992-36-9Relevant academic research and scientific papers
Alternate syntheses of pyrromethanes and porphyrins using acid-modified montmorillonite K-10 clay
Freeman, Beverly A.,Smith, Kevin M.
, p. 1843 - 1855 (1999)
A variety of porphyrins and pyrromethanes are prepared using Montmorillonite clay mixed with a variety of acids (p-TsOH, BF3 · Et2O). The ease of use of the naturally occurring clay as a co-catalyst makes it an attractive reagent for
Corrole-Substituted Fluorescent Heme Proteins
Lemon, Christopher M.,Marletta, Michael A.
, p. 2716 - 2729 (2021/02/16)
Although fluorescent proteins have been utilized for a variety of biological applications, they have several optical limitations, namely weak red and near-infrared emission and exceptionally broad (>200 nm) emission profiles. The photophysical properties of fluorescent proteins can be enhanced through the incorporation of novel cofactors with the desired properties into a stable protein scaffold. To this end, a fluorescent phosphorus corrole that is structurally similar to the native heme cofactor is incorporated into two exceptionally stable heme proteins: H-NOX from Caldanaerobacter subterraneus and heme acquisition system protein A (HasA) from Pseudomonas aeruginosa. These yellow-orange emitting protein conjugates are examined by steady-state and time-resolved optical spectroscopy. The HasA conjugate exhibits enhanced fluorescence, whereas emission from the H-NOX conjugate is quenched relative to the free corrole. Despite the low fluorescence quantum yields, these corrole-substituted proteins exhibit more intense fluorescence in a narrower spectral profile than traditional fluorescent proteins that emit in the same spectral window. This study demonstrates that fluorescent corrole complexes are readily incorporated into heme proteins and provides an inroad for the development of novel fluorescent proteins.
Functionalization of 3,5,8-trichlorinated BODIPY dyes
Wang, Haijun,Fronczek, Frank R.,Vicente, M. Graa H.,Smith, Kevin M.
, p. 10342 - 10352 (2015/02/19)
Catalytic hydrogenation of dibenzyl 5-dipyrroketone-2,9-dicarboxylates followed by decarboxylative iodination affords a 2,9-diiododipyrroketone which gives a 2,5,9-trichlorodipyrromethene hydrochloride after nucleophilic addition/elimination, with adventitious chloride to replace the two iodide groups. Treatment with BF3·Et2O gives a 3,5,8-trichloro-BODIPY that readily undergoes regioselective Stille coupling at the 8-position, or homo/mixed couplings at the 3,8- or 3,5- and 8-positions. Stepwise and controlled replacement of the 3,5- and 8-chlorine atoms using Stille reagents results in formation of a completely unsymmetrical trisubstituted BODIPY. Several examples of unsymmetrical BODIPYs were synthesized and characterized using this methodology. Structure features of new BODIPYs are discussed within the context of 14 new X-ray structures, and photophysical parameters of all new BODIPY compounds are reported and discussed.
Total synthesis of hematoporphyrin and protoporphyrin; A conceptually new approach
Martin, Pierre,Mueller, Markus,Flubacher, Dietmar,Boudier, Andreas,Spielvogel, Dirk
, p. 204 - 206 (2013/07/05)
The total synthesis of protoporphyrin IX and its disodium salt using a new alternative method to the classical MacDonald condensation is reported. The key step is the reaction of the new unsymmetrical diiodo dipyrrylmethane 1 with the known dipyrrylmethane 2. Coupling of the two fragments leads directly to porphyrin 3 without the need of an oxidizing agent. The new methodology is well suited for the synthesis of protoporphyrin IX derivatives on a multi-100 g scale in good quality without the need for chromatography. Furthermore, these preparations are completely free of any contaminant of animal origin, which represents a real improvement in the manufacturing of protoporphyrin IX derivatives. Schweizerische Chemische Gesellschaft.
Fabrications of potential imaging probes based on a β-alkyl substituted porphyrin with a terpyridine external coordination site
Suzuki, Masaaki,Uehara, Tomoya,Arano, Yasushi,Hoshino, Tyuji,Neya, Saburo
scheme or table, p. 7164 - 7167 (2012/02/14)
We report synthesis and coordination properties of β-alkyl porphyrin derivatives bearing terpyridylphenyl substituents at the meso-position and propionate side chains at the β-positions. Rhenium(I) carbonyl ion was encapsulated not in the core but in the
Total synthesis of hematoporphyrin and protoporphyrin: A conceptually new approach
Martin, Pierre,Mueller, Markus,Flubacher, Dietmar,Boudier, Andreas,Blaser, Hans-Ulrich,Spielvogel, Dirk
, p. 799 - 804 (2011/03/19)
The total synthesis of protoporphyrin IX and its disodium salt using a new alternative method to the classical MacDonald condensation is reported. The key step is the reaction of the new unsymmetrical diiodo dipyrrylmethane 1 with the known dipyrrylmethane 2. Coupling of the two fragments leads directly to porphyrin 3 without the need of an oxidizing agent. The new methodology is well suited for the synthesis of protoporphyrin IX derivatives on a multi 100 g scale in good quality without the need for chromatography. Furthermore, these preparations are completely free of any contaminant of animal origin, which represents a real improvement in the manufacturing of protoporphyrin IX derivatives.
Synthetic porphyrins bearing β-propionate chains as photosensitizers for photodynamic therapy
Pereira, Nelson,Serra, Arménio C.,Pineiro, Marta,Gonsalves, António M. D'A. Rocha,Abrantes, Margarida,Laranjo, Mafalda,Botelho, Filomena
experimental part, p. 438 - 445 (2010/12/18)
Porphyrins with different numbers of β-propionate chains mimicking natural porphyrins were prepared via the 2+2 MacDonald type approach. Photodynamic activity against WiDr colon adenocarcinoma cells showed that activity is related to the number of β-propi
Meso-unsubstituted iron corrole in hemoproteins: Remarkable differences in effects on peroxidase activities between myoglobin and horseradish peroxidase
Matsuo, Takashi,Hayashi, Akihiro,Abe, Masato,Matsuda, Takaaki,Hisaeda, Yoshio,Hayashi, Takashi
supporting information; experimental part, p. 15124 - 15125 (2010/01/30)
(Figure Presented) Myoglobin (Mb) and horseradish peroxidase (HRP) were both reconstituted with a meso-unsubstituted iron corrole and their electronic configurations and peroxidase activities were investigated. The appearance of the 540 nm band upon incorporation of the iron corrole into apoMb indicates axial coordination by the proximal histidine imidazole in the Mb heme pocket. Based on 1H NMR measurements using the Evans method, the total magnetic susceptibility of the iron corrole reconstituted Mb was evaluated to be S = 3/2. In contrast, although a band does not appear in the vicinity of 540 nm during reconstitution of the iron corrole into the matrix of HRP, a spectrum similar to that of the iron corrole reconstituted Mb is observed upon the addition of dithionite. This observation suggests that the oxidation state of the corrole iron in the reconstituted HRP can be assigned as +4. The catalytic activities of both proteins toward guaiacol oxidation are quite different; the iron corrole reconstituted HRP decelerates H2O2-dependent oxidation of guaiacol, while the same reaction catalyzed by iron corrole reconstituted Mb has the opposite effect and accelerates the reaction. This finding can be attributed to the difference in the oxidation states of the corrole iron when these proteins are in the resting state.
Process For Preparing Porphyrin Derivatives, Such As Protoporphyrin (IX) And Synthesis Intermediates
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Page/Page column 12-13; 18, (2008/12/07)
The present invention relates to a process for preparing a porphyrin of formula (I), optionally in the form of a salt with an alkali metal and/or in the form of a metal complex: in which: R and R′ are as defined in claim 1, comprising: a step of condensation, in an acidic medium, between a dipyrromethane of formula (II): in which R′b is as defined above for (I), and a dipyrromethane of formula (III): in which R″ is as defined in claim 1, and also the compounds of formula (III).
Fluorinated photosensitizers: Synthesis, photophysical, electrochemical, intracellular localization, in vitro photosensitizing efficacy and determination of tumor-uptake by 19F in vivo NMR spectroscopy
Pandey, Suresh K.,Gryshuk, Amy L.,Graham, Andrew,Ohkubo, Kei,Fukuzumi, Shunichi,Dobhal, Mahabeer P.,Zheng, Gang,Ou, Zhongping,Zhan, Riqiang,Kadish, Karl M.,Oseroff, Allan,Ramaprasad,Pandey, Ravindra K.
, p. 10059 - 10073 (2007/10/03)
For in vivo NMR studies, starting from pyrroles, a series of fluorinated porphyrins were synthesized by following the MacDonald reaction conditions. Upon reaction with osmium tetroxide, a fluorinated porphyrin containing four trifluoromethyl groups (12 fl
