ZABADAL, Miroslav, Petr KLÁN, Dominik HEGER and Zdeněk KŘÍŽ. Intramolecular Triplet-Triplet Energy Transfer in Short Flexible Bichromophoric Amino Acids, Dipeptides and Carboxylic Acid Diester. Collect. Czech. Chem. Commun. Praha, 2004, vol. 69, No 4, p. 776-796. ISSN 0010-0765.
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Basic information
Original name Intramolecular Triplet-Triplet Energy Transfer in Short Flexible Bichromophoric Amino Acids, Dipeptides and Carboxylic Acid Diester
Name in Czech Intramolekulární tripletový přenos energie u krátkých bichromoforních aminokyselin
Authors ZABADAL, Miroslav (203 Czech Republic), Petr KLÁN (203 Czech Republic, guarantor), Dominik HEGER (203 Czech Republic) and Zdeněk KŘÍŽ (203 Czech Republic).
Edition Collect. Czech. Chem. Commun. Praha, 2004, 0010-0765.
Other information
Original language English
Type of outcome Article in a journal
Field of Study 10401 Organic chemistry
Country of publisher Czech Republic
Confidentiality degree is not subject to a state or trade secret
Impact factor Impact factor: 1.062
RIV identification code RIV/00216224:14310/04:00009947
Organization unit Faculty of Science
UT WoS 000220854200004
Keywords in English photochemistry; energy transfer
Tags energy transfer, Photochemistry
Tags International impact
Changed by Changed by: prof. RNDr. Petr Klán, Ph.D., učo 32829. Changed: 23/6/2009 15:42.
Abstract
Efficiencies of the intramolecular triplet-triplet energy transfer (ITET) in various bichromophoric amino acids (glycine, valine, phenylalanine, and sarcosine), dipeptides (glycylglycine, phenylalanylphenylalanine), and a simple diester, with the benzoyl and naphthyl terminal groups serving as donor and acceptor, respectively, have been determined by the steady-state photokinetic measurements. The magnitude of the transfer rate constants (>10 exp8 s-1) and the number of bonds separating the chromophores (8 or 11 atoms) suggest a through-space exothermic exchange mechanism in all cases. The influence of interchromophore distance, the character of the connecting chain as well as of side chains, was evaluated. While the most efficient energy transfer was found in a flexible diester and in valine- and sarcosine-based molecules due to the steric effect of the side hydrocarbon groups, the benzyl groups in the phenylalanine and phenylalanylphenylalanine-based bichromophores had a suppressing effect on ITET. Rigidity of the peptide bond in short bichromophoric compounds causes that a large number of favorable geometries preexist already before excitation; thus the intramolecular processes are controlled by ground-state conformational distribution. Replacing this bond by a less rigid ester moiety would allow that certain unfavorable conformations may coil to favorable ones within the excited-state lifetime (a rotation-controlled photochemical model). Some conclusions were supported by a conformational search of the potential energy surface and molecular dynamics simulations.
Abstract (in Czech)
Intramolekulární tripletový přenos energie u krátkých bichromoforních aminokyselin
Links
MSM 143100005, plan (intention)Name: Strukturně-funkční vztahy biomolekul a jejich role v metabolismu
Investor: Ministry of Education, Youth and Sports of the CR, Biomolecular Structure-function Relationships and their role in the Metabolism
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