Journal
ANALYTICAL CHEMISTRY
Volume 84, Issue 2, Pages 1104-1111Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ac202761x
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Funding
- National Science Foundation [OISE-0809328]
- National Institutes of Health [1R01 EB005225-01]
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [0809328] Funding Source: National Science Foundation
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It is well known that the selectivity of an ion-selective electrode (ISE) depends on the stoichiometry of the complexes between its ionophore and the target and interfering ions. It is all the more surprising that the possibility for the simultaneous occurrence of multiple target ion complexes with different complex stoichiometries was mostly ignored in the past. Here, we report on the simultaneous formation of 1:1 and 1:2 complexes of a fluorophilic crown ether in fluorous ISE membranes and how this results in what looks like super-Nernstian responses. These increased response slopes are not caused by mass transfer limitations and can be readily explained with a phase boundary model, a finding that is supported by experimentally determined complex formation constants and excellent fits of response curves. Not only Cs+ but also the smaller ions Li+, Na+, K+, and NH4+ form 1:1 and 1:2 complexes with the fluorophilic crown ether, with cumulative formation constants of up to 10(15.0) and 10(21.0) for of the 1:1 and 1:2 complexes, respectively. Super-Nernstian responses of the type observed with these electrodes are probably not particularly rare but have lacked in the past an adequate discussion in the literature, remaining ignored or misinterpreted. Preliminary calculations also predict sub-Nernstian responses and potential dips of a similar origin. The proper understanding of such phenomena will facilitate the development of new ISEs based on ionophores that form complexes of higher stoichiometries.
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