Ultrafast pump-probe study of excited-state charge-transfer dynamics in umecyanin from horseradish root (Articolo in rivista)

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  • Ultrafast pump-probe study of excited-state charge-transfer dynamics in umecyanin from horseradish root (Articolo in rivista) (literal)
Anno
  • 2006-01-01T00:00:00+01:00 (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#doi
  • 10.1021/jp062904y (literal)
Alternative label
  • Delfino, I; Manzoni, C; Sato, K; Dennison, C; Cerullo, G; Cannistraro, S (2006)
    Ultrafast pump-probe study of excited-state charge-transfer dynamics in umecyanin from horseradish root
    in The journal of physical chemistry. B
    (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#autori
  • Delfino, I; Manzoni, C; Sato, K; Dennison, C; Cerullo, G; Cannistraro, S (literal)
Pagina inizio
  • 17252 (literal)
Pagina fine
  • 17259 (literal)
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  • http://pubs.acs.org/doi/abs/10.1021/jp062904y (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#numeroVolume
  • 110 (literal)
Rivista
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  • 8 (literal)
Note
  • Scopu (literal)
  • ISI Web of Science (WOS) (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#affiliazioni
  • Univ Tuscia, CNISM, Biophys & Nanosci Ctr, I-00100 Rome, Italy; Politecn Milan, Dipartimento Fis, ULTRAS, CNR,INFM, I-20133 Milan, Italy; Univ Newcastle Upon Tyne, Inst Cell & Mol Biosci, Sch Med, Newcastle Upon Tyne NE2 4HH, Tyne & Wear, England (literal)
Titolo
  • Ultrafast pump-probe study of excited-state charge-transfer dynamics in umecyanin from horseradish root (literal)
Abstract
  • We have applied femtosecond pump-probe spectroscopy to investigate the excited-state dynamics of umecyanin from horseradish roots, by exciting its 600-nm ligand-to-metal charge-transfer band with a 15-fs pulse and probing over a broad range in the visible region. The decay of the pump-induced ground-state bleaching is modulated by clearly visible oscillations and occurs exponentially with a time constant depending on the observed spectral component of the transmission difference signal, ranging from 270 fs up to 700 fs. The slower decaying process characterizes the spectral component corresponding to the metal-to-ligand charge-transfer transition. The excited-state decay rate is significantly lower than in other blue copper proteins, probably because of the larger energy gap between ligand- and metal-based orbitals in umecyanin. Wavelength dependence of the recovery times could be due to either the excitation of several transitions or the occurrence of intramolecular vibrational relaxation within the excited state. We also find evidence of a hot ground-state absorption, at 700 nm, persisting for several picoseconds. The vibrational coherence induced by the ultrashort pump pulse allows vibrational activity to be observed, mainly in the ground state, as expected in a system with fast excited-state decay. However, we find evidence of a rapidly damped oscillation, which we assign to the excited state. Finally, the Fourier transform of the oscillatory component of the signal presents additional bands in the low-frequency region which are assigned to collective motions of the protein. (literal)
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