Papkovsky, Dmitri B. and Ponomarev, Gelii V. and Wolfbeis, Otto S. (1997) Protonation of porphyrins in liquid PVC membranes: Effects of anionic additives and application to pH-sensing. JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY, 104 (1-3). pp. 151-158. ISSN 1010-6030
Full text not available from this repository.Abstract
We report on a study on the protonation of representative prophyrins, metallopolphyrins, porphyrin-ketones and a Pd-porphyrin Schiff base in aqueous solution and when dissolved in plasticized PVC membranes. The respective protolytic forms were characterized by absorption and emission spectra as well as apparent pK(a) values. It is shown that the protonation of porphyrins dissolved in PVC membranes is much more difficult than in solution, resulting in an extraordinarily large decrease in the apparent pK(a) values which can be as large as 5 units when compared to the corresponding data for the porphyrins in solution. In certain cases, no protonation at all occurred within the pH 2-12 range. At the same time, N-MeEP which is much more basic (its intrinsic pK being 11.2) can be protonated in such membranes into the monocation at weakly acidic pH, but the apparent pK(a) also is lowered by about 6 units. On addition of a tetraphenylborate anion to the PVC membranes, protonation was found to proceed much easier. Both the monocation and dication was identified in case for the porphyrins, while for the prophyrin-ketones direct protonation into dication took place, and N-methyletioporphyrin was present as the monocation over the whole pH 2-12 range. Membranes composed of solutions of porphyrin-ketones or the Pd-porphyrin Schiff base in plasticized PVC were identified as being useful for purposes of continuously sensing pH in the physiological range. Their response time, calibration curves, signal stability and effects of buffer ionic strength and temperature were investigated in more detail. (C) Elsevier Science S.A.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | prophyrins; protonation; pK(a) values; plasticized PVC membranes; optical pH sensors |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Analytische Chemie, Chemo- und Biosensorik |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 11 May 2023 09:03 |
| Last Modified: | 11 May 2023 09:03 |
| URI: | https://pred.uni-regensburg.de/id/eprint/50954 |
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