HISTORY

In 1931 Polyakov and co workers, from Kiev, reported some unusual adsorption properties in silica particles prepared using a novel synthesis procedure.1 Sodium silicate had been polymerized in water using (NH4)2CO3 as the gelating agent. After two weeks, additives (benzene, toluene or xylene) had been added. The silica was subsequently allowed to dry for 20 30 days, after which the additive was removed by extensive washing in hot water. Subsequent adsorption studies revealed a higher capacity for uptake of the additive by the silica than for structurally related ligands, i.e. some kind of memory for the additive was apparent, at least in the cases of benzene and toluene Linus Pauling,2 in 1940 proposed that antibody formation took place in the presence of an antigen, captured by the cell, which served as a template for antibody formation. Pauling suggested that the primary structure of any antibody was identical and that the template-induced conformational effect gave rise to the remarkable selectivities exhibited by antibodies. In addition, he proposed that this ability could be investigated by precipitating globulins under denaturing conditions in the presence of an antigen and by slow removal and redissolution of the globulins. The globulins would then exhibit specificity for the antigen. A similar methodology to that of Polyakov, was carried out by Dickey 3 in 1949 in his laboratory ,but in this case methyl orange (and other alkyl orange dyes) was used as the template. The results of Dickey were striking demonstrating pronounced selectivity for the pattern dye which had been present during polymerization as related to the other dyes After two decades of rather intense research in the area, a decline of molecular imprinting in silica appears to have coincided with the introduction of molecular imprinting in organic polymers, made independently by Wulff and Klotzin 19724-5, Owens et al6 in 1999 reviewed the potential of MIP-based analytical techniques in bioand pharmaceutical analysis They mentioned that earlier work of MIP-based chiral stationary phases (CSPs) was almost exclusively carried out with LC and that the number of MIP applications for CE and CEC was relatively small despite their usefulness. Ansell 7 in 2005 reviewed the literature on chiral separation of drug enantiomers using MIPs via HPLC, TLC,csupercritical fluid chromatography (SFC), and CEC. . Wei and Mizaikoff 8 in 2007 gave a review on recent advances of noncovalent MIPs for affinity separations. They reviewed MIP applications in affinity separations as well as biomimetic assays emphasizing the preparation of shape- and size-uniform particles authors concluded that to complete the great potential of MIPs as selective separation phases, better understandingof the fundamental interactions in MIP formation and the imprinting mechanism should be achieved first in the future. Vasapollo et al.9 in 2011 presented a very comprehensive review on present and future prospective of MIPs aiming to summarize the molecularly imprinting processes and principal application fields of MIPs, focusing on separation science (mostly HPLC), chemical sensing, drug delivery, and catalysis.

REFERENCES 1. Polyakov MV. 1931. Adsorption properties and structure of silica gel. Zhur. Fiz. Khim. 2: 799805. 2. Pauling L. 1940. A theory of the structure and process of formation of antibodies. J. Am. Chem. Soc. 62: 2643 2657. 3 .Dickey FH. 1949. The preparation of specific adsorbents. Proc. Natl. Acad. Sci. USA 35: 227 229. 4.Wulff G, Sarhan A. 1972. The use of polymers with enzyme-analogous structures for the resolution of racemates. Angew. Chem., Intl. Ed. Engl. 11: 341. DOI: 10.1002/anie.197203341 5. Takagishi T, Klotz IM. 1972. Macromolecule-small molecule interactions; introduction of additional binding sites in polyethyleneimine by disulfide cross-linkages. Biopolymers 11: 483491. DOI: 10.1002/bip.1972. 360110213 6 Owens, P. K., Karlsson, L., Lutz, E. S. M., Andersson, L. I., Trends Anal. Chem. 1999, 18, 146154. 7 Ansell, D. J., Adv. Drug Delivery Rev. 2005, 57, 18091835. 8 Wei, S., Mizaikoff, B., J. Sep. Sci. 2007, 30, 17941805. 9 Vasapollo, G., Sole, R. D., Mergola, L., Lazzoi, M. R., Scardino, A., Scorrano, S.,Mele, G., Int. J. Mol. Sci. 2011, 12, 59085945.