Photochemical Electron Transfer in the System Polypyrrole-Methylene Blue

1994 ◽  
Vol 47 (6) ◽  
pp. 1163 ◽  
Author(s):  
D Matthews ◽  
A Altus ◽  
A Hope
Keyword(s):  
Methylene Blue ◽  
Electron Transfer ◽  
Absorption Spectrum ◽  
Absorption Spectra ◽  
Flash Photolysis ◽  
Laser Flash Photolysis ◽  
Laser Flash ◽  
Vitamin K1 ◽  
Photochemical Reduction ◽  
Long Chain

Methylene Blue incorporated into colloidal oxidized polypyrrole was investigated by absorption spectroscopy and laser flash photolysis. The absorption spectra of Methylene Blue and polypyrrole were unaffected by incorporation. Flash photolysis transients of Methylene Blue and triplet Methylene Blue in ethanol were affected by 1,4-benzoquinone and 1,4-benzoquinol but not by the long-chain naphthoquinone Vitamin K1. Incorporation of Methylene Blue in polypyrrole produced distinct changes in the flash photolysis transients of Methylene Blue and triplet Methylene Blue. Very long-lived transients, with lifetimes of the order of 10 ms, were observed. These effects were accompanied by long-lived changes in the absorption spectrum of Methylene Blue. The transients were modified by the addition of 1,4-benzoquinone but not 1,4-benzoquinol. The results indicate photochemical reduction of oxidized polypyrrole by triplet Methylene Blue with the production of stable long-lived species capable of reducing 1,4-benzoquinone.

Photochemical Electron Transfer Between Methylene Blue and Quinones

1994 ◽  
Vol 47 (2) ◽  
pp. 209 ◽  
Author(s):  
M Misran ◽  
D Matthews ◽  
P Valente ◽  
A Hope
Keyword(s):  
Methylene Blue ◽  
Electron Transfer ◽  
Flash Photolysis ◽  
Laser Flash Photolysis ◽  
Lipid Vesicles ◽  
Laser Flash ◽  
Electron Transfer Reaction ◽  
Vitamin K1 ◽  
Photochemical Oxidant ◽  
Back Electron Transfer

Methylene Blue is a well known photochemical oxidant. In this paper we present results of cyclic voltammetry and laser flash photolysis experiments which demonstrate that Methylene Blue may function also as a photochemical reductant. Laser flash photolysis studies of Methylene Blue were carried out in aqueous solution at pH 10, in ethanol and in aqueous dispersions of lipid vesicles in the presence of benzoquinol , benzoquinone and the long-chain naphthoquinone Vitamin K1. Both the quinones and the quinol affected the transient of the decay of triplet Methylene Blue to its ground electronic state. The transients were biphasic and characteristic of an initial electron transfer reaction between triplet Methylene Blue and the quinone or quinol , followed by back electron transfer between the products. For Vitamin K1 and Methylene Blue in ethanol the back electron transfer was very slow (lifetime about 4 ms). This slow back electron transfer is favourable to the use of this system for energy storage via photosynthetic solar energy conversion.

Laser flash-photolysis of methylene blue solutions

1979 ◽  
Vol 44 (7) ◽  
pp. 2015-2023 ◽  
Author(s):  
Viktor Řehák ◽  
Jaroslav Poskočil
Keyword(s):  
Methylene Blue ◽  
Electron Transfer ◽  
Energy Transfer ◽  
Rate Constants ◽  
Flash Photolysis ◽  
Laser Flash Photolysis ◽  
Laser Flash ◽  
Kinetic Measurements ◽  
Methanolic Solution ◽  
Triplet Excimer

Besides population and relaxation of T1 state of methylene blue in methanolic solution it has been possible to observe increase and decomposition of a transient with longer lifetime which is probably a triplet excimer of the dyestuff. Kinetic measurements have enabled to determine the lifetime of the T1 excimer, rate constants of energy-transfer to oxygen and electron-transfer from pyrrolidine to T1 of the dyestuff.

Synthesis and photodynamics of diphenylethynyl-bridged porphyrin-quinoidal porphyrin hybrids

2015 ◽  
Vol 19 (01-03) ◽  
pp. 219-232 ◽  
Author(s):  
Shuhei Sakatani ◽  
Takuya Kamimura ◽  
Kei Ohkubo ◽  
Shunichi Fukuzumi ◽  
Fumito Tani
Keyword(s):  
Electron Transfer ◽  
Absorption Spectra ◽  
Zinc Complex ◽  
Flash Photolysis ◽  
Laser Flash Photolysis ◽  
Laser Flash ◽  
Electrochemical Analysis ◽  
Coupling Reactions ◽  
Free Base ◽  
Electronic Communications

As new donor–acceptor hybrids for energy and/or electron transfer, zinc complex and free-base of a porphyrin-quinoidal porphyrin dyad linked by a diphenylethynyl bridge were prepared via Sonogashira and subsequent Takahashi coupling reactions. The quinoidal porphyrin units have two dicyanomethylene groups at the opposite meso-positions. The UV-vis absorption spectra of the dyads were almost linear summations of the absorption spectra of each component in comparison with those of the monomeric reference compounds, indicating very weak electronic interactions between the chromophores at the ground state. Both zinc complex and free-base of the reference porphyrin exhibited fluorescence in the range of ca. 600–700 nm upon photoexcitation, while the quinoidal porphyrin monomers showed no fluorescence. The considerable quenching (more than 99%) of the porphyrin fluorescence in the dyads suggested significant electronic communications between the subunits of the excited state. The electrochemical analysis confirmed that the first oxidations of the dyads occur at the porphyrin units and the first reductions take place at the quinoidal porphyrin units. Femtosecond laser flash photolysis of the zinc dyad with photoexcitation at 393 nm showed both ultrafast (<1 ps) energy and electron transfer from the porphyrin unit to the quinoidal porphyrin one, which processes resulted in the quenching of the porphyrin fluorescence. On the other hand, the free-base dyad underwent only energy transfer.

Electron transfer sensitized photolysis of 'onium salts

1988 ◽  
Vol 66 (2) ◽  
pp. 319-324 ◽  
Author(s):  
R. J. DeVoe ◽  
M. R. V. Sahyun ◽  
Einhard Schmidt ◽  
N. Serpone ◽  
D. K. Sharma
Keyword(s):  
Electron Transfer ◽  
Flash Photolysis ◽  
Laser Flash Photolysis ◽  
Laser Flash ◽  
Quantitative Model ◽  
Intersystem Crossing ◽  
Single Electron Transfer ◽  
Onium Salts ◽  
Encounter Complex ◽  
Back Electron Transfer

We have studied the anthracene-sensitized photolyses of both diphenyliodonium and triphenylsulphonium salts in solution using both steady-state and laser flash photolysis techniques. Photoproducts, namely, phenylated anthracenes along with iodobenzene or diphenylsulphide, respectively, are obtained from both salts with quantum efficiencies of ca. 0.1 at 375 nm. We infer the intermediacy of diphenyliodo and triphenylsulphur radicals formed by single electron transfer from the singlet-excited anthracene. We have developed a quantitative model of this chemistry, and identify the principal sources of inefficiency as back electron transfer, which occurs at nearly the theoretically limiting rate, intersystem crossing from the initially formed sensitizer–'onium salt encounter complex, and in-cage radical recombination.

Laser flash photolysis studies of intramolecular electron transfer in milk xanthine oxidase

Biochemistry ◽  
1983 ◽  
Vol 22 (23) ◽  
pp. 5270-5279 ◽  
Author(s):  
Anjan Bhattacharyya ◽  
Gordon Tollin ◽  
Michael Davis ◽  
Dale E. Edmondson
Keyword(s):  
Electron Transfer ◽  
Xanthine Oxidase ◽  
Flash Photolysis ◽  
Laser Flash Photolysis ◽  
Laser Flash ◽  
Intramolecular Electron Transfer
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