Article Dendron-mediated control over self-assembly of chlorophyll rosettes into columnar vs. discrete aggregates

Ryo Kudo ; Hiroki Hanayama ; Balaraman Vedhanarayanan ORCID ; Hitoshi Tamiaki ORCID ; Nobuyuki Hara ; Sarah E. Rogers ORCID ; Martin J. Hollamby ORCID ; Biplab Manna SAMURAI ORCID ; Koji Harano SAMURAI ORCID ; Shiki Yagai ORCID

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Ryo Kudo, Hiroki Hanayama, Balaraman Vedhanarayanan, Hitoshi Tamiaki, Nobuyuki Hara, Sarah E. Rogers, Martin J. Hollamby, Biplab Manna, Koji Harano, Shiki Yagai. Dendron-mediated control over self-assembly of chlorophyll rosettes into columnar vs. discrete aggregates. Organic Chemistry Frontiers. 2024, 11 (22), 6304-6310. https://doi.org/10.1039/d4qo01629g
SAMURAI

Description:

(abstract)

Photosynthetic bacteria have evolved highly efficient light-harvesting systems by organizing chlorophyll (Chl) pigments into circular and tubular supramolecular arrays. To construct these surapmoelcular Chl arrays from the same molecular design, we synthesized two hydrogen-bonding chlorins using natural Chl-a as the starting material: free-base chlorin functionalized with hydrogen-bonding barbituric acid and second- or third-generation alkyl dendrons (G2 and G3, respectively). The barbituric acid moiety promotes the formation of a hydrogen-bonded cyclic hexamer known as rosette. In chloroform, both the synthetic Chl-a derivatives formed rosettes; however, in methylcyclohexane as a low-polarity solvent, the G2-dendron chlorin formed columnar structures by stacking rosettes, while the G3-dendron chlorin formed disc-shaped particles. AFM revealed the formation of extended helical fibers for the former and homogeneous nanoparticles, possibly single rosettes, for the latter. These results suggest that the third-generation of the dendron can inhibit the stacking of rosettes, leading to the formation of two distinct types of chlorin aggregates: circular and tubular.

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Keyword: Supramolecular chemistry, Dendrimers, Atomic force microscopy, Transmission electron microscopy

Date published: 2024-10-08

Publisher: Royal Society of Chemistry (RSC)

Journal:

  • Organic Chemistry Frontiers (ISSN: 20524129) vol. 11 issue. 22 p. 6304-6310

Funding:

  • Japan Society for the Promotion of Science JP22H00331
  • Japan Society for the Promotion of Science JP22H02203
  • Japan Society for the Promotion of Science JP23H04874
  • Japan Society for the Promotion of Science JP23H04873
  • National Science Foundation DMR-0520547
  • Horizon 2020 Framework Programme 654000

Manuscript type: Publisher's version (Version of record)

MDR DOI:

First published URL: https://doi.org/10.1039/d4qo01629g

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Updated at: 2024-11-06 16:30:30 +0900

Published on MDR: 2024-11-06 16:30:30 +0900

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