Self-aggregates of a synthetic cadmium chlorin in solid film as a photosynthetic antenna model

Molecular structures of (bacterio)chlorophylls [=(B)Chls] in photosynthetic apparatus are surveyed, and a diversity of the ester groups of the 17-propionate substituent is particularly focused on in this review. In oxygenic photosynthetic species including green plants and algae, the ester of Chl molecules is limited to a phytyl group. Geranylgeranyl and farnesyl groups in addition to phytyl are observed in (B)Chl molecules inside photosynthetic proteins of anoxygenic bacteria. In main lightharvesting antennas of green bacteria (chlorosomes), a greater variety of ester groups including long straight chains are used in the composite BChl molecules. This diversity is ascribable to the fact that chlorosomal BChls self-aggregate to form a core part of chlorosomes without any specific interaction of oligopeptides. Biological significance of the long chains is discussed in photosynthetic apparatus, especially in chlorosomes.

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“…The same tendency was observed in cadmium complexes 3a / b (see right drawing of Fig. 6): λ max (Q y ) = ca 740 nm (65,66).…”

Section: Significance Of Long Chains In Ester Of Chlorosomal Chlorophsupporting

confidence: 77%

The 17‐Propionate Function of (Bacterio)chlorophylls: Biological Implication of Their Long Esterifying Chains in Photosynthetic Systems^†

Tamiaki

Shibata

Mizoguchi

2007

Photochem & Photobiology

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192

105

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“…The FTIR spectrum of monomeric Zn‐1 in THF in transmission mode showed a peak at 1690 cm −1 for 13‐C=O stretching (Figure h, green line). This spectroscopic evidence indicates that hydrogen bonding of 3 1 ‐OH with 13‐C=O (O−H ⋅⋅⋅ O=C) occurred in the solid self‐assemblies of Zn‐1 . Compound Zn‐2 also showed similar FTIR peak shifts of 3 1 ‐OH and 13‐C=O to those of Zn‐1 due to the chlorosomal assembly (O−H ⋅⋅⋅ O=C) (Figures b and i).…”

Section: Resultsmentioning

confidence: 83%

“…This spectroscopic evidencei ndicates that hydrogen bonding of 3 1 -OH with 13-C=O(O ÀH···O=C) occurred in the solid self-assemblies of Zn-1. [84,98] Compound Zn-2 also showeds imilarF TIR peak shifts of 3 1 -OH and 13-C=Ot ot hose of Zn-1 due to the chlorosomala ssembly (OÀH···O=C) ( Figures 3b and i).T he FTIR absorption peaks of 17 2 -C=Oi nZn-1 and Zn-2 were observed at around1 740 and 1650cm À1 ,r espectively (see black dotted straightl ines of Figures 3h and i). These peaks were not greatlys hifted both in solution and in solid films, and thus the ester of Zn-1 andt ertiary amide of Zn-2 were free of any otherf unctional groups.…”

Section: Self-assembly Of Zinc Bchl-d Analoguesmentioning

confidence: 86%

Self‐Assemblies of Zinc Bacteriochlorophyll‐d Analogues Having Amide, Ester, and Urea Groups as Substituents at 17‐Position and Observation of Lamellar Supramolecular Nanostructures

et al. 2018

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Chlorosomes are unique light-harvesting apparatuses in photosynthetic green bacteria. Single chlorosomes contain a large number of bacteriochlorophyll (BChl)-c, -d, -e, and -f molecules, which self-assemble without protein assistance. These BChl self-assemblies involving specific intermolecular interactions (Mg⋅⋅⋅O3 -H⋅⋅⋅O=C13 and π-π stacks of chlorin skeletons) in a chlorosome have been reported to be round-shaped rods (or tubes) with diameters of 5 or 10 nm, or lamellae with a layer spacing of approximately 2 nm. Herein, the self-assembly of synthetic zinc BChl-d analogues having ester, amide, and urea groups in the 17-substituent is reported. Spectroscopic analyses indicate that the zinc BChl-d analogues self-assemble in a nonpolar organic solvent in a similar manner to natural chlorosomal BChls with additional assistance by hydrogen-bonding of secondary amide (or urea) groups (CON-H⋅⋅⋅O=CNH). Microscopic analyses of the supramolecules of a zinc BChl-d analogue bearing amide and urea groups show round- or square-shaped rods with widths of about 65 nm. Cryogenic TEM shows a lamellar arrangement of the zinc chlorin with a layer spacing of 1.5 nm inside the rod. Similar thick rods are also visible in the micrographs of self-assemblies of zinc BChl-d analogues with one or two secondary amide moieties in the 17-substituent.

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“…Ultimately, the study of these modified aggregates will help to explain the self-organization process in vivo. Various spectroscopic techniques have provided converging evidence for Cd···OH···OC bonding, similar to the Mg···OH···OC moieties in the natural system . From low-resolution diffraction data, a distance between the molecular planes of 6.4 Å was resolved.…”

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confidence: 99%

MAS NMR Structure of a Microcrystalline Cd-Bacteriochlorophyll d Analogue

et al. 2003

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Solid-state NMR is an emerging method to obtain structural information in molecular biology and nanotechnology for systems that are inaccessible to solution NMR or diffraction methods. While solution NMR generally converges upon families of structures in a bottom-up approach, solid NMR structure determination will have to take into account the top-down constraints that follow from the additional requirement that the entire 3D space must be packed in an orderly fashion. We used MAS NMR together with molecular modeling calculations in steps to establish a detailed model of the local crystal structure of an aggregate of uniformly 13C- and 15N-labeled Cd-chlorophyllide d, a model for the chlorosomal antennae. In this way we converge upon a space group P21 with a = 14.3 A, b = 27.3 A, c = 6.4 A, beta = 147.2 degrees and Z = 2.

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Self-aggregates of a synthetic cadmium chlorin in solid film as a photosynthetic antenna model

Cited by 12 publications

References 13 publications

The 17‐Propionate Function of (Bacterio)chlorophylls: Biological Implication of Their Long Esterifying Chains in Photosynthetic Systems^†

The 17‐Propionate Function of (Bacterio)chlorophylls: Biological Implication of Their Long Esterifying Chains in Photosynthetic Systems^†

Self‐Assemblies of Zinc Bacteriochlorophyll‐d Analogues Having Amide, Ester, and Urea Groups as Substituents at 17‐Position and Observation of Lamellar Supramolecular Nanostructures

MAS NMR Structure of a Microcrystalline Cd-Bacteriochlorophyll d Analogue

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Self-aggregates of a synthetic cadmium chlorin in solid film as a photosynthetic antenna model

Cited by 12 publications

References 13 publications

The 17‐Propionate Function of (Bacterio)chlorophylls: Biological Implication of Their Long Esterifying Chains in Photosynthetic Systems†

The 17‐Propionate Function of (Bacterio)chlorophylls: Biological Implication of Their Long Esterifying Chains in Photosynthetic Systems†

Self‐Assemblies of Zinc Bacteriochlorophyll‐d Analogues Having Amide, Ester, and Urea Groups as Substituents at 17‐Position and Observation of Lamellar Supramolecular Nanostructures

MAS NMR Structure of a Microcrystalline Cd-Bacteriochlorophyll d Analogue

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Product

Resources

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The 17‐Propionate Function of (Bacterio)chlorophylls: Biological Implication of Their Long Esterifying Chains in Photosynthetic Systems^†

The 17‐Propionate Function of (Bacterio)chlorophylls: Biological Implication of Their Long Esterifying Chains in Photosynthetic Systems^†