Kavanagh, Andrew, Hilder, Matthius, Clark, Noel, Diamond, Dermot ORCID: 0000-0003-2944-4839 and Radu, Aleksandar (2010) The inherent physical, optical and conductivity properties of ionic liquid - polymeric membranes; a self indicating, simultaneous response upon coordination to transition metal ions. In: Macro 2010: 43rd IUPAC World Polymer Congress, 11-16 July 2010, Glasgow, Scotland.
Abstract
Ionic Liquids (IL’s) are organic salts that are liquid at room temperature. Typically, they contain a bulky,
asymmetric organic cation and a small inorganic/organic anion held together via weak electrostatic
interactions, which prevents them from forming a structured lattice.
They exhibit many favourable physical and chemical characteristics, which has led to their use in a variety
of analytical techniques 1. All IL’s display a measured ionic conductivity, plus liquid properties such as
density and viscosity can be controlled by correct choice and/or chemical functionalisation of the ion pair 2.
Ion Selective Electrodes (ISE’s) utilise polymeric membranes for the detection of a target ion in trace
amounts. They typically require a polymer and plasticizer, plus also an ion-exchanging salt and an
ionophore which will selectively bind to a target ion 3. The response of a target ion binding to an ionophore
can be monitored electrochemically, or optically if the ion-ionophore complex produces a colour.
There are several reports in which IL’s plasticize both polyvinylchloride (PVC) and polymethylmethacrylate
(PMMA) based membranes for use in ISE’s 4. Furthermore IL’s also act as ion-exchangers, thereby
eliminating the need for facilitated transport of target ions from aqueous to organic phase.
We will describe the work done to date on the IL trihexyltetradecylphosphonium dicyanamide [P6,6,6,14][DCA]
and its use in polymeric membranes typical of ISE’s. Once solidified into a PVC membrane, [P6,6,6,14][DCA]
can not only act as the plasticizer and ion-exchanger, but also as the ionophore, producing a colorimetric
response upon coordination to Cu2+ (yellow), Co2+ (blue), but also both ions simultaneously (green).
The multifunctionality of [P6,6,6,14][DCA] leads to a dramatic simplification of membrane components,
producing a system capable of a self-indicating, simultaneous, colorimetric response.
As well as a selective optical response, we have also explored the possibility to see if the inherent
conducting properties of these membranes can be exploited. Radio frequency (RF) detection provides a
technique which can monitor the conductivity of a sample wirelessly, but also has the required sensitivity
and is non-invasive on the sample.
RF can not only discriminate between the coordinated and non-coordinated membranes, but also between
the individual co-ordinated membranes. The resultant downward trend in conductivity from Blank > Cobalt
> Mixture > Copper has been validated by Electrochemical Impedance Spectroscopy (EIS) and by portable
X-Ray Fluorescence (XRF).
XRF shows that the results obtained from RF and EIS are directly related to the binding selectivity of the
ligand [DCA]-. We have observed the highest binding levels for membranes exposed to Cu2+ ions, thereby
producing the lowest RF conductivity signal and the highest impedance values. The opposite applies for
Co2+, we have observed lower binding values, conversely producing the highest co-ordinated RF signal
and the lowest coordinated impedance values.
IL’s have been shown to bind to a variety of heavy metal ions 5, lanthanide ions6 plus important target
analytes such as CO2
7 . If a change in conductivity can be presumed upon binding to the analyte, then the
inherent conductivity of IL’s could be exploited in future electrochemical sensing.
Metadata
Item Type: | Conference or Workshop Item (Speech) |
---|---|
Event Type: | Conference |
Refereed: | No |
Subjects: | Physical Sciences > Electrochemistry Physical Sciences > Chemistry |
DCU Faculties and Centres: | Research Initiatives and Centres > CLARITY: The Centre for Sensor Web Technologies |
Official URL: | http://www.rsc.org/ConferencesAndEvents/RSCConfere... |
Use License: | This item is licensed under a Creative Commons Attribution-NonCommercial-Share Alike 3.0 License. View License |
Funders: | Science Foundation Ireland, Enterprise Ireland |
ID Code: | 15521 |
Deposited On: | 03 Aug 2010 10:41 by Andrew Kavanagh . Last Modified 18 Sep 2018 11:59 |
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