The University of Southampton
University of Southampton Institutional Repository

Molecular recognition at an organic-aqueous interface: heterocalixarenes as anion binding agents in liquid polymeric membrane ion-selective electrodes

Molecular recognition at an organic-aqueous interface: heterocalixarenes as anion binding agents in liquid polymeric membrane ion-selective electrodes
Molecular recognition at an organic-aqueous interface: heterocalixarenes as anion binding agents in liquid polymeric membrane ion-selective electrodes
Poly(vinyl chloride) (PVC)-derived ion-selective electrodes (ISEs) have been prepared from a neutral anion binding receptor, meso-octamethylcalix[4]pyrrole (1). Analogous systems were also prepared from the novel pyridine-containing analogues of 1, namely dichlorocalix[2]pyrrole[2]pyridine (2) and tetrachlorocalix[4]pyridine (3). At lower pH values (i.e., 3.5 and 5.5), ISEs derived from 1 display strong anionic (negative slope) responses towards Br-, Cl-, and H2PO4- and, to a much lesser extent, F-. By contrast, at high pH (i.e. pH 9.0) ISEs derived from 1 not only display cationic (positive slope) responses towards chloride and bromide anions but also selectivities (i.e., Br- < Cl- < OH- ? F- < HPO42-) that are non-Hofmeister in nature. This is considered consistent with the PVC-supported receptor 1 behaving as a direct anion binding agent at low pH but acting, at least in part, as an hydroxide-complexing receptor at higher pH. For the ISEs based on 2 and 3, no special non-Hofmeister selectivity is observed at pH 9.0. However, at lower pH values both increased anionic responses and improved selectivities for hydrophilic anions (e.g., F- and H2PO4-) are observed. These observations are rationalized in terms of protonation effects involving the pyridine-containing receptors from which these ISEs are derived. For all the receptors discussed in this report, the addition of tridodecylmethylammonium chloride (TDDMA), a known lipophilic additive, serves to increase the magnitude of the ISE response but only at the price of greatly reduced anion selectivity.
anion selective electrode, calixpyrrole, sensor
0002-7863
8771-8775
Král, Vladimir
5d78b97d-203c-4fd9-9a4e-fb788cd78cd1
Sessler, Jonathan L.
d793ea76-a3a2-4ce1-a8d5-aca7d3307fbe
Shishkanova, Tatiana V.
7de89e0c-027d-4424-94a4-5160797e943e
Gale, Philip A.
ce0aa62f-d081-408b-8b00-6d954058afab
Wolf, Radko
3abe3781-554b-4178-ba8e-57c919e0c515
Král, Vladimir
5d78b97d-203c-4fd9-9a4e-fb788cd78cd1
Sessler, Jonathan L.
d793ea76-a3a2-4ce1-a8d5-aca7d3307fbe
Shishkanova, Tatiana V.
7de89e0c-027d-4424-94a4-5160797e943e
Gale, Philip A.
ce0aa62f-d081-408b-8b00-6d954058afab
Wolf, Radko
3abe3781-554b-4178-ba8e-57c919e0c515

Král, Vladimir, Sessler, Jonathan L., Shishkanova, Tatiana V., Gale, Philip A. and Wolf, Radko (1999) Molecular recognition at an organic-aqueous interface: heterocalixarenes as anion binding agents in liquid polymeric membrane ion-selective electrodes. Journal of the American Chemical Society, 121 (38), 8771-8775. (doi:10.1021/ja991044e).

Record type: Article

Abstract

Poly(vinyl chloride) (PVC)-derived ion-selective electrodes (ISEs) have been prepared from a neutral anion binding receptor, meso-octamethylcalix[4]pyrrole (1). Analogous systems were also prepared from the novel pyridine-containing analogues of 1, namely dichlorocalix[2]pyrrole[2]pyridine (2) and tetrachlorocalix[4]pyridine (3). At lower pH values (i.e., 3.5 and 5.5), ISEs derived from 1 display strong anionic (negative slope) responses towards Br-, Cl-, and H2PO4- and, to a much lesser extent, F-. By contrast, at high pH (i.e. pH 9.0) ISEs derived from 1 not only display cationic (positive slope) responses towards chloride and bromide anions but also selectivities (i.e., Br- < Cl- < OH- ? F- < HPO42-) that are non-Hofmeister in nature. This is considered consistent with the PVC-supported receptor 1 behaving as a direct anion binding agent at low pH but acting, at least in part, as an hydroxide-complexing receptor at higher pH. For the ISEs based on 2 and 3, no special non-Hofmeister selectivity is observed at pH 9.0. However, at lower pH values both increased anionic responses and improved selectivities for hydrophilic anions (e.g., F- and H2PO4-) are observed. These observations are rationalized in terms of protonation effects involving the pyridine-containing receptors from which these ISEs are derived. For all the receptors discussed in this report, the addition of tridodecylmethylammonium chloride (TDDMA), a known lipophilic additive, serves to increase the magnitude of the ISE response but only at the price of greatly reduced anion selectivity.

Full text not available from this repository.

More information

Published date: 1999
Keywords: anion selective electrode, calixpyrrole, sensor

Identifiers

Local EPrints ID: 13961
URI: http://eprints.soton.ac.uk/id/eprint/13961
ISSN: 0002-7863
PURE UUID: f8577187-90ea-4edf-940b-5a73dd04f8bd

Catalogue record

Date deposited: 21 Dec 2004
Last modified: 15 Jul 2019 19:33

Export record

Altmetrics

Download statistics

Downloads from ePrints over the past year. Other digital versions may also be available to download e.g. from the publisher's website.

View more statistics

Atom RSS 1.0 RSS 2.0

Contact ePrints Soton: eprints@soton.ac.uk

ePrints Soton supports OAI 2.0 with a base URL of http://eprints.soton.ac.uk/cgi/oai2

This repository has been built using EPrints software, developed at the University of Southampton, but available to everyone to use.

We use cookies to ensure that we give you the best experience on our website. If you continue without changing your settings, we will assume that you are happy to receive cookies on the University of Southampton website.

×