caa a22 4500 467920346 CHVBK 20180406152915.0 cr unu---uuuuu 170328e20060201xx s 000 0 eng 10.1007/s00706-005-0418-4 doi (NATIONALLICENCE)springer-10.1007/s00706-005-0418-4 Concerning the Thermal Diastereomerization of the Green Fluorescent Protein Chromophore [Elektronische Daten] [Beate Hager, Bettina Schwarzinger, Heinz Falk] Summary.: Two model compounds for the green fluorescent protein chromophore were prepared. One of them incorporates the natural 4-hydroxybenzylidene group of the natural tyrosin derived chromophore, the other one bears a methyl group instead of the hydroxy group. Whereas the photochemically prepared (E)-diastereomer of the first compound very effectively reverted thermally (room temperature) to the thermodynamically stable (Z)-diastereomer, the (E)-diastereomer of the second derivative proved to be stable even at elevated temperatures for more than a day. This finding can be rationalized by constructing the appropriate resonance structures showing that only in the first case an effective delocalization enables partial single bond character of the benzylidene double bond. From the standpoint of chemical etiology, only Nature's choice of the tyrosin derived chromophore of the green fluorescent protein provides an efficient radiationless thermal relaxation channel for the unwanted photo-diastereomerization product formed after excitation besides the dominating fluorescence channel of its chromophore. Springer-Verlag/Wien, 2005 Keywords. Green fluorescent protein nationallicence Benzylideneimidazolinones nationallicence Thermal barrier nationallicence Chemical etiology nationallicence Radiationless relaxation nationallicence Hager Beate Institute of Organic Chemistry, Johannes Kepler University Linz, 4040, Linz, Austria aut Schwarzinger Bettina Institute of Organic Chemistry, Johannes Kepler University Linz, 4040, Linz, Austria aut Falk Heinz Institute of Organic Chemistry, Johannes Kepler University Linz, 4040, Linz, Austria aut Monatshefte für Chemie / Chemical Monthly Springer-Verlag 137/2(2006-02-01), 163-168 0026-9247 137:2<163 2006 137 706 https://doi.org/10.1007/s00706-005-0418-4 text/html Onlinezugriff via DOI 1 research-article jats NATIONALLICENCE 856 40 https://doi.org/10.1007/s00706-005-0418-4 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Hager Beate Institute of Organic Chemistry, Johannes Kepler University Linz, 4040, Linz, Austria aut NATIONALLICENCE 700 1- Schwarzinger Bettina Institute of Organic Chemistry, Johannes Kepler University Linz, 4040, Linz, Austria aut NATIONALLICENCE 700 1- Falk Heinz Institute of Organic Chemistry, Johannes Kepler University Linz, 4040, Linz, Austria aut NATIONALLICENCE 773 0- Monatshefte für Chemie / Chemical Monthly Springer-Verlag 137/2(2006-02-01), 163-168 0026-9247 137:2<163 2006 137 706 Metadata rights reserved Springer special CC-BY-NC licence nationallicence BK010053 XK010053 XK010000 NATIONALLICENCE NATIONALLICENCE NL-springer