Palette of lipophilic bioconjugatable bacteriochlorins for construction of biohybrid light-harvesting architectures

Reddy, Kanumuri Ramesh; Jiang, Jianbing; Krayer, Michael; Harris, Michelle A.; Springer, Joseph W.; Yang, Eunkyung; Jiao, Jieying; Niedzwiedzki, Dariusz M.; Pandithavidana, Dinesh R.; Parkes-Loach, Pamela S.; Kirmaier, Christine; Loach, Paul A.; Bocian, David F.; Holten, Dewey; Lindsey, Jonathan S.

doi:10.1039/c3sc22317e

Cited by 47 publications

(103 citation statements)

References 63 publications

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“…The geranylgeranyl bacteriochlorophyll a is hereafter referred to as BChl a for simplicity. The synthetic maleimido–bacteriochlorins B1 ( Q y λ max = 712 nm) and B2 ( Q y λ max = 755 nm) were synthesized as described previously . The synthetic bacteriochlorins exhibit spectroscopic and photochemical features resembling those of native bacteriochlorophylls .…”

Section: Methodsmentioning

confidence: 99%

Enhanced Light‐Harvesting Capacity by Micellar Assembly of Free Accessory Chromophores and LH1‐like Antennas

Harris

Sahin

Jiang

et al. 2014

Photochem & Photobiology

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Biohybrid light-harvesting antennas are an emerging platform technology with versatile tailorability for solar-energy conversion. These systems combine the proven peptide scaffold unit utilized for light harvesting by purple photosynthetic bacteria with attached synthetic chromophores to extend solar coverage beyond that of the natural systems. Herein, synthetic unattached chromophores are employed that partition into the organized milieu (e.g. detergent micelles) that house the LH1-like biohybrid architectures. The synthetic chromophores include a hydrophobic boron-dipyrrin dye (A1) and an amphiphilic bacteriochlorin (A2), which transfer energy with reasonable efficiency to the bacteriochlorophyll acceptor array (B875) of the LH1-like cyclic oligomers. The energy-transfer efficiencies are markedly increased upon covalent attachment of a bacteriochlorin (B1 or B2) to the peptide scaffold, where the latter likely acts as an energy-transfer relay site for the (potentially diffusing) free chromophores. The efficiencies are consistent with a Förster (through-space) mechanism for energy transfer. The overall energy-transfer efficiency from the free chromophores via the relay to the target site can approach those obtained previously by relay-assisted energy transfer from chromophores attached at distant sites on the peptides. Thus, the use of free accessory chromophores affords a simple design to enhance the overall light-harvesting capacity of biohybrid LH1-like architectures.

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Section: Methodsmentioning

confidence: 99%

Enhanced Light‐Harvesting Capacity by Micellar Assembly of Free Accessory Chromophores and LH1‐like Antennas

Harris

Sahin

Jiang

et al. 2014

Photochem & Photobiology

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“…25,26,49,[59][60][61][62][63] The design, synthesis, and physicochemical characterization of the substituted bacteriochlorins described herein provide a small step toward this goal. Ultimately one goal is not only to solubilize bacteriochlorin monomers but to be able to create multipigment architectures containing bacteriochlorins that are water-soluble for use in diverse scientific applications.…”

Section: Discussionmentioning

confidence: 99%

“…Sonication was carried out in a benchtop sonication bath. Following a general procedure, 49 samples of BC-Br 3,13 (45 mg, 80 mmol), Pd(PPh 3 ) 4 (28 mg, 24 mmol) and anhydrous K 2 CO 3 (0.13 g, 0.96 mmol) were placed in a Schlenk flask and dried under high vacuum for 1 h. Toluene/DMF [8.0 mL (2 : 1), degassed by bubbling with argon for 10 min] was added along with 1 (0.12 g, 0.24 mmol), and the resulting reaction mixture was degassed by three freeze-pumpthaw cycles. Following a general procedure, 45 a mixture of 1-bromo-3,5-dimethylbenzene (14.8 g, 80.0 mmol), NBS (28.5 g, 160 mmol), and AIBN (0.657 g, 4.00 mmol, 5 mol%) in acetonitrile (400 mL) was refluxed under argon for 5 h. The mixture was concentrated.…”

Section: Methodsmentioning

confidence: 99%

Synthetic bacteriochlorins bearing polar motifs (carboxylate, phosphonate, ammonium and a short PEG). Water-solubilization, bioconjugation, and photophysical properties

et al. 2015

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Bacteriochlorins are potentially excellent chromophores for near-infrared (NIR) photochemical andspectroscopic studies yet the intrinsically hydrophobic macrocycle core has stymied work in aqueous media. Herein, a set of bacteriochlorins bearing distinct polar motifs is reported. The motifs include phosphonate (pH-dependent anionic, BC1), carboxylate (pH-dependent anionic, BC2), ammonium (permanently cationic) without (BC3) or with (BC4) a linker ester moiety, and tetraethyleneoxy (a short PEG, polar non-ionic, BC5). The groups are located at the 3,5-positions of each of two aryl groups at the bacteriochlorin 3,13-sites. Synthesis of the bacteriochlorins entails the Suzuki coupling of a common 3,13-dibromobacteriochlorin building block with a set of aryl boronates. Five factors were selected for comparisons among the polar motifs upon attachment to the bacteriochlorins: (1) synthesis yield and ease of purification, (2) amenability toward subsequent derivatization, (3) water-solubility, (4) full-width-at-halfmaximum (fwhm) of the long-wavelength (Q y ) absorption and fluorescence bands, singlet excited-state lifetime (t S ) and fluorescence quantum yield (F f ), and (5) stability in the dark or under illumination. Watersolubility was assessed by examination of the absorption spectra across a 1000-fold concentration range (B0.2-0.6 mM to B200-600 mM). With the exception of BC4, all displayed good aqueous solubility, photostability, and photophysical properties in aqueous solution (fwhm = 23-31 nm, F f = 0.10-0.16, t S = 1.9-2.7 ns). The modestly lower F f and t S values for the bacteriochlorins in aqueous versus organic (N,N-dimethylformamide) media are traced to an increased rate constant for excited-state internal conversion. Upon consideration of all factors, the ammonium (short linker) and short PEG groups were most attractive for solubilization of the bacteriochlorins in aqueous media. The studies prompted the synthesis of two water-soluble (ammonium-substituted) bacteriochlorins bearing N-hydroxysuccinimide esters. † Electronic supplementary information (ESI) available: Attempted synthesis of a phosphatidylcholine bacteriochlorin (BC6); mass spectrometry analysis for BC1-BC5, BC7, and BC8; and additional data concerning the photophysical properties of bacteriochlorins. See macrocycles can be incorporated with peptides to give selfassembled light-harvesting architectures. 25,26 The tetrapyrroles of present interest are bacteriochlorins, which absorb strongly in the near-infrared (NIR) region. A second objective -a spinoff thereof -aims to use hydrophilic bacteriochlorins in biomedical applications. A variety of bacteriochlorins with appended polar motifs has been previously prepared; representative members are shown in Chart 1. Compounds I, 27 II 27 and III 28 were derived by semisynthesis 29,30 from bacteriochlorophyll a; IV 13 by hydrogenation of the corresponding porphyrin; 31 and V-IX by de novo synthesis. 32,33 Methods of bacteriochlorin synthesis have been reviewed. 34,35 An attractive design element for...

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“…A general finding is that placement of auxochromes at the b-pyrrole positions (i.e. 2, 3, 12, 13 sites) can impart a significant bathochromic shift in the position of the long-wavelength (Q y ) absorption band [2,26,27]. To date, the Q y band has been tuned from 690 nm to ~900 nm [27].…”

Section: Introductionmentioning

confidence: 99%

Elaboration of an unexplored substitution site in synthetic bacteriochlorins

Zhang

Reddy

Jiang

et al. 2015

J. Porphyrins Phthalocyanines

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The ability to introduce substituents at designated sites about the perimeter of synthetic bacteriochlorins -analogs of bacteriochlorophylls of bacterial photosynthesis -remains a subject of ongoing study. Here, the self-condensation of a dihydrodipyrrin-dioxolane affords a 5-[2-(trimethylsiloxy) ethoxy]bacteriochlorin. Like a 5-methoxybacteriochlorin, the latter undergoes regioselective bromination at the 15-position, directed by the distal 5-alkoxy group. On the other hand, attempted bromination of a bacteriochlorin bearing a 5-(2-hydroxyethoxy) group resulted in intramolecular ether formation with the adjacent b-pyrroline position to give an annulated dioxepine ring (confirmed by single-crystal X-ray structural analysis). The hydroxyethoxy group at the 5-position can be derivatized by acylation. In addition, the installation of auxochromes (methoxycarbonyl, phenylethynyl) at the b-pyrrole rings causes a substantial bathochromic shift of the long-wavelength absorption band (812 nm) and companion fluorescence emission band (821 nm). Taken together, the modification of the 5-substituent complements existing methods for installing a single substituent on the bacteriochlorin macrocycle. J. Porphyrins Phthalocyanines 2015.19:887-902. Downloaded from www.worldscientific.com by EMORY UNIVERSITY on 07/30/15. For personal use only. G1 G2 2 A J K Scheme 5. Proposed mechanism leading to the 5-(2-alkoxyethoxy)bacteriochlorin J (top) and balanced equation (bottom) J. Porphyrins Phthalocyanines 2015.19:887-902. Downloaded from www.worldscientific.com by EMORY UNIVERSITY on 07/30/15. For personal use only.

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Palette of lipophilic bioconjugatable bacteriochlorins for construction of biohybrid light-harvesting architectures

Cited by 47 publications

References 63 publications

Enhanced Light‐Harvesting Capacity by Micellar Assembly of Free Accessory Chromophores and LH1‐like Antennas

Enhanced Light‐Harvesting Capacity by Micellar Assembly of Free Accessory Chromophores and LH1‐like Antennas

Synthetic bacteriochlorins bearing polar motifs (carboxylate, phosphonate, ammonium and a short PEG). Water-solubilization, bioconjugation, and photophysical properties

Elaboration of an unexplored substitution site in synthetic bacteriochlorins

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