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On-column titration and investigation of metal complex formation for aminopolycarboxylate functionalised monoliths using scanning contactless conductivity detection

✍ Scribed by Eoin Gillespie; Damian Connolly; Pavel N. Nesterenko; Brett Paull


Publisher
John Wiley and Sons
Year
2009
Tongue
English
Weight
584 KB
Volume
32
Category
Article
ISSN
1615-9306

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✦ Synopsis


Abstract

The application of scanning capacitively coupled contactless conductivity detection (SC^4^D) for the determination of pH dependant behaviour of two aminopolycarboxylates immobilised onto the surface of a monolithic capillary column is described. The use of SC^4^D to visualise changes in conductivity of the discrete zones of functional groups within monolithic capillary columns allows for the effects of immobilisation on the physicochemical properties of zones to be compared to that of the functional group in solution. The perturbation of the p__K__~a~ values of the functional groups can be attributed to the change in chemical environment experienced by the functional group through the presence of local hydrogen bonding and surface induced effects. These bonds, both between adjacent functional groups and with the monolithic polymethacrylate scaffold, result in a modification of the electron density on the functional group and therefore a change in p__K__~a~. Changes in the p__K__~a~ of N‐(2‐acetamido)iminodiacetic acid (ADA) from 2.48 to 5.2 for one of the acidic protons, with little change in the p__K__~a~ of the amine group, were observed, which correlates to similar changes in aggregated systems of aminopolycarboxylates. Similar results were obtained for the iminodiacetic acid (IDA) once immobilised onto the surface of the monolith. Furthermore, the ability to measure changes in the charge of such discrete zones of functional groups allows for the visualisation of complexation events occurring directly on‐column, where such complexes result in a change in charge of the functional group. This potentially useful technique is illustrated within for the formation of aminopolycarboxylate complexes with a selection of metal ions.