Synthesis of caffeic acid molecularly imprinted polymer microspheres and HPLC evaluation of their sorption properties

Peter Cormack, Á. Valero Navarro, M. Gómez Romero, J.F. Fernández Sánchez, A. Segura Carretero, P.A.G. Cormack and A. Fernández Gutiérrez

Research output: Chapter in Book/Report/Conference proceedingConference contribution book

Abstract

In the current work, a molecularly imprinted polymer (MIP) has been synthesised and used to enable the extraction of a naturally-occurring antioxidant from complex media. More specifically, we describe the first example of a caffeic acid (CA) MIP which has been synthesised in the form of well-defined polymer microspheres, and its use for the extraction of CA from fruit juice sample. The CA MIP was synthesised by precipitation polymerisation using 4-vinylpyridine as functional monomer, divinylbenzene-80 as crosslinker and acetonitrile:toluene (75/25, v/v) as porogen. The particle sizing and morphological characterisation of the polymers was carried out by means of scanning electron microscopy (narrow particle size distribution; ∼5 and 1.5 μm particle diameters for the MIP and NIP [non-imprinted polymer], respectively) and nitrogen sorption porosimetry (specific surface areas of 340 and 350 m(2)g(-1), and specific pore volumes of 0.17 and 0.19 cm(3)g(-1) for the MIP and NIP, respectively). The polymers were evaluated further by batch rebinding experiments, and from the derived isotherms their binding capacity and binding strength were determined (number of binding sites (N(K))=0.6 and 0.3 mmol g(-1) for the MIP and NIP, respectively, and apparent average adsorption constant (K(N))=10.0 and 1.6L mmol(-1) for the MIP and NIP, respectively). To evaluate the molecular 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 composition, flow rate, and the elution profile were then optimised in order to improve the peak shape without negatively affecting the imprinting factor (IF). Very interesting, promising properties were revealed. The imprinting factor (IF) under the optimised conditions was 11.9. Finally, when the imprinted LC column was used for the selective recognition of CA over eight related compounds, very good selectivity was obtained. This outcome enabled the direct extraction of CA in commercial apple juice samples with recoveries in excess of 81% and, rather significantly, without any need for a clean-up step prior to the extraction.
LanguageEnglish
Title of host publicationProceedings of the European Polymer Congress
Pages1325
Publication statusPublished - 2011

Fingerprint

Microspheres
Sorption
Polymers
divinyl benzene
caffeic acid
Fruit juices
Molecular recognition
Stainless Steel
Toluene
Phase composition
Specific surface area
Particle size analysis
Particles (particulate matter)
Isotherms
Nitrogen
Antioxidants
Monomers

Keywords

  • polymer microspheres
  • sorption

Cite this

Á. Valero Navarro, M. Gómez Romero, J.F. Fernández Sánchez, A. Segura Carretero, P.A.G. Cormack and A. Fernández Gutiérrez (2011). Synthesis of caffeic acid molecularly imprinted polymer microspheres and HPLC evaluation of their sorption properties. In Proceedings of the European Polymer Congress (pp. 1325)
Á. Valero Navarro, M. Gómez Romero, J.F. Fernández Sánchez, A. Segura Carretero, P.A.G. Cormack and A. Fernández Gutiérrez. / Synthesis of caffeic acid molecularly imprinted polymer microspheres and HPLC evaluation of their sorption properties. Proceedings of the European Polymer Congress. 2011. pp. 1325
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title = "Synthesis of caffeic acid molecularly imprinted polymer microspheres and HPLC evaluation of their sorption properties",
abstract = "In the current work, a molecularly imprinted polymer (MIP) has been synthesised and used to enable the extraction of a naturally-occurring antioxidant from complex media. More specifically, we describe the first example of a caffeic acid (CA) MIP which has been synthesised in the form of well-defined polymer microspheres, and its use for the extraction of CA from fruit juice sample. The CA MIP was synthesised by precipitation polymerisation using 4-vinylpyridine as functional monomer, divinylbenzene-80 as crosslinker and acetonitrile:toluene (75/25, v/v) as porogen. The particle sizing and morphological characterisation of the polymers was carried out by means of scanning electron microscopy (narrow particle size distribution; ∼5 and 1.5 μm particle diameters for the MIP and NIP [non-imprinted polymer], respectively) and nitrogen sorption porosimetry (specific surface areas of 340 and 350 m(2)g(-1), and specific pore volumes of 0.17 and 0.19 cm(3)g(-1) for the MIP and NIP, respectively). The polymers were evaluated further by batch rebinding experiments, and from the derived isotherms their binding capacity and binding strength were determined (number of binding sites (N(K))=0.6 and 0.3 mmol g(-1) for the MIP and NIP, respectively, and apparent average adsorption constant (K(N))=10.0 and 1.6L mmol(-1) for the MIP and NIP, respectively). To evaluate the molecular 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 composition, flow rate, and the elution profile were then optimised in order to improve the peak shape without negatively affecting the imprinting factor (IF). Very interesting, promising properties were revealed. The imprinting factor (IF) under the optimised conditions was 11.9. Finally, when the imprinted LC column was used for the selective recognition of CA over eight related compounds, very good selectivity was obtained. This outcome enabled the direct extraction of CA in commercial apple juice samples with recoveries in excess of 81{\%} and, rather significantly, without any need for a clean-up step prior to the extraction.",
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Á. Valero Navarro, M. Gómez Romero, J.F. Fernández Sánchez, A. Segura Carretero, P.A.G. Cormack and A. Fernández Gutiérrez 2011, Synthesis of caffeic acid molecularly imprinted polymer microspheres and HPLC evaluation of their sorption properties. in Proceedings of the European Polymer Congress. pp. 1325.

Synthesis of caffeic acid molecularly imprinted polymer microspheres and HPLC evaluation of their sorption properties. / Á. Valero Navarro, M. Gómez Romero, J.F. Fernández Sánchez, A. Segura Carretero, P.A.G. Cormack and A. Fernández Gutiérrez.

Proceedings of the European Polymer Congress. 2011. p. 1325.

Research output: Chapter in Book/Report/Conference proceedingConference contribution book

TY - GEN

T1 - Synthesis of caffeic acid molecularly imprinted polymer microspheres and HPLC evaluation of their sorption properties

AU - Cormack, Peter

AU - Á. Valero Navarro, M. Gómez Romero, J.F. Fernández Sánchez, A. Segura Carretero, P.A.G. Cormack and A. Fernández Gutiérrez

PY - 2011

Y1 - 2011

N2 - In the current work, a molecularly imprinted polymer (MIP) has been synthesised and used to enable the extraction of a naturally-occurring antioxidant from complex media. More specifically, we describe the first example of a caffeic acid (CA) MIP which has been synthesised in the form of well-defined polymer microspheres, and its use for the extraction of CA from fruit juice sample. The CA MIP was synthesised by precipitation polymerisation using 4-vinylpyridine as functional monomer, divinylbenzene-80 as crosslinker and acetonitrile:toluene (75/25, v/v) as porogen. The particle sizing and morphological characterisation of the polymers was carried out by means of scanning electron microscopy (narrow particle size distribution; ∼5 and 1.5 μm particle diameters for the MIP and NIP [non-imprinted polymer], respectively) and nitrogen sorption porosimetry (specific surface areas of 340 and 350 m(2)g(-1), and specific pore volumes of 0.17 and 0.19 cm(3)g(-1) for the MIP and NIP, respectively). The polymers were evaluated further by batch rebinding experiments, and from the derived isotherms their binding capacity and binding strength were determined (number of binding sites (N(K))=0.6 and 0.3 mmol g(-1) for the MIP and NIP, respectively, and apparent average adsorption constant (K(N))=10.0 and 1.6L mmol(-1) for the MIP and NIP, respectively). To evaluate the molecular 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 composition, flow rate, and the elution profile were then optimised in order to improve the peak shape without negatively affecting the imprinting factor (IF). Very interesting, promising properties were revealed. The imprinting factor (IF) under the optimised conditions was 11.9. Finally, when the imprinted LC column was used for the selective recognition of CA over eight related compounds, very good selectivity was obtained. This outcome enabled the direct extraction of CA in commercial apple juice samples with recoveries in excess of 81% and, rather significantly, without any need for a clean-up step prior to the extraction.

AB - In the current work, a molecularly imprinted polymer (MIP) has been synthesised and used to enable the extraction of a naturally-occurring antioxidant from complex media. More specifically, we describe the first example of a caffeic acid (CA) MIP which has been synthesised in the form of well-defined polymer microspheres, and its use for the extraction of CA from fruit juice sample. The CA MIP was synthesised by precipitation polymerisation using 4-vinylpyridine as functional monomer, divinylbenzene-80 as crosslinker and acetonitrile:toluene (75/25, v/v) as porogen. The particle sizing and morphological characterisation of the polymers was carried out by means of scanning electron microscopy (narrow particle size distribution; ∼5 and 1.5 μm particle diameters for the MIP and NIP [non-imprinted polymer], respectively) and nitrogen sorption porosimetry (specific surface areas of 340 and 350 m(2)g(-1), and specific pore volumes of 0.17 and 0.19 cm(3)g(-1) for the MIP and NIP, respectively). The polymers were evaluated further by batch rebinding experiments, and from the derived isotherms their binding capacity and binding strength were determined (number of binding sites (N(K))=0.6 and 0.3 mmol g(-1) for the MIP and NIP, respectively, and apparent average adsorption constant (K(N))=10.0 and 1.6L mmol(-1) for the MIP and NIP, respectively). To evaluate the molecular 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 composition, flow rate, and the elution profile were then optimised in order to improve the peak shape without negatively affecting the imprinting factor (IF). Very interesting, promising properties were revealed. The imprinting factor (IF) under the optimised conditions was 11.9. Finally, when the imprinted LC column was used for the selective recognition of CA over eight related compounds, very good selectivity was obtained. This outcome enabled the direct extraction of CA in commercial apple juice samples with recoveries in excess of 81% and, rather significantly, without any need for a clean-up step prior to the extraction.

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BT - Proceedings of the European Polymer Congress

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Á. Valero Navarro, M. Gómez Romero, J.F. Fernández Sánchez, A. Segura Carretero, P.A.G. Cormack and A. Fernández Gutiérrez. Synthesis of caffeic acid molecularly imprinted polymer microspheres and HPLC evaluation of their sorption properties. In Proceedings of the European Polymer Congress. 2011. p. 1325