Selective Masking of Amino Groups during Fluorescence Derivatization in the Presence of a Molecular Imprint Polymer

Abstract

Fluorescence derivatization is a widely used technique for the analysis of biological compounds or synthetic chemicals. 1,2 Detection limits of the fluorescence derivatives are usually on the order of femto moles, therefore, a sensitive determination should be possible. As for the selectivity of the reaction, the derivatization reaction usually occurs with compounds having the same kind of functional group, making molecular selective derivatization difficult. However, selective derivatization should be useful for the analysis of biological samples, in which a large number of compounds are present, and we tried to establish a method using molecular selective masking of a specified amino group. The reaction of amino groups with DNS-Cl (1dimethylaminonaphthalene-5-sulfonyl chloride) was used for the model of fluorescence derivatization, and molecular selective masking was performed during the reaction. To recognize the molecule and to selectively mask the target amino group, a molecular imprint polymer (MIP) was used. The synthetic polymer has recognition sites complimentary to the print molecule and is widely used for the recognition of biological substances. 3-8 As the model compounds having amino groups, amino acid anilides were used, because they are reported to be good target molecules of the MIP. 9-11 In the presence of an MIP, the print molecules bind to the specific recognition sites and the bound molecules may be protected during the derivatization reaction. In a previous study, 12 we reported an enantio-selective derivatization of Land D-Phe-anilide in the presence of the L-Phe-anilide imprint polymer. In the present investigation, we prepared the L-Phe-and L-Ala-anilide imprint polymers; molecular selectivity in addition to the enantioselectivity of the derivatization reaction was examined using eight amino acid anilides. RP-HPLC determination of DNS-amino acid-anilides The HPLC system consisted of a 655 A-12 pump (Hitachi,

Molecular imprinting science and technology: a survey of the literature for the years up to and including 2003

“…Imprinted polymers have been used as synthetic aids for reduction, 488 regioselective acylation 345 and enantiospecific fluorescent tagging. 1406,1407 An elegant set of experiments has been described by Yu et al that utilized imprinted polymers not just as reactors for synthesis, but as drug screening aids. In this work polymers were imprinted with known inhibitors of the enzyme kallikrein, a medicinally important proteinase, to generate new inhibitors of the same enzyme, in what the authors described as an anti-idiotypic approach.…”

Analytical Investigation of Fluorescent Complexes of Valine-8-hydroxyquinoline and Valine-8-hydroxyquinaldine in Aqueous Phase Using Spectroscopic Techniques

“…Fluorescence derivatization is a widely used technique for the analysis of biological compounds or synthetic chemicals. Detection limits of the fluorescence derivatives are usually on the order of femto moles, therefore, a sensitative determination should be possible (Hamase et al, 2000). The reaction of amino groups with DNS-CI (1-dimethylaminonaphthalene-5-sulfonyl chloride) was used for model of fluorescence derivatization, and molecular selective masking was performed during the reaction (Hamase et al, 2000).…”