Alexander V Shtemenko

Ukrainian State University of Chemical Technology · Department of Inorganic Chemistry

In the view of developing a synthetic route for the controlled insertion of distinct organometallic moieties into peptide nucleic acid (PNA) oligomers, a proof-of-principle study of the chemoselective insertion of three different organometallics into a building block containing both a PNA backbone and an alkyne side-chain is presented in this study...

Liposomal formulations of dinuclear cluster rhenium (Re) compounds were used in biochemical trials. Interaction of liposomal forms of some Re compounds with red blood cells in experiments in vitro showed strong cell-stabilizing properties. In the models of tumor growth and hemolytic anemia in vivo, liposomal forms had better therapeutic effects in...

Previous investigations showed antitumor properties of dirhenium carboxylate introduced to tumor-bearing animals at high doses. The development of liposomal forms of rhenium substances and the activity of dichlorotetra-mu-isobutyratodirhenium (III) (Re1) in stabilizing red blood cells (RBC) shown in experiments in vitro and in vivo enabled the use...

Ionic lattices of two new Lindqvist polyoxometalates (HCaf)2[Mo6O19]⋅2EtOH (1) and (HThe)2[Mo6O19]⋅H2O (2) [Caf = caffeine, The = theophylline] reveal extensive anion⋅⋅⋅π interactions, which result in the generation of dense stacks of the electron deficient aromatic cations to the faces of metal-oxide polyhedra with interplanar distances of 2.989(5...

The synthesis of four dirhenium(III) cis-dicarboxylates with the α-amino acids residues Asp (I), Glu (II), Phe (III) and Tyr (IV) is presented. The G–quadruplex stabilization potential was evaluated by fluorescence resonance energy transfer – melting analysis. All derivatives show specific binding to c-kit1 quadruplex, while II and IV have also str...

We report about the interactions of dirhenium(III) compound cis-[Re2(Trp)2Cl4(CH3CN)2]Cl2 (I) with bovine serum protein (BSA) and guanine (G4) quadruplexes DNA by UV-Vis titration. Addition of I to BSA led to the interaction between these compounds with binding constant 5.6103 M–1 and hyperchromism (20.9%) of the main protein absorption band (280...

The purpose of the investigation was to elaborate the methods of extraction of surface lipids from Kalanchoe Degremona plants and preparation of solid lipid nanoparticles containing a dirhenium(III) cluster compound. The procedure of growing plants and increasing the quantity of surface lipids by means of adaptation biochemistry to toxicants was us...

The work continues the study on the peculiarities of the interaction of 1,3,7-trimethylxanthine (caffeine) compounds with polyoxometalates of molybdenum and tungsten with the artificial radical of 1,3,5- triphenylverdazyl (TFV). Using the example of a model reaction with the TFV radical, these compounds showed a special antiradical action. Based on...

The aim of the study. The aim of the work was to investigate in vivo anticancer activity of cis- and trans-diadamanthylcarboxylates of dirhenium(III) alone and together with cisplatin in form of nanobins. Materials and methods. Model of tumor growth, Guerin’s carcinoma; intraperitoneal administration of cisplatin, dirhenium(III) compounds in lipos...

The previously developed methods for the synthesis of cis-tetrachlorodi--carboxylates of dirhenium(III) were modified, due to which the derivatives of Re26+ with proteinogenic amino acids (AA) isoleucine, serine and proline were synthesized for the first time. The composition and structure of these substances with the general formula cis-[Re2(АA)2...

Anion...π interactions are newly recognized weak supramolecular forces which are relevant to many types of electron-deficient aromatic substrates. Being less competitive with respect to conventional hydrogen bonding, anion...π interactions are only rarely considered as a crystal-structure-defining factor. Their significance dramatically increases f...

Hydrolysis of a dirhenium(III) complex compound with β-alanine ligands was investigated by UV-vis, IR- and NMR-spectroscopy methods. Electronic absorption spectra (EAS) of cis[Re2(β-Ala)2(H2O)2Cl4]Cl2 in physiological solution over time showed a gradual decrease in the absorbance of a characteristic absorption maximum at 15630 cm-1 during 3 days. C...

Present work reports the synthesis of zirconium phosphate nanoparticles containing dirhenium(III) substance bis-dimethylsulfoxide-cis-tetrachlorodi-μ-pivalatodirhenium(III) with formula cis-Re2(C(CH3)3COO)2Cl4∙2DMSO (I) and q-zirconium phosphate with formula q-Zr(HPO4)2∙6H2O (ZrP). The intercalation process was monitored by EAS. Due to the spectral...

The actual problem of creating a nanoscale delivery form of a combined system of rhenium(III) complex / cisplatin system with enhancing each other’s actions, which has pronounced antitumor properties and low toxicity, is revealed in the work. The need to create combination drugs for the treatment of cancer caused by the toxic effects of many substa...

Earlier we have shown that cluster rhenium compounds not only inhibited tumor growth in vivo but also supported the antioxidant state of experimental animals. Further investigation of new dirhenium(III) and cluster rhenium compounds in human leukemic cells is of great importance. The aim of the recent work was to investigate the cytotoxic activity...

Contemporary investigations of mechanisms of resistance to platinides showed the key role of copper metabolism in cancer patients and proposed possible methods to attenuate the resistance by modulation of copper transporting mechanisms. In this vein, investigation of ceruloplasmin (Cp) levels – the main copper-containing protein in blood, in experi...

Using the method of differential thermal analysis and the method of isothermal effects, we investigated the thermal transformations of the inter-calation products of representatives of dirhenium(III) complexes of all structural types into the interlayer space of zirconium phosphate. Each of the samples was heated in the temperature range from 40 to...

Study of hydrolysis of cis-tetrachlorodi-m-carboxylates of dirhenium (III) was carried out due to the electronic adsorption and IR spectroscopy and pHmeter. As a result, itwas shown that the hydrolysis is a multistage process which can be attributed to the reactions of the pseudo-first order. It is also shown that the electronic absorption spectros...

Study of hydrolysis of cis-tetrachlorodi-m-carboxylates of dirhenium (III) was carried out due to the electronic adsorption and IR spectroscopy and pHmeter. As a result, itwas shown that the hydrolysis is a multistage process which can be attributed to the reactions of the pseudo-first order. It is also shown that the electronic absorption spectros...

The use of nanotechnology in modern medicine is a contemporary area of research. Both rhenium(III) cluster compounds and rhenium(I) tricarbonyls have a whole spectrum of biological activity. Red blood cells are a convenient model for studying of the biocompatibility and toxicity of nanocomposites. Thus, the purpose of the work was synthesis of fluo...

Two methods for the synthesis of dirhenium derivatives were developed. Depending on the initial products, complex compounds of two structural types, octachlorodirhenate(III) and cis-tetrachlorodicarboxylate of dirhenium(III) with threonine, were synthesized for the first time. The preparation of (ThrÍ) 2 Re 2 Cl 8 ( ²⁾ was performed in a mixture of...

Complex compounds of dirhenium(III) with bridge carboxylates and halide ligands show various types of bioactivity, and the entry into the internal coordination sphere of the central “atom”- complexing the ligands that have their own physiological activity may extend the range of useful properties of dirhenium(III) complex compounds. From this persp...

Ionic polyoxometales (Hcaf)3[PM12O40]·6H2O [M = Mo, W; caf = caffeine] exhibit unusual supramolecular structure dominated by multiple anion-π interactions, which occur at both axial sides of the caffeinium cations. These cations, when stacked to every of six square faces of POM cuboctahedra, afford supramolecular boxes and the resulting non-covalen...

Reactions of individual trans-tetrachloro-di-μ-propionato dirhenium(III) thermal decomposition in dynamic inert atmosphere were investigated. Using a radical reaction of transportation in gaseous phase, Cu-Re and Pb-Re composites were obtained on a ceramic surface. Free radicals C2H5• were detected by reaction with metal Cu and Pb mirrors. Cu-Re an...

Zirconium phosphate nanoparticles loaded with trichlorotri-1-carboxylates of dirhenium(III) of the general formula Re2(RCOO)3Cl3 (where R=C2H5, C3H7, i-C3H7) were synthesized. The intercalation process was carried out in an acetonitrile medium. The obtained nanoparticles with the loading of dirhenium(III) complex in the substance/ZrP ratio 1:5 and...

One of the important areas of modern science is the selection of the right forms of drug delivery. Layered inorganic nanoparticles, such as zirconium phosphate, have proven themselves well in this area. The study of the properties of these systems and methods of their preparation makes it possible to determine a rational technology of their manufac...

Two charge-transfer salts of ET (bis(ethylenedithio)tetrathiafulvalene or BEDT-TTF) molecule and the anions containing multiple Re–Re bond have been investigated using Raman scattering and electron spin resonance (ESR) spectroscopies. Q-band ESR study allowed to record well-split ESR spectra and determine spectroscopic splitting coefficients of ET+...

Aminoferrocene-based prodrugs are activated in cancer cells by reactive oxygen species (ROS). They were shown to exhibit high cytotoxicity towards a variety of cancer cell lines and primary cancer cells, but remain not toxic towards non-malignant cells. However, these prodrugs have rather high lipophilicity leading to relatively low water solubilit...

Voltammetric study of the system consisted of cis-tetrachlorodi-μ-carboxylate dirhenium(III) and stable radical was conducted for detailization of the mechanism of interaction between the Re(III) coordination compounds with the metal-metal quadruple bond and the artificial radical. As a result of voltammetric studies, the electrochemical behavior o...

This review provides an overlook of design (in short), antitumor and other biological activity of quadruple-bonded cluster dirhenium(III) compounds and their synergism with cisplatin. In particular, we describe the work of the rhenium-platinum antitumor system (introduction of rhenium and platinum compounds). Among known metal-based anticancer drug...

In the title compound, [ReBr(C 16 H 16 N 4 O 3 )(CO) 3 ]·CH 3 OH, the Re I atom adopts a distorted octahedral coordination sphere with a facial arrangement of the three carbonyl ligands. Two N atoms of the chelating 5-(3,4,5-trimethoxyphenyl)-3-(pyridin-2-yl)-1 H -1,2,4-triazole ligand and two carbonyl ligands define the equatorial plane of the com...

Tricarbonyl rhenium(I) complexes have a great potential like biomarkers. It is caused their biological stability, low toxicity, large Stokes shifts, and long luminescence lifetimes. Rhenium tricarbonyl complexes fac-[Re(CO)3(N^N)], where N^N is a ligand with low π* orbitals are excellent candidates as imaging dyes. The method of obtaining potential...

The method of synthesis was developed and new tricarbonyl rhenium(I) complex with 4-methyl-2,2′-bipirydyn-4′-carboxylic acid was synthesized. The structure of the obtained complex compound was investigated by infrared spectroscopy and X-ray analysis. There are bands of asymmetric and symmetric stretching vibration of CO in the IR spectrum which ind...

The catalase activity of some dirhenium(III) clusters in vitro was investigated in this work for the first time. It was shown that dicarboxylate dirhenium (III) clusters with cis-configuration with isobutyric and acetylaminoadamantate ligands have their own catalase activity that reaches practically 40% in comparison to the activity of the native c...

Exothermic reactions for dirhenium(III) trans-tetrachloro-di-μ-carboxylates (trans- [Re2Cl4(RCOO)2], were R = C2H5; C3H7; (CH3)2CH; (CH3)3C) of burning in air were investigated. The products of burning by methods of chemical analysis were studied. The experimental enthalpy changes of reactions of complexes burning were obtained by the DTA curves. S...

Методом електронної абсорбційної спектроскопії досліджено антирадикальну активність цис-тетрахлороди-m-карбоксилатів диренію(III) по реакції з вільним ради-калом 2,2-дифеніл-1-пікрилгідразілом. Показано, що комплексні сполуки ренію(III) мають антирадикальну активність. Встановлено, що використання кластерів диренію(III) з екваторіальними лігандами,...

Effects of the different modes of administration of dichlorotetra-µ.-isobutyratodirhenium(III) - I - (in water solution, liposomes, nanoliposomes and together with cisplatin - in the rhenium-platinum system) on the intensity of lipid peroxidation (LP) in blood plasma and the activity of the erythrocyte antioxidant enzymes were investigated on the m...

Complex compounds of dirhenium(III), containing an unique quadruple metal-metal bond with low toxicity have a number of useful biological properties, such as antitumoral, antihemolytic, antiradical, hepato- and nephroprotective that stimulates the expansion of the range of such compounds due to the diversity of the ligand sphere. The method of synt...

The asymmetric unit of the title salt, (C$sb 10$H$sb 8$S$sb 8$)[Re$sb 2$Br$sb 6$(CH$sb 3$COO)]$cdot$0.5C$sb 2$H$sb 3$Cl$sb 3$, contains one bis-(ethyl-enedi-thio)-tetra-thia-fulvalene (ET) radical cation, one $mu$$sb 2$-acetato-bis-[tri-bromido-rhenate(III)] anion and a 1,1,2-tri-chloro-ethane mol-ecule with half-occupancy disordered about a twofol...

In the molecule of the title compound, [Re(C 5 H 10 NO 2 )(CO) 3 (H 2 O)], the Re I atom adopts a distorted octahedral coordination sphere defined by one aqua and three carbonyl ligands as well as one amino N and one carboxylate O atom of the chelating valinate anion. The carbonyl ligands are arranged in a fac -configuration around the Re I ion. In...

In order to obtain unknown thermodynamic properties, such as enthalpy of formation, of trans-tetrachlorodi-μ-carboxylate dirhenium(iii) (trans-[Re2Cl4(RCOO)2] (R = C2H5; C3H7; (CH3)2CH; (CH3)3C)) exothermic reactions of burning in oxygen were investigated. The products of burning were studied by chemical analysis. The experimental enthalpy changes...

The title compound, [Re 2 (C 3 H 7 COO) 2 Cl 4 {(CH 3 ) 2 SO} 2 ], comprises binuclear complex molecules [Re—Re = 2.24502 (13) Å] involving cis -oriented double carboxylate bridges, four equatorial chloride ions and two weakly bonded O atoms from dimethyl sulfoxide ligands in the axial positions at the Re III atoms. In the crystal, molecules are li...

The new fac-[Re(CO)3]+ complexes with bidentate ligands (5-phenyl-3-(pyridin-2-yl)-1,2,4-triazole L1; 5-(2-aminophenyl)- 3-(pyridin-2-yl)-1,2,4-triazole L2; 5-(2-hydroxyphenyl)-3-(pyridin-2-yl)-1,2,4-triazole L3; 5-phenyl-2-(pyridin-2-yl)-5,6-dihydro-[1,2,4]triazolo[1,5-c]quinazoline L4) were obtained by refluxing [Re(CO)5Br] and the ligand in benz...

The dirhenium complex Re2(i-C3H7COO)4Cl2 was synthesized and characterized by X-ray crystallography, (1)H NMR and electronic spectroscopies, and electrospray ionization-mass spectrometry. The reactions of Re2(i-C3H7COO)4Cl2 with the substituted DNA purine nucleobases guanine (9-methylguanine and 9-ethylguanine) and adenine (9-methyladenine and 9-et...

Biochemical characteristics of kidneys, pe- ripheral blood and bone marrow of rats in model of tumor growth under introduction of cisplatin and cis-tetrachlorodi-μ-isobutyratodirhenium(III), cis-Re2(i-C3H7COO)2Cl4 (I) have been investigated. It was shown that introduction of I alone and together with cisplatin led to decrease of biochemical markers...

The structure of the title compound, [Re2Cl6(C3H7NO2)2]·1.5H2O, comprises a dinuclear complex cation [Re-Re = 2.2494 (3) Å] involving cis-oriented double carboxyl-ate bridges, four equatorial chloride ions and two weakly bonded chloride ligands in the axial positions at the two rhenium(III) atoms. In the crystal, two complex mol-ecules and two wate...

Biochemical characteristics of kidneys, peripheral blood and bone marrow of rats in model of tumor growth under introduction of cisplatin and cis-tetrachlorodi-μ-isobutyratodirhenium(III), cis-Re2(i-C3H7COO)2Cl4 (I) have been investigated. It was shown that introduction of I alone and together with cisplatin led to decrease of biochemical markers o...

In the title compound, [ReBr(C13H10N4)(CO)3], the Re(I) atom has a distorted octa-hedral coordination environment. Two N atoms of the 5-phenyl-3-(pyridin-2-yl)-1H-1,2,4-triazole ligand and two of the three carbonyl groups occupy the equatorial plane of the complex, with the third carbonyl ligand and the bromide ligand in the axial positions. The th...

Abstract Liposomes loaded with the rhenium compound (bis-dimethylsulfoxido-cis-tetrachlorodi-μ-pivalatodirhenium(III) (cis-Re2((CH3)3CCOO)2Cl4ċ2DMSO, I) and cisplatin in the molar ratio of 4:1 as well as those loaded only with I were synthesized and characterized by scanning electron microscopy, transmission electron microscopy, dynamic light scatt...

Procedures were proposed for the synthesis of the heteroligand copper(II) complexes with N-(2-hydroxyethyl)iminodiacetic acid (H2Heida) and 2-aminoethanol and ethylenediamine ligands. The optimal parameters of solutions for the isolation of ternary complexes were found. Heteroligand complexes Cu(Heida)En · 3H2O (I) and Cu(Heida)Mea (II) (En is ethy...

In this study we report the synthesis, the X-ray crystal structure and the in vivo tumor growth suppression and nephroprotective activity of bis-dimethylsulfoxide-cis-tetrachlorodi-μ-pivalatodirhenium(III), cis-Re2[(CH3)3CCOO]2Cl4·2(CH3)2SO (I). The interactions of I with DNA were also investigated by electrophoretic mobility shift assays, electron...

A method to obtain new copper-rhenium composites on a steel substrate using a complex of dirhenium(III) cis-tetrachlorodi-µ-propionate with axial N,N-dimethylacetamide (cis-[Re 2 Cl 4 (C 2 H 5 COO) 2 (DMAA) 2 ]) and copper metal as starting materials for low-temperature chemical vapor deposition, was investigated. The obtained copper-rhenium compos...

The antioxidant and anticancer properties of dirhenium dicarboxylates of cis- and transconfiguration with different organic ligands in a model of tumor growth (Guerin carcinoma) were studied. It was shown that compounds of different configuration had similar antitumor effect, and dirhenium (III) cis-dicarboxylates were characterized by higher antio...

Aim. To investigate differences in the interactions of binuclear cluster rhenium(III) compounds of cis(I)and trans(II)-configuration with bovine serum albumin (BSA) and human serum albumin (HSA). Methods. Electronic spectroscopy, tryptophan fluorescence and circular dichroism spectroscopy. Results. It was shown that in the process of interaction of...

Aim. To investigate differences in the interactions of binuclear cluster rhenium(ІІІ) compounds of cis(I)- and trans(II)-configuration with bovine serum albumin (BSA) and human serum albumin(НSA). Меthods. Electronic spectroscopy, tryptophan fluorescence and circular dichroism spectroscopy. Results. It was shown that in the process of interaction o...

Influence of the antitumour rhenium-platinum system on biochemical liver characteristics in the model of tumor growth (Guerin carcinoma) was studied and possible hepatoprotective activity of rhenium cluster compounds when introducing them in different forms was shown, that was confirmed by decreasing of diagnostic enzymes activity in blood (aminotr...

Influence of complex compounds of nickel(II), copper(II) and zinc(II) with nitrogen containing ligands on conductivity of bilayer lipid membranes (BLMs) was studied. The role of conditions (pH, metal and ligand concentration) on complex formation and interaction with BLMs was evaluated. Composition and form of complex ions in solution which maximal...

A new dirhenium(III) complex cis-[Re2(GABA)2Cl5(H2O)]Cl.2H2O with zwitterionic gamma-aminobutyrate ligands was prepared and characterized by spectral methods and crystallography. The structure of the compound is comprised of dinuclear complex cations (Re-Re 2.2437(3) A) involving cis-oriented double carboxylate bridges, four equatorial chloride ion...

Synthesis of five structural types of cluster dirhenium(III) compounds with halogenide and carboxylates ligands is elaborated. It was shown that binuclear cluster fragment Re26+ actively reacted with artificial radicals; the rate of such interactions depended on the ligand environment of the cluster center Re26+, especially from the inductive effec...

The catalysis of breaking the oxidation chains of organic compounds by binuclear clusters cis–[Re2(O2CCH3)2Cl4x2H2O] is detected. The effective breaking constant of acidification chains of benzylperoxy radicals on (I) k = (2,1± 0,4)x10^4 l/(mol s).

The interaction cis-Re2(RCOO)2Cl4, trans-Re2(RCOO)2Cl4, Re2(RCOO)3Cl3, Re2(RCOO)4Cl2 (where R - alkyl group) with 1,3,5-triphenylverdazyle radical in 1,2-dichlorethane was investigated. It is discovered, that gradual substitution of halogenide ligands by carboxylates in dirhenium(III) clusters led to slowing down of reaction with a radical due to d...

The complex [Re2(HPO4)2(H2PO4)2(H2O)2] · 4H2O (I) was synthesized and investigated by conductometric, potentiometric, electronic and vibration spectroscopic methods. Thermal behavior of the title compound was studied and its molecular structure was determined from X-ray diffraction data. In the dimeric neutral complex, the bridging pairs of the hyd...

The compound (NH4)2[Re2(HPO4)4 · 2H2O] has been synthesized and characterized by electronic and vibrational spectroscopy. The molecular structure has been determined by X-ray diffraction (MoK α radiation, λ = 0.71073 Å). The (NH4)2[Re2(HPO4)4 · 2H2O] coordination units form centrosymmetrical binuclear ordering with each metal atom being coordinated...

Versatile procedures for the synthesis of possible structural types of dirhenium(III) halocarboxylates with adamantanecarboxylic acids were developed. A comprehensive study of the synthesis and interconversions of isomeric dirhenium(III) trans-and cis-tetrahalodi-μ-carboxylates led us to a discovery of a versatile route of prepation of trans deriva...

Compound [Re2(CH3COO)2Cl4((CH3)2NCOCH3)2] is synthesized. The influence of parameters of the hydrothermal synthesis under elevated pressure on the yield of a target product and its molecular structure and physicochemical properties is studied. In the neutral complex with cis-arrangement of the bridging acetate and terminal chloride ligands with res...

Glycinium and β-alaninium compounds [GlyH]2Re2Cl8·H2O 1, [β-AlaH]2Re2Cl82, and [GlyH]4(Re2Cl8)Cl23 were synthesized and characterized by X-ray diffraction. The Re2Cl8 2− anion in structure 3 has a partially staggered conformation with unprecedentedly high rotational distortion (16.2°). The forced geometry is influenced by cooperative demands of fou...

The antioxidant action of rhenium cluster complexes with isobutiric and gamma-aminobutiric acids were studied in vitro. It was established that strong antiradical properties were found in the reaction with stable radical diphenylpycrylhydrazile Re2(i-C3H7COO)4Cl2, [Re2(GABA)2Cl5(H2O)]Cl.2H2O. The chemiluminescence investigation of antioxidant prope...

The electron absorption spectra of halogenides and halogencarboxylate complex compounds of rhenium (III) having cluster structure with phosphatydilcholine and their lyposome forms were investigated. Some results which evidence for the interaction of these compounds with phosphatydilcholine were obtained. The possible mechanism of this interaction i...