supposed to be the most stable form of MAAP. 1. Introduction The MAAP, which has a electron rich aromatic ring, was first synthesized using antipyrine, a hydroxy radical capture and spectroscopic reagent for phenols, and used for a method described for removal of phenolic compounds with nitrophenol imprinted polymer based on - and hydrogen bonding interactions [1]. Then, it was used in analyzing the selective binding behavior of paraoxon and parathion compounds on surface imprinted polymers prepared using both charge transfer (MAAP) and ligand-exchange (MAAP-Gd) monomers [2]. Today, one can easily reach many papers published where it is one of the most important organic chemical product for the molecularly imprinted polymers [1–5]. For instance, it has been used in researching the biomimetic immunoassay based on molecularly imprinted polymer [3], the 8-Hydroxy-2′-deoxyguanosine (8-OHdG), which is one of the most abundant oxidative DNA lesions resulting from reactive oxygen species, and the 8-OHdG level in blood serum from a breast cancer patient [4], and new 8-OHdG imprinted quartz crystal microbalance sensor [5]. Furthermore, it is taken part in adsorption of phenol and its derivatives from water using synthetic resins and low-cost natural adsorbents [6]. Vibrational spectroscopy has been widely used as the standard tool for structural characterization of molecular systems together with DFT calculations [7–14]. DFT is popular as it is a cost-effective procedure for studying the physical properties of molecules. Unlike the Hartree Fock theory,
References
[1]
A. Ers？z, A. Denizli, ？. ？ener, A. At？l？r, S. Diltemiz, and R. Say, “Removal of phenolic compounds with nitrophenol-imprinted polymer based on - and hydrogen-bonding interactions,” Separation and Purification Technology, vol. 38, no. 2, pp. 173–179, 2004.
[2]
R. Say, “Creation of recognition sites for organophosphate esters based on charge transfer and ligand exchange imprinting methods,” Analytica Chimica Acta, vol. 579, no. 1, pp. 74–80, 2006.
[3]
Z. X. Xu, H. J. Gao, L. M. Zhang, X. Q. Chen, and X. G. Qiao, “The biomimetic immunoassay based on molecularly imprinted polymer: a comprehensive review of recent progress and future prospects,” Journal of Food Science, vol. 76, no. 2, pp. R69–R75, 2011.
[4]
A. Ers？z, S. E. Diltemiz, A. A. ？zcan, A. Denizli, and R. Say, “8-OHdG sensing with MIP based solid phase extraction and QCM technique,” Sensors and Actuators B, vol. 137, no. 1, pp. 7–11, 2009.
[5]
R. Say, A. Gültekin, A. A. ？zcan, A. Denizli, and A. Ers？z, “Preparation of new molecularly imprinted quartz crystal microbalance hybride sensor system for 8-hydroxy-2′-deoxyguanosine determination,” Analytica Chimica Acta, vol. 640, no. 1-2, pp. 82–86, 2009.
[6]
S. H. Lin and R. S. Juang, “Adsorption of phenol and its derivatives from water using synthetic resins and low-cost natural adsorbents: a review,” Journal of Environmental Management, vol. 90, no. 3, pp. 1336–1349, 2009.
[7]
A. P. Scott and L. Radom, “Harmonic vibrational frequencies:？an evaluation of Hartree-Fock, M？ller-Plesset, Quadratic Configuration Interaction, Density Functional Theory, and Semiempirical Scale Factors,” The Journal of Physical Chemistry, vol. 100, no. 41, pp. 16502–16513, 1996.
[8]
G. Rauhut and P. Pulay, “Transferable scaling factors for density functional derived vibrational force fields,” Journal of Physical Chemistry, vol. 99, no. 10, pp. 3093–3100, 1995.
[9]
J. R. Durig, A. Ganguly, A. M. El Defrawy et al., “Conformational stability, r0 structural parameters, barriers to internal rotation and vibrational assignment of cyclobutylamine,” Journal of Molecular Structure, vol. 918, no. 1–3, pp. 64–76, 2009.
[10]
E. Güne？ and C. Parlak, “DFT, FT-Raman and FT-IR investigations of 5-methoxysalicylic acid,” Spectrochimica Acta A, vol. 82, no. 1, pp. 504–512, 2011.
[11]
C. Parlak, “Theoretical and experimental vibrational spectroscopic study of 4-(1-Pyrrolidinyl)piperidine,” Journal of Molecular Structure, vol. 966, no. 1–3, pp. 1–7, 2010.
[12]
？. Alver and C. Parlak, “Vibrational spectroscopic investigation and conformational analysis of 1-pentylamine: A Comparative Density Functional Study,” Journal of Theoretical and Computational Chemistry, vol. 9, no. 3, pp. 667–685, 2010.
[13]
？. Alver and C. Parlak, “DFT, FT-Raman, FT-IR, liquid and solid state NMR studies of 2,6-dimethoxyphenylboronic acid,” Vibrational Spectroscopy, vol. 54, no. 1, pp. 1–9, 2010.
[14]
？. Ba？layan, M. F. Kaya, C. Parlak, and M. ？enyel, “FT-IR and Raman spectroscopic and quantum chemical investigations of some metal halide complexes of 1-phenylpiperazine,” Spectrochimica Acta A, vol. 88, pp. 144–155, 2012.
[15]
M. J. Frisch, G. W. Trucks, H. B. Schlegel, et al., Gaussian 09, Revision A. 1, Gaussian, Wallingford, Conn, USA, 2009.
[16]
R. D. Dennington, T. A. Keith, and J. M. Millam, GaussView 5. 0. 8, Gaussian, 2008.
[17]
Spartan 10, Version 1.10, 92612, Wavefunction, Irvine, Calif, USA, 2011.
[18]
M. H. Jamróz, “Vibrational energy distribution analysis: VEDA 4 program,” Warsaw, 2004, http://smmg.pl/index.php/software/sowtware-veda.html.
[19]
T. H？kelek, Z. K？l？？, M. I？？klanand, and M. Hayval？, “Crystal Structure of 4-{[(1E)-(2-Hydroxynaphthyl)methylidene]amino}-1,5-dimethyl-2-phenyl-2,3-dihydro-1H-pyrazol-3-one,” Analytical Science, vol. 18, no. 2, pp. 215–216, 2002.
[20]
M. J. Percinoa, V. M. Chapela, C. Rodriguez-Barbarin, and S. Bernes, “X-ray crystal structure of two different phases (triclinic and orthorhombic) of p-methacryloylaminophenylarsonic acid monomer,” Journal of Molecular Structure, vol. 562, no. 1–3, pp. 45–53, 2001.
[21]
N. A. Besley, “Ab initio modeling of amide vibrational bands in solution,” Journal of Physical Chemistry A, vol. 108, no. 49, pp. 10794–10800, 2004.
