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Papers by Niamh Holland

Research paper thumbnail of Thermal desorption characterisation of molecularly imprinted polymers. Part II: Use of direct probe GC–MS analysis to study crosslinking effects

Analytical and Bioanalytical Chemistry, 2008

A powerful method utilising direct probe thermal desorption GC–MS is presented for the study of m... more A powerful method utilising direct probe thermal desorption GC–MS is presented for the study of molecularly imprinted polymers (MIPs). A series of 2-aminopyridine (2-apy)-imprinted methacrylic acid–ethyleneglycol dimethacrylate (MAA–EGDMA) copolymers were prepared under identical conditions but with varying amounts of EGDMA (crosslinking monomer). The use of appropriate temperature programmes permitted template removal, and the subsequent assessment of polymer affinity and specificity, all of which were found to be dependent on polymer composition and morphology. The system was sufficiently sensitive to identify a specific response of imprinted polymers over nonimprinted counterparts. Correlations were found to exist between thermal desorption analysis and solution phase binding, which was assessed by UV spectroscopy, where specificity was found to diminish with decreasing EGDMA concentration. This was attributed to the increased number of free carboxyl groups in those polymers containing a lower percentage of EGDMA. Thermal desorption profiles obtained for the analyte were found to be unaffected by the physical and chemical properties of the solvent used for analyte reloading.

Research paper thumbnail of Thermal desorption characterisation of molecularly imprinted polymers. Part II: Use of direct probe GC–MS analysis to study crosslinking effects

Analytical and Bioanalytical Chemistry, 2008

Research paper thumbnail of The influence of polymer morphology on the performance of molecularly imprinted polymers

Polymer, 2010

This is the first in-depth study examining the effect of morphology on the performance of 2-amino... more This is the first in-depth study examining the effect of morphology on the performance of 2-aminopyridine (2-apy) imprinted polymers. A series of polymers were prepared by varying the amount of crosslinking monomer (EGDMA) whilst the other polymer components remained constant. Physical characterisation was carried out using conventional techniques, such as nitrogen sorption porosimetry and solvent swelling studies. The use of a novel thermal desorption GC-MS technique suggested higher levels of polymer degradation with prolonged exposure to elevated temperatures for those polymers formed with lower amounts of EGDMA. The thermal desorption GC-MS profiles obtained correlated with the physical characteristics of the polymers, where higher levels of polymer bleed was found to occur with larger average pore diameters. Polymer physical characteristics were also found to correlate with the binding parameters (number of binding sites and polymer-template association energy) obtained from the Langmuir-Freundlich Isotherm (L-FI) and affinity distribution spectra (AD). The flexibility of the polymers formed from lower amounts of EGDMA combined the swelling effect of the solvents on the polymers resulted in an increase in affinity, which was both specific and non-specific in nature.

Research paper thumbnail of Thermal desorption characterisation of molecularly imprinted polymers. Part II: Use of direct probe GC–MS analysis to study crosslinking effects

Analytical and Bioanalytical Chemistry, 2008

A powerful method utilising direct probe thermal desorption GC–MS is presented for the study of m... more A powerful method utilising direct probe thermal desorption GC–MS is presented for the study of molecularly imprinted polymers (MIPs). A series of 2-aminopyridine (2-apy)-imprinted methacrylic acid–ethyleneglycol dimethacrylate (MAA–EGDMA) copolymers were prepared under identical conditions but with varying amounts of EGDMA (crosslinking monomer). The use of appropriate temperature programmes permitted template removal, and the subsequent assessment of polymer affinity and specificity, all of which were found to be dependent on polymer composition and morphology. The system was sufficiently sensitive to identify a specific response of imprinted polymers over nonimprinted counterparts. Correlations were found to exist between thermal desorption analysis and solution phase binding, which was assessed by UV spectroscopy, where specificity was found to diminish with decreasing EGDMA concentration. This was attributed to the increased number of free carboxyl groups in those polymers containing a lower percentage of EGDMA. Thermal desorption profiles obtained for the analyte were found to be unaffected by the physical and chemical properties of the solvent used for analyte reloading.

Research paper thumbnail of Thermal desorption characterisation of molecularly imprinted polymers. Part II: Use of direct probe GC–MS analysis to study crosslinking effects

Analytical and Bioanalytical Chemistry, 2008

Research paper thumbnail of The influence of polymer morphology on the performance of molecularly imprinted polymers

Polymer, 2010

This is the first in-depth study examining the effect of morphology on the performance of 2-amino... more This is the first in-depth study examining the effect of morphology on the performance of 2-aminopyridine (2-apy) imprinted polymers. A series of polymers were prepared by varying the amount of crosslinking monomer (EGDMA) whilst the other polymer components remained constant. Physical characterisation was carried out using conventional techniques, such as nitrogen sorption porosimetry and solvent swelling studies. The use of a novel thermal desorption GC-MS technique suggested higher levels of polymer degradation with prolonged exposure to elevated temperatures for those polymers formed with lower amounts of EGDMA. The thermal desorption GC-MS profiles obtained correlated with the physical characteristics of the polymers, where higher levels of polymer bleed was found to occur with larger average pore diameters. Polymer physical characteristics were also found to correlate with the binding parameters (number of binding sites and polymer-template association energy) obtained from the Langmuir-Freundlich Isotherm (L-FI) and affinity distribution spectra (AD). The flexibility of the polymers formed from lower amounts of EGDMA combined the swelling effect of the solvents on the polymers resulted in an increase in affinity, which was both specific and non-specific in nature.

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