Annibaldi, Valeria (2010) Polypyrrole modified with sulfated β-cyclodextrin: characterization and application in the sensing of viologens. PhD thesis, National University of Ireland Maynooth.
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Abstract
In this thesis a conducting polypyrrole (ppy) matrix doped with the anionic
sulfated β-cyclodextrin (sβ-CD) was electrosynthesized and characterized. This
modified polymer, ppysβ-CD, was used as a sensor for the detection of three
compounds, methyl, ethyl and benzyl viologen. Methyl viologen is commonly
known as paraquat and it is one of the most commonly used herbicides
worldwide.
The sβ-CD was permanently immobilized within the ppy backbone during the
potentiostatic growth of the polymer. The incorporation of the macrocycle was
confirmed by means of cyclic voltammetry (CV), quartz crystal microbalance
(QCM) and differential scanning calorimetry (DSC). The large dopant was found
not to significantly alter certain properties of the polymer such as diffusion of a
probe analyte to the surface and charge transfer rate constant. The cyclodextrin
modified polymer was shown to have cation exchange properties and this
characteristic was used towards the sensing of the three electroactive viologen
compounds. The three viologens were detected by means of differential pulse
voltammetry (DPV), while for methyl viologen constant potential amperometry
(CPA) experiments were also performed. These techniques gave a good linear
response for the current measured at the polymer surface, as a function of the
viologen concentration. Detection limits of 1.00 x 10-4 M for ethyl viologen
(DPV), 2.50 x 10-5 M for benzyl viologen (DPV) and 1.56 x 10-5 M for methyl
viologen (CPA) were measured experimentally.
A detailed analysis was performed on the interaction of the sβ-CD with methyl,
ethyl and benzyl viologen, using both electrochemistry (CV and RDV) and
spectroscopy (UV-Vis, 1H NMR). It was established that a 1:1 interaction occurs
between the sβ-CD and each of the viologens. The formation of inclusion
complexes was verified not to occur. The generation of association complexes
was instead suggested. These complexes result from an ion pairing interaction
between the sβ-CD and the viologens, either in their dication state or in their
radical state.
Item Type: | Thesis (PhD) |
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Keywords: | Polypyrrole; sulfated β-cyclodextrin; viologens; |
Academic Unit: | Faculty of Science and Engineering > Chemistry |
Item ID: | 2268 |
Depositing User: | IR eTheses |
Date Deposited: | 19 Nov 2010 16:14 |
URI: | https://mural.maynoothuniversity.ie/id/eprint/2268 |
Use Licence: | This item is available under a Creative Commons Attribution Non Commercial Share Alike Licence (CC BY-NC-SA). Details of this licence are available here |
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