文献类型：期刊文献

英文题名：Pyro-Phyllobilins: Elusive Chlorophyll Catabolites Lacking a Critical Carboxylate Function of the Natural Chlorophylls

作者：Li, Chengjie[1,2,4,5];Wurst, Klaus[3];Berghold, Joachim[1,2];Podewitz, Maren[3];Liedl, Klaus R.[3];Kraeutler, Bernhard[1,2]

机构：[1]Univ Innsbruck, Inst Organ Chem, Innrain 80-82, A-6020 Innsbruck, Austria;[2]Univ Innsbruck, Ctr Mol Biosci, Innrain 80-82, A-6020 Innsbruck, Austria;[3]Univ Innsbruck, Inst Gen Inorgan & Theoret Chem, Innrain 80-82, A-6020 Innsbruck, Austria;[4]East China Univ Sci & Technol, Sch Chem & Mol Engn, Key Lab Adv Mat, Meilong Rd 130, Shanghai 200237, Peoples R China;[5]East China Univ Sci & Technol, Sch Chem & Mol Engn, Inst Fine Chem, Meilong Rd 130, Shanghai 200237, Peoples R China

年份：2018

卷号：24

期号：12

起止页码：2987

外文期刊名：CHEMISTRY-A EUROPEAN JOURNAL

收录：;EI(收录号：20180504695397);WOS:【SCI-EXPANDED(收录号:WOS:000429415200027)】；

基金：We thank T. Muller and G. Scherzer (Innsbruck) for help with mass spectrometry and HPLC analyses. This work was supported by the Austrian Science Fund (FWF, I-563 and P-28522 to B.K.) M.P. would like to thank FWF for a generous postdoctoral fellowship (M-2005). The computational results presented have been obtained using the HPC infrastructure of the University of Innsbruck.

语种：英文

外文关键词：cycloaddition; photoisomerization; phyllobilin; porphyrinoids; self-assembly

摘要：A beta-keto ester grouping is a characteristic of ring E of the chlorophylls (Chls). Its presence has also reinforced the original identification of nonfluorescent Chl catabolites (NCCs) as colorless, amphiphilic phyllobilins (PBs). Polar NCCs were also detected in higher plants, in which a free carboxyl group replaced the ring E ester group. Such NCCs are surprisingly resistant to loss of this carboxyl unit, and NCCs lacking the latter, that is, pyro-NCCs (pyNCCs), have not been reported. Intrigued by the question of the natural occurrence of pyro-phyllobilins (pyPBs), we have prepared a representative pyNCC by decarboxylation of a natural NCC. We also converted the pyNCC into its yellow oxidation product, a pyro-YCC (pyYCC). The solution structures of pyNCC and of pyYCC, and a crystal structure of the pyYCC methyl ester (pyYCC-Me) were obtained. pyYCC-Me features the same remarkable H-bonded and p-stacked dimer structure as the corresponding natural yellow Chl catabolite (YCC) with the ringE methyl ester group. Indeed, the latter substituent has little effect on the structure, as well as on the unique self-assembly and photoswitch behavior of yellow