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The meso‐imino derivatives of the palladium (II) and nickel (II) complexes of coproporphyrins I and II and β‐octaethylporphyrin were obtained by the Vilsmeier formylation followed by interaction with amines. The metal complexes of the azomethines obtained were transformed to the corresponding complexes of cyclopentane and cyclopentane‐pyrrolidone f...
Two novel complex conjugates (containing three functional units: pyropheophorbide a, 17α-substituted testosterone, and lipophylic hexadecyl chain, connected with L-lysine joining block) were synthesized. The scheme consisted of condensation of N(α)-Fmoc-N(ε)-Boc-Lys with hexadecyl amine, followed by consecutive removal of N-protective groups and co...
Solubilization with pluronic F-127 gave water-soluble forms of hydrophobic photosensitizers—steroid derivatives of pyropheophorbide a. Solubilization was performed by evaporating the chloroform co-solutions of photosensitizer and pluronic (triple block copolymer of ethylene and propylene oxide) and subsequently dissolving the resulting dry residue...
The reaction between coproporphyrin I tetraethyl ester and ruthenium(II) dodecacarbonyl in toluene is investigated. The formation of two different products, complexes 2 and 3 of ruthenium(II) with coproporphyrin I tetraethyl ester, studied by means of mass spectrometry, electronic absorption spectroscopy, NMR, X-ray diffraction, and thermogravimetr...
The features of porphyrins defining their functionality are related to their conformational flexibility. The degree of nonplanarity of metalloporphyrins depends directly on the number of substituents, their size and their location. The introduction of substituents in the meso positions of β-substituted porphyrins increases the steric interaction an...
Porphyrin complexes of ruthenium are widely used as models for the heme protein system, for modelling naturally occurring iron–porphyrin systems and as catalysts in epoxidation reactions. The structural diversity of ruthenium complexes offers an opportunity to use them in the design of multifunctional supramolecular assemblies. Coproporphyrins and...
Two new conjugates of pyropheophorbide a with testosterone and dihydrotestosterone: 17³[2-(17β-hydroxy-3-oxopregn-4-en-21-oylamido)ethylamido]pyropheophorbide a (10) and 17³[2-(17β-hydroxy-3-oxopregnan-21-oylamido)ethyl-amido]pyropheophorbide a (11) were synthesized. IC50 for conjugates 10 and 11 at 96 h incubation in LNCaP and PC-3 prostate carcin...
N-substituted hydrazones of nickel complexes of β-octaethylporphyrin and tetraethyl ester of coproporphyrin I were obtained. These compounds can serve as intermediate compounds for the preparation of meso-functionalized derivatives of porphyrins by means of various reactions. In the first stage Vilsmeier-Haack reaction was carried out by the intera...
The reaction between pyropheophorbide a methyl ester (1) and hydrazine hydrate has been studied. It was shown that the reagents ratio governs the particular reaction product formation. Treatment of 1 by excess of hydrazine hydrate (more than 3 eq.) yielded methylmesopyropheophorbide a hydrazone (2) as a major product. On the other hand, only methyl...
The authors regret that several unintentional technical errors were missed in the published article at the stage of submission and would like to rectify these mistakes. Two authors were inadvertently omitted from the title page, and the presentation of certain results should be improved. The corrected text is available as Electronic Supplementary I...
Phthalocyanine-methylpheophorbide a covalently linked conjugate was first synthesized via transesterification of the α-keto methyl ester in methylpheophorbide a with 2-(2-hydroxymethylbenzyloxy)-9(10),16(17),23(24)-tri-tert-butylphthalocyanine under mild conditions. UV-Vis absorption spectrum of the dyad exhibits panchromatic behavior owing to comb...
Diamidophosphite andphosphite ligands with (S)-2-(anilinomethyl)pyrrolidine or (Sα-BINOL backbone and porphyrin cores were obtained. The use of these ligands provides up to 92% ee (enantiomeric excess) in Pd-catalyzed asymmetric alkylation of (E)-1,3-diphenylallyl acetate with dimethyl malonate, up to 82%> ee in its sulfonylation with sodium p-tolu...
Various isomers of azomethine derivatives of mesoporphyrin IX were first obtained in the form of palladium complexes by the interaction of the so-called “phosphorus complex”, produced in situ in the Vilsmeier-Haack reaction of allylamine and methylamine. The compounds were identified and characterized using the methods of NMR 1D and 2D NOESY, and e...
Three recently synthesized tetrapyrrole compounds: (E)-32-bromopyropheophorbide a methyl ester (1) and its derivatives with p-conjugated acrylate (2) and phenyl (3) substituents are structurally characterized using X-ray diffraction along with 1D and 2D NMR spectroscopy. All compounds are crystallized in chiral space groups. The planar molecules fo...
Effects of disodium salt 2,4-di(1-metoxyethyl)-deuteroporphyrine-IX (Dimegin) and the light from Soret band (»395-405 nm) at the viability of microbial cells and at their potential to form microbial biofilms have been compared with traditional antiseptics. Irradiation of microbial cells of S. aureus, E. coli, C. albicans and others with diode light...
Regioselective bromination of methyl pyropheophorbide a at the C32-position of the terminal double bond has been carried out as a one-pot two-step addition/elimination process. The elimination occurs with 100% stereoselectivity and bromovinyl 4 has E-configuration of the C3-double bond. The reactivity of unsaturated bromide 4 has been evaluated in...
The effective synthesis of Pd(II) monofunctional azomethine derivatives of coproporphyrin isomers I and II is reported. The proposed method is based on the interaction of a "phosphorus complex", generated in situ by Vilsmeier-Haack reaction, with various amines. The reaction with palladium complex of coproporphyrin II gave Schiff bases as a mixture...
The chemical synthesis of six lipophilic conjugates of chlorins was carried out, in which lipophilic fragment (either hexadecyl- or cholest-5-en-3β-yloxyethyl-) bound to 13(1)-, 15(2)-, 17(3)-positions of macrocycle by formation of related carboxamides. Structure of synthesized conjugates was studied by spectral methods and molecular modeling. Lipo...
We describe a novel technique for heme removal and replacement in the heme domain of P450BM-3 (BMP). The method was applied to obtain the aluminum-protoporphyrin IX (Al-PP) substituted derivative of BMP (Al-BMP). The overall yield of the purified Al-BMP was about 15% as related to the initial amount of the hemeprotein. Al-BMP possesses extensive fl...
The recombinant producer strain expressing Rhodospirillum rubrum L-asparaginase (RrA) has been obtained and a purification procedure of RrA has been developed. The purified enzyme, RrA, has the following biochemical and catalytic characteristics: Km for L-Asn of 0.22 mM, pH optimum at 9.2; temperature optimum at 54°C, pI = 5.1. RrA exhibited a sign...
Accumulation of photosensibilisators - derivatives of E6 chlorines ("Radachlorine", "Photoditazine", "Zelevsky's balsam") in the mucous membrane and selection of most effective sources of emission have been investigated in 30 patients with rhinosinusitis and 10 with tonsillitis. As a source of emission we used light emitting diode (LED) matrix devi...
Platinum(II) and palladium(II) complexes of coproporphyrin-I tetraisopropyl ester and coproporphyrin-II tetraethyl ester, as well as platinum(II) complexes of mesopyropheophorbide a methyl ester and mesochlorin e(6) trimethyl ester were synthesized. Five of them (platinum(II) mesochlorin e(6) trimethyl ester is amorphous) were prepared as single cr...
The novel synthesis of chlorin 15(2)-carboxamides from methyl pheophorbide, which passed without cleavage of exocycle E, is developed. The combination of this approach together with known method of opening exocycle E by amines allows easy prepartion of 13(1)- and 15(2)-carboxamides of chlorin e(6) and methyl pheophorbide a, comprising various subst...
A panel of phosphorescent oligoarginine conjugates of tetracarboxylic Pt(II)-coproporphyrin I dye (PtCP), monosubstituted with long peptides or tetra-substituted with short peptides and having different linkers and peripheral groups, is described. Their photophysical properties, cell loading efficiency, and mechanisms of transport into the cell wer...
Isatin (indole-dione-2,3) is an endogenous indole that exhibits a wide spectrum of biological and pharmacological activities. Physiologically relevant concentrations of isatin (ranged from 1 nM to 10 M) did not influence basal activity of soluble human platelet guanylate cyclase (sGC), but caused a bell-shaped inhibition of the NO-activated enzyme....
To study long-term prognosis in patients with non-ST elevation acute myocardial infarction (AMI) with reference to changes in myocardial tissue dopplerography (MTD) in the course of treatment.
MTD echocardiography was conducted in 88 non-ST elevation AMI (mean age 58.0-9.8 years) and 34 healthy volunteers (mean age 58.0 +/- 9.8 years). Measurements...
Isatin (indole-dione-2,3) is an endogenous indole that exhibits a wide spectrum of biological and pharmacological activities. Physiologically relevant concentrations of isatin (ranged from 1 nM to 10 M) did not influence basal activity of soluble human platelet guanylate cyclase (sGC), but caused a bell-shaped inhibition of the NO-activated enzyme....
A new sensor is described based on a phosphorescent metalloporphyrin dye incorporated in a polymeric membrane, which allows measurement of the two important analytes, oxygen and pH. In such a sensor, the bifunctional dye is quenched by O(2) altering its phosphorescence intensity and lifetime (0-21 kPa O(2)), whereas protonation of the dye causes a...
Research on cell-penetrating peptides for the intracellular delivery of porphyrin compounds has mainly focused on the use of trans-activator of transcription (TAT)-derived peptides and, to a lesser extent, on proline-rich peptides and phosphorescent metalloporphyrins. In this article, we describe a novel phosphorescent oxygen-sensitive probe for in...
New types of chlorin e6 derivatives containing organophosphorus units were synthesized under microwave irradiation.
Several new derivatives of the phosphorescent Pt(II)-coproporphyrin (PtCP) were evaluated with respect to the sensing of intracellular oxygen by phosphorescence quenching. Despite the more favorable molecular charge compared to PtCP, self-loading into mammalian cells was rather inefficient for all the dyes, while cell loading by facilitated transpo...
Synthesis of 13'[(cholest-5-en)-3beta-yloxyethoxycarbamoyl]-chlorin e6 starting from methylpheophorbide and 3beta(2-hydroxy)-ethoxycholest-5-ene is presented, as well as the preparation of related copper complex. Both conjugates obtained may be simply incorporated in phosphatidyl choline vesicles.
A new previously unknown double intramolecular cyclization has been discovered on thermolyzing nickel complexes of Schiff's bases of porphyrins containing propionic acid ester residues. This leads to the formation of cyclopentaneporphyrin lactams. Using coproporphyrin-I and -II derivatives as examples, the corresponding lactams were obtained, the s...
The chemical synthesis and characteristics of two natural chlorins modified with cholesterol moieties: 17''[(cholest- 5-en)-3β-yloxyethoxycarbamoyl]pyropheophorbide a and 13'[(cholest-5-en)-3b-yloxyethoxycarbamoyl]chlorin are presented, as well as the preparation of the related copper complexes. Both conjugates obtained, as well as their copper com...
Probing of molecular oxygen in mammalian cells is important for the analysis of mitochondrial function, metabolic responses, and energetic status of the cells. We describe a new panel of intracellular O(2)-sensitive probes based on phosphorescent porphyrin dyes conjugated to cell-penetrating peptides. The probes comprising the uncharged derivatives...
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...
In this work the synthesis, optical and luminescence spectroscopic characterization of the new ytterbium complexes with asymmetric porphyrins of hematoporphyrin group, modified by two β-diketone fragments are presented. All ligands and complexes are investigated by the methods of molecular mechanics, elemental analysis, UV-vis, IR, luminescence, ma...
A simple, minimally invasive methodology for the analysis of intracellular oxygen in populations of live mammalian cells is described. Loading of the cells with the phosphorescent O(2)-sensing probe, MitoXpress, is achieved by passive liposomal transfer or facilitated endocytosis, followed by monitoring in standard microwell plates on a time-resolv...
The results of studies on the catalysis of the chain transfer reactions in radical polymerisation and stereoselective olefin oxidation reactions in the presence of metalloporphyrins are surveyed. The problems of the synthesis of metalloporphyrins for catalytic studies are discussed.
The bibliography includes 44 references.
The development and application of a methodology for measurement of oxygen within single mammalian cells are presented, which employ novel macromolecular near infrared (NIR) oxygen probes based on new metalloporphyrin dyes. The probes, which display optimal spectral characteristics and sensitivity to oxygen, excellent photostability, and low cytoto...
Quenching of phosphorescent platinum(II) and palladium(II) coproporphyrin (MeCP) labelled oligonucleotides was investigated. Strong hybridization-specific quenching was observed in duplex DNA structures with a variety of quenchers and with two identical porphyrin labels when in close proximity. Classical resonance energy transfer mechanism was rule...
Base-assisted ring opening in 1,2-oxazinochlorin derivatives led selectively to the corresponding meso-cyanohydroxychlorin derivatives. The latter could then undergo acid-mediated carbocation formation followed by nucleophilic treatment to give different products, depending on the nature of the nucleophile reagent. Treatment of (E)- and/or (Z)-2-et...
The influence of protoporphyrin IX derivatives--2,4-di(1-methoxyethyl)-deuteroporphyrin IX disodium salt (dimegin) and hematoporphyrin IX (HP)--on the activation of human platelet soluble guanylate cyclase by sodium nitroprusside was investigated. Dimegin and HP, like 1-benzyl-3-(hydroxymethyl-2-furyl)indazole (YC-1), produce synergistic effects on...
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 exampl...
Photodynamic therapy (PDT) is frequently accompanied by induction of systemic immunosuppression. Photochemical mechanisms underlying this effect are not completely understood. Here, we demonstrate the immunosuppressive activity of photooxidation products of protoporphyrin IX dimethyl ester (PPIX) in a murine model of contact hypersensitivity (CHS)...
Photodynamic therapy (PDT) is frequently accompanied by induction of systemic immunosuppression. Photochemical mechanisms underlying this effect are not completely understood. Here, we demonstrate the immunosuppressive activity of photooxidation products of protoporphyrin IX dimethyl ester (PPIX) in a murine model of contact hypersensitivity (CHS)...
Phosphorescent platinum(II) coproporphyrin label (PtCP) is evaluated for the detection of cellular proteases by time-resolved fluorescence in homogeneous format. An octameric peptide containing the recognition motif for the caspase-3 enzyme was dual labeled with a new maleimide derivative of PtCP and with the dark quencher dabcyl. Following photoph...
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.
Phosphorescent platinum(II)-coproporphyrin label (PtCP) was evaluated in post-PCR detection of nucleic acids by time-resolved fluorescence (TR-F) using three common formats. PtCP-labelled oligonucleotide primers and PtCP-dUTP were incorporated in a PCR to produce labelled amplified target −173 or 305 bp DNA. Alternatively, aminoallyl-dUTP was incor...
[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...
A preparative procedure is proposed for the synthesis of α-aminophosphonates of natural porphyrins by the microwave-assisted Kabachnik—Fields reaction.
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 mod...
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 diffrac...
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 mod...
Chlorin e(6) and its derivatives are promising sensitizers for photodynamic therapy (PDT). In order to compare the photodynamic effects of 8 novel derivatives of chlorin e(6) and to explore some mechanisms of their effects at the cellular level, we studied PDT-induced changes in bioelectric activity of crayfish mechanoreceptor neuron that was used...
Porphyrins possessing meso-dimethylaminomethyl or alkoxyethyl groups and also peripheral (1-alkoxy)-ethyl or alkoxymethyl groups which are capable to generate carbocations of benzyl type are known to readily react with b-diketones (acetylacetone, benzo-ylacetone etc.) to furnish derivatives containing b-diketone moieties [133]. Aiming at designing...
The first synthesis of a-amino phosphonates comprising porphyrin core was accomplished. Three methods of obtaining alpha-amino phosphonates 5-8 were compared. Conventional heating of formylporphyrins 1-4 with t-BuNH2 and (EtO)(2)P(O)H in various solvents was ultimately unsuccessful for preparing 5-8 whereas the use of microwave irradiation made it...
In this paper we describe the preparation of a series of new phosphorescent labelling reagents, based on monosubstituted palladium(II) coproporphyrin-I and the isothiocyanato reactive group. The labelling reagents differ with respect to the chemical composition of the linker unit that combines the reactive group and the porphyrin chromophore. Altog...
A comparative analysis of the ability of 4-(1-methyl-3-hydroxybutyl)-deuteroporphyrin-IX (I) and 2,4-di-(1-methyl-3-hydroxybutyl)-deuteroporphyrin-IX (II) to photosensitize hemolysis of human erythrocytes was performed. The photohemolytic efficiency of dye I was shown to be about 60 times higher than that of dye II. It was found that a part of each...
Synthesis of monofunctional derivatives of platinum(II) and palladium(II) coproporphyrin-II with the isothiocyanato reactive group is presented. The compounds exhibit strong phosphorescence at room temperature in deoxygenated aqueous solutions and they enable facile covalent labeling of proteins and other biomolecules under slightly alkaline condit...
A method is described for preparation of monosubstituted derivatives of platinum and palladium coproporphyrin-I. The method is based on chemical differentiation of one of the four alkoxycarbonyl groups of the starting coproporphyrin-I tetraalkyl ester by selective acid hydrolysis. The hydrolysis results after chromatographic purification to pure mo...
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 monom...
Syntheses of octaethylporphine-diketone (OEPDK) and its platinum(II) and palladium(II) complexes (PtOEPDK, PdOEPDK) were optimized, and the dyes were isolated in a pure form in preparative quantities. They were characterized by the NMR, UV-VIS absorption and emission spectroscopy. Electronic spectra of these dyes (absorption and luminescence) were...
The photodynamic effects of 6 new deuteroporphyrin IX derivatives with different amphiphilicity and lipophilicity, as well as effects of known hematoporphyrin derivatives Photofrin II and Photoheme on isolated crayfish mechanoreceptor neurons were studied. After 30 min photosensitization, neurons were irradiated with He-Ne laser (632.8 nm, 0.3 W/cm...