| 1. |
- Ghanem, Raed, et al.
(författare)
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Light-driven tyrosine radical formation in a ruthenium-tyrosine complex attached to nanoparticle TiO2
- 2002
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Ingår i: Inorganic Chemistry. - : American Chemical Society (ACS). - 0020-1669 .- 1520-510X. ; 41:24, s. 6258-6266
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Tidskriftsartikel (refereegranskat)abstract
- We demonstrate a possibility of multistep electron transfer in a supramolecular complex adsorbed on the surface of nanocrystalline TiO2. The complex mimics the function of the tyrosinez and chlorophyll unit P-680 in natural photosystem II (PSII). A ruthenium(II) tris(bipyridyl) complex covalently linked to a L-tyrosine ethyl ester through an amide bond was attached to the surface of nanocrystalline TiO2 via carboxylic acid groups linked to the bpy ligands. Synthesis and characterization of this complex are described. Excitation (450 nm) of the complex promotes an electron to a metal-to-ligand charge-transfer (MLCT) excited state, from which the electron is injected into TiO2. The photogeneration of Ru(III) is followed by an intramolecular electron transfer from tyrosine to Ru(III), regenerating the photosensitizer Ru(II) and forming the tyrosyl radical. The tyrosyl radical is formed in less than 5 us with a yield of 15%. This rather low yield is a result of a fast back electron transfer reaction from the nanocrystalline TiO2 to the photogenerated Ru(III).
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| 2. |
- Ilagan, R P, et al.
(författare)
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Femtosecond time-resolved absorption spectroscopy of astaxanthin in solution and in alpha-crustacyanin
- 2005
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Ingår i: The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory. - : American Chemical Society (ACS). - 1520-5215. ; 109:14, s. 3120-3127
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Tidskriftsartikel (refereegranskat)abstract
- Steady-state absorption and femtosecond time-resolved spectroscopic studies have been carried out on astaxanthin dissolved in CS2, methanol, and acetonitrile, and in purified alpha-crustacyanin. The spectra of the S-0 -> S-2 and S-1 -> S-n transitions were found to be similarly dependent on solvent environment. The dynamics of the excited-state decay processes were analyzed with both single wavelength and global fitting procedures. In solution, the S-1 lifetime of astaxanthin was found to be similar to 5 ps and independent of solvent. In alpha-crustacyanin, the lifetime was noticeably shorter at similar to 1.8 ps. Both fitting procedures led to the conclusion that the lifetime of the S-2 state was either comparable to or shorter than the instrument response time. The data support the idea that dimerization of astaxanthin in alpha-crustacyanin is the primary molecular basis for the bathochromic shift of the S-0 -> S-2 and S-1 - S-n transitions. Planarization of the astaxanthin molecule, which leads to a longer effective pi-electron conjugated chain and a lower S-1 energy, accounts for the shorter tau(1) in the protein.
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| 3. |
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| 4. |
- Nemec, Hynek, et al.
(författare)
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Influence of the Electron-Cation Interaction on Electron Mobility in Dye-Sensitized ZnO and TiO2 Nanocrystals: A Study Using Ultrafast Terahertz Spectroscopy
- 2010
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Ingår i: Physical Review Letters. - 1079-7114. ; 104:19
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Tidskriftsartikel (refereegranskat)abstract
- Charge transport and recombination in nanostructured semiconductors are poorly understood key processes in dye-sensitized solar cells. We have employed time-resolved spectroscopies in the terahertz and visible spectral regions supplemented with Monte Carlo simulations to obtain unique information on these processes. Our results show that charge transport in the active solar cell material can be very different from that in nonsensitized semiconductors, due to strong electrostatic interaction between injected electrons and dye cations at the surface of the semiconductor nanoparticle. For ZnO, this leads to formation of an electron-cation complex which causes fast charge recombination and dramatically decreases the electron mobility even after the dissociation of the complex. Sensitized TiO2 does not suffer from this problem due to its high permittivity efficiently screening the charges.
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| 5. |
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