Synthesis of chlorophyll-c derivatives by modifying natural chlorophyll-a

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• 作者：Meiyun Xu ; Yusuke Kinoshita ; Shogo Matsubara ; Hitoshi Tamiaki
• 关键词：Acrylate residue ; Biosynthetic pathway ; Fluorescence emission spectrum ; Light ; harvesting antenna pigment ; Substitution effect ; Visible absorption spectrum
• 刊名：Photosynthesis Research
• 出版年：2016
• 出版时间：March 2016
• 年：2016
• 卷：127
• 期：3
• 页码：335-345
• 全文大小：533 KB
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• 作者单位：Meiyun Xu (1)
  Yusuke Kinoshita (1)
  Shogo Matsubara (1)
  Hitoshi Tamiaki (1)
  
  1. Graduate School of Life Sciences, Ritsumeikan University, Kusatsu, 525-8577, Shiga, Japan
  
• 刊物类别：Biomedical and Life Sciences
• 刊物主题：Life Sciences
  Plant Physiology
  
• 出版者：Springer Netherlands
• ISSN：1573-5079

文摘

Chlorophyll-a (Chl-a) was extracted from cyanobacterial cells and modified to methyl pyropheophorbide-a. The 3-vinyl-chlorin was transformed to zinc complex of the corresponding 3-acetyl-porphyrin. The zinc porphyrin was oxidized to give cis-7,8- and 17,18-dihydroxy-chlorins as well cis-7,8-cis-17,18-tetrahydroxybacteriochlorin. After zinc-demetallation, the isolated cis-7,8- and 17,18-diols were reduced at the 3-acetyl group and triply dehydrated under acidic conditions to afford two regioisomeric 3-vinyl-porphyrins, methyl divinyl-pyroprotopheophorbide-a possessing the 8-vinyl group and 17-propionate residue (one of the divinyl-protoChl-a derivatives) and methyl pyropheophorbide-c ₁ possessing the 8-ethyl group and 17-acrylate residue (one of the Chl-c ₁ derivatives), respectively. The resulting 7,8,17,18-tetrol was reduced and then acidically treated, giving five-fold dehydrated free base porphyrin, methyl pyropheophorbide-c ₂ possessing the 3,8-divinyl groups and 17-acrylate residue (one of the Chl-c ₂ derivatives). The visible absorption and fluorescence emission spectra of the three semi-synthetic 3-vinyl-porphyrins in dichloromethane were compared with those of the corresponding 8-ethyl-porphyrin bearing the 17-propionate residue, methyl pyroprotopheophorbide-a (one of the protoChl-a derivatives). The Soret and Qy absorption maxima were shifted to longer wavelengths with an increase of π-conjugation in a molecule: protoChl-a (8-CH₂CH₃/17-CH₂CH₂COOCH₃) < divinyl-protoChl-a (8-CH=CH₂/17-CH₂CH₂COOCH₃) < Chl-c ₁ (8-CH₂CH₃/17-CH=CHCOOCH₃) < Chl-c ₂ derivatives (8-CH=CH₂/17-CH=CHCOOCH₃). The 171,172-dehydrogenation broadened the absorption bands. The emission maxima were bathochromically shifted in the same order. The reaction mechanism of the present dehydration indicates that the biosynthetic pathway of Chls-c would include the hydroxylation of the 17-propionate reside at the 171-position and successive dehydration to the 17-acrylate residue.