The requisite level of theory for the computational design of molecularly imprinted silica xerogels.

The present manuscript reports the first application of molecular modelling to the design of molecularly imprinted polymers (MIPs) prepared by alkoxysilane sol-gel polymerization. The major goal was to determine the requisite level of theory for the selection of suitable alkoxysilane functional monomers. A comparative study, applied to the design of a MIP for beta-damascenone, involving different levels of theory, basis set superposition error (BSSE) correction and basis set augmentation and also semi-empirical methods, was performed. The computations results suggest that the use of the 3-21G basis set concomitantly with a method for BSSE correction represents a good compromise between theory level and computation time for the successful screening of functional monomers. Additionally, a few selected MIPs and their corresponding non-imprinted congeners (NIPs) were prepared and tested in the role of solid-phase extraction (SPE) sorbents. The confrontation of the computational results with the observed performance and morphological characteristics of the prepared MIPs suggest that besides the strength and type of interactions existing between template and functional monomers other concomitant features, related with the sol-gel process, must also be accounted for so that effective molecular imprinting is achieved in an alkoxysilane xerogel. Nevertheless, since an optimal template-functional monomer interaction is a necessary condition for successful imprinting, the choice of the best monomers is still of the greatest importance and the proposed computational method may constitute an expeditious and reliable screening tool.

[1]  Zheng Liu,et al.  A computational and experimental investigation of the interaction between the template molecule and the functional monomer used in the molecularly imprinted polymer , 2005 .

[2]  T. Takeuchi,et al.  Novel strategy for molecular imprinting of phenolic compounds utilizing disulfide templates. , 2003, Journal of pharmaceutical and biomedical analysis.

[3]  F. Dickert,et al.  Synthetic receptors for chemical sensors--subnano- and micrometre patterning by imprinting techniques. , 2004, Biosensors & bioelectronics.

[4]  A. Turner,et al.  "Bite-and-Switch" approach using computationally designed molecularly imprinted polymers for sensing of creatinine. , 2001, Biosensors & bioelectronics.

[5]  J. Tomasi,et al.  Electrostatic interaction of a solute with a continuum. A direct utilizaion of AB initio molecular potentials for the prevision of solvent effects , 1981 .

[6]  S. Jang,et al.  Novel Syntheses of Isomers of Damascenone from Ethyl 2,6,6-Trimethyl-4- oxo-2-cyclohexene-1-carboxylate. , 1991 .

[7]  Marta Elena Díaz-García,et al.  Molecular Imprinting in Sol-Gel Materials: Recent Developments and Applications , 2005 .

[8]  Meiping Zhao,et al.  Theoretical and experimental study of nicotinamide molecularly imprinted polymers with different porogens , 2005 .

[9]  Brett M. Bode,et al.  MacMolPlt: a graphical user interface for GAMESS. , 1998, Journal of molecular graphics & modelling.

[10]  Antonino Famulari,et al.  Implementation of gradient-optimization algorithms and force constant computations in BSSE-free direct and conventional SCF approaches , 1998 .

[11]  Börje Sellergren,et al.  Molecularly imprinted polymers : man-made mimics of antibodies and their applications in analytical chemistry , 2001 .

[12]  Sergey A. Piletsky,et al.  Custom synthesis of molecular imprinted polymers for biotechnological application. Preparation of a polymer selective for tylosin , 2004 .

[13]  P. Carr,et al.  Study of solute retention in reversed-phase high-performance liquid chromatography on hydrocarbonaceous and three fluorinated bonded phases , 1984 .

[14]  Mark S. Gordon,et al.  General atomic and molecular electronic structure system , 1993, J. Comput. Chem..

[15]  Iva Chianella,et al.  How to find effective functional monomers for effective molecularly imprinted polymers? , 2005, Advanced drug delivery reviews.

[16]  M. C. Blanco-López,et al.  Computational approach to the rational design of molecularly imprinted polymers for voltammetric sensing of homovanillic acid. , 2005, Analytical chemistry.

[17]  Toshifumi Takeuchi,et al.  Molecular Imprinting: From Fundamentals to Applications , 2003 .

[18]  Sergey A. Piletsky,et al.  Rational design of a polymer specific for microcystin-LR using a computational approach. , 2002, Analytical chemistry.

[19]  Tomohiko Yamazaki,et al.  A molecularly imprinted catalyst designed by a computational approach in catalysing a transesterification process. , 2004, Biosensors & bioelectronics.

[20]  M. Stoll,et al.  Structure et synthèse de la damascénone (triméthyl-2,6,6-trans-crotonoyl-1-cyclohexadiène-1,3), constituant odorant de l'essence de rose bulgare (rosa damascena Mill. , 1970 .

[21]  Liqing Wu,et al.  Study properties of molecular imprinting polymer using a computational approach , 2003 .

[22]  A. Leach.  Molecular Modelling: Principles and Applications , 1996 .