Analytica Chimica Acta 408 (2000) 57–64
Ion-selective field effect transistor (ISFET)-based calcium ion sensor
with photocured polyurethane membrane suitable for ionised calcium
determination in milk
Andrey Bratov
∗
, Natalia Abramova, Carlos Dom´ ınguez, Antonio Baldi
Centre Nacional de Microelectrónica, Campus UAB, 08193 Bellaterra, Barcelona, Spain
Received 1 July 1999; received in revised form 15 November 1999; accepted 17 November 1999
Abstract
Ca
2+
-ion-sensitive ISFETs with photocured polyurethane-based polymer membranes with alkylphosphate exchanger
(DOPPCa) and three neutral carrier ionophores (ETH 1001, ETH 129 and ETH 5234) and dioctylsebacate as plasticizer
have been studied in pure CaCl
2
solutions and in background solutions containing Na
+
,K
+
, Mg
2+
ions in concentrations
normally found in milk. In case of DOPPCa and ETH 1001 the influence of Mg
2+
ions on the slope of the response curve
is reported. ISFETs with membranes containing ETH 129 are shown to have high selectivity, more than 6 weeks life-time in
constant contact with a solution and high precision of ionised calcium determination. Experimental results on determination
of calcium ions in a whole milk are presented. ©2000 Elsevier Science B.V. All rights reserved.
Keywords: ISFET; Photocured polymer membrane; Ca-ion sensor; Milk
1. Introduction
Calcium ion-selective sensors based on a poly(vinyl
chloride) (PVC) polymer membranes impregnated
with different ionophores find wide applications in
electroanalytical practice [1]. They are widely used in
medical and biological investigations as well as in the
food industry. An important application is the control
of calcium (Ca
2+
) ion concentration in milk and milk
products especially in cheese production during the
processes of coagulation [2,3].
To exploit the advantages offered by modern tech-
nologies in the fabrication of solid-state chemical
sensors based on ISFETs [4,5] new requirements are
∗
Corresponding author. Fax: +34-93-580-1496.
E-mail address: andrey@cnm.es (A. Bratov).
imposed on a polymer matrix for ion sensor mem-
branes. They are the adhesion of a polymer to a solid
substrate and the compatibility of an ion-sensitive
membrane deposition process with microelectronic
technology. From this point of view photocurable
polymers [6–9] offer attractive advantages over tradi-
tional PVC membranes, because they can be deposited
by screen-printing or by spin-coating and patterned
using standard photolithography processes. Also, the
polymer curing process occurs very fast in comparison
with other methods of polymer ion-selective mem-
brane formation. Acrylate and methacrylate-based
compositions are possible photocurable polymers that
can be applied as ion-selective membrane matrices
[10,11]. Among different polymers studied as a pos-
sible polymer matrix for ion sensors polyurethane
[12–16] showed most promising properties. Earlier
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