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PEROXIDASE CATALYZED GENERATION OF TRIPLET ACETONE
Author(s) -
Bechara Etelvino J. H.,
Oliveira Olga M. M. Faria,
Duran Nelson,
Baptista Roberto Casadei de,
Cilento Giuseppe
Publication year - 1979
Publication title -
photochemistry and photobiology
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.818
H-Index - 131
eISSN - 1751-1097
pISSN - 0031-8655
DOI - 10.1111/j.1751-1097.1979.tb07121.x
Subject(s) - chemistry , acetone , horseradish peroxidase , photochemistry , singlet state , quenching (fluorescence) , absorption (acoustics) , triplet state , energy transfer , excited state , organic chemistry , fluorescence , molecule , materials science , chemical physics , atomic physics , physics , quantum mechanics , composite material , enzyme
— Triplet acetone generated in the isobutanal/horseradish peroxidase/O, system is quenched by collisional agents of the diene type. A Stern‐Volmer analysis indicates that collision is considerably impeded, the barrier being largely entropic. Triplet‐triplet energy transfer to biacetyl is also observed. Quenching of triplet acetone by energy transfer to 9 ,10‐dibromoanthracene‐2‐sulfonate (DBAS) is a much faster process than energy transfer to these collisional agents, in accordance with the earlier inference that transfer to DBAS is a long‐range triplet‐singlet transfer process. The fraction of the triplet acetone which undergoes reduction to isopropanol is not interceptable by quenchers. Absorption and circular dichroism studies suggest that peroxidase shuttles between Compound II and I when generating the precursor hydroperoxide.