Synthesis of caffeic acid molecularly imprinted polymer microspheres and high-performance liquid chromatography evaluation of their sorption properties

Angel Valero-Navarro, Maria Gomez-Romero, Jorge F. Fernandez-Sanchez, Peter A. G. Cormack, Antonio Segura-Carretero, Alberto. Fernandez-Gutierrez

Research output: Contribution to journalArticle

35 Citations (Scopus)

Abstract

In the current work, a molecularly imprinted polymer (MIP) has been synthesized and used to enable the extn. of a naturally-occurring antioxidant from complex media. More specifically, we describe the first example of a caffeic acid (CA) MIP which has been synthesized in the form of well-defined polymer microspheres, and its use for the extn. of CA from fruit juice sample. The CA MIP was synthesized by pptn. polymn. using 4-vinylpyridine as functional monomer, divinylbenzene-80 as crosslinker and acetonitrile:toluene (75/25, vol./vol.) as porogen. The particle sizing and morphol. characterization of the polymers was carried out by means of SEM (narrow particle size distribution; ∼5 and 1.5 μm particle diams. for the MIP and NIP [non-imprinted polymer], resp.) and nitrogen sorption porosimetry (sp. surface areas of 340 and 350 m2 g-1, and specific pore vols. of 0.17 and 0.19 cm3 g-1 for the MIP and NIP, resp.). The polymers were evaluated further by batch rebinding expts., and from the derived isotherms their binding capacity and binding strength were detd. (no. of binding sites (N K) = 0.6 and 0.3 mmol g-1 for the MIP and NIP, resp., and apparent av. adsorption const. (K N) = 10.0 and 1.6 L mmol-1 for the MIP and NIP, resp.). To evaluate the mol. recognition character of the MIP it was packed into a stainless steel column (50 mm × 4.6 mm i.d.) and evaluated as an HPLC-stationary phase. The mobile phase compn., flow rate, and the elution profile were then optimized in order to improve the peak shape without neg. affecting the imprinting factor (IF). Very interesting, promising properties were revealed. The imprinting factor (IF) under the optimized conditions was 11.9. Finally, when the imprinted LC column was used for the selective recognition of CA over eight related compds., very good selectivity was obtained. This outcome enabled the direct extn. of CA in com. apple juice samples with recoveries in excess of 81% and, rather significantly, without any need for a clean-up step prior to the extn.
Original languageEnglish
Pages (from-to)7289-7296
Number of pages8
JournalJournal of Chromatography A
Volume1218
Issue number41
DOIs
Publication statusPublished - 14 Oct 2011

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High performance liquid chromatography
Microspheres
Sorption
Polymers
High Pressure Liquid Chromatography
divinyl benzene
caffeic acid
Fruit juices
Character recognition
Stainless Steel
Toluene
Malus
Particle Size
Particle size analysis
Particles (particulate matter)
Adsorption
Isotherms

Keywords

  • caffeic acid
  • polymer microspheres
  • chromatography

Cite this

Valero-Navarro, Angel ; Gomez-Romero, Maria ; Fernandez-Sanchez, Jorge F. ; Cormack, Peter A. G. ; Segura-Carretero, Antonio ; Fernandez-Gutierrez, Alberto. / Synthesis of caffeic acid molecularly imprinted polymer microspheres and high-performance liquid chromatography evaluation of their sorption properties. In: Journal of Chromatography A . 2011 ; Vol. 1218, No. 41. pp. 7289-7296.
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Synthesis of caffeic acid molecularly imprinted polymer microspheres and high-performance liquid chromatography evaluation of their sorption properties. / Valero-Navarro, Angel; Gomez-Romero, Maria; Fernandez-Sanchez, Jorge F.; Cormack, Peter A. G.; Segura-Carretero, Antonio; Fernandez-Gutierrez, Alberto.

In: Journal of Chromatography A , Vol. 1218, No. 41, 14.10.2011, p. 7289-7296.

Research output: Contribution to journalArticle

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T1 - Synthesis of caffeic acid molecularly imprinted polymer microspheres and high-performance liquid chromatography evaluation of their sorption properties

AU - Valero-Navarro, Angel

AU - Gomez-Romero, Maria

AU - Fernandez-Sanchez, Jorge F.

AU - Cormack, Peter A. G.

AU - Segura-Carretero, Antonio

AU - Fernandez-Gutierrez, Alberto.

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N2 - In the current work, a molecularly imprinted polymer (MIP) has been synthesized and used to enable the extn. of a naturally-occurring antioxidant from complex media. More specifically, we describe the first example of a caffeic acid (CA) MIP which has been synthesized in the form of well-defined polymer microspheres, and its use for the extn. of CA from fruit juice sample. The CA MIP was synthesized by pptn. polymn. using 4-vinylpyridine as functional monomer, divinylbenzene-80 as crosslinker and acetonitrile:toluene (75/25, vol./vol.) as porogen. The particle sizing and morphol. characterization of the polymers was carried out by means of SEM (narrow particle size distribution; ∼5 and 1.5 μm particle diams. for the MIP and NIP [non-imprinted polymer], resp.) and nitrogen sorption porosimetry (sp. surface areas of 340 and 350 m2 g-1, and specific pore vols. of 0.17 and 0.19 cm3 g-1 for the MIP and NIP, resp.). The polymers were evaluated further by batch rebinding expts., and from the derived isotherms their binding capacity and binding strength were detd. (no. of binding sites (N K) = 0.6 and 0.3 mmol g-1 for the MIP and NIP, resp., and apparent av. adsorption const. (K N) = 10.0 and 1.6 L mmol-1 for the MIP and NIP, resp.). To evaluate the mol. recognition character of the MIP it was packed into a stainless steel column (50 mm × 4.6 mm i.d.) and evaluated as an HPLC-stationary phase. The mobile phase compn., flow rate, and the elution profile were then optimized in order to improve the peak shape without neg. affecting the imprinting factor (IF). Very interesting, promising properties were revealed. The imprinting factor (IF) under the optimized conditions was 11.9. Finally, when the imprinted LC column was used for the selective recognition of CA over eight related compds., very good selectivity was obtained. This outcome enabled the direct extn. of CA in com. apple juice samples with recoveries in excess of 81% and, rather significantly, without any need for a clean-up step prior to the extn.

AB - In the current work, a molecularly imprinted polymer (MIP) has been synthesized and used to enable the extn. of a naturally-occurring antioxidant from complex media. More specifically, we describe the first example of a caffeic acid (CA) MIP which has been synthesized in the form of well-defined polymer microspheres, and its use for the extn. of CA from fruit juice sample. The CA MIP was synthesized by pptn. polymn. using 4-vinylpyridine as functional monomer, divinylbenzene-80 as crosslinker and acetonitrile:toluene (75/25, vol./vol.) as porogen. The particle sizing and morphol. characterization of the polymers was carried out by means of SEM (narrow particle size distribution; ∼5 and 1.5 μm particle diams. for the MIP and NIP [non-imprinted polymer], resp.) and nitrogen sorption porosimetry (sp. surface areas of 340 and 350 m2 g-1, and specific pore vols. of 0.17 and 0.19 cm3 g-1 for the MIP and NIP, resp.). The polymers were evaluated further by batch rebinding expts., and from the derived isotherms their binding capacity and binding strength were detd. (no. of binding sites (N K) = 0.6 and 0.3 mmol g-1 for the MIP and NIP, resp., and apparent av. adsorption const. (K N) = 10.0 and 1.6 L mmol-1 for the MIP and NIP, resp.). To evaluate the mol. recognition character of the MIP it was packed into a stainless steel column (50 mm × 4.6 mm i.d.) and evaluated as an HPLC-stationary phase. The mobile phase compn., flow rate, and the elution profile were then optimized in order to improve the peak shape without neg. affecting the imprinting factor (IF). Very interesting, promising properties were revealed. The imprinting factor (IF) under the optimized conditions was 11.9. Finally, when the imprinted LC column was used for the selective recognition of CA over eight related compds., very good selectivity was obtained. This outcome enabled the direct extn. of CA in com. apple juice samples with recoveries in excess of 81% and, rather significantly, without any need for a clean-up step prior to the extn.

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