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Photophysics and photochemistry of oxygen sensors based on luminescent transition-metal complexes

Carraway, E. R. and Demas, J. N. and DeGraff, B. A. and Bacon, J. R. (1991) Photophysics and photochemistry of oxygen sensors based on luminescent transition-metal complexes. Analytical Chemistry, 63 (4). pp. 337-342. ISSN 0003-2700. https://resolver.caltech.edu/CaltechAUTHORS:20170808-152518677

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Abstract

A detailed study of the photophysics and photochemistry of polymer-immobilized luminescent transition-metal complex oxygen sensors is presented. Emphasis is on understanding the underlying origin of the nonlinear Stern-Volmer quenching response. Microheterogeneity is important in both photophysical and photochemical behavior, and the nonlinear quenching responses in RTV 118 silicone rubber can be adequately described by a two-site model, although detailed lifetime measurements suggest a more complex Underlying system. Counterion studies with quenching counterions are shown to be useful probes of the structure of the complex in the polymer. While oxygen enhances photochemical instability, singlet oxygen is not directly implicated in sensor decomposition. In the photochemistry there is at least one reactive and one much less reactive site, although the photochemistry and quenching measurements probably sample different populations of sites. The existence of reactive sites suggests that stability can be enhanced by a preliminary photolysis to eliminate the more reactive sites.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/ac00004a007DOIArticle
http://pubs.acs.org/doi/abs/10.1021/ac00004a007PublisherArticle
Additional Information:© 1991 American Chemical Society. Received for review August 3, 1990. Accepted November 1, 1990. We gratefully acknowledge the support of the National Science Foundation (Grants CHE 86-00012 and 88-17809). We thank Seth Snyder for his assistance with the time-correlated single-photon lifetime system and with the deconvolution software.
Funders:
Funding AgencyGrant Number
NSFCHE 86-00012
NSFCHE 88-17809
Issue or Number:4
Record Number:CaltechAUTHORS:20170808-152518677
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20170808-152518677
Official Citation:Photophysics and photochemistry of oxygen sensors based on luminescent transition-metal complexes E. R. Carraway, J. N. Demas, B. A. DeGraff, and J. R. Bacon Analytical Chemistry 1991 63 (4), 337-342 DOI: 10.1021/ac00004a007
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:79968
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:09 Aug 2017 18:15
Last Modified:03 Oct 2019 18:26

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