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• W2107364621 abstract "The radiation-induced formation of some haematoporphyrin (HP) transients in aqueous solution was studied by pulse radiolysis. The OH radicals attack HP (rate constant k = (1·3 ± 0·2) × 1010 dm3 mol−1 s−1) and the resulting transients decay with 2k = (2·5 ± 0·2) × 108 dm3 mol−1 s−1. The spectrum of the HP-OH species shows several maxima in the range of 450–850 nm (ϵ590 = 3880, ϵ640 = 3850, ϵ800 = 3670 dm3 mol−1 cm−1). k for one electron reduction of HP (radical anion, HP.−) was determined by a direct e−aq attack on HP (at pH 9·0,k = (1·6 ± 0·2) × 1010 dm3 mol−1 s−1) as well as by electron transfer from hydroxyisopropyl radicals to the substrate (at pH 8·6, k = (3·2 ± 0·1) × 108, at pH 3·8, k = (4·0 ± 0·2) × 108, and at pH 2·0, k = (2·1 ± 0·1) × 109 dm3 mol−1 s−1). In slightly alkaline media (pH 8·6–9·5) the HP.− transients have main absorption bands at λ < 450 and 640 nm (ϵ660 = 7500 dm3 mol−1 cm−1), whereas at pH 2·0 they are at λ < 430 and 640 nm (ϵ640 = 8170 dm3 mol−1 cm−1) and 710 nm (ϵ710 = 8500 dm3 mol−1 cm−1). The one-electron oxidation of HP (formation of HP.+, radical cation) was studied by means of N.3 or SO·−4 species as electron acceptors. Using N.3 at pH 9·5 k (HP + N.3) = (3·2 ± 0·2) × 109 and for the decay 2k = (3·5 ± 0·3) × 108 dm3 mol−1 s−1 were determined; at pH 3·6, k = (HP + N.3) = (7·1 ± 0·3) × 108 and 2k = (2·6 ± 0·3) × 107 dm3 mol−1 s−1 were found. In the case of SO·−4 at pH9·8 a buildup (5·6 ± 0·3) × 10·7 dm3 mol−1 s−1) was obtained. The spectrum of the HP.+ transients at pH 9·6 possesses several maxima with ϵ345 = 38 800, ϵ450 = 2400, ϵ595 = 2880, and ϵ660 = 3300 dm3 mol−1 cm−1. The corresponding values at pH 3·8 are: ϵ640 = 2450, ϵ710 = 2600, and ϵ780 = 1580 dm3 mol−1 cm−1. It is conceivable that the reported HP transients might be formed also in tumour cells during the radiation or photodynamic treatment of patients when HP is used as sensitizer." @default.
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• W2107364621 date "1995-01-01" @default.
• W2107364621 modified "2023-09-26" @default.
• W2107364621 title "Radiation-induced Formation of Haematoporphyrin-transients in Aqueous Solution. A Pulse Radiolysis Study" @default.
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• W2107364621 doi "https://doi.org/10.1080/09553009514550741" @default.
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