De novo synthesis and properties of analogues of the self-assembling chlorosomal bacteriochlorophylls

Mass, Olga A.; Pandithavidana, Dinesh R.; Ptaszek, Marcin; Santiago, Koraliz; Springer, Joseph W.; Jiao, Jieying; Tang, Qun; Kirmaier, Christine; Bocian, David F.; Holten, Dewey; Lindsey, Jonathan S.

doi:10.1039/c1nj20611g

Cited by 18 publications

(35 citation statements)

References 59 publications

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“…†Source of the original data. (1) This study; (2) Ref 21; (3) Ref 22; (4) Ref 26; (5) Ref 34. Some of the Φ f and τ S values from Ref 21 were changed (by <15%) to reflect averaging with additional repeat measurements (including using a second technique for the τ S measurements as noted in the ).…”

Section: Methodsmentioning

confidence: 99%

“…†Source of the original data. (1) This study; (2) Ref 21; (3) Ref 22; (4) Ref 26; (5) Ref 34. ‡The reference compound used for calculation of the Δ values for each of the spectral and photophysical parameters.…”

Section: Methodsmentioning

confidence: 99%

“…Preparation of 3,13‐diacetyl‐17,18‐dihydro‐18,18‐dimethyl‐10‐mesitylporphyrin (FbC‐A 3 M 10 A 13 ; 20,34 ). A solution of ZnC‐Br 3 M 10 Br 13 (78.0 mg, 0.115 mmol) in CH 2 Cl 2 (3.0 mL) was treated dropwise with trifluoroacetic acid (266 μL, 22.2 mmol) over a 2 min period.…”

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confidence: 99%

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Effects of Substituents on Synthetic Analogs of Chlorophylls. Part 3: The Distinctive Impact of Auxochromes at the 7‐ versus 3‐Positions

Springer

Faries

Diers

et al. 2012

Photochem & Photobiology

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Assessing the effects of substituents on the spectra of chlorophylls is essential for gaining a deep understanding of photosynthetic processes. Chlorophyll a and b differ solely in the nature of the 7-substituent (methyl versus formyl), whereas chlorophyll a and d differ solely in the 3-substituent (vinyl versus formyl), yet have distinct long-wavelength absorption maxima: 665 (a) 646 (b) and 692 nm (d). Herein, the spectra, singlet excited-state decay characteristics, and results from DFT calculations are examined for synthetic chlorins and 13(1)-oxophorbines that contain ethynyl, acetyl, formyl and other groups at the 3-, 7- and/or 13-positions. Substituent effects on the absorption spectra are well accounted for using Gouterman's four-orbital model. Key findings are that (1) the dramatic difference in auxochromic effects of a given substituent at the 7- versus 3- or 13-positions primarily derives from relative effects on the LUMO+1 and LUMO; (2) formyl at the 7- or 8-position effectively "porphyrinizes" the chlorin and (3) the substituent effect increases in the order of vinyl < ethynyl < acetyl < formyl. Thus, the spectral properties are governed by an intricate interplay of electronic effects of substituents at particular sites on the four frontier MOs of the chlorin macrocycle.

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Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

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Effects of Substituents on Synthetic Analogs of Chlorophylls. Part 3: The Distinctive Impact of Auxochromes at the 7‐ versus 3‐Positions

Springer

Faries

Diers

et al. 2012

Photochem & Photobiology

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“…Chlorosomal-like assembly processes of ZnOP-He 3 M 10 ( He is an abbreviation for α-hydroxyethyl; see the Appendix, "Substituent Abbreviations" section, for nomenclature) were suggested by the characteristic spectral changes upon dissolution at increasing concentration or by use of a only a trace amount of a coordinating solvent (THF) in the nonpolar solvent n -hexane. 290 …”

Section: Bromination Of Chlorinsmentioning

confidence: 99%

“…Indeed, access to the 2, 255,296,298,299 3, 265,290,298,299 5, 254,256,269 7, 277,283,2908,277 10, 254,256,269 12, 255,284,299 13, 265,286,289,299 15, 263,270,283,286,299 17, 257,270,299 18, 257 and 20 263,283 positions has been achieved, as has installation of the isocyclic ring 267,289 (and 6-membered imide analogues 286,300 ) characteristic of native chlorophylls. The following sections describe novel chlorin architectures obtained chiefly by application of aforementioned methodology for (1) precursor synthesis, (2) macrocycle formation, and (3) bromination of the chlorin macrocycle under neutral or acidic conditions.…”

Section: Smorgasbord Of Chlorinsmentioning

confidence: 99%

De NovoSynthesis of Gem-Dialkyl Chlorophyll Analogues for Probing and Emulating Our Green World

2015

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Woodward reported his infamous synthesis of chlorin e 6 trimethyl ester, a known synthetic precursor to chlorophyll a. [59][60][61][62][63][64]124 The work was posited on a half-century of intensive studies by many investigators in tetrapyrrole chemistry and began a decade after the close of Fischer's lifetime of research 125−128 (which included an uncompleted synthetic program directed toward chlorophylls 15 ). Indeed, "he read all the umpteen papers on the chlorophylls written by Willstaẗter and Fischer, including the experimental parts." 129 The Woodward synthesis of chlorin e 6 trimethyl ester required 46 steps, of which 24 were spent on converting the sole precursor, Knorr's pyrrole, to the four pyrroles destined to form rings A−D; 7 additional steps accrued to obtain the dipyrromethanes that constitute the Eastern and Western halves (Scheme 13, the step numbers are identical to those shown in ref 64.). The first step formed the Knorr pyrrole (in several kg quantities), the next 24 steps were divided into four parallel paths, whereas the remaining 21 steps proceeded in linear fashion. Remarkable features of the synthesis include the directed intramolecular joining (via an imine) of the Eastern and Western halves (step 33), construction of the acrylate Scheme 10. Hydrogenation of a Porphyrin to Form a Chlorin Scheme 11. Representative meso-Tetraarylchlorins Scheme 12. Methyl Pyropheophorbide a

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Chlorosome antenna complexes from green photosynthetic bacteria

2013

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Chlorosomes are the distinguishing light-harvesting antenna complexes that are found in green photosynthetic bacteria. They contain bacteriochlorophyll (BChl) c, d, e in natural organisms, and recently through mutation, BChl f, as their principal light-harvesting pigments. In chlorosomes, these pigments self-assemble into large supramolecular structures that are enclosed inside a lipid monolayer to form an ellipsoid. The pigment assembly is dictated mostly by pigment-pigment interactions as opposed to protein-pigment interactions. On the bottom face of the chlorosome, the CsmA protein aggregates into a paracrystalline baseplate with BChl a, and serves as the interface to the next energy acceptor in the system. The exceptional light-harvesting ability at very low light conditions of chlorosomes has made them an attractive subject of study for both basic and applied science. This review, incorporating recent advancements, considers several important aspects of chlorosomes: pigment biosynthesis, organization of pigments and proteins, spectroscopic properties, and applications to bio-hybrid and bio-inspired devices.

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De novo synthesis and properties of analogues of the self-assembling chlorosomal bacteriochlorophylls

Cited by 18 publications

References 59 publications

Effects of Substituents on Synthetic Analogs of Chlorophylls. Part 3: The Distinctive Impact of Auxochromes at the 7‐ versus 3‐Positions

Effects of Substituents on Synthetic Analogs of Chlorophylls. Part 3: The Distinctive Impact of Auxochromes at the 7‐ versus 3‐Positions

De NovoSynthesis of Gem-Dialkyl Chlorophyll Analogues for Probing and Emulating Our Green World

Chlorosome antenna complexes from green photosynthetic bacteria

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