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In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
12 Photoinduced Electron and Proton Transfer in a Molecular Triad
Downloaded by 95.157.17.76 on October 20, 2009 | http://pubs.acs.org Publication Date: April 17, 1998 | doi: 10.1021/ba-1998-0254.ch012
SuChun Hung, Alisdair N. Macpherson, Su Lin, Paul A. Liddell, Gilbert R. Seely, Ana L. Moore, Thomas A. Moore*, and Devens Gust Department of Chemistry and Biochemistry, Center for the Study of Early Events in Photosynthesis, Arizona State University, Tempe, AZ 852871604
A series of molecular triads, consisting of a porphyrin (P) covalently linked to a carotenoid polyene (C) and a naphthoquinone moiety (Q), have been prepared. Triad 1 features a quinone with an internally hydrogen-bonded carboxylic acid group. The photochemical properties of these molecules have been studied using steady-state and transient absorption and emission spectroscopies in three solvents: benzonitrile, dichloromethane, and chloroform. Each of the triads undergoes photoinduced electron transfer from the C1PQ singlet state to yield the charge-separated state C-P. -Q.-. An electron transfer reaction from C to yield C .+ -P-Q.- competes with fast electron-hole recombination in C-P.+-Q.-. Triad 1 produces the final C . + - P - Q . - state with the 0.22), a factor of ca. 2 higher highest quantum yield of the series than for reference triads. Following the initial photoinduced electron transfer, a fast (k ~ 10 s-1) proton shift from the carboxylic acid to Q.- generates the semiquinone, increasing the lifetime of P.+ and the yield of electron donation by C. In model P-Q dyads, the species P.+ is shown to be longer livedfor quinones thatfeature an internal hydrogen bond. A thermodynamic model is proposed in which the increase in the lifetime of the P.+ moiety by the proton shift is attributed to the pK of the Q/Q.- couple, which dramatically lowers the driving force for electron-hole recombination. +
12
Natural photosynthetic reaction centers, which are responsible for the conver sion of light energy into chemical energy in photosynthetic organisms, employ a multistep electron transfer strategy to achieve charge separation across mem branes with a total quantum yield near unity. Thus, at each intermediate step * Corresponding author. ©1998 American Chemical Society
In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
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In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
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In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
15
Downloaded by 95.157.17.76 on October 20, 2009 | http://pubs.acs.org Publication Date: April 17, 1998 | doi: 10.1021/ba-1998-0254.ch015
Studies of Superoxide with Manganese Complexes and Manganese Superoxide Dismutase from Escherichia coli Diane Esther Cabelli Chemistry Department, Brookhaven National Laboratory, Upton, NY 119735000
II
11
The reactions of TTHA (Mn -triethylenetetraminehexaacetate) complexes with HO -O - radicals were studied (pH 2.5-9.5), and a mechanism was suggested that involves the formation of a transient Mn -) complex. At low pH, this complex is protonated, with the release of H O . At higher pH, the dismutation of O - from the Mn TTHA + O -) is comequilibrium complex (Mn TTHA(O -)3petitive with protonation. At low pH, the results indicate that there is a rapid first-order process that may be an isomerization from end-bound to side-bound of the attached superoxide radical. In contrast, the kinetics of the dismutation of superoxide radical by Escherichia coli MnSOD (manganese superoxide dismutase) were measured and shown to fit a mechanism involving the rapid reduction of Mn SOD by superoxide followed by both the direct reoxidation of Mn SOD by superoxide and the formation of a Mn SOD(O -) complex. The differences in the mechanisms are discussed. 2
II
2
3-
2
2
2
2
II
II
2
2
3+
2+
II
2
The reactions of superoxide radicals with metal complexes have received much attention as 0 ~ can play a role in cycling oxidation states in metal complexes ( J ). This feature has been implicated in catalytic processes such as the Fenton type chemistry (M + H 0 — M + HO + OH"; M + 0 M + 0 ), which is thought to be involved in hydroxylation processes (2). Reactions involving 0 ~ radicals have also been tied to the deleterious effects of oxygen upon aerobic organisms (1,3), probably as a result of similar Fenton type chemical reactions. Superoxide dismutases (SODs) are thought to have evolved as nature's 2
n+
( n + 1 ) +
2
( f l + 1 ) +
2
n +
2
2
©1998 American Chemical Society
In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
247
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In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
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)
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V f f
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2
+
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wavelength,
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In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
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In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
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Scheme I.
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)
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In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
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258
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20
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In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
15.
259
2 +
Mn S0D +
0
2H
2 +
Mn SOD + 0 [Mn
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2
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)]
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2
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Scheme II.
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In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
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I
10
11
~ (O)
3 +
Mn S0D + 0
3 +
2
s : [Mn S0D(0
2
=
+ Mn
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[Mn
S0D(0
2
)] — )]
—
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0
2
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f Mn
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In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
2
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In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
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In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
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In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
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In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
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f f c
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In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
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c
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In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
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BOUNDARY . OSCILLATIONS
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In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
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In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
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In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
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•
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In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
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In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
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In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
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In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
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c
In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
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In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
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In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
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(X+)nH20.... .(e:CI)n*H20
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