Models for the Pigment Organization in the Chlorosomes of Photosynthetic Bacteria: Diastereoselective Control of in-vitro Bacteriochlorophyll cs Aggregation

Chiefari, John; Griebenow, Kai; Griebenow, Nils; Balaban, Teodor Silviu; Holzwarth, Alfred R.; Schaffner, Kurt

doi:10.1021/j100004a041

Cited by 118 publications

(152 citation statements)

References 8 publications

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“…FT-IR spectra of BChls show a similar large shift of the CϭO to Ϸ1,645 cm Ϫ1 (27). This allows us to draw an unprecedented analogy between our synthetic mimics and the chlorosomal BChl self-assemblies.…”

Section: Thementioning

confidence: 63%

“…This allows us to draw an unprecedented analogy between our synthetic mimics and the chlorosomal BChl self-assemblies. The large shift to lower wavenumbers that occurs on self-assembly of BChls has been previously interpreted as due to an exceptionally strong hydrogen-bonding interaction (27). In two crystal structures of 3-Zn (21,22), despite the presence of a hydroxyethyl group, no hydrogen bonding is possible because of the weak electrostatic interaction between the acetyl groups and the central zinc atom in a neighboring porphyrin that is -stacked.…”

Section: Thementioning

confidence: 99%

“…7 Upper Left Inset, and biexponential in the other three insets. (13,14,27,30). (Right) Newly proposed supramolecular interactions leading to a paradigm shift in the interpretation of the large displacement to lower wavenumbers of the CϭO due to the weak zinc ligation instead of a strong hydrogen bonding network depicted at Left.…”

Section: Thementioning

confidence: 99%

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The supramolecular organization of self-assembling chlorosomal bacteriochlorophyll c , d , or e mimics

Jochum

Reddy

Eichhöfer

et al. 2008

Proc. Natl. Acad. Sci. U.S.A.

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Bacteriochlorophylls (BChls) c, d, and e are the main light-harvesting pigments of green photosynthetic bacteria that self-assemble into nanostructures within the chlorosomes forming the most efficient antennas of photosynthetic organisms. All previous models of the chlorosomal antennae, which are quite controversially discussed because no single crystals could be grown so far from these organelles, involve a strong hydrogen-bonding interaction between the 3 1 hydroxyl group and the 13 1 carbonyl group. We have synthesized different self-assemblies of BChl c mimics having the same functional groups as the natural counterparts, that is, a hydroxyethyl substituent, a carbonyl group and a divalent metal atom ligated by a tetrapyrrole. These artificial BChl mimics have been shown by single crystal x-ray diffraction to form extended stacks that are packed by hydrophobic interactions and in the absence of hydrogen bonding. Time-resolved photoluminescence proves the ordered nature of the self-assembled stacks. FT-IR spectra show that on self-assembly the carbonyl frequency is shifted by Ϸ30 cm ؊1 to lower wavenumbers. From the FT-IR data we can infer the proximal interactions between the BChls in the chlorosomes consistent with a single crystal x-ray structure that shows a weak electrostatic interaction between carbonyl groups and the central zinc atom. chlorosome model ͉ crystal structure ͉ FT-IR ͉ light-harvesting ͉ time-resolved fluorescence

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Section: Thementioning

confidence: 63%

Section: Thementioning

confidence: 99%

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The supramolecular organization of self-assembling chlorosomal bacteriochlorophyll c , d , or e mimics

Jochum

Reddy

Eichhöfer

et al. 2008

Proc. Natl. Acad. Sci. U.S.A.

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“…We prefer here the former connotation and reserve type I and type II as a structural terminology for aggregates exhibiting Q y maxima at shorter wavelengths (typically 700 ± 710 nm), attributed to aggregates of closed dimers as building blocks, and for aggregates absorbing at longer wavelengths (typically 740 ± 750 nm), attributed to chlorosome-type aggregates, respectively [9]. 4 ) This apparent restructuring of the aggregate at 55 8 is noteworthy also in view of the fact that this is the optimum temperature for culturing the non-sulfur green bacterium Chloroflexus aurantiacus where it is most abundant.…”

Section: à3mentioning

confidence: 99%

“…[9]. Nonetheless, the precise supramolecular structure of chlorosome-type BChl c aggregates is still debated [10] [11].…”

mentioning

confidence: 99%

Self-Assembly of Synthetic Zinc Chlorins in Aqueous Microheterogeneous Media to an Artificial Supramolecular Light-Harvesting Device

Miyatake¹,

Tamiaki²,

Holzwarth³

et al. 1999

HCA

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The structure of an aggregate form of bacteriochlorophyllc showing theQy absorption at 705 nm as determined by the ring-current effects on1H and13C nuclei and by1H-1H intermolecular NOE correlations

et al. 1999

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13C‐enriched bacteriochlorophyll c (R[E, E] BChl cF) was suspended in chloroform to form an aggregate showing the Qy absorption at 705 nm. (1) The aggregate exhibited several largely split 13C‐NMR signals suggesting the presence of nonequivalent BChl c molecules in the form of the piggyback dimer. (2) Changes in the 13C chemical shifts were traced when methanol was titrated to dissolve the aggregate, and the aggregation shifts (in reference to the monomeric state) were determined as a function of the amount of methanol titrated, and they were analyzed empirically. (3) The ring‐current effects were calculated based on the loop‐current approximation, and the results were compared with the observed aggregation shifts for 13C and 1H nuclei (the 1H aggregation shifts were determined by extrapolation of the data taken from Mizoguchi, T.; Limantara, L.; Matsuura, K.; Shimada, K.; Koyama, Y. J Mol Structure 1996, 379, 249–265). The results showed that the assembly of two straight columns consisting of the piggyback dimer stacked in the antiparallel orientation is the best choice as a model for the B705 aggregate. (4) Three‐dimensional F1 13C‐edited F3 13C‐filtered heteronuclear single‐quantum nuclear‐Overhauser‐effect spectroscopy was applied to the aggregate consisting of a 1 : 1 mixture of 13C‐labeled and unlabeled BChl c in order to selectively detect the intermolecular 1H–1H NOE correlations. The NOE correlations were explained in terms of a straight column, supporting the above model. © 1999 John Wiley & Sons, Inc. Biospectroscopy 5: 63–77, 1999

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Models for the Pigment Organization in the Chlorosomes of Photosynthetic Bacteria: Diastereoselective Control of in-vitro Bacteriochlorophyll cs Aggregation

Cited by 118 publications

References 8 publications

The supramolecular organization of self-assembling chlorosomal bacteriochlorophyll c , d , or e mimics

The supramolecular organization of self-assembling chlorosomal bacteriochlorophyll c , d , or e mimics

Self-Assembly of Synthetic Zinc Chlorins in Aqueous Microheterogeneous Media to an Artificial Supramolecular Light-Harvesting Device

The structure of an aggregate form of bacteriochlorophyllc showing theQy absorption at 705 nm as determined by the ring-current effects on1H and13C nuclei and by1H-1H intermolecular NOE correlations

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