Sergey A. Syrbu

• Ivanovo State University of Chemistry and Technology

Asymmetrically substituted porphyrin containing a guanine residue at the periphery of the porphyrin cycle was synthesized in an acetic acid medium using the C—H activation method. The quaternization of the product was carried out to prepare water-soluble porphyrin. The structure of the porphyrin was confirmed by electronic absorption spectroscopy,...

Relevance. The development of antimicrobial drugs and alternative methods, technologies and means of prevention, diagnosis and treatment of human infectious diseases caused by antibiotic-resistant microorganisms is one of the priorities of ensuring the biological safety of the country. Aims. To evaluate the bactericidal activity of tetrapyrrole mac...

Palladium-catalyzed heterylation of monobromophenyl-substituted zinc(II) porphyrin with small heterocycles (benzothiazole, benzoxazole, and N-methylbenzimidazole) was carried out. As a result, unsymmetrical heterylphenyl-substituted zinc(II) porphyrins soluble in organic solvents were obtained. The interaction of heteryl-substituted zinc(II) porphy...

In this work the bimetallic composites formation via electrochemical co-deposition of Fe(III)Cl-5,10,15,20-tetrakis(4-aminophenyl)porphyrin and Mn(III)Cl-5,10,15,20-tetrakis(4- aminophenyl)porphyrin has been studied. The composites were obtained by superoxide-assisted electrochemical deposition from mixed DMSO solutions with equal concentrations of...

The effect of amino acid fragments in tetraphenylporphin derivatives on the pH range of porphyrin dominance as a dication was studied. For this purpose, the protonation processes of unsymmetrically substituted derivatives of 5,10,15,20-tetraphenylporphyrin: 5-(4′-aminophenyl)-10,15,20-triphenylporphine, 5-(4′-tyrosinylamidophenyl)-10,15,20-tripheny...

The paper presents the results of spectrophotometric study of the basic properties of glycosylated substituted derivatives of 5,10,15,20-tetraphenylporphyrin, namely 5-(4′- O -galactosylphenyl)-10,15,20-tris( N -methylpyridin-3-yl)porphine, 5,15-bis(4′- O -galactosylphenyl)-10,20-bis( N -methylpyridin-3-yl)porphine, 5,10,15,20-tetra( N -methylpyrid...

Water-soluble asymmetrically substituted porphyrins containing the heterocyclic fragments (benzoxazole, N-methylbenzimidazole, and benzothiazole residues) at the periphery of the porphyrin ring were synthesized using the C-H-activation method. The compounds were identified by electron absorption spectroscopy, 1H NMR spectroscopy, and mass spectrome...

The multistage purposeful synthesis of 5,15-bis(4′-l-N-tyrosinylamidophenyl)-10,20-bis(N-methylpyridin-3′-yl)porphine diiodide was carried out, and the optimum synthesis conditions were determined. 5,15-Bis(4′-nitrophenyl)-10,20-bis(pyridin-3′-yl)porphine served as the starting porphyrin. The structure, individual character, and purity of the targe...

The results of experimental studies of the interaction of the S-protein with a monohetaryl-substituted porphyrin containing a benzimidazole residue are presented. It has been revealed that the S-protein forms high-affinity complexes with the specified porphyrin. The porphyrin binding by the SARS-CoV-2 S-protein has proceeded stepwise; at the first...

The directed synthesis of asymmetrically substituted porphyrins—tetraphenylporphyrine derivatives containing amino acid residues as a functional group, which can be used as “anchor” groups, for incorporation into the structure of a protein molecule, was carried out. The obtained compounds were characterized by a number of spectral methods confirmin...

Novel porphyrin compounds containing benzothiazole, benzoxazole, and benzimidazole moieties have been prepared and their structures have been confirmed. Molecular docking of non-symmetric hetaryl-substituted porphyrins and chlorin e6 with SARS-CoV-2 helicase has been carried out. The affinity of hetaryl-substituted porphyrins to this protein has be...

Asymmetrically substituted 5,10,15,20-tetraphenylporphyrin derivatives such as 5-(4-aminophenyl)10,15,20-triphenylporphine, 5-[4-(tyrosinylamino)phenyl]-10,15,20-triphenylporphine and 5-{4-[(N-tert-butoxycarbonyltyrosinyl)amino]phenyl}-10,15,20-triphenylporphine were synthesized. Their spectral and acid-base properties were studied. The acid-base i...

The synthesis of 5,10,15,20-tetrakis [4 '- (benzoxazol-2-yl) phenyl] -21,23-dithiaporphyrin was carried out by the reaction of metal complex catalysis. In this work, quantum chemical calculations were performed in the DFT approximation (hybrid functional B3LYP) with a set of 6-21G basis functions. The resulting compound was identified by electron a...

The work reports first studied kinetics of complexation between copper and heterosubstituted porphyrins, namely 5,10,15,20-tetraphenyl-21-thiaporphyrin and 5,10,15,20-tetraphenyl-21-oxaporphyrin, as well as comparison with the structural analogue being tetraphenylporphyrin. Spectrophotometric titration allowed for determination of basicity constant...

The synthesis of the porphyrin-calix[4]arene conjugates was carried out using the Pd(0)-catalyzed amination of Zn(II) meso-(3-bromophenyl)porphyrinate with bis(3-aminopropoxy)substituted calix[4]arenes (in cone and 1,3-alternate conformations). One of the conjugates was demetalated to give free porphyrin base derivative. The investigation of the fl...

Acidity and metal ion coordination are described for three porphyrin derivatives, different in their macrocycle conformation and electronic substitution effects due to bromine substitution in pyrrole rings and trifluorometyl or phenyl groups in meso-positions. Combination of these facts allows modulating both steric and electronic effects on the ma...

The basic and spectral properties of a series of meso-substituted porphyrins with alkyl and aryl substituents were investigated. Quantum-chemical calculations of meso-substituted porphyrins were performed in the DFT approximation (hybrid functional B3LYP). It is shown that the introduction of four bulk substituents (tert-butyl groups) causes signif...

Copper and cobalt complexes of nitro derivatives of planar and nonplanar derivatives of 5,15-diphenyl- 3,7,13,17-tetramethyl-2,8,12,18-tetraethylporphyrin are synthesized and their stability in proton-donor media is investigated. It is established that the kinetic parameters of the dissociation reactions of copper and cobalt complexes of the studie...

The results of investigation of the interrelation between the geometric structure and coordination, acid, and spectral properties of a series of porphyrins with different systems of meso and β substituents are presented. The geometry of polysubstituted porphyrins was optimized at the DFT B3LYP/6-311G level of theory using Gaussian 09. It was shown...

The behavior of bovine serum albumin as a function of the pH of the medium and the presence in the test systems of symmetrical and asymmetrical hydrophobic porphyrins was investigated. It was established that 4-[(tert-butoxycarbonylamino)acetamido]phenyl group favors stronger protein binding to porphyrin, and this effect enhances in an alkaline med...

Spectral and basic properties of heterosubstituted porphyrins of anionic type have studied by means of spectrophotometric titration in comparison with their structural analog — tetraphenylporphine tetrasulfonic acid. The parameters of electronic absorption spectra and concentration ranges of existence of the mono- and diprotonated forms of the stud...

The state of tetrakis(1,2,5-thiadizole)porphyrazine in the DMSO medium was studied. The protontransfer complex that formed was found to be quite stable. This complex was shown to decompose in some strong base solutions after some delay. The influence of either the nature of nitrogen-containing base and NH acidity of the porphyrazine macrocycle on t...

Presented work shows results of synthesis and spectrophotometric researches on properties of meso-dinitrosubstituted derivatives of 5,15-diphenyl-β-octaalkylporphyrin nitroderivatives in comparison with 2,8,12,18,3,7,13,17-octaethylporphyrin and 2,3,7,8,12,13,17,18-octaethyl-5,15-dinitroporphyrin. The method of spectrophotometric titration with per...

Using Pd(0)-catalyzed amination reaction of zinc 5,15-bis(4-bromophenyl)porphyrinate with diazatrioxamacrocy-cle – derivative of 3,3’-disubstituted biphenyl – a series of polymacrocyclic compounds was obtained. The investigation of their fluorescence in the presence of 18 metal cations revealed that two of them can act as molecular probes for Cu(II...

A series unsymmetrical amino acid substituted porphyrins and their Zn-complexes were synthesized and full characterized by¹H NMR and UV-Vis spectroscopy and MALDI-TOF spectrometry. Starting with meso-tetraphenylpor-phyrin (H2 TPP) 1, porphyrin 2 with one nitro group was synthesized via regioselective nitration reaction. Reduction of the 5-(4’-nitro...

Macrocycle acidity and Zn2+ ion coordination are reported for three porphyrin derivatives which differ in both steric and electronic substitution effects on the macrocycle π-conjugated system. The role of the electronic substitution effects in the macrocycle deprotonation and metal ion chelating was found to be dominating whereas the macrocycle non...

Copolymers of methyl methacrylate with various porphyrin monomers were prepared by radical copolymerization in solution. The yields, molecular weight characteristics of the copolymers and the molar content of porphyrin in the copolymers were determined. Copper and zinc complexes of the synthesized porphyrin polymers were obtained.

Methods were developed for the synthesis of nitro derivatives of 5,15-diphenyl-3,7,13,17-tetramethyl-2,8,12,18-tetraethylporphyrin containing nitro groups at the meso positions of the porphyrin core and at the para positions of the phenyl substituents. The formation kinetics of the zinc, copper, and cobalt complexes of the resultant porphyrins in p...

The novel porphyrin–β-cyclodextrin (Por-β-CD) conjugate 3 was synthesized and investigated. Addition of four β-CD units to the porphyrin macrocycle leads to formation of non-aggregated water-soluble covalently linked conjugate, which does not demonstrate any self-assembled species even at high concentrations. New conjugate 3 forms inclusion complex...

Electrophilic substitution reactions in the meso-phenylporphyrins are described. The relative reactivity of the various positions of the porphyrin cycle to attack by electrophiles was discussed.

The methods for the synthesis of water-soluble copolymers having porphyrin units in the side chain are described. Molecular-mass characteristics of the copolymers and mole content of porphyrin in copolymers are determined.

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The conditions for the porphyrin synthesis by condensation of α-unsubstituted dipyrromethanes and ortho-formic ester in the presence of organic acids are investigated. The optimal reaction conditions are found, and a series of β- and meso-substituted porphyrins is synthesized. The methods of the α-unsubstituted dipyrromethanes synthesis from pyrrol...

The Pd0- and CuI-catalyzed amination of meso-(halogenophenyl)substituted porphyrins and their Zn complexes withpropane-1,3-diamine and trioxadiamine was carried out to produce mono- and diaminated derivatives. Conditionsfor the synthesis of bis- and trismacrocyclic porphyrin-azacrown conjugates with trimethylenediamine linkers viaPd0-catalyzed amin...

Pyrrolic precursors and benzaldehydes were used to afford meso-carboxyphenylporphyrins bearing one or four carboxyl groups. The reaction conditions for the acylation of alcohols with the obtained carboxyphenylporphyrins in the presence of carbodiimides were studied. Optimal reaction conditions were found and a series of phenylporphyrin esters of va...

A higher reactivity of 4-nitrophthalonitrile as compared to phthalonitrile and 4-amino-phthalonitrile in the reaction with sodium methoxide in methanol was demonstrated by theoretical (semiempirical, ab initio calculations) and experimental methods. The regioisomeric composition of substituted methoxyiminoisoindolenines was studied by analysis of p...

Trimeric porphyrin H6TP as well as its binuclear Cu2H2TP and trinuclear Cu3TP copper complexes have been prepared. Kinetic features of H6TP and Cu2H2TP complexes formation with copper(II) acetate in acetic acid as well as dissociation kinetics of Cu2H2TP and Cu3TP in acetic acid medium in the presence of sulfuric acid have been studied.

The spectrophotometric study of the acid-base equilibria and complexation with metal ions has been carried out for 5,10,15,20-tetrakis(trifluoromethyl)porphine and 5,10,15,20-tetrakis(iso-buthyl)porphine in acetonitrile solutions. Protonation and deprotonation of these porphyrins was found to be stepwise with sequential formation of mono- and doubl...

The behavior of tetra(1,2,5-thiadiazolo)porphyrazine in dimethyl sulfoxide has been studied, and fairly high stability of the resulting proton-transfer complex has been revealed. The complex is kinetically unstable in strongly basic media. The effects of the nitrogen-containing base and NH acidity of the porphyrazine macrocycle on the rate and acti...

In the present work interaction of the cationic and anionic porphyrins with bovine serum albumin in aqueous solutions with different pH has been studied. For strongly associated porphyrin study was conducted in a mixed solvent containing 0.19 M DMF, which shifted the associative equilibrium towards monomerization. It was found that the complexation...

The methods for the synthesis of porphyrins containing active vinyl groups on a periphery of the tetrapyrrole macroheterocycle are described. The possibility of their usage as comonomers in a copolymerization reaction with methyl methacrylate is given.

Optimization principles are proposed for composing additives to mesogenic compounds of LCA used for metal working structural steels. The considered additives were found to positively affect the drilling process. The problems of their use in practice are discussed.

Conditions of acylation of aminotetraphenylporphyrins in the presence of carbodiimides were studied. Optimal reaction conditions were determined and a number of tetraphenylporphyrin amides of various structure were synthesized.

In present work interactions of bovine serum albumin with 5,10,15,20-tetrakis(4-N-methylpyridil) tetra iodide porphyrin have been studied by electron absorption and fluorescence spectroscopy. The studies were carried out in aqueous media at different pH and in water-dimethylformamide mixtures containing up to 0.19M of the organic solvent. It has be...

Spectrophotometric titration method was used to study the acidic properties of 2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetraphenylporphyrin in the presence of a deprotonated agent, 1,8-diazabicyclo[5.4.0] undec-7-ene, in acetonitrile. The spectral characteristics of the ionized forms and combined ionization constant for the first and second stages...

The review is focused on the current state of the synthesis of glycosylated phthalocyanines and their precursors, mono-, di-, and tetraglycosyl phthalonitriles. Features of the synthesis of phthalogen conjugates with carbohydrates and the formation of related metal phthalocyanine complexes are discussed. The formation of aggregates of phthalocyanin...

The mono-meso-allyloxy- and acrylamidophenylporphyrins were synthesized from the corresponding hydroxy- and aminophenylporphyrins. All the compounds were characterized by IR, UV-Vis, 1H NMR and mass spectra.

Acylation of hydroxyphenylporphyrins by carboxylic acids in the presence of carbodiimides was studied and the optimal reaction conditions were determined. Some new esters of various hydroxyphenylporphyrins were synthesized.

New 5-(4-bromophenyl)-3,7,12,13,17,18-hexamethyl-2,8-dipentyl- and 5,15-bis(4-bromophenyl)-2,8,12,18-tetramethyl-2,8,12,18-tetrapentylporphyrins (H2P-1 and H2P-2) and their zinc metal complexes (ZnP-1 and ZnP-2, respectively) were synthesized in high yields by condensation of beta-tetraalkyl-substituted dipyrromethanes with 2-formyl-3,4-dialkylpyrr...

The first part of this review summarizes methods for the syntheses of mono-, di-, and tetra-substituted glycosylated phthalonitriles, which are the main starting materials for the preparation of the corresponding glycosylated metal phthalocyanines. In the second part the preparation of symmetrically and unsymmetrically tetra- and octa-glycosylated...

Copper porphyrinates are generally known to display a less diverse reactivity compared to their iron counterparts. Here, we examine a water-soluble copper porphyrinate for its ability to engage in reactions involving axial ligation to the copper or possible redox cycling. Although UV–vis spectra indicate an expected lack of reactivity, electron par...

The 5,15-diphenyl-3,7,13,17-tetramethyl-2,8,12,18-tetraethylporphyrin nitro derivatives containing the nitro groups in the meso-positions of the porphyn ring and/or para-positions of phenyl rings were synthesized. Porphyrins were characterized by electron absorption, 1H NMR, and IR spectra. The purity and individuality of the synthesized compounds...

Nitration system NaNO2-TFA for regioselective nitration of the meso-positions of 5-phenyl-2,3,7,8,12,18-hexamethyl- 13,17-diethylporphine (1) was examined. The degree of nitration is easily controlled by the amount of NaNO2 used and by the reaction time. All compounds are characterized by MS, UV-Vis-, and 1H NMR-spectroscopy as well as massspectrom...

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

The influence of the deformation of the tetrapyrrole aromatic macrocycle and the electronic effects of substituents on the kinetic parameters in the formation and dissociation reactions of cobalt complexes of porphyrins are discussed on the basis of a study of the kinetics of the formation and dissociation of cobalt complexes with meso-phenyl octa(...

Controlled radical polymerization of methyl methacrylate and styrene initiated by azobisisobutironitrile or benzoyl peroxide in the presence of a chlorine-containing complex of FeIII with 5,15-bis(4’-tert-butylphenyl)-2,8,12,18-tetra(n-butyl)-3,7,13,17-tetramethylporphyrin was investigated.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Study on the nitration of phenyl-substituted porphyrins showed that protonation of the porphyrin macroring does not affect the relative reactivity of the meso- and β-positions and phenyl groups.

The influence of some cholesterical liquid-crystal additives on the properties of standard lubricating oils under friction is investigated. The solubility of the additives in base oils is studied. Their tribological effectiveness is demonstrated. The mechanism of formation of a protective lubricating film is discussed.

The effect of accumulation of the tert-butyl groups in the phenyl rings of tetraphenylporphine on the complex formation rate of tetra(3,5-di-tert-butylphenyl)porphine (I) with copper(II), zinc(II), and cadmium(II) acetates in acetic acid and in a mixed ethanol-benzene solvent was studied by the chemical kinetics method with spectrophotometric monit...

The free-radical polymerization of methyl methacrylate in the presence of chlorine-containing complexes of Fe(III) with 5,10,15,20-tetrakis(3′,5′-di-tert-butylphenyl)porphyrin and 5,10,15,20-tetrakis(3′-butoxyphenyl)porphyrin, as well as in the presence of the acetate complex of Co(III) 5,10,15,20-tetrakis(3′,5′-di-tert-butylphenyl)porphyrin, has b...

Using 1 H NMR spectroscopy and semiempirical calculations (AM1) the solvation state of tetra(3,5-di-tert-butylphenyl) porphin (I) was studied in the binary mixtures, containing electrondonating solvating solvent and CCl 4 ,. The stability constants and thermodynamic characteristics of octasubstituted tetraphenylporphin H-complexes with electrondona...

Peculiarities of the unique structure of porphyrins, possibilities of their peripheral functionalization, ability of metal complexes to extracoordination allow to use them for inclusion in porphyrin-polymer systems in order to endow them with specific properties, determined by tetrapyrrole macrocyclic compounds and their complexes. Porphyrins and t...

The condensation of biladiene-a,c dihydrobromides with benzaldehyde gives 5-phenylporphyrins. The reaction conditions have been studied and optimized; it is shown that synthesis of biladiene-a,c dihydrobromides can be combined with their following condensation with benzaldehyde.

5,15-Bis(4-bromophenyl)-2,8,12,18-tetraethyl-3,7,13,17-tetramethylporphyrin and 5-(4-bromophenyl)-13,17-dibutyl-2,3,7,8,12,18-hexamethylporphyrin were synthesized, and their palladium-catalyzed amination with a number of cyclic secondary amines, including hydroxypiperidines, was studied [Pd(OAc) 2, ligand, THF or dioxane, t-BuONa, 80-100°C]. The re...

The novel metalloporphyrins (M=HH, Fe, Mn, Co, Cu, Zn) bearing 2,6-di-tert-butylphenol pendants as antioxidant substituents, and a long chain hydrocarbon palmitoyl group have been synthesized. The oxidation of compounds by PbO2 leads to the formation of the corresponding 2,6-di-tert-butylphenoxyl radicals studied by EPR. The activity of porphyrins...

5,15-Bis(4-bromophenyl)-2,8,12,18-tetraethyl-3,7,13,17-tetramethylporphyrin and 5-(4-bromophenyl)-13,17-dibutyl-2,3,7,8,12,18-hexamethylporphyrin were synthesized, and their palladium-catalyzed amination with a number of cyclic secondary amines, including hydroxypiperidines, was studied [Pd(OAc)2, ligand, THF or dioxane, t-BuONa, 80–100°C]. The rea...

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

New amino derivatives of porphyrins containing cyclic amino and hydroxypiperidine groups bound through the meso phenyl rings are prepared by the Pd-catalyzed amination of meso-bromophenyl(polyalkyl)porphyrins. The reaction allows for the introduction of piperidine, morpholine, 3- and 4-hydroxypiperidine groups with 50-80% product yields, but in the...

Data on the synthesis of symmetrical and unsymmetrical meso-phenyl-substituted porphyrins, which are building blocks for porphyrin-based polymers of different structure, are analyzed. Methods for the porphyrin ring construction and modification by active functional groups for further immobilization onto a polymer or preparation of porphyrin monomer...

Coordination of imidazole with chromium(II) (acetate)tetraphenylpophyrinate involves consecutive substitution of alcohol molecules in the sixth coordination position of the complex. Axial coordination of imidazole produces no charged species.

For Abstract see ChemInform Abstract in Full Text.

For Abstract see ChemInform Abstract in Full Text.

A method was developed for the synthesis of a series of meso-phenyl-substituted octaalkylporphyrins with various numbers of phenyl groups at various positions. Some of their properties were studied.

New data on the spectral properties and solution enthalpies of unsymmetrically substituted 2-(alkyl-2-pyrrolylmethylidene)methylpyrrolium bromides (or α,α-dipyrrylmethene hydrobromides), their α,β-, β,β-isomers, as well as their oxa and thia analogs, that is, 2-(2-furylmethylidene)- and 2-(2-thienylmethylidene)-3,4,5-trimethyl-1H-pyrrolium bromides...

Experimental data on the dynamic viscosity of 3β-n-alkanoyloxycholestene-5 homologues at various temperatures were used to calculate the activation energies of viscous flow of the cholesteric and isotropic liquid phases. An approach based on statistical thermodynamics was applied to calculate various physicochemical characteristics of macroscopic e...

Extra coordination of zinc complexes of bromo-substituted tetraphenylporphyrins was studied by spectrophotometry. It was found that the stability of complexes thus formed markedly increases upon -bromo-substitution in tetraphenylporphine. The effects of electronic and structural factors on the extra coordination were discussed. The stability consta...

The temperature dependences of the dielectric permittivity of 4-(2,3-epoxypropoxy)-4'-alkoxyazoxybenzenes (n = 1-10) and 4-propoxy-4'-alkoxyazoxybenzenes (n = 1-10) with mesomorphic properties were measured by dielectrometry. The introductrion of the terminal epoxy group increases the dielectric permittivity and its anisotropy. The dipole moments o...

The viscosity of seven homologues of 3β-n-alcyloxycarbonyloxycholestenes-5 (C2-C6, C8, C9) was experimentally determined as a function of the temperature. The energies of activation of viscous flows in cholesteric and isotropic-liquid phases were calculated. A thermodynamic-statistical technique developed previously for nematics was used to study c...

The electronic and steric effects of peripheral substituents on the yield of 5,15-diphenyloctaalkylporphines were studied. It was found that the electronic nature of substituents in the starting benzaldehydes exerts almost no yield effect. At the same time, there is some optimal size of substituents, which provides the highest possible yield of por...