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Publications (10 of 17) Show all publications
Golker, K., Olsson, G. D. & Nicholls, I. A. (2017). The influence of a methyl substituent on molecularly imprinted polymer morphology and recognition – Acrylic acid versus methacrylic acid. European Polymer Journal, 92, 137-149
Open this publication in new window or tab >>The influence of a methyl substituent on molecularly imprinted polymer morphology and recognition – Acrylic acid versus methacrylic acid
2017 (English)In: European Polymer Journal, ISSN 0014-3057, E-ISSN 1873-1945, Vol. 92, p. 137-149Article in journal (Refereed) Published
Abstract [en]

In this report, we have investigated factors contributing to the morphology and template recognition of bupivacaine-imprinted copolymers of methacrylic acid (MAA) and ethyleneglycol dimethacrylate (EGDMA). To this end, MAA, the most commonly used functional monomer in non-covalent molecular imprinting protocols, was compared and contrasted with the closely related acrylic acid (AA) in terms of polymer morphologies, recognition characteristics, and molecular level events in the corresponding pre-polymerization mixtures. Two series of analogous bupivacaine-imprinted EGDMA-copolymers containing increasing fractions of either AA or MAA were studied through all-component MD simulations in the pre-polymerization phase, equilibrium binding experiments on corresponding synthesized polymers and morphology characterization by N2-sorption measurements. A higher degree of hydrogen bonding frequency between respective functional monomer and bupivacaine was recorded for the mixtures containing AA compared to those containing MAA. In contrast, results from binding experiments demonstrated higher binding capacities for the polymers prepared with MAA than for those prepared with AA, which is explained by differences in polymer morphology. The surface areas and pore volumes of the AA-polymers were higher than for the MAA-polymers and the overall pore structure in the AA-polymers was ink-bottle shaped while the pores in the MAA-polymers were slit-shaped. We suggest that the methyl substituent of MAA contributes to differences in the reaction kinetics for AA and MAA during polymerization and resulted in different morphologies, in particular pore shape, which affected mass-transfer and consequently the binding qualities of the materials. © 2017 Elsevier Ltd

Place, publisher, year, edition, pages
Elsevier, 2017
Keywords
Acrylic acid, Methacrylic acid, Molecular dynamics, Molecular recognition, Molecularly imprinted polymer, Morphology
National Category
Polymer Chemistry
Research subject
Chemistry, Organic Chemistry
Identifiers
urn:nbn:se:lnu:diva-64636 (URN)10.1016/j.eurpolymj.2017.04.043 (DOI)000404315600013 ()2-s2.0-85018458746 (Scopus ID)
Available from: 2017-06-02 Created: 2017-06-02 Last updated: 2018-11-02Bibliographically approved
Golker, K. & Nicholls, I. A. (2016). The effect of crosslinking density on molecularly imprinted polymer morphology and recognition. European Polymer Journal, 75, 423-430
Open this publication in new window or tab >>The effect of crosslinking density on molecularly imprinted polymer morphology and recognition
2016 (English)In: European Polymer Journal, ISSN 0014-3057, E-ISSN 1873-1945, Vol. 75, p. 423-430Article in journal (Refereed) Published
Abstract [en]

In this report, the crosslinking density of bupivacaine molecularly imprinted methacrylic acid (MAA)-ethylene glycol dimethacrylate (EGDMA) copolymers was investigated through replacement of EGDMA by methyl methacrylate (MMA). The effects were examined using a series of full-scale MD simulations of pre-polymerization mixtures, equilibrium rebinding studies on the corresponding synthesized polymers and morphology characterization through nitrogen sorption measurements. While the extent of hydrogen bonding between the functional monomer MAA and bupivacaine observed in the MD pre-polymerization mixtures was comparable in each of the systems studied, the decrease in degree of crosslinking impacted directly on polymer morphology as observed in BET and BJH studies of surface area and porosity. Further, decreases in the crosslinking density induced reductions in template rebinding capacity as seen from a series of radio-ligand binding studies, demonstrating the importance of crosslinking on the performance of molecularly imprinted MAA-EGDMA copolymers, the polymer system most commonly used in molecular imprinting science and technology. (C) 2016 Elsevier Ltd. All rights reserved.

Keywords
Molecularly imprinted polymer, Molecular dynamics, Molecular recognition, Molecular imprinting, Morphology, Crosslinking
National Category
Chemical Sciences
Research subject
Chemistry, Organic Chemistry
Identifiers
urn:nbn:se:lnu:diva-51069 (URN)10.1016/j.eurpolymj.2016.01.008 (DOI)000370309400036 ()2-s2.0-84954090378 (Scopus ID)
Available from: 2016-03-18 Created: 2016-03-18 Last updated: 2018-11-02Bibliographically approved
Golker, K., Karlsson, B. C. G., Wiklander, J. G., Rosengren, A. M. & Nicholls, I. A. (2015). Hydrogen bond diversity in the pre-polymerization stage contributes to morphology and MIP-template recognition–MAA versus MMA. European Polymer Journal, 66, 558-568
Open this publication in new window or tab >>Hydrogen bond diversity in the pre-polymerization stage contributes to morphology and MIP-template recognition–MAA versus MMA
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2015 (English)In: European Polymer Journal, ISSN 0014-3057, E-ISSN 1873-1945, Vol. 66, p. 558-568Article in journal (Refereed) Published
Abstract [en]

This report demonstrates that the diversity of hydrogen bond interactions present in molecularly imprinted polymer pre-polymerization mixtures, typically associated with binding-site heterogeneity, can also contribute to morphological characteristics that may influence polymer–template recognition. Comparisons have been made between a series of bupivacaine molecularly imprinted methacrylic acid (MAA)–ethylene glycol dimethacrylate (EGDMA) copolymers and a series of analogous methyl methacrylate (MMA)–EGDMA copolymers using comprehensive molecular dynamics studies of the respective pre-polymerization mixtures, template–polymer binding studies and detailed BET surface area and BJH porosity analyses. The role of the carboxylic acid functionality of MAA, and in particular the acidic proton, in generating morphological features conducive to analyte access (slit-like rather than ink bottle-like structures) and recognition is discussed.

Place, publisher, year, edition, pages
Pergamon Press, 2015
National Category
Materials Chemistry
Research subject
Chemistry, Organic Chemistry
Identifiers
urn:nbn:se:lnu:diva-42601 (URN)10.1016/j.eurpolymj.2015.03.018 (DOI)000353854000057 ()2-s2.0-84928389138 (Scopus ID)
Available from: 2015-04-15 Created: 2015-04-15 Last updated: 2020-03-20Bibliographically approved
Nicholls, I. A., Chavan, S., Golker, K., Karlsson, B. C. G., Olsson, G. D., Rosengren, A. M., . . . Wiklander, J. G. (2015). Theoretical and Computational Strategies for the Study of the Molecular Imprinting Process and Polymer Performance. In: Mattiasson, B. & Ye, L. (Ed.), Molecularly Imprinted Polymers in Biotechnology: (pp. 25-50). Berlin: Springer
Open this publication in new window or tab >>Theoretical and Computational Strategies for the Study of the Molecular Imprinting Process and Polymer Performance
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2015 (English)In: Molecularly Imprinted Polymers in Biotechnology / [ed] Mattiasson, B. & Ye, L., Berlin: Springer, 2015, p. 25-50Chapter in book (Refereed)
Abstract [en]

The development of in silico strategies for the study of the molecular imprinting process and the properties of molecularly imprinted materials has been driven by a growing awareness of the inherent complexity of these systems and even by an increased awareness of the potential of these materials for use in a range of application areas. Here we highlight the development of theoretical and computational strategies that are contributing to an improved understanding of the mechanisms underlying molecularly imprinted material synthesis and performance, and even their rational design.

Place, publisher, year, edition, pages
Berlin: Springer, 2015
Series
Advances in Biochemical Engineering-Biotechnology, ISSN 0724-6145 ; 150
National Category
Polymer Technologies
Research subject
Chemistry, Organic Chemistry
Identifiers
urn:nbn:se:lnu:diva-42600 (URN)10.1007/10_2015_318 (DOI)000365222300003 ()2-s2.0-84938411248 (Scopus ID)978-3-319-20729-2 (ISBN)978-3-319-20728-5 (ISBN)
Available from: 2015-04-15 Created: 2015-04-15 Last updated: 2020-03-20Bibliographically approved
Golker, K., Karlsson, B. C. G., Rosengren, A. M. & Nicholls, I. A. (2014). A Functional Monomer Is Not Enough: Principal Component Analysis of the Influence of Template Complexation in Pre-Polymerization Mixtures on Imprinted Polymer Recognition and Morphology. International Journal of Molecular Sciences, 15(11), 20572-20584
Open this publication in new window or tab >>A Functional Monomer Is Not Enough: Principal Component Analysis of the Influence of Template Complexation in Pre-Polymerization Mixtures on Imprinted Polymer Recognition and Morphology
2014 (English)In: International Journal of Molecular Sciences, ISSN 1422-0067, E-ISSN 1422-0067, Vol. 15, no 11, p. 20572-20584Article in journal (Refereed) Published
Abstract [en]

In this report, principal component analysis (PCA) has been used to explore the influence of template complexation in the pre-polymerization phase on template molecularly imprinted polymer (MIP) recognition and polymer morphology. A series of 16 bupivacaine MIPs were studied. The ethylene glycol dimethacrylate (EGDMA)-crosslinked polymers had either methacrylic acid (MAA) or methyl methacrylate (MMA) as the functional monomer, and the stoichiometry between template, functional monomer and crosslinker was varied. The polymers were characterized using radioligand equilibrium binding experiments, gas sorption measurements, swelling studies and data extracted from molecular dynamics (MD) simulations of all-component pre-polymerization mixtures. The molar fraction of the functional monomer in the MAA-polymers contributed to describing both the binding, surface area and pore volume. Interestingly, weak positive correlations between the swelling behavior and the rebinding characteristics of the MAA-MIPs were exposed. Polymers prepared with MMA as a functional monomer and a polymer prepared with only EGDMA were found to share the same characteristics, such as poor rebinding capacities, as well as similar surface area and pore volume, independent of the molar fraction MMA used in synthesis. The use of PCA for interpreting relationships between MD-derived descriptions of events in the pre-polymerization mixture, recognition properties and morphologies of the corresponding polymers illustrates the potential of PCA as a tool for better understanding these complex materials and for their rational design.

Keywords
molecularly imprinted polymer, molecular dynamics, molecular recognition, molecular imprinting, principal component analysis, chemometrics
National Category
Organic Chemistry
Research subject
Chemistry, Organic Chemistry
Identifiers
urn:nbn:se:lnu:diva-39134 (URN)10.3390/ijms151120572 (DOI)000345529200072 ()2-s2.0-84910128229 (Scopus ID)
Available from: 2015-01-15 Created: 2015-01-15 Last updated: 2018-11-02Bibliographically approved
Golker, K. (2014). Fundamental Studies on Molecularly Imprinted Materials. (Doctoral dissertation). Växjö: Linnaeus University Press
Open this publication in new window or tab >>Fundamental Studies on Molecularly Imprinted Materials
2014 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The thesis focuses on fundamental studies aimed at elucidating factors that influence molecularly imprinted polymer (MIP) formation and ligand recognition. To this end, a series of computational techniques, in particular chemometrics and molecular dynamics (MD) in conjunction with polymer synthesis and physical characterization studies have been employed.

 

In Paper I, the multivariate analysis method principal component analysis (PCA) was used to investigate the role of incubation media on polymer-ligand recognition, and results highlighted the importance of several solvent parameters on recognition. In Paper II, all-component MD simulations were used to examine the role of polymerization mixture stoichiometry on MIP-template recognition. Correlations between nature and extent of template complexation and recognition were observed. The influence of the acidic functionality of the methacrylic acid used in these polymers on polymer-template recognition and morphology was examined in Paper III. PCA was then used in Paper IV to identify relationships between interactions in the pre-polymerization mixture, polymer functionality, recognition and morphology using the polymers described in Paper II and III.

Place, publisher, year, edition, pages
Växjö: Linnaeus University Press, 2014. p. 58
Series
Linnaeus University Dissertations ; 179/2014
Keywords
Chemometrics, molecular dynamics, molecularly imprinted polymer, molecular imprinting, morphology, polymer, principal component analysis
National Category
Chemical Sciences
Identifiers
urn:nbn:se:lnu:diva-38651 (URN)978-91-87427-94-7 (ISBN)
Public defence
2014-06-17, N2007, Kalmar, 09:30 (English)
Opponent
Supervisors
Available from: 2015-01-09 Created: 2014-12-17 Last updated: 2018-11-16Bibliographically approved
Golker, K., Karlsson, B. C. G., Olsson, G. D., Rosengren, A. M. & Nicholls, I. A. (2013). Influence of composition and morphology on template recognition in molecularly imprinted polymers. Macromolecules, 46(4), 1408-1414
Open this publication in new window or tab >>Influence of composition and morphology on template recognition in molecularly imprinted polymers
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2013 (English)In: Macromolecules, ISSN 0024-9297, E-ISSN 1520-5835, Vol. 46, no 4, p. 1408-1414Article in journal (Refereed) Published
Abstract [en]

A combination of theoretical and experimental studies has provided correlations between molecularly imprinted polymer composition, morphology, and recognition behavior obtained using a series of bupivacaine-imprinted methacrylic acid (MAA)–ethylene glycol dimethacrylate copolymers differing in molar ratios of the respective monomers. Results extracted from analysis of molecular dynamics (MD) trajectory data demonstrated that stability and frequency of interactions between bupivacaine and the monomers in the prepolymerization phase were strongly affected by minor changes in polymer composition, which in turn affected binding site affinity and heterogeneity of the imprinted polymers. Moreover, through the characterization of polymer morphology, we show that higher molar fractions of MAA resulted in polymeric materials with increased pore size, a feature that enhanced the binding capacity of the polymers. Furthermore, the results presented point at the strength of MD for predicting MIP-template binding capacity and affinity.

National Category
Chemical Sciences
Research subject
Chemistry, Organic Chemistry
Identifiers
urn:nbn:se:lnu:diva-24758 (URN)10.1021/ma3024238 (DOI)000315618800019 ()2-s2.0-84874402610 (Scopus ID)
Available from: 2013-03-12 Created: 2013-03-12 Last updated: 2018-11-02Bibliographically approved
Nicholls, I. A., Andersson, H. S., Golker, K., Henschel, H., Karlsson, B. C. G., Olsson, G. D., . . . Wikman, S. (2013). Rational molecularly imprinted polymer design: theoretical and computational strategies. In: Ye, L (Ed.), Molecular Imprinting: Principles and Applications of Micro- and Nanostructured Polymers (pp. 71-104). London: Pan Stanford Publishing
Open this publication in new window or tab >>Rational molecularly imprinted polymer design: theoretical and computational strategies
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2013 (English)In: Molecular Imprinting: Principles and Applications of Micro- and Nanostructured Polymers / [ed] Ye, L, London: Pan Stanford Publishing, 2013, p. 71-104Chapter in book (Refereed)
Place, publisher, year, edition, pages
London: Pan Stanford Publishing, 2013
National Category
Organic Chemistry
Research subject
Chemistry, Organic Chemistry
Identifiers
urn:nbn:se:lnu:diva-8867 (URN)2-s2.0-84974679377 (Scopus ID)9789814310994 (ISBN)
Available from: 2010-10-08 Created: 2010-10-08 Last updated: 2020-03-20Bibliographically approved
Nicholls, I. A., Andersson, H. S., Golker, K., Henschel, H., Karlsson, B. C. G., Olsson, G. D., . . . Wikman, S. (2011). Rational Design of Biomimetic Molecularly Imprinted Materials: Theoretical and Computational Strategies for Guiding Nanoscale Structured Polymer Development. Analytical and Bioanalytical Chemistry, 400, 1771-1786
Open this publication in new window or tab >>Rational Design of Biomimetic Molecularly Imprinted Materials: Theoretical and Computational Strategies for Guiding Nanoscale Structured Polymer Development
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2011 (English)In: Analytical and Bioanalytical Chemistry, ISSN 1618-2642, E-ISSN 1618-2650, Vol. 400, p. 1771-1786Article, review/survey (Refereed) Published
Abstract [en]

In principle, molecularly imprinted polymer science and technology provides a means for ready access to nano-structured polymeric materials of predetermined selectivity. The versatility of the technique has brought it to the attention of many working with the development of nanomaterials with biological or biomimetic properties for use as therapeutics or in medical devices. Nonetheless, the further evolution of the field necessitates the development of robust predictive tools capable of handling the complexity of molecular imprinting systems. The rapid growth in computer power and software over the past decade has opened new possibilities for simulating aspects of the complex molecular imprinting process. We present here a survey of the current status of the use of in silico-based approaches to aspects of molecular imprinting. Finally, we highlight areas where ongoing and future efforts should yield information critical to our understanding of the underlying mechanisms sufficient to permit the rational design of molecularly imprinted polymers.

National Category
Theoretical Chemistry Organic Chemistry Analytical Chemistry Polymer Chemistry
Research subject
Chemistry, Organic Chemistry
Identifiers
urn:nbn:se:lnu:diva-16276 (URN)10.1007/s00216-011-4935-1 (DOI)2-s2.0-84961983789 (Scopus ID)
Available from: 2011-12-21 Created: 2011-12-21 Last updated: 2020-03-20Bibliographically approved
Rosengren, A. M., Golker, K., Wiklander, J. G. & Nicholls, I. A. (2010). Identification of Solvent Properties Influencing Binding to Molecularly Imprinted Polymers. In: : . Paper presented at MIP2010: The 6th International Conference on Molecular Imprinting, New Orleans.
Open this publication in new window or tab >>Identification of Solvent Properties Influencing Binding to Molecularly Imprinted Polymers
2010 (English)Conference paper, Published paper (Refereed)
Abstract [en]

In order to examine the physical mechanisms underlying molecularly imprinted polymer1 (MIP)–ligand recognition, polymers with selectivity for the local anaesthetic bupivacaine have been synthesised and their ligand-recognition characteristics examined. As several previous studies have pointed at the complexity of the rebinding characteristics and the dependence on rebinding media,2-4 we used chemometric strategies for the analysis of ligand-MIP binding in various media.5

In a previous study we presented results from a chemometric analysis showing that rebinding of bupivacaine to the MIP in different solvent mixtures and at different temperatures follow a complicated non-linear relationship.6 The results from that analysis, motivated an investigation into the significance of the solvent physical characteristics (molecular and bulk) on rebinding properties. In this work,7 principal component analysis was employed to identify the factors with the greatest influence on binding. While the dielectric constant made a significant contribution to describing the observed binding, the influence of polarity as reflected in the Snyder polarity index was also demonstrated to also make a significant contribution. The use of solvents containing hydroxyl functionality was observed to exert unique effects on recognition. The variation in solvent influence on binding at constant dielectricity motivates more complex analyses when studying MIP-ligand recognition.

(1)      Alexander, C.; Andersson, H.S.; Andersson, L.I.; Ansell, R.J.; Kirsch, N.; Nicholls, I.A.; O'Mahony, J.; Whitcombe, M.J. Molecular imprinting science and technology: A survey of the literature for the years up to and including 2003. Journal of Molecular Recognition 2006, 19, 106-180.

(2)      Andersson, L.I. Efficient sample pre-concentration of bupivacaine from human plasma by solid-phase extraction on molecularly imprinted polymers. Analyst 2000, 125, 1515-1517.

(3)      Karlsson, J.G.; Andersson, L.I.; Nicholls, I.A. Probing the molecular basis for ligand-selective recognition in molecularly imprinted polymers selective for the local anaesthetic bupivacaine. Analytica Chimica Acta 2001, 435, 57-64.

(4)      Karlsson, J.G.; Karlsson, B.; Andersson, L.I.; Nicholls, I.A. The roles of template complexation and ligand binding conditions on recognition in bupivacaine molecularly imprinted polymers. Analyst 2004, 129, 456-462.

(5)      Nicholls, I.A.; Andersson, H.S.; Charlton, C.; Henschel, H.; Karlsson, B.C.G.; Karlsson, J.G.; O’Mahony, J.; Rosengren, A.M.; Rosengren, K.J.; Wikman, S. Theoretical and computational strategies for rational molecularly imprinted polymer design. Biosensors and Bioelectronics 2009, 25, 543-552.

(6)      Rosengren, A.M.; Karlsson, J.G.; Andersson, P.O.; Nicholls, I.A. Chemometric models of template-molecularly imprinted polymer binding. Analytical Chemistry 2005, 77, 5700-5705.

(7)      Rosengren, A.M; Golker, K.; Wiklander, J.G.; Nicholls, I.A. Dielectric constants are not enough: Principal component analysis of the influence of solvent properties on molecularly imprinted polymer–ligand rebinding. Biosensors and Bioelectronics 2009, 25, 553-557.

National Category
Organic Chemistry
Research subject
Natural Science, Organic Chemistry
Identifiers
urn:nbn:se:lnu:diva-6724 (URN)
Conference
MIP2010: The 6th International Conference on Molecular Imprinting, New Orleans
Available from: 2010-07-07 Created: 2010-07-07 Last updated: 2020-03-20Bibliographically approved
Organisations
Identifiers
ORCID iD: ORCID iD iconorcid.org/0000-0002-0413-2735

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