Contribution to the development of optical sensors for anions
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1 Research Collection Doctoral Thesis Contribution to the development of optical sensors for anions Author(s): Tan, Susie Sok Si Publication Date: 1991 Permanent Link: Rights / License: In Copyright - Non-Commercial Use Permitted This page was generated automatically upon download from the ETH Zurich Research Collection. For more information please consult the Terms of use. ETH Library
2 Diss. ETH No Contribution to the Development of Opticai Sensors for Anions A dissertation submitted to the SWISS FEDERAL INSTITUTE OF TECHNOLOGY ZURICH for the degree of Doctor of Natural Sciences presented by Susie Sok Si Tan M. Sc. Chem. La Trobe University, Melbourne born on November 1, 1961 of Johor Bahru, Malaysia accepted on the recommendation of Prof. Dr. W. Simon, examiner Prof. Dr. R. Schwarzenbach, co-examiner Zürich 1991
3 13 Summary Several topics related to the development of Sensors for anions have been investigated. These include optodes with selectivities according to the Hofmeister sequence (so-called Hofmeister optodes), studies of the influence of the membrane matrix on these selectivities, optode measurements with a photodiode-based system, as well as the development of an optode whose selectivities diff er from the Hofmeister series (anti Hofmeister optode) and its application in clinical analysis. Optically sensing membranes that respond to anions according to their lipophilicity, i.e. following the Hofmeister selectivity pattern, are described. In such Systems, anions are coextracted with protons into a thin membrane that contains a lipophilized ph indicator. The anion activity is indicated indirectly through the protonation of the ph indicator. It was found that two different chemical Systems could be employedfor this purpose. The influence ofthe membrane matrix on the response behaviour and selectivity was investigated. A new type of an optical sensor using photodiodes with built-in spectral filters was assembled and tested. The use of ambient light makes the device very simple. In combination with the newly developed Hofmeister optode membranes, it was applied to the determination of nitrate in vegetables. Based on findings from the work with optode membranes, an attempt to construct ion-selective electrodes with a narrow selectivity pattern is reported. Such a sensor maintains the Hofmeister selectivity sequence but with low selectivity coefficients, i.e. the selectivity values lie close together. In some applications, such as the determination of Chloride in biological samples, this can be as useful as a system with good selectivity for the measuring ion. The development of optode membranes which show a better selectivity for Chloride than the Hofmeister optode membranes is also described. The initial experiments were made with an anion-selective porphyrin derivative previously used in Potentiometrie studies. When incorporated
4 14 together with a suitable lipophilized ph indicator into optically sensing membranes, its preference for chloride was confirmed but spectral interference from the porphyrin caused problems. Trioctyltin chloride proved to be more favourable as an anion carrier and its Performance was studied in combination with a number of lipophilized ph indicators. One such system was successfully applied to the determination of chloride in human plasma.
5 15 Zusammenfassung Die vorliegende Arbeit ist ein Beitrag zur Entwicklung von optischen Sensoren für die analytische Bestimmung von Anionen. Es werden optische Sensormembranen beschrieben, die gemäss der Hofmeister-Reihe auf Anionen ansprechen (sogen. Hofmeister- Optodenmembranen). Dabei werden Anionen und Protonen aus dem Messgut zusammen in eine dünne Membran extrahiert, die einen lipophilisierten ph-indikator enthält. Die Aktivität der Anionen wird indirekt durch die Protonierung des ph-indikators angezeigt. Es wurden zwei verschiedene Typen von chemischen Systemen verwendet, wobei auch der Einfluss der Membranmatrix auf das Selektivitäts- und Ansprechverhalten untersucht wurde. Weiter wird ein neuartiger Typ eines optischen Sensors beschrieben, der auf Photodioden mit eingebauten Spektralfiltern beruht und dank der Verwendung des Umgebungslichtes sehr einfach aufgebaut ist. In Kombination mit einer Hofmeister-Optodenmembran wurde er zur Bestimmung von Nitrat in Gemüse eingesetzt. Basierend auf den mit Optodenmembranen erhaltenen Ergebnissen wurde versucht, eine ionenselektive Elektrode zu entwickeln, deren Selektivitätswerte zwar der Hofmeister-Reihe folgen, aber klein sind, d. h. nahe beieinander liegen. Für gewisse Anwendungen, wie z. B. die Bestimmung von Chlorid in biologischen Proben, kann ein solches Verhalten günstiger sein als das einer Elektrode mit guter Selektivität für das Mession. Schliesslich wurden anionenselektive Optodenmembranen entwickelt, die bevorzugt auf Chlorid ansprechen. Die ersten Versuche wurden mit einem Porphyrinderivat durchgeführt, das bereits bei potentiometrischen Untersuchungen verwendet worden war. In Optodenmembranen ergab es in Kombination mit einem geeigneten lipophilisierten ph-indikator zwar eine hohe Selektivität für Chlorid, spektrale Interferenzen beeinträchtigten jedoch die Präzision der Analysen. Dagegen schien Trioctylzinnchlorid als Anionencarrier vielversprechender. Kombiniert
6 16 mit verschiedenen lipophilisierten ph-indikatoren wurde sein Verhalten in Optodenmembranen untersucht. Eine dieser Membranen wurde erfolgreich zur optischen Bestimmung von Chlorid in Plasma eingesetzt.
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