title: Carbon monoxide recombination dynamics in truncated hemoglobins studied with visible-pump midIR-probe spectroscopy.
abstract: Carbon monoxide recombination dynamics upon photodissociation with visible light has been characterized by means of ultrafast visible-pump/MidIR probe spectroscopy for the truncated hemoglobins from Thermobifida fusca and Bacillus subtilis. Photodissociation has been induced by exciting the sample at two different wavelengths: 400 nm, corresponding to the heme absorption in the B-band, and 550 nm, in the Q-bands. The bleached iron-CO coordination band located at 1850-1950 cm(-1) and the free CO absorption band in the region 2050-2200 cm(-1) have been observed by probe pulses tuned in the appropriate infrared region. The kinetic traces measured at 1850-1950 cm(-1) reveal multiexponential subnanosecond dynamics that have been interpreted as arising from fast geminate recombination of the photolyzed CO. A compared analysis of the crystal structure of the two proteins reveals a similar structure of their distal heme pocket, which contains conserved polar and aromatic amino acid residues closely interacting with the iron ligand. Although fast geminate recombination is observed in both proteins, several kinetic differences can be evidenced, which can be interpreted in terms of a different structural flexibility of the corresponding heme distal pockets. The analysis of the free CO band-shape and of its dynamic evolution brings out novel features about the nature of the docking site inside the protein cavity.
authors: LENS (European Laboratory for Nonlinear Spectroscopy), via N. Carrara 1, 50019 Sesto Fiorentino (FI), Italy.
authors: Andrea
authors: A
authors: Lapini
authors: Mariangela
authors: M
authors: Di Donato
authors: Barbara
authors: B
authors: Patrizi
authors: Agnese
authors: A
authors: Marcelli
authors: Manuela
authors: M
authors: Lima
authors: Roberto
authors: R
authors: Righini
authors: Paolo
authors: P
authors: Foggi
authors: Natascia
authors: N
authors: Sciamanna
authors: Alberto
authors: A
authors: Boffi
mesh_terms: D000192:Actinomycetales / Q000378:metabolism; D001412:Bacillus subtilis / Q000378:metabolism; D002248:Carbon Monoxide / Q000737:chemistry*; D006418:Heme / Q000737:chemistry; D007700:Kinetics; D008027:Light; D010782:Photolysis; D013055:Spectrophotometry, Infrared; D054793:Truncated Hemoglobins / Q000737:chemistry* / Q000378:metabolism
chemical_list: D054793:Truncated Hemoglobins; D006418:Heme; D002248:Carbon Monoxide