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Anisotropic Organization and Microscopic Manipulation of Self-Assembling Synthetic Porphyrin Microrods That Mimic Chlorosomes: Bacterial Light-Harvesting Systems

Chappaz-Gillot, Cyril ; Marek, Peter L. ; Blaive, Bruno J. ; Canard, Gabriel ; Bürck, Jochen ; Garab, Győző ; Hahn, Horst ; Jávorfi, Tamás ; Kelemen, Loránd ; Krupke, Ralph ; Mössinger, Dennis ; Ormos, Pál ; Reddy, Chilla Malla ; Roussel, Christian ; Steinbach, Gábor ; Szabó, Milán ; Ulrich, Anne S. ; Vanthuyne, Nicolas ; Vijayaraghavan, Aravind ; Zupcanova, Anita ; Balaban, Teodor Silviu (2012)
Anisotropic Organization and Microscopic Manipulation of Self-Assembling Synthetic Porphyrin Microrods That Mimic Chlorosomes: Bacterial Light-Harvesting Systems.
In: Journal of the American Chemical Society, 134 (2)
doi: 10.1021/ja203838p
Article, Bibliographie

Abstract

Being able to control in time and space the positioning, orientation, movement, and sense of rotation of nano- to microscale objects is currently an active research area in nanoscience, having diverse nanotechnological applications. In this paper, we demonstrate unprecedented control and maneuvering of rod-shaped or tubular nanostructures with high aspect ratios which are formed by self-assembling synthetic porphyrins. The self-assembly algorithm, encoded by appended chemical-recognition groups on the periphery of these porphyrins, is the same as the one operating for chlorosomal bacteriochlorophylls (BChl's). Chlorosomes, rod-shaped organelles with relatively long-range molecular order, are the most efficient naturally occurring light-harvesting systems.(1, 2) They are used by green photosynthetic bacteria to trap visible and infrared light of minute intensities even at great depths, e.g., 100 m below water surface or in volcanic vents in the absence of solar radiation. In contrast to most other natural light-harvesting systems, the chlorosomal antennae are devoid of a protein scaffold to orient the BChl's; thus, they are an attractive goal for mimicry by synthetic chemists, who are able to engineer more robust chromophores to self-assemble. Functional devices with environmentally friendly chromophores—which should be able to act as photosensitizers within hybrid solar cells, leading to high photon-to-current conversion efficiencies even under low illumination conditions—have yet to be fabricated. The orderly manner in which the BChl's and their synthetic counterparts self-assemble imparts strong diamagnetic and optical anisotropies and flow/shear characteristics to their nanostructured assemblies, allowing them to be manipulated by electrical, magnetic, or tribomechanical forces.

Item Type: Article
Erschienen: 2012
Creators: Chappaz-Gillot, Cyril ; Marek, Peter L. ; Blaive, Bruno J. ; Canard, Gabriel ; Bürck, Jochen ; Garab, Győző ; Hahn, Horst ; Jávorfi, Tamás ; Kelemen, Loránd ; Krupke, Ralph ; Mössinger, Dennis ; Ormos, Pál ; Reddy, Chilla Malla ; Roussel, Christian ; Steinbach, Gábor ; Szabó, Milán ; Ulrich, Anne S. ; Vanthuyne, Nicolas ; Vijayaraghavan, Aravind ; Zupcanova, Anita ; Balaban, Teodor Silviu
Type of entry: Bibliographie
Title: Anisotropic Organization and Microscopic Manipulation of Self-Assembling Synthetic Porphyrin Microrods That Mimic Chlorosomes: Bacterial Light-Harvesting Systems
Language: English
Date: 18 January 2012
Journal or Publication Title: Journal of the American Chemical Society
Volume of the journal: 134
Issue Number: 2
DOI: 10.1021/ja203838p
Abstract:

Being able to control in time and space the positioning, orientation, movement, and sense of rotation of nano- to microscale objects is currently an active research area in nanoscience, having diverse nanotechnological applications. In this paper, we demonstrate unprecedented control and maneuvering of rod-shaped or tubular nanostructures with high aspect ratios which are formed by self-assembling synthetic porphyrins. The self-assembly algorithm, encoded by appended chemical-recognition groups on the periphery of these porphyrins, is the same as the one operating for chlorosomal bacteriochlorophylls (BChl's). Chlorosomes, rod-shaped organelles with relatively long-range molecular order, are the most efficient naturally occurring light-harvesting systems.(1, 2) They are used by green photosynthetic bacteria to trap visible and infrared light of minute intensities even at great depths, e.g., 100 m below water surface or in volcanic vents in the absence of solar radiation. In contrast to most other natural light-harvesting systems, the chlorosomal antennae are devoid of a protein scaffold to orient the BChl's; thus, they are an attractive goal for mimicry by synthetic chemists, who are able to engineer more robust chromophores to self-assemble. Functional devices with environmentally friendly chromophores—which should be able to act as photosensitizers within hybrid solar cells, leading to high photon-to-current conversion efficiencies even under low illumination conditions—have yet to be fabricated. The orderly manner in which the BChl's and their synthetic counterparts self-assemble imparts strong diamagnetic and optical anisotropies and flow/shear characteristics to their nanostructured assemblies, allowing them to be manipulated by electrical, magnetic, or tribomechanical forces.

Divisions: 11 Department of Materials and Earth Sciences > Material Science > Fachgebiet Molekulare Nanostrukturen
11 Department of Materials and Earth Sciences > Material Science > Joint Research Laboratory Nanomaterials
11 Department of Materials and Earth Sciences > Material Science
11 Department of Materials and Earth Sciences
Date Deposited: 27 Aug 2012 09:28
Last Modified: 16 Jun 2014 12:23
PPN:
Funders: Partial financial support was granted by the Deutsche Forschungsgemeinschaft through the Center for Functional Nanostructures at the Universität Karlsruhe (Projects C3.5 and C3.5b to S.T.B., E1.2 to A.S.U.). , The collaborative work between Marseille and Karlsruhe was facilitated by the CNRS through PICS No. 3777 allocated to C.R., Funding from the Initiative and Networking Fund of the Helmholtz-Gemeinschaft Deutscher Forschungszentren (VH- NG-126) is acknowledged by R.K. and A.V., This work was in part supported by the Hungarian Scientific Research Fund (OTKA/ NKTH CNK 80345 to G.G., GOP-1.1.2-07/1-2008-0007 to G.S. who thanks Biofotonika R&D Ltd. for additional funding).
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