The photodynamic properties of a new photosensitizer—dimegin (disodium salt of 2,4-di(1- methoxyethyl)-deuteroporphyrin-IX)—are studied in comparison with the properties of photosensitizers used in medical practice, namely, Photoditazine (dimethylglucamine salt of chlorin e6) and Radachlorin (trisodium salt of chlorin e6). The spectral characteristics, singlet oxygen generation ability, luminescence efficiency, and photostability of these photosensitizers are studied upon irradiation by light-emitting diode arrays in different spectral ranges. The ability of photosensitizers to generate singlet oxygen was estimated with the use of tryptophan as a chemical trap. The photostability was estimated by a change in the optical density of solutions in the Soret band after irradiation. It is shown that the photodynamic properties are related to the specific features of the optical absorption spectrum of the material. The results of this work testify to the possibility of using the Dimegin photosensitizer as an efficient drug for photodynamic therapy and fluorescent diagnostics. Comparative studies of luminescence, singlet oxygen generation, and photostability have shown that Dimegin surpasses Photoditazine and Radachlorin in many characteristics. In the future, these studies will help to choose the most efficient irradiation sources for photodynamic therapy and fluorescent diagnostic.

Tookad® (Pd-Bpheid) as bacteriochlorophylls derivative is third generation of photosensitizer having great promises and efficacy for some cancers treatment. The understanding of the photosensitizer stability in vitro is important and fundamental studies before photodynamic therapy (PDT) pre-clinical treatment, especially their responses to aggregation, acidification, and irradiation. Tookad® stability testing was performed by spectroscopic methods using Varian Cary 50 UV-Vis and Light-Volpi Intralux 1200. The result shows that Tookad® aggregated by water titration and degradation is due to the acidification and day-light irradiation. The day-light irradiation caused Tookad® degradation on Soret and Qy band. The degradation product indicates 3-Acetil-chl and Chlorin.

Several phosphorescent platinum(II) and palladium(II) complexes of tetrapyrrole dyes are prepared in an attempt to improve the compatibility with red laser diodes. The nature of meso-substituents in benzoporphyrin macrocycle is found to affect mainly the position of the Soret band and has little influence on the Q-bands. In rigid polymeric matrices these dyes possess more favourable photochemical properties than corresponding meso-tetraphenyltetrabenzoporphyrins. Platinum(II) chlorins show good compatibility with 635nm laser diode and 632.8 line of He–Ne laser, and have moderate brightness with emission yields ∼2%. Photophysical properties and photostability of these dyes is assessed and compared with the known NIR-emitting oxygen indicators.

A preparative procedure is proposed for the synthesis of α-aminophosphonates of natural porphyrins by the microwave-assisted Kabachnik—Fields reaction.

The vinyl groups in protoporphyrin IX and chlorophyll a derivatives were selectively transformed into hydroxymethyl and acetoxymethyl substituents. The reactivities of β-hydroxymethyl and β-acetoxymethyl groups in porphyrins and chlorins toward nucleophilic reagents were compared for the first time using the reaction with acetylacetone as an example. Peripheral acetylacetone moieties in porphyrins and chlorins were shown to be promising as building blocks for generation of exo heterocyclic structures.

[structure: see text] A racemic mixture of the ethane-bridged bis(zinc octaethylchlorin) was successfully resolved for the first time to yield two enantiomers that exhibit substantial CD signals in the regions of chlorin B and Q transitions. The absolute configuration of the corresponding enantiomers was assigned and the origin of its high optical activity was rationalized through a combined spectral, crystallographic, and theoretical analysis.

The synthesis has been carried out of nickel complexes of oximes of two isomers of meso-formyletioporphyrin-II and their conversion in the heterophase system methylene chloride-water into nickel complexes of tripyrrolylisoxazoles has been studied. The structure of one of them was established by X-ray structural analysis.

Starting from the nickel meso-formyloctaethylporphyrin oxime complex, the meso-cyanooctaethylporphyrin N-oxide complex was synthesized for the first time. The new complex enters into 1,3-cycloaddition to olefins. The double addition of the nitrile oxide to 2,5-norbornadiene affords a porphyrin dimer, whose structure was established by X-ray diffraction analysis.

The extensive published data on methods for the modification of peripheral substituents in chlorophylls a and b and their various semisynthetic derivatives are classified and analyzed. Special attention is paid to specific transformations arising from the presence of the unique macrocyclic tetrapyrrole fragment. Data on certain main pathways to modification of the exocyclic fragment of chlorophylls are also presented.

ChemInformVolume 35, Issue 20 Heterocyclic Compounds Synthesis of Pyrazoleporphyrins and Pyrazolechlorins by Cyclization of Peripheral β-Diketone Groups of Porphyrins and Chlorins with Phenylhydrazines. G. V. Ponomarev, G. V. Ponomarev Orekhovich Res. Inst., Russ. Acad. Med. Sci., Moscow 119121, RussiaSearch for more papers by this authorV. Yu. Pavlov, V. Yu. Pavlov Orekhovich Res. Inst., Russ. Acad. Med. Sci., Moscow 119121, RussiaSearch for more papers by this authorI. O. Konstantinov, I. O. Konstantinov Orekhovich Res. Inst., Russ. Acad. Med. Sci., Moscow 119121, RussiaSearch for more papers by this authorV. P. Timofeev, V. P. Timofeev Orekhovich Res. Inst., Russ. Acad. Med. Sci., Moscow 119121, RussiaSearch for more papers by this authorB. G. Kimel, B. G. Kimel Orekhovich Res. Inst., Russ. Acad. Med. Sci., Moscow 119121, RussiaSearch for more papers by this author G. V. Ponomarev, G. V. Ponomarev Orekhovich Res. Inst., Russ. Acad. Med. Sci., Moscow 119121, RussiaSearch for more papers by this authorV. Yu. Pavlov, V. Yu. Pavlov Orekhovich Res. Inst., Russ. Acad. Med. Sci., Moscow 119121, RussiaSearch for more papers by this authorI. O. Konstantinov, I. O. Konstantinov Orekhovich Res. Inst., Russ. Acad. Med. Sci., Moscow 119121, RussiaSearch for more papers by this authorV. P. Timofeev, V. P. Timofeev Orekhovich Res. Inst., Russ. Acad. Med. Sci., Moscow 119121, RussiaSearch for more papers by this authorB. G. Kimel, B. G. Kimel Orekhovich Res. Inst., Russ. Acad. Med. Sci., Moscow 119121, RussiaSearch for more papers by this author First published: 21 April 2004 https://doi.org/10.1002/chin.200420098Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onEmailFacebookTwitterLinkedInRedditWechat No abstract is available for this article. References G. V. Ponomarev, V. Yu. Pavlov, I. O. Konstantinov, V. P. Timofeev, B. G. Kimel, Synthesis of Pyrazoleporphyrins and Pyrazolechlorins by Cyclization of Peripheral β-Diketone Groups of Porphyrins and Chlorins with Phenylhydrazines., Russ. J. Org. Chem., 2003, 39, 1683–1684. 10.1023/B:RUJO.0000013152.87007.ea CASWeb of Science®Google Scholar Volume35, Issue20May 18, 2004 ReferencesRelatedInformation

The first synthesis of α-amino phosphonates comprising porphyrin core was accomplished. Three methods of obtaining α-amino phosphonates 5-8 were compared. Conventional heating of formylporphyrins 1-4 with t-BuNH 2 and (EtO) 2 P(O)H in various solvents was ultimately unsuccessful for preparing 5-8 whereas the use of microwave irradiation made it possible to obtain 5-8 in good yields. Regioselective preparation of 5-8 in excellent yields was achieved by combining microwave-assisting conditions and catalysis with CdI 2 . Efficient synthetic procedures of obtaining formylporphyrins 3,4 in large scale were also proposed.

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Monomeric and covalently bound dimeric Mn porphyrinates (MnP) were found to have catalase activity in the decomposition of hydrogen peroxide in the presence of a nitrogen base (imidazole). The reaction occurred in the region of the organic phase (chloroform)-water interface. The factors were identified that determined the catalytic activity of monomeric and covalently bound dimeric MnP with ethane and ethylene bonds between metalloporphyrin rings in the decomposition of hydrogen peroxide. In particular, imidazole concentration variations proved to be an effective factor controlling the kinetics of the reaction. The degree of hydrogen peroxide conversion in the reactions under investigation was found to depend on the type of the central ion in metalloporphyrins.