Online Hyphenation of Multimodal Microsolid Phase Extraction Involving Renewable Molecularly Imprinted and Reversed-Phase Sorbents to Liquid Chromatography for Automatic Multiresidue Assays

• Type: Article in International Scientific Journal
• Date: 2010

Authors

Warunya Boonjob (Author) Other; Yongliang L Yu (Author) Other; Manuel Miro (Author) Other; Marcela A Segundo (Author) FFUP; Jianhua H Wang (Author) Other; Victor Cerda (Author) Other

Journal

Title: Analytical Chemistry

Vol. 82 No. 7

Pages: 3052-3060

ISSN: 0003-2700

Publisher: American Chemical Society

Indexing

ISI Web of Knowledge - 39 Citations

ISI Web of Science

Scopus - 39 Citations

Scientific classification

FOS: Natural sciences > Chemical sciences

CORDIS: Health sciences

Other information

Authenticus ID: P-003-7M5

DOI: 10.1021/ac100185s

Resumo (PT): Molecular imprinted polymers (MIP) have recently drawn much attention as highly selective solid-phase materials for handling and isolation of organic pollutants in complex matrices. Because of the impaired retention capacity for target species as compared with reversed-phase materials and irreversible sorption of interfering compounds by nonspecific interactions, the implementation of MIP-based solid-phase reactors as permanent components in automatic flow-systems has not received widespread acceptance as of yet. To tackle this limitation, a dynamic microscale solid phase extraction (μSPE) method capitalizing on the principle of programmable flow and bead injection analysis is herein proposed as a front end to liquid chromatography for multiresidue assays. It involves in-line renewable tandem-SPE microcolumns composed of molecularly imprinted polymers and copolymeric N-vinylpyrrolidone/divinylbenzene beads integrated within the flow network for multimodal extraction. Chlorotriazine herbicides (namely, atrazine, simazine, propazine) and principal degradation products thereof (namely, deisopropylatrazine and deethylatrazine) were selected as model analytes. The effect of several parameters, including the dimensions and chemical composition of the sorptive microcolumns, the sample loading flow rate, the type and volume of eluent, the interface with liquid chromatography (LC), and the disposable nature of the column on the analytical performance were investigated in detail. The assembled flow setup features appropriate removal of interfering organic species via solvent switch with toluene, the circumvention of analyte band-broadening in LC by in-line merging of the eluate with a water stream, and the transfer of the overall analyte-containing eluate into the LC. For 10-mL sample percolation, limits of detection (S/N = 3) of 0.02−0.04 ng mL−1, limits of quantification (S/N = 10) of 0.07−0.12 ng mL−1, absolute recovery percentages >79%, precision within 1.4−5.5%, and enrichment factors of 46−49 were obtained for the suite of assayed herbicides. The multimodal μSPE method with renewable beads was applied to the multiresidue determination of the target herbicides in crude soil extracts and untreated environmental waters at concentration levels below those endorsed by the current EU Water Framework Directives following appropriate sample preconcentration and/or cleanup. <br> <br> <a target="_blank" href="http://pubs.acs.org/doi/abs/10.1021/ac100185s"> Texto integral </a> <br> <br>

Abstract (EN): Molecular imprinted polymers (MIP) have recently drawn much attention as highly selective solid-phase materials for handling and isolation of organic pollutants in complex matrices. Because of the impaired retention capacity for target species as compared with reversed-phase materials and irreversible sorption of interfering compounds by nonspecific interactions, the implementation of MIP-based solid-phase reactors as permanent components in automatic flow-systems has not received widespread acceptance as of yet. To tackle this limitation, a dynamic microscale solid phase extraction (mu SPE) method capitalizing on the principle of programmable flow and bead injection analysis is herein proposed as a front end to liquid chromatography for multiresidue assays. It involves in-line renewable tandem-SPE microcolumns composed of molecularly imprinted polymers and copolymeric N-vinylpyrrolidone/divinylbenzene beads integrated within the flow network for multimodal extraction. Chlorotriazine herbicides (namely, atrazine, simazine, propazine) and principal degradation products thereof (namely, deisopropylatrazine and deethylatrazine) were selected as model analytes. The effect of several parameters, including the dimensions and chemical composition of the sorptive microcolumns, the sample loading flow rate, the type and volume of eluent, the interface with liquid chromatography (LC), and the disposable nature of the column on the analytical performance were investigated in detail. The assembled flow setup features appropriate removal of interfering organic species via solvent switch with toluene, the circumvention of analyte band-broadening in LC by in-line merging of the eluate with a water stream, and the transfer of the overall analyte-containing eluate into the LC. For 10-mL sample percolation, limits of detection (S/N = 3) of 0.02-0.04 ng mL(-1), limits of quantification (S/N = 10) of 0.07-0.12 ng mL(-1), absolute recovery percentages >79%, precision within 1.4-5.5%, and enrichment factors of 46-49 were obtained for the suite of assayed herbicides. The multimodal mu SPE method with renewable beads was applied to the multiresidue determination of the target herbicides in crude soil extracts and untreated environmental waters at concentration levels below those endorsed by the current EU Water Framework Directives following appropriate sample preconcentration and/or cleanup.

Language: English

Type (Professor's evaluation): Scientific

No. of pages: 9