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.
Structure-property relationships for self-assembled zinc chlorin light-harvesting dye aggregates
Huber, Valerie,Sengupta, Sanchita,Wuerthner, Frank
, p. 7791 - 7807 (2008)
A series of zinc 31-hydroxymethyl chlorins 10 a-e and zinc 31-hydroxyethyl chlorins 17 with varied structural features were synthesized by modifying naturally occurring chlorophyll a. Solvent-, temperature-, and concentration-depende
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.
Controlled stacking and unstacking of peripheral chlorophyll units drives the spring-like contraction and expansion of a semi-artificial helical polymer
Numata, Munenori,Kinoshita, Daiki,Hirose, Naoya,Kozawa, Tomohiro,Tamiaki, Hitoshi,Kikkawa, Yoshihiro,Kanesato, Masatoshi
, p. 1592 - 1598 (2013)
Developing new strategies for controlling polymer conformations through precise molecular recognition can potentially generate a machine-like motion that is dependent on molecular information - an important process for the preparation of new intelligent nanomaterials (e.g., polymer-based nanomachines) in the field bordering between polymer chemistry and conventional supramolecular sciences. Herein, we propose a strategy to endow a helical polymer chain with dynamic spring-like (contraction/expansion) motion through the one-dimensional self-assembly (aggregation/disaggregation) of peripheral amphiphilic molecules. In this developing system, we employed a semi-artificial helical polysaccharide presenting peripheral amphiphilic chlorophyll units as a power device that undergoes contractive motion in aqueous media, driven by strong π-π interactions of its chlorophyll units or by cooperative molecular recognition of bipyridyl-type ligands through pairs of chlorophyll units, thereby converting molecular information into the regulated motion of a spring. In addition, this system also undergoes expansive motion through coordination of pyridine. We anticipate that this strategy will be applicable (when combined with the established wrapping chemistry of the helical polysaccharide) to the development of, for example, drug carriers (e.g., nano-syringes), actuators (stimuli-responsive films), and directional transporters (nano-railways), thereby extending the frontiers of supramolecular science. Copyright
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
Stereoselective reduction, methylation, and phenylation of the 13-carbonyl group in chlorophyll derivatives
Tamiaki, Hitoshi,Monobe, Rie,Koizumi, Shun,Miyatake, Tomohiro,Kinoshita, Yusuke
, p. 677 - 682 (2013)
Regioselective reduction of the 13-carbonyl group on the five-membered exo-ring of methyl pyropheophorbide-a, one of the chlorophyll-a derivatives, with sodium borohydride gave an epimeric mixture of (131R/S)-hydroxy- chlorins. The stereoselectivity was controlled by the steric effect of the (17S)-methoxycarbonylethyl group to afford the (131S)-rich secondary alcohol (25% de). The use of sterically large lithium tri(sec-butyl)borohydride as the reductant enhanced the stereoselectivity to 55% de. The regio- and stereoselective methylation and phenylation of the 13-CO of pyropheophorbide-a were observed using methyl and phenyl lithium, respectively. The major diastereomer of the tertiary alcohols obtained had the same configuration at the 131-stereogenic center as in the reduced product. All of the anion species (H-, CH3-, and C6H 5-) favorably attacked the 131-carbon atom from the reverse side of the 17-propionate residue, that is, the less sterically crowded face of the 13-CO plane.
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.
Stereoselective reduction, methylation, and phenylation of the 13-carbonyl group in chlorophyll derivatives
Tamiaki, Hitoshi,Monobe, Rie,Koizumi, Shun,Miyatake, Tomohiro,Kinoshita, Yusuke
, p. 967 - 972 (2013)
Regioselective reduction of the 13-carbonyl group on the five-membered exo-ring of methyl pyropheophorbide-a, one of the chlorophyll-a derivatives, with sodium borohydride gave an epimeric mixture of (131R/S)-hydroxy- chlorins. The stereoselect
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.
Conjugates of natural chlorins and isobornylphenols with a different length of the spacer between the chlorin and terpenephenolic fragments: synthesis and antioxidant activity
Khudyaeva,Belykh,Shevchenko,Maximova,Zainullina,Vakhitova, Yu. V.,Shchukina,Buravlev,Chukicheva, I. Yu.,Kutchina
, p. 2157 - 2164 (2017)
Conjugates containing chlorine and isobornylphenolic fragments, which are connected by spacers of different lengths, were synthesized from methyl pheophorbide a. The toxicity and antioxidant activity of the obtained compounds were studied. Derivatives of pyropheophorbide a containing the most distant from the macrocycle terpenephenolic fragment combine a low toxicity with the high antioxidant activity, and are the most promising for further designing of new medicinal agents for the treatment of diseases associated with a disorder in oxidation-reduction processes in the body.
