24533-72-0Relevant articles and documents
In depth analysis of photovoltaic performance of chlorophyll derivative-based "all solid-state" dye-sensitized solar cells
Beljonne, David,Bouclé, Johann,Cangiotti, Michela,Chevrier, Michèle,Clément, Sébastien,Dubois, Philippe,Fattori, Alberto,Kotras, Clément,Lasser, Laurent,Lazzaroni, Roberto,Mehdi, Ahmad,Ottaviani, Maria Francesca,Richeter, Sébastien,Rose, Clémence,Surin, Mathieu
, (2020)
Chlorophyll a derivatives were integrated in "all solid-state" dye sensitized solar cells (DSSCs) with a mesoporous TiO2 electrode and 2′,2′,7,7′-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9′-spirobifluorene as the hole-transport material. Despite modest power conversion efficiencies (PCEs) between 0.26% and 0.55% achieved for these chlorin dyes, a systematic investigation was carried out in order to elucidate their main limitations. To provide a comprehensive understanding of the parameters (structure, nature of the anchoring group, adsorption ?) and their relationship with the PCEs, density functional theory (DFT) calculations, optical and photovoltaic studies and electron paramagnetic resonance analysis exploiting the 4-carboxy-TEMPO spin probe were combined. The recombination kinetics, the frontier molecular orbitals of these DSSCs and the adsorption efficiency onto the TiO2 surface were found to be the key parameters that govern their photovoltaic response.
Intramolecular interaction of synthetic chlorophyll heterodyads with different π-skeletons
Fukai, Kazuhiro,Nakamura, Soichi,Tamiaki, Hitoshi
, p. 332 - 340 (2020)
Two heterodyads were prepared from the chemical modification of naturally occurring (bacterio)chlorophyll-a and composed of a chlorin π-skeleton linked to a porphyrin or bacteriochlorin π-system. Zinc methyl pyropheophorbide-a, one of the chlorophyll-a derivatives, was covalently linked with its 17,18-didehydrogenated species (zinc methyl pyroprotopheophorbide-a) or its trans-7,8-dihydrogenated analog (zinc methyl pyrobacteriopheophorbide-a as one of the bacteriochlorophyll-a derivatives) through ethylene glycol diester at their 17-propionate residues. In benzene, the central zinc atoms of the synthetic conjugates were coordinated by two methanol molecules which were hydrogen-bonded with the 13-keto-carbonyl groups in a dyad molecule. The methanol locked, y-axis aligned, and slipped cofacial conformers showed two apparent Qy bands at longer wavelengths than those of the composite zinc complex monomers. The red-shifted Qy bands are ascribable to the exciton coupling of the two different π-systems in the folded heterodyad conformers. The synthetic heterodyads could be models of chlorophyll-a/c dimers in the light-harvesting antennas of chromophytes including fucoxanthin-chlorophyll proteins in diatoms and also chlorophyll-a species interacting with bacteriochlorophyll-a or g species in the charge-separating reaction centers of green sulfur bacteria or heliobacteria, respectively.
Self-assembly of amphiphilic molecules in droplet compartments: An approach toward discrete submicrometer-sized one-dimensional structures
Numata, Munenori,Kinoshita, Daiki,Taniguchi, Nobuko,Tamiaki, Hitoshi,Ohta, Akio
, p. 1844 - 1848 (2012)
Self-assembly in a droplet: A supramolecular system that governs self-assembly events over hierarchies from the nano- to the micrometer range has been developed by combining a bottom-up strategy based on molecular programming with top-down droplet microsc
Triterpenoid chlorin esters: Water column transformation products of chlorophyll a
Harradine, Paul J.,Peakman, Torren M.,Maxwell, James R.
, p. 13427 - 13440 (1996)
The (22R)-30a,30b-dihomohopan-30b-yl and tetrahymanyl esters of pyrophaeophorbide a, chlorophyll a transformation products resulting from zooplankton herbivory, occur in an extract of surface sediment from Lake Valencia (Venezuela). The former was identified by HPLC-PDA-MS comparison with a standard and the latter after reduction of the extract and GC-MS analysis of the released alcohols.
Peroxide decoloration of CI acid orange 7 catalyzed by manganese chlorophyll derivatives at the surfaces of micelles and lipid bilayers
Ishigure, Shuichi,Mitsui, Tatsuro,Ito, Shingo,Kondo, Yuji,Kawabe, Shigeki,Kondo, Masaharu,Dewa, Takehisa,Mino, Hiroyuki,Itoh, Shigeru,Nango, Mamoru
, p. 7774 - 7782 (2010)
Manganese-substituted chlorophyll a derivatives (MnChls) were synthesized. We first report peroxidative oxidation of an azo dye, CI Acid Orange 7, catalyzed by MnChls at the surfaces of micelles and lipid bilayers with hydrogen peroxide (H2O2) under mild conditions (pH 8.0, 25 °C). Peroxide decoloration depended upon the structures of MnChls, surfactants, lipids, and the presence of imidazole. Surprisingly, a largest decoloration rate was observed for MnChls dimer, MnPChlide a-K(MnPChlide a)-His 5 in cetyltrimethylammonium bromide (CTAB) micellar solution, especially when imidazole was present: this observation is analogous to the decoloration using horseradish peroxidase (HRP). Interestingly, the dimer complexes showed enhanced decoloration in comparison to the corresponding MnChls monomer in the micellar solution. In contrast, the MnChls monomer showed enhanced decoloration in comparison with the MnChls dimer in liposomal suspensions. Further, the imidazole residue covalently linked to the MnChls plays an important role in increasing the decoloration in both micellar and liposomal suspensions as well as in addition of imidazole into the solutions. It is interesting that the electron paramagnetic resonance (EPR) spectra of MnPChlide a ME 2, MnPChlide a-His 3, and MnMPMME-His 7 have 16 peaks around g = 2 in Egg PC or DMPC liposomal suspension with H2O2, which is typical of a mixed-valence Mn(III)-Mn(IV) complex with coupling between two ions. The higher decoloration performance obtained by the monomer porphyrin compounds at the surface of the lipid bilayers appears to be related to the stability of this mixed-valence Mn(III)-Mn(IV) species formed in the lipid bilayers. This finding should provide useful information to note that MnChls, which are easily found in a number of biological systems, are involved in functions such as hydrogen peroxide decomposition in bacteria and the oxidation of water during photosynthesis as well as the peroxidases function such as the peroxidative decoloration as bleaching agents.
Novel carotenoid pyropheophorbide A esters from abalone
Maoka, Takashi,Etoh, Tetsuji,Akimoto, Naoshige,Yasui, Hiroyuki
, p. 3012 - 3015 (2011)
A series of carotenoid pyropheophorbide A esters, fucoxanthin pyropheophorbide A ester (1), halocynthiaxanthin 3′-acetate pyropheophorbide A ester (2), lutein pyropheophorbide A esters (3) and (4), and mutatoxanthin pyropheophorbide A ester (5), were isolated from the viscera of the abalone Haliotis diversicolor aquatilis. These structures were determined based on UV-vis, MS, and NMR spectroscopic data.
Efficient synthesis of pyropheophorbide-a and its derivatives
Pallenberg, Alexander J.,Dobhal, Mahabeer P.,Pandey, Ravindra K.
, p. 287 - 290 (2004)
A new and simplified method of preparing hexyloxy pyropheophorbide-a (HPPH), a promising agent used in photodynamic therapy, is described. This method is carried out in two processing steps, replacing an older method requiring five steps. This is accomplished by means of a Dieckmann condensation and subsequent thermal decarboxylation, both occurring in the same high-boiling solvent, thus reversing the long-standing trend in which naturally occurring chlorin derivatives with exocyclic rings are often subjected to conditions that open this ring to obtain chlorin derivatives. In the new process, a raw material without an exocyclic ring is used to construct a product containing the exocyclic ring. The new method does not require cryogenic processing or chromatography, removing the most significant obstacles to large-scale preparation of HPPH and its homologues.
Efficient two-electron reduction of dioxygen to hydrogen peroxide with one-electron reductants with a small overpotential catalyzed by a cobalt chlorin complex
Mase, Kentaro,Ohkubo, Kei,Fukuzumi, Shunichi
, p. 2800 - 2808 (2013)
A cobalt chlorin complex (CoII(Ch)) efficiently and selectively catalyzed two-electron reduction of dioxygen (O2) by one-electron reductants (ferrocene derivatives) to produce hydrogen peroxide (H 2O2) in the presence of perchloric acid (HClO4) in benzonitrile (PhCN) at 298 K. The catalytic reactivity of Co II(Ch) was much higher than that of a cobalt porphyrin complex (CoII(OEP), OEP2- = octaethylporphyrin dianion), which is a typical porphyrinoid complex. The two-electron reduction of O2 by 1,1′-dibromoferrocene (Br2Fc) was catalyzed by Co II(Ch), whereas virtually no reduction of O2 occurred with CoII(OEP). In addition, CoII(Ch) is more stable than CoII(OEP), where the catalytic turnover number (TON) of the two-electron reduction of O2 catalyzed by CoII(Ch) exceeded 30000. The detailed kinetic studies have revealed that the rate-determining step in the catalytic cycle is the proton-coupled electron transfer reduction of O2 with the protonated CoII(Ch) ([CoII(ChH)]+) that is produced by facile electron-transfer reduction of [CoIII(ChH)]2+ by ferrocene derivative in the presence of HClO4. The one-electron-reduction potential of [CoIII(Ch)]+ was positively shifted from 0.37 V (vs SCE) to 0.48 V by the addition of HClO4 due to the protonation of [CoIII(Ch)]+. Such a positive shift of [Co III(Ch)]+ by protonation resulted in enhancement of the catalytic reactivity of [CoIII(ChH)]2+ for the two-electron reduction of O2 with a lower overpotential as compared with that of [CoIII(OEP)]+.
Synthesis of zinc chlorophyll homo/hetero-dyads and their folded conformers with porphyrin, chlorin, and bacteriochlorin π-systems
Tamiaki, Hitoshi,Fukai, Kazuhiro,Shimazu, Hideki,Shoji, Sunao
, p. 121 - 128 (2014)
Zinc complex of pyropheophorbide-b, a derivative of chlorophyll-b, was covalently dimerized through ethylene glycol diester. The synthetic homo-dyad was axially ligated with two methanol molecules from the β-face and both the diastereomerically coordinating methanol species were hydrogen bonded with the keto-carbonyl groups of the neighboring chlorin in a complex. The resulting folded conformer in a solution was confirmed by visible, 1H NMR and IR spectra. All the synthetic zinc chlorin homo- and hetero-dyads consisting of pyropheophorbides-a, b and/or d took the above methanol-locked and π-π stacked supramolecules in 1% (v/v) methanol and benzene to give redmost (Qy) electronic absorption band(s) at longer wavelengths than those of the corresponding monomeric chlorin composites. The other zinc chlorin and bacteriochlorin homo-dyads completely formed similar folded conformers in the same solution, while zinc inverse chlorin and porphyrin homo-dyads partially took such supramolecules. The J-type aggregation to folded conformers and the redshift values of composite Qy bands were dependent on the electronic and steric factors of porphyrinoid moieties in dyads. Synthetic zinc chlorophyll dyads were intramolecularly folded with two methanol molecules to form their supramolecules by doubly coordinating and hydrogen-bonding. The resulting π-π stacked J-aggregates gave red-shifted Qy bands in a solution.
Semi-synthesis and HPLC analysis of (bacterio)chlorophyllides possessing a propionic acid residue at the C17-position
Teramura, Misato,Tamiaki, Hitoshi
, p. 423 - 436 (2018/03/21)
Various chlorophyll and bacteriochlorophyll derivatives possessing a magnesium or zinc atom at the central position and a free carboxylic acid group at the C172-position, also known as (bacterio)chlorophyllides, were synthesized through a combination of organic synthesis techniques and enzymatic steps. The semi-synthetic (bacterio)chlorophyllides were purified and analyzed using reversed-phase high-performance liquid chromatography with UV-vis spectroscopy and mass spectrometry. These free propionic acid-containing chlorophyllous pigments can be useful research materials for the study of (bacterio)chlorophyll metabolisms.
