89 results on '"Vadim V. Yanshole"'
Search Results
2. Water-Soluble Polyoxometal Clusters of Molybdenum (V) with Pyrazole and Triazole: Synthesis and Study of Cytotoxicity and Antiviral Activity
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Anna V. Konkova, Iulia V. Savina, Darya V. Evtushok, Tatiana N. Pozmogova, Maria V. Solomatina, Alina R. Nokhova, Alexander Y. Alekseev, Natalia V. Kuratieva, Ilia V. Eltsov, Vadim V. Yanshole, Aleksander M. Shestopalov, Anton A. Ivanov, and Michael A. Shestopalov
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polyoxometal cluster ,molybdenum ,pyrazole ,triazole ,cytotoxicity ,antiviral activity ,Organic chemistry ,QD241-441 - Abstract
Among well-studied and actively developing compounds are polyoxometalates (POMs), which show application in many fields. Extending this class of compounds, we introduce a new subclass of polyoxometal clusters (POMCs) [Mo12O28(μ-L)8]4− (L = pyrazolate (pz) or triazolate (1,2,3-trz or 1,2,4-trz)), structurally similar to POM, but containing binuclear Mo2O4 clusters linked by bridging oxo- and organic ligands. The complexes obtained by ampoule synthesis from the binuclear cluster [Mo2O4(C2O4)2(H2O)2]2− in a melt of an organic ligand are soluble and stable in aqueous solutions. In addition to the detailed characterization in solid state and in aqueous solution, the biological properties of the compounds on normal and cancer cells were investigated, and antiviral activity against influenza A virus (subtype H5N1) was demonstrated.
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- 2023
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3. PEGylation of Terminal Ligands as a Route to Decrease the Toxicity of Radiocontrast Re6-Clusters
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Aleksei S. Pronin, Tatiana N. Pozmogova, Yuri A. Vorotnikov, Georgy D. Vavilov, Anton A. Ivanov, Vadim V. Yanshole, Alphiya R. Tsygankova, Tatiana Ya. Gusel’nikova, Yuri V. Mironov, and Michael A. Shestopalov
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octahedral chalcogenide rhenium cluster ,phosphine ,PEGylation ,cytotoxicity ,acute toxicity ,X-ray contrast media ,Biology (General) ,QH301-705.5 ,Chemistry ,QD1-999 - Abstract
The development of novel radiocontrast agents, mainly used for the visualization of blood vessels, is still an emerging task due to the variety of side effects of conventional X-ray contrast media. Recently, we have shown that octahedral chalcogenide rhenium clusters with phosphine ligands—Na2H14[{Re6Q8}(P(C2H4COO)3)6] (Q = S, Se)—can be considered as promising X-ray contrast agents if their relatively high toxicity related to the high charge of the complexes can be overcome. To address this issue, we propose one of the most widely used methods for tuning the properties of proteins and peptides—PEGylation (PEG is polyethylene glycol). The reaction between the clusters and PEG-400 was carried out in acidic aqueous media and resulted in the binding of up to five carboxylate groups with PEG. The study of cytotoxicity against Hep-2 cells and acute toxicity in mice showed a twofold reduction in toxicity after PEGylation, demonstrating the success of the strategy chosen. Finally, the compound obtained has been used for the visualization of blood vessels of laboratory rats by angiography and computed tomography.
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- 2023
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4. Animal Metabolite Database: Metabolite Concentrations in Animal Tissues and Convenient Comparison of Quantitative Metabolomic Data
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Vadim V. Yanshole, Arsenty D. Melnikov, Lyudmila V. Yanshole, Ekaterina A. Zelentsova, Olga A. Snytnikova, Nataliya A. Osik, Maxim V. Fomenko, Ekaterina D. Savina, Anastasia V. Kalinina, Kirill A. Sharshov, Nikita A. Dubovitskiy, Mikhail S. Kobtsev, Anatolii A. Zaikovskii, Sofia S. Mariasina, and Yuri P. Tsentalovich
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database ,quantitative metabolomics ,data reuse ,data exchange ,animal tissues ,NMR spectroscopy ,Microbiology ,QR1-502 - Abstract
The Animal Metabolite Database (AMDB, https://amdb.online) is a freely accessible database with built-in statistical analysis tools, allowing one to browse and compare quantitative metabolomics data and raw NMR and MS data, as well as sample metadata, with a focus on the metabolite concentrations rather than on the raw data itself. AMDB also functions as a platform for the metabolomics community, providing convenient deposition and exchange of quantitative metabolomic data. To date, the majority of the data in AMDB relate to the metabolite content of the eye lens and blood of vertebrates, primarily wild species from Siberia, Russia and laboratory rodents. However, data on other tissues (muscle, heart, liver, brain, and more) are also present, and the list of species and tissues is constantly growing. Typically, every sample in AMDB contains concentrations of 60–90 of the most abundant metabolites, provided in nanomoles per gram of wet tissue weight (nmol/g). We believe that AMDB will become a widely used tool in the community, as typical metabolite baseline concentrations in tissues of animal models will aid in a wide variety of fundamental and applied scientific fields, including, but not limited to, animal modeling of human diseases, assessment of medical formulations, and evolutionary and environmental studies.
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- 2023
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5. Chemical Diversity of Mo5S5 Clusters with Pyrazole: Synthesis, Redox and UV-vis-NIR Absorption Properties
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Iulia V. Savina, Anton A. Ivanov, Ilia V. Eltsov, Vadim V. Yanshole, Natalia V. Kuratieva, Andrey Y. Komarovskikh, Mikhail M. Syrokvashin, and Michael A. Shestopalov
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molybdenum ,metal cluster ,pyrazole ,EPR ,NMR ,cyclic voltammetry ,Biology (General) ,QH301-705.5 ,Chemistry ,QD1-999 - Abstract
The chemistry of transition metal clusters has been intensively developed in the last decades, leading to the preparation of a number of compounds with promising and practically useful properties. In this context, the present work demonstrates the preparation and study of the reactivity, i.e., the possibility of varying the ligand environment, of new square pyramidal molybdenum chalcogenide clusters [{Mo5(μ3-S)i4(μ4-S)i(μ-pz)i4}(pzH)t5]1+/2+ (pzH = pyrazole, i = inner, t = terminal). The one-step synthesis starting from the octahedral Mo6Br12 cluster as well as the substitution of the apical pyrazole ligand or the selective bromination of the inner pyrazolate ligands were demonstrated. All the obtained compounds were characterized in detail using a series of physicochemical methods both in solid state (X-ray diffraction analysis, etc.) and in solution (nuclear magnetic resonance spectroscopy, mass spectrometry, etc.). In this work, redox properties and absorption in the ultraviolet-visible and near-infrared region of the obtained compounds were studied.
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- 2023
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6. From K6[Re6−xMoxS8(CN)5] Solid Solution to Individual Cluster Complexes: Separation and Investigation of [Re4Mo2S8(CN)6]n− and [Re3Mo3S8(CN)6]n− Heterometallic Clusters
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Tatiana I. Lappi, Yakov M. Gayfulin, Adèle Renaud, Carmelo Prestipino, Pierric Lemoine, Vadim V. Yanshole, Viktoria K. Muravieva, Stéphane Cordier, and Nikolai G. Naumov
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metal cluster ,heterometallic ,crystal structure ,electronic structure ,DFT calculations ,EXAFS ,Organic chemistry ,QD241-441 - Abstract
A series of new cluster compounds with {Re4Mo2S8} and {Re3Mo3S8} cores has been obtained and investigated. The clusters with different Re/Mo ratios were isolated as individual compounds, which made it possible to study their spectroscopic and electrochemical properties. The geometry of the new clusters was studied using a combination of X-ray diffraction analysis, XAS and quantum chemical DFT calculations. It was shown that the properties of the new clusters, such as the number and position of electrochemical transitions, electronic structure and change in geometry with a change in charge, are similar to the properties of clusters based on the {Re4Mo2Se8} and {Re3Mo3Se8} cores described earlier.
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- 2023
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7. Quantitative Metabolomic Dataset of Avian Eye Lenses
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Ekaterina A. Zelentsova, Sofia S. Mariasina, Vadim V. Yanshole, Lyudmila V. Yanshole, Nataliya A. Osik, Kirill A. Sharshov, and Yuri P. Tsentalovich
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quantitative metabolomics ,NMR spectroscopy ,eye lens ,birds ,Bibliography. Library science. Information resources - Abstract
Metabolomics is a powerful set of methods that uses analytical techniques to identify and quantify metabolites in biological samples, providing a snapshot of the metabolic state of a biological system. In medicine, metabolomics may help to reveal the molecular basis of a disease, make a diagnosis, and monitor treatment responses, while in agriculture, it can improve crop yields and plant breeding. However, animal metabolomics faces several challenges due to the complexity and diversity of animal metabolomes, the lack of standardized protocols, and the difficulty in interpreting metabolomic data. The current dataset includes quantitative metabolomic profiles of eye lenses from 26 bird species (111 specimens) that can aid researchers in developing new experiments, mathematical models, and integrating with other “-omics” data. The dataset includes raw 1H NMR spectra, protocols for sample preparation, and data preprocessing, with the final table containing information on the abundance of 89 reliably identified and quantified metabolites. The dataset is quantitative, making it relevant for supplementing with new specimens or comparison groups, followed by data mining and expected new interpretations. The data were obtained using the bird specimens collected in compliance with ethical standards and revealed potential differences in metabolic pathways due to phylogenetic differences or environmental exposure.
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- 2023
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8. A previously unknown way of heme detoxification in the digestive tract of cats
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Alexandr B. Duzhak, Petr S. Sherin, Vadim V. Yanshole, Sergey L. Veber, Sergey I. Baiborodin, Olga I. Sinitsyna, and Yuri P. Tsentalovich
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Medicine ,Science - Abstract
Abstract Free heme is a highly toxic molecule for a living organism and its detoxification is a very important process, especially for carnivorous animals. Here we report the discovery of a previously unknown process for neutralizing free heme in the digestive tract of domestic cats. The cornerstone of this process is the encapsulation of heme into carbonated hydroxyapatite nanoparticles, followed by their excretion with faeces. This way of heme neutralization resembles the formation of insoluble heme-containing particles in the digestive tracts of other hematophagous species (for example, the formation of insoluble hemozoin crystals in malaria-causing Plasmodium parasites). Our findings suggest that the encapsulation of heme molecules into a hydroxyapatite matrix occurs during the transition from the acidic gastric juice to the small intestine with neutral conditions. The formation of these particles and their efficiency to include heme depends on the bone content in a cat’s diet. In vitro experiments with heme-hydroxyapatite nanoparticles confirm the proposed scenario.
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- 2021
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9. Influence of Ecological Factors on the Metabolomic Composition of Fish Lenses
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Yuri P. Tsentalovich, Ekaterina A. Zelentsova, Ekaterina D. Savina, Vadim V. Yanshole, and Renad Z. Sagdeev
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freshwater fish ,metabolomics ,dissolved oxygen level ,water pollution ,NMR spectroscopy ,Biology (General) ,QH301-705.5 - Abstract
Multiple stressors related to changes in environmental conditions (such as water temperature, salinity, and natural and anthropogenic pollution) may cause biological responses of aquatic organisms that lead to significant variations in the biochemical reactions in their tissues and thereby change the concentrations of metabolites. We used a quantitative NMR-based metabolomic analysis of the fish lens for the evaluation of the influence of environmental factors on metabolic processes in aquatic animals. For this purpose, three species of freshwater fish—Perca fluviatilis, Rutilus rutilus lacustris, and Gymnocephalus cernua—were caught at approximately the same time at three locations in Siberia (Russia) that differed in levels of dissolved oxygen (LDO) and water purity, and the concentrations of 57 major metabolites in the fish lenses were determined. We found that the metabolomic profiles of the fish lenses strongly depended on the location. The obtained data demonstrated that two typical stressors for aquatic animals—a reduced LDO and anthropogenic water pollution—caused a largely similar metabolic response in the fish lenses that led to an increase in the concentrations of several amino acids and a decrease in sarcosine and phosphoethanolamine. At the same time, the composition of the major lens osmolytes depended mostly on the oxygen level, while variations in AMP (decrease) and NAD (increase) corresponded to the water pollution. We suggest that the eye lens is a very convenient tissue for studying the impact of ecological factors on the metabolic state of aquatic animals, fish in particular.
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- 2022
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10. The Application of Quantitative Metabolomics for the Taxonomic Differentiation of Birds
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Ekaterina A. Zelentsova, Lyudmila V. Yanshole, Yuri P. Tsentalovich, Kirill A. Sharshov, and Vadim V. Yanshole
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quantitative metabolomics ,phylogeny ,hierarchical clustering analysis ,NMR spectroscopy ,eye lens ,birds ,Biology (General) ,QH301-705.5 - Abstract
In the current pilot study, we propose the use of quantitative metabolomics to reconstruct the phylogeny of vertebrates, namely birds. We determined the concentrations of the 67 most abundant metabolites in the eye lenses of the following 14 species from 6 orders of the class Aves (Birds): the Black kite (Milvus migrans), Eurasian magpie (Pica pica), Northern raven (Corvus corax), Eurasian coot (Fulica atra), Godlewski’s bunting (Emberiza godlewskii), Great crested grebe (Podiceps cristatus), Great tit (Parus major), Hawfinch (Coccothraustes coccothraustes), Hooded crow (Corvus cornix), House sparrow (Passer domesticus), Rock dove (Columba livia), Rook (Corvus frugilegus), Short-eared owl (Asio flammeus) and Ural owl (Strix uralensis). Further analysis shows that the statistical approaches generally used in metabolomics can be applied for differentiation between species, and the most fruitful results were obtained with hierarchical clustering analysis (HCA). We observed the grouping of conspecific samples independently of the sampling place and date. The HCA tree structure supports the key role of genomics in the formation of the lens metabolome, but it also indicates the influence of the species lifestyle. A combination of genomics-based and metabolomics-based phylogeny could potentially resolve arising issues and yield a more reliable tree of life.
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- 2022
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11. Novel Copper(II) Complexes with Dipinodiazafluorene Ligands: Synthesis, Structure, Magnetic and Catalytic Properties
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Iakov S. Fomenko, Medhanie Afewerki, Marko I. Gongola, Eugene S. Vasilyev, Lidia S. Shul’pina, Nikolay S. Ikonnikov, Georgiy B. Shul’pin, Denis G. Samsonenko, Vadim V. Yanshole, Vladimir A. Nadolinny, Alexander N. Lavrov, Alexey V. Tkachev, and Artem L. Gushchin
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copper(II) ,complexes ,dipinodiazafluorenes ,synthesis ,crystal structure ,magnetic properties ,Organic chemistry ,QD241-441 - Abstract
The reactions of CuX2 (X = Cl, Br) with dipinodiazafluorenes yielded four new complexes [CuX2L1]2 (X = Cl (1), Br (2), L1 = (1R,3R,8R,10R)-2,2,9,9-Tetramethyl-3,4,7,8,9,10-hexahydro-1H-1,3:8,10-dimethanocyclopenta [1,2-b:5,4-b’]diquinolin-12(2H)-one) and [(CuX2)2L2]n (X = Cl (3), Br (4), L2 = (1R,3R,8R,10R,1’R,3’R,8’R,10’R)-2,2,2’,2’,9,9,9’,9’-Octamethyl-1,1’,2,2’,3,3’,4,4’,7,7’,8,8’,9,9’,10,10’-hexadecahydro-1,3:1’,3’:8,10:8’,10’-tetramethano-12,12’-bi(cyclopenta [1,2-b:5,4-b’]diquinolinylidene). The complexes were characterized by IR and EPR spectroscopy, HR-ESI-MS and elemental analysis. The crystal structures of compounds 1, 2 and 4 were determined by X-ray diffraction (XRD) analysis. Complexes 1–2 have a monomeric structure, while complex 4 has a polymeric structure due to additional coordinating N,N sites in L2. All complexes contain a binuclear fragment {Cu2(μ-X)2×2} (X = Cl, Br) in their structures. Each copper atom has a distorted square-pyramidal coordination environment formed by two nitrogen atoms and three halogen atoms. The Cu-Nax distance is elongated compared to Cu-Neq. The EPR spectra of compounds 1–4 in CH3CN confirm their paramagnetic nature due to the d9 electronic configuration of the copper(II) ion. The magnetic properties of all compounds were studied by the method of static magnetic susceptibility. For complexes 1 and 2, the effective magnetic moments are µeff ≈ 1.87 and 1.83 µB (per each Cu2+ ion), respectively, in the temperature range 50–300 K, which are close to the theoretical spin value (1.73 µB). Ferromagnetic exchange interactions between Cu(II) ions inside {Cu2(μ-X)2X2} (X = Cl, Br) dimers (J/kB ≈ 25 and 31 K for 1 and 2, respectively) or between dimers (θ′ ≈ 0.30 and 0.47 K for 1 and 2, respectively) were found at low temperatures. For compounds 3 and 4, the magnetic susceptibility is well described by the Curie–Weiss law in the temperature range 1.77–300 K with µeff ≈ 1.72 and 1.70 µB for 3 and 4, respectively, and weak antiferromagnetic interactions (θ ≈ −0.4 K for 3 and −0.65 K for 4). Complexes 1–4 exhibit high catalytic activity in the oxidation of alkanes and alcohols with peroxides. The maximum yield of cyclohexane oxidation products reached 50% (complex 3). Based on the data on the study of regio- and bond-selectivity, it was concluded that hydroxyl radicals play a decisive role in the oxidation reaction. The initial products in reactions with alkanes are alkyl hydroperoxides.
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- 2022
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12. Easy Ligand Activation in the Coordination Sphere of Ru inside the [PW11O39]7– Backbone
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Anna A. Mukhacheva, Artem L. Gushchin, Vadim V. Yanshole, Pavel A. Abramov, and Maksim N. Sokolov
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ruthenium ,polyoxometalate ,azide ,CV ,HR-ESI-MS ,Organic chemistry ,QD241-441 - Abstract
Irradiation of the Keggin-type [PW11O39{Ru(NO)}]4− (Ru-NO) polyoxometalate in CH3CN results in rapid NO ligand elimination with the formation of [PW11O39{RuIII(CH3CN)}]4− (Ru-CH3CN). This complex offers an easy entry into the Ru-based chemistry of the {PW11Ru} complex. Attempts to substitute N3− for CH3CN in the presence of an NaN3 excess lead a variety of products: (i) [PW11O39{RuIII(N3)}]4− (Ru-N3); (ii) [PW11O39{RuIII(N4HC-CH3)}]4− (Ru-Tz) as a click-reaction product; and (iii) [PW11O39{RuII(N2)}]5− (Ru-N2). UV-VIS, CV, and HR-ESI-MS techniques were used for the reaction monitoring and characterization of the products.
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- 2020
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13. Seasonal Variations and Interspecific Differences in Metabolomes of Freshwater Fish Tissues: Quantitative Metabolomic Profiles of Lenses and Gills
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Yuri P. Tsentalovich, Vadim V. Yanshole, Lyudmila V. Yanshole, Ekaterina A. Zelentsova, Arsenty D. Melnikov, and Renad Z. Sagdeev
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freshwater fish ,metabolomics ,dissolved oxygen level ,mass spectrometry ,nmr spectroscopy ,Microbiology ,QR1-502 - Abstract
This work represents the first comprehensive report on quantitative metabolomic composition of tissues of pike-perch (Sander lucioperca) and Siberian roach (Rutilus rutilus lacustris). The total of 68 most abundant metabolites are identified and quantified in the fish lenses and gills by the combination of LC-MS and NMR. It is shown that the concentrations of some compounds in the lens are much higher than that in the gills; that indicates the importance of these metabolites for the adaptation to the specific living conditions and maintaining the homeostasis of the fish lens. The lens metabolome undergoes significant seasonal changes due to the variations of dissolved oxygen level and fish feeding activity. The most season-affected metabolites are osmolytes and antioxidants, and the most affected metabolic pathway is the histidine pathway. In late autumn, the major lens osmolytes are N-acetyl-histidine and threonine phosphoethanolamine (Thr-PETA), while in winter the highest concentrations were observed for serine phosphoethanolamine (Ser-PETA) and myo-inositol. The presence of Thr-PETA and Ser-PETA in fish tissues and their role in cell osmotic protection are reported for the first time. The obtained concentrations can be used as baseline levels for studying the influence of environmental factors on fish health.
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- 2019
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14. Ovothiol A is the Main Antioxidant in Fish Lens
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Vadim V. Yanshole, Lyudmila V. Yanshole, Ekaterina A. Zelentsova, and Yuri P. Tsentalovich
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antioxidant ,mass spectrometry ,freshwater fish ,NMR spectroscopy ,ovothiol A ,Microbiology ,QR1-502 - Abstract
Tissue protection from oxidative stress by antioxidants is of vital importance for cellular metabolism. The lens mostly consists of fiber cells lacking nuclei and organelles, having minimal metabolic activity; therefore, the defense of the lens tissue from the oxidative stress strongly relies on metabolites. Protein-free extracts from lenses and gills of freshwater fish, Sander lucioperca and Rutilus rutilus lacustris, were subjected to analysis using high-field 1H NMR spectroscopy and HPLC with optical and high-resolution mass spectrometric detection. It was found that the eye lenses of freshwater fish contain high concentrations of ovothiol A (OSH), i.e., one of the most powerful antioxidants exciting in nature. OSH was identified and quantified in millimolar concentrations. The concentration of OSH in the lens and gills depends on the fish genus and on the season. A possible mechanism of the reactive oxygen species deactivation in fish lenses is discussed. This work is the first to report on the presence of OSH in vertebrates. The presence of ovothiol in the fish tissue implies that it may be a significantly more common antioxidant in freshwater and marine animals than was previously thought.
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- 2019
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15. Blatter Radical-Decorated Silica as a Prospective Adsorbent for Selective NO Capture from Air
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Artem S. Poryvaev, Eva Gjuzi, Anastasiya A. Yazikova, Daniil M. Polyukhov, Yana N. Albrekht, Aleksandr A. Efremov, Nikita A. Kudriavykh, Vadim V. Yanshole, Frank Hoffmann, Michael Fröba, and Matvey V. Fedin
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General Materials Science - Published
- 2023
16. Coordination of Pt(IV) by {P8W48} Macrocyclic Inorganic Cavitand: Structural, Solution, and Electrochemical Studies
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Anna A. Kuznetsova, Victoria V. Volchek, Vadim V. Yanshole, Anastasiya D. Fedorenko, Nikolay B. Kompankov, Vasily V. Kokovkin, Artem L. Gushchin, Pavel A. Abramov, and Maxim N. Sokolov
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Inorganic Chemistry ,Physical and Theoretical Chemistry - Published
- 2022
17. Self-assembly patterns of non-metalloid silver thiolates: structural, HR-ESI-MS and stability studies
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Pavel A. Abramov, Veronica S. Sulyaeva, Vadim V. Yanshole, Vasily V. Kokovkin, Anastasia Chupina, and Maksim Nailyevich Sokolov
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Inorganic Chemistry ,Crystallography ,Chemistry ,Electrospray ionization ,Cationic polymerization ,Redistribution (chemistry) ,Orthorhombic crystal system ,Metalloid ,Self-assembly - Abstract
Screening of AgNO3/AgStBu solutions in DMF, DMSO and NMP resulted in an isolation of three novel nanosized silver/thiolate complexes with a torus-like {Ag20(StBu)10} core. The structures of [NO3@Ag20(StBu)10(NO3)9(DMF)6] (1) and [NO3@Ag20(tBuS)10(NO3)8(NMP)8][NO3@Ag19(tBuS)10(NO3)8(NMP)6]2(NO3) (2) were studied by SCXRD. The self-assembly process leading to 1 can be switched to a different outcome by Br–, resulting in [Br@Ag16(StBu)8(NO3)5(DMF)3](NO3)2 (3), which is the one of the few genuine host-guest complex in the silver/thiolate systems. Solutions of the individual complexes in CH3CN were studied by HR-ESI-MS techniques, which revealed a dynamic behavior for each complex, driven by a redistribution of the {AgNO3} units. This dynamics results in the appearance of both cationic and anionic species, based on unchanged silver-thiolate cores. Day light causes degradation of 3 with the formation of a composite material based on defective orthorhombic Ag2S with a porous morfology, as observed with SEM technique. Electrocatalytic HER activity of such material was studied.
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- 2022
18. Heterometallic Re/Mo and Re/W cubane-type cluster complexes
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Aleksei S. Pronin, Yuri V. Mironov, Vadim V. Yanshole, A. N. Lavrov, Taisiya S. Sukhikh, and Yakov M. Gayfulin
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Inorganic Chemistry ,Crystallography ,Aqueous solution ,Materials science ,chemistry ,Tetrahedron ,Cluster (physics) ,chemistry.chemical_element ,Crystal structure ,Electrochemistry ,Redox ,Cubane-type cluster ,Selenium - Abstract
A series of heterometallic tetrahedral cluster complexes with the general formula [{MxRe4−xSe4}(CN)12]n− (M = Mo, W; x = 2, 3) were obtained using the reaction of ReI3 and MO3 with selenium and KCN at elevated temperatures. Compounds [ReW3Se4(CN)12]6− and [Re2W2Se4(CN)12]6− are the first rhenium–tungsten heterometallic clusters. Crystal structures, electrochemical properties in aqueous solutions and magnetic properties of crystalline samples have been studied in detail. It has been shown that new cluster anions demonstrate a regular change in geometric characteristics and redox potentials depending on the composition of the cluster core.
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- 2022
19. Direct UV photodegradation of nalidixic acid in aqueous solutions: A mechanistic study
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Yuliya E. Tyutereva, Olga A. Snytnikova, Roman G. Fedunov, Vadim V. Yanshole, Victor F. Plyusnin, Jing Xu, and Ivan P. Pozdnyakov
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Environmental Engineering ,Health, Toxicology and Mutagenesis ,Public Health, Environmental and Occupational Health ,Environmental Chemistry ,General Medicine ,General Chemistry ,Pollution - Published
- 2023
20. A new view on the mechanism of UV photodegradation of the tricyclic antidepressant carbamazepine in aqueous solutions
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Mikhail V. Novikov, Olga A. Snytnikova, Roman G. Fedunov, Vadim V. Yanshole, Vyacheslav P. Grivin, Victor F. Plyusnin, Jing Xu, and Ivan P. Pozdnyakov
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Environmental Engineering ,Health, Toxicology and Mutagenesis ,Public Health, Environmental and Occupational Health ,Environmental Chemistry ,General Medicine ,General Chemistry ,Pollution - Published
- 2023
21. Activation of H2O2 over Zr(IV). Insights from Model Studies on Zr-Monosubstituted Lindqvist Tungstates
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Albert Solé-Daura, Olga V. Zalomaeva, R. John Errington, Gennadii M. Maksimov, Ilia V. Eltsov, Irina D. Ivanchikova, T.S. Glazneva, Yuriy A. Chesalov, Vasilii Yu. Evtushok, Vadim V. Yanshole, Pavel A. Abramov, Jorge J. Carbó, Josep M. Poblet, Oxana A. Kholdeeva, and Nataliya V. Maksimchuk
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chemistry.chemical_compound ,Zirconium ,Chemistry ,Inorganic chemistry ,chemistry.chemical_element ,General Chemistry ,Hydrogen peroxide ,Catalysis - Published
- 2021
22. In Vitro 1H NMR Metabolic Profiles of Liver, Brain, and Serum in Rats After Chronic Consumption of Alcohol
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Mikhail P. Moshkin, Vadim V. Yanshole, Oleg B. Shevelev, Mariya S. Pravdivtseva, Igor V. Koptyug, and A. E. Akulov
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0303 health sciences ,medicine.medical_specialty ,Ethanol ,Alcohol ,Glutathione ,Metabolism ,Atomic and Molecular Physics, and Optics ,In vitro ,03 medical and health sciences ,chemistry.chemical_compound ,0302 clinical medicine ,Endocrinology ,chemistry ,Internal medicine ,medicine ,030211 gastroenterology & hepatology ,Analysis of variance ,Proline ,030304 developmental biology ,Blood sampling - Abstract
The impact of alcohol on the body can be investigated with NMR spectroscopy in vitro, which can detect a wide range of metabolites but preparing samples includes tissue biopsy. Blood sampling is less invasive, but blood metabolic content might not reflect the changes occurring in other tissues. Thus, this study aimed to investigate the liver, brain, and serum metabolism and evaluate the link between tissues and serum metabolic content. Two experimental groups with ten outbred rats each were provided intragastrically with water (control group) and 50% ethanol solution (alcohol group) for 28 days. 1H NMR spectroscopy in vitro was performed on the brain cortex, liver, and serum samples. Student’s t test with Holm–Bonferroni correction was used to investigate significant differences between groups. Partial least-squares discriminant analysis (PLS-DA) and two-way ANOVA were performed to compare liver and serum, brain and serum. In all, 38, 37, and 21 metabolites were identified in the liver, brain, and serum samples, respectively. Significant differences for three metabolites were found in the liver (alanine, proline, and glutathione, p p r > 0.65) between serum and liver samples. PLS-DA determined separation between all tissues (p p
- Published
- 2021
23. Stabilization of Re37+/Re38+ Metalloclusters by Cyanide Ligands in New Trinuclear Rhenium Cluster Complexes [{Re3X3}(CN)9]4–/[{Re3X3}(CN)9]5– (X = Br or I)
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Yakov M. Gayfulin, Yuri V. Mironov, Vadim V. Yanshole, Spartak S. Yarovoy, and Anton I. Smolentsev
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Aqueous solution ,010405 organic chemistry ,Cyanide ,Halide ,chemistry.chemical_element ,Formal charge ,Rhenium ,010402 general chemistry ,01 natural sciences ,Magnetic susceptibility ,0104 chemical sciences ,Inorganic Chemistry ,chemistry.chemical_compound ,Crystallography ,chemistry ,Physical and Theoretical Chemistry ,Cyclic voltammetry ,Valence electron - Abstract
The interaction of rhenium(III) halides Re3Br9 and Re3I9 with aqueous solution of sodium cyanide resulted in the formation of the first trinuclear halide-cyanide rhenium cluster complexes [{Re3X3}(CN)9]5-/[{Re3X3}(CN)9]4- (X = Br or I) crystallized as salts of the compositions Cs4Na[{Re3Br3}(CN)9]·5.25H2O (1), Cs4Na[{Re3I3}(CN)9]·6H2O (2), Cs4[{Re3Br3}(CN)9]·2H2O·0.5CsCl (3), and Cs4[{Re3I3}(CN)9]·(4). All of the compounds are stable in air in the solid state and in aqueous solution. The substitution of apical halide ligands in the parent compounds Re3X9 by cyanides led to reduction of the original metallocluster Re39+ (12 cluster valence electrons (CVEs)) to Re37+ (14 CVEs), forming the compounds 1 and 2. The apical CN- ligands affect the electronic structure of the Re3 metallocluster stabilizing reduced form. Complexes 1 and 2 represent the first examples of triangular rhenium clusters with the Re37+ metallocluster. The reaction of 1 and 2 with H2O2 resulted in formation of compounds 3 and 4 with the formal charge of the Re3 metallocluster equal to 8+, and no further oxidation to Re39+ occurred. The compounds were characterized by the X-ray diffraction analysis, NMR and UV-vis spectroscopies, mass spectrometry, cyclic voltammetry, and magnetic susceptibility measurements.
- Published
- 2021
24. Keggin-type polyoxometalate 1 : 1 complexes of Pb(<scp>ii</scp>) and Bi(<scp>iii</scp>): experimental, theoretical and luminescence studies
- Author
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Nikolay B. Kompankov, Maxim R. Ryzhikov, Vadim V. Yanshole, Anna A. Mukhacheva, Maxim N. Sokolov, Alexey S. Berezin, Pavel A. Abramov, Artem L. Gushchin, Taisiya S. Sukhikh, and Tatiana Asanova
- Subjects
Inorganic Chemistry ,NMR spectra database ,Crystallography ,Extended X-ray absorption fine structure ,Oxidation state ,Chemistry ,Polyoxometalate ,Nuclear magnetic resonance spectroscopy ,Cyclic voltammetry ,Lone pair ,XANES - Abstract
Bi3+ and Pb2+ uptake by a monolacunary Keggin-type [PW11O39]7- anion leads to the formation of [PW11O39Bi]4- and [PW11O39Pb]5- complexes with a stereochemically active lone pair at the incorporated heterometal. The two complexes were isolated as (TBA)4[PW11O39Bi] (1) and (TBA)5[PW11O39Pb] (2) and characterized by 31P and 183W NMR spectroscopy, high-resolution electrospray mass-spectrometry (HR-ESI-MS) and cyclic voltammetry (CV). EXAFS and XANES data confirm the unchanged oxidation state and ψ-square pyramidal geometry of Bi3+ and Pb2+ in 1 and 2. DFT calculations were used in order to (i) confirm the absence of ligands attached to the heterometal sites in both complexes and localize the lone pair, and (ii) assign all signals in the 183W NMR spectra. Complexes 1 and 2 demonstrate photoluminescence (PL). A reversible change in the PL spectra of both complexes in the presence of water vapor has been detected. On the contrary, PL data for sandwich-type ((CH3)4N)4K3[H4(PW11O39)2Bi]·25H2O (3) do not show sensitivity to water vapor.
- Published
- 2021
25. Most abundant metabolites in tissues of freshwater fish pike-perch (Sander lucioperca)
- Author
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Vadim V. Yanshole, Ekaterina A. Zelentsova, Iliya M. Odud, Yuri P. Tsentalovich, and Lyudmila V. Yanshole
- Subjects
0301 basic medicine ,Milt ,Taurine ,Magnetic Resonance Spectroscopy ,Molecular biology ,Metabolite ,lcsh:Medicine ,Biochemistry ,Article ,03 medical and health sciences ,Ovothiol A ,chemistry.chemical_compound ,0302 clinical medicine ,Metabolomics ,Animals ,Tissue Distribution ,Amino Acids ,lcsh:Science ,Perch ,Multidisciplinary ,Ecology ,biology ,lcsh:R ,biology.organism_classification ,030104 developmental biology ,chemistry ,Perches ,Osmolyte ,030221 ophthalmology & optometry ,Freshwater fish ,lcsh:Q ,Zoology - Abstract
Quantitative metabolomic analysis was performed for eleven tissues of freshwater fish pike-perch (Sander lucioperca), including gill, heart, liver, kidney, spleen, muscle, brain, milt, lens, aqueous (AH) and vitreous (VH) humors with the use of NMR spectroscopy. The absolute values of concentrations were determined for more than 65 most abundant metabolites in every tissue. It was found that from the metabolomic viewpoint, kidney and gill are the most similar tissues, while the metabolomic compositions of ocular tissues—lens, AH, and VH significantly differ from that of other tissues. The combinations of intracellular osmolytes and antioxidants are specific for every tissue. In particular, the concentration of antioxidant ovothiol A in the lens is much higher than in any other tissue, while the brain enjoys the elevated level of ascorbate. The most abundant osmolyte in the fish spleen, muscle, and heart is taurine, and in the brain, gill, and lens—myo-inositol. Other important osmolytes specific for particular tissues are N-acetyl-histidine, N-acetyl-aspartate, betaine, threonine-phosphoethanolamine, and serine-phosphoethanolamine. The quantitative data obtained in the present work can be used as the baseline metabolite concentrations in the fish tissues to evaluate the influence of seasonal, ecological and other factors on the fish metabolism.
- Published
- 2020
26. Evidences of the Non-Stoichiometry and Control of the Composition of Thecluster-Based Solid Solution K6[Re6-Xmoxs8(Cn)5] (X=2.75-3.63)
- Author
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Tatiana I. Lappi, Yakov M. Gaifulin, Vadim V. Yanshole, Stephane Cordier, Nikolay G. Naumov, Nikolaev Institute of Inorganic Chemistry [Novosibirsk] (NIC), Siberian Branch of the Russian Academy of Sciences (SB RAS), Novosibirsk State University (NSU), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
- Subjects
Molybdenum ,History ,Polymers and Plastics ,[CHIM.INOR]Chemical Sciences/Inorganic chemistry ,Condensed Matter Physics ,Industrial and Manufacturing Engineering ,Electronic, Optical and Magnetic Materials ,Solid state chemistry ,Inorganic Chemistry ,Rhenium ,Materials Chemistry ,Ceramics and Composites ,Metal Sulfides ,Physical and Theoretical Chemistry ,Business and International Management ,Octahedral cluster - Abstract
International audience; In this work, we investigated a high-temperature reaction between ReS2, MoS2 and KCN resulting in the formation of the cluster-based K6[Re6-xMoxS8(CN)5] solid solution. The crystal structure is based on chains of [Re6-xMoxS8(CN)6] cluster units. It was found that both the sintering temperature of starting sulfides and the reaction temperature with KCN have an influence on the composition of the product allowing x to be varied within the range x = 2.75-3.63. The molar ration of ReS2:MoS2:KCN loaded composition is fixed to 3:3:14 in all experiments. Energy dispersive spectroscopy (EDS), powder X-ray diffraction (PXRD) and high-resolution electrospray (ESI) mass spectrometry were used to characterize the solid solution K6[Re6-xMoxS8(CN)5]. It was shown by mass spectrometry that the solid solution with fractional x contains anions based on the {Re4Mo2S8}, {Re3Mo3S8} and {Re2Mo4S8} cluster cores in different proportions depending on the above-mentioned factors. Particularly, the rise of the temperature of the synthesis or temperature of sintering of metal sulfides led to increase of the rhenium content in the solid solution.
- Published
- 2022
27. Influence of Ecological Factors on Metabolomic Composition of the Fish Lens
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Yuri P. Tsentalovich, Ekaterina A. Zelentsova, Ekaterina D. Savina, Vadim V. Yanshole, and Renad Z. Sagdeev
- Subjects
History ,Polymers and Plastics ,Business and International Management ,Industrial and Manufacturing Engineering - Published
- 2022
28. The {Re4} Tetrahedral Cyanometalate Cluster Anion [{Re4(μ3-CCN)4}(CN)12]8– with Inner (μ3-CCN)3– Ligands and Its Features in Coordination of Cu2+ Cations
- Author
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Anton I. Smolentsev, Vadim V. Yanshole, Svetlana G. Kozlova, Yakov M. Gayfulin, Aleksei S. Pronin, and Yuri V. Mironov
- Subjects
Inorganic Chemistry ,Crystallography ,010405 organic chemistry ,Chemistry ,Tetrahedron ,Cluster (physics) ,Cyanometalate ,Physical and Theoretical Chemistry ,010402 general chemistry ,01 natural sciences ,0104 chemical sciences ,Ion - Abstract
A reaction between ReI3 and KCN at elevated temperature led to the formation of the new cyanometalate cluster anion [{Re4(μ3-CCN)4}(CN)12]8– (1). The anion contains μ3-CCN3– ligands, which are stab...
- Published
- 2020
29. Mechanism of photochromic transformations and photodegradation of an asymmetrical 2,3-diarylcyclopentenone
- Author
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Vjacheslav P. Grivin, Evgeni M. Glebov, Anton V. Yadykov, Vladislav A. Nichiporenko, Ilya M. Magin, Vadim V. Yanshole, Victor F. Plyusnin, Valerii Z. Shirinian, Marina V. Parkhats, Ivan P. Pozdnyakov, Vladimir V Vyazovkin, Maria V Oplachko, and Artem B. Smolentsev
- Subjects
Materials science ,Quenching (fluorescence) ,010405 organic chemistry ,Singlet oxygen ,General Physics and Astronomy ,010402 general chemistry ,Photochemistry ,01 natural sciences ,0104 chemical sciences ,chemistry.chemical_compound ,Photochromism ,chemistry ,Thiophene ,Flash photolysis ,Physical and Theoretical Chemistry ,Triplet state ,Photodegradation ,Isomerization - Abstract
A mechanistic study of the photochromic properties and photodegradation processes of an asymmetrical diarylcyclopentenone bearing thiophene and benzothiophene units using stationary photolysis, nanosecond laser flash photolysis and time-resolved luminescence was performed. It was found that the light-induced reversible isomerization of (3-(2,5-dimethyltiophen-3-il)-2-(2-methyl-1-benzylthiophen-3-il)cyclopent-2-en-1-one, compound 1) from open to closed form is a common photochromic transformation inherent to diarylethenes, while the photodegradation process proceeds in two ways. The first is a formal 1,2-dyotropic rearrangement, proceeding without the participation of oxygen. The second is the oxygen-dependent mechanism involving the excitation of the open form 1A into the triplet state, quenching of the latter by dissolved oxygen, and oxidation of the initial compound by singlet oxygen.
- Published
- 2020
30. Deep Learning for the Precise Peak Detection in High-Resolution LC–MS Data
- Author
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Arsenty D Melnikov, Vadim V. Yanshole, and Yuri P. Tsentalovich
- Subjects
Flexibility (engineering) ,Chemistry ,business.industry ,Deep learning ,Pipeline (computing) ,010401 analytical chemistry ,High resolution ,Pattern recognition ,010402 general chemistry ,01 natural sciences ,Convolutional neural network ,0104 chemical sciences ,Analytical Chemistry ,Peak detection ,Liquid chromatography–mass spectrometry ,Artificial intelligence ,MIT License ,business - Abstract
This letter is devoted to the application of machine learning, namely, convolutional neural networks to solve problems in the initial steps of the common pipeline for data analysis in metabolomics. These steps are the peak detection and the peak integration in raw liquid chromatography-mass spectrometry (LC-MS) data. Widely used algorithms suffer from rather poor precision for these tasks, yielding many false positive signals. In the present work, we developed an algorithm named peakonly, which has high flexibility for the detection or exclusion of low-intensity noisy peaks, and shows excellent quality in the detection of true positive peaks, approaching the highest possible precision. The current approach was developed for the analysis of high-resolution LC-MS data for the purposes of metabolomics, but potentially it can be applied with several adaptations in other fields, which utilize high-resolution GC- or LC-MS techniques. Peakonly is freely available on GitHub ( https://github.com/arseha/peakonly ) under an MIT license.
- Published
- 2019
31. Tailoring Heterometallic Cluster Functional Building Blocks: Synthesis, Separation, Structural and DFT Studies of [Re 6− x Mo x Se 8 (CN) 6 ] n −
- Author
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Nikolay G. Naumov, Maxim R. Ryzhikov, Carmelo Prestipino, Vadim V. Yanshole, Yakov M. Gayfulin, Pierric Lemoine, Stéphane Cordier, and Viktoria K. Muravieva
- Subjects
Extended X-ray absorption fine structure ,Structure analysis ,010405 organic chemistry ,Chemistry ,Organic Chemistry ,General Chemistry ,Electronic structure ,Composition (combinatorics) ,010402 general chemistry ,01 natural sciences ,Redox ,Catalysis ,0104 chemical sciences ,Metal ,Crystallography ,Octahedron ,visual_art ,Cluster (physics) ,visual_art.visual_art_medium - Abstract
Influence of the metal core composition and geometry on the structure, spectroscopic properties and redox potentials was investigated for the first time for heterometallic (Re/Mo)6 octahedral clusters. The discrete anionic clusters [Re6-x Mox Se8 (CN)6 ]n- (x=2, 3; n=4, 5) were obtained as individual salts. Their isomeric composition and bond-length distribution were inspected using a combination of single-crystal X-ray structure analysis, NMR, EXAFS, and DFT calculations.
- Published
- 2019
32. Direct UV photodegradation of herbicide triclopyr in aqueous solutions: A mechanistic study
- Author
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Ivan P. Pozdnyakov, Olga A. Snytnikova, Vadim V. Yanshole, Roman G. Fedunov, Vyacheslav P. Grivin, and Victor F. Plyusnin
- Subjects
Kinetics ,Environmental Engineering ,Photolysis ,Herbicides ,Health, Toxicology and Mutagenesis ,Public Health, Environmental and Occupational Health ,Environmental Chemistry ,Water ,General Medicine ,General Chemistry ,Pollution ,Water Pollutants, Chemical ,Glycolates - Abstract
Mechanism of direct UV photolysis of pyridine herbicide triclopyr (TRI) was revealed by the combination of nanosecond laser flash photolysis, steady-state photolysis coupled with high resolution LC-MS and DFT quantum-chemical calculations. Both the detection of short-lived intermediates and the detailed identification of final products were done for the first time. The quantum yield of TRI photodegradation is about 4% at both UVC (254 nm) and UVB (308 nm) excitation. The primary stage is the heterolytic cleavage of C-Cl bond in dissociative triplet state of TRI with the formation of phenyl cation followed by a fast nucleophilic attack by a solvent molecule. The minor channel is the photohydrolysis leading to the formation of 3,5,6-trichloropyridin-2-ol. Primary photoproducts undergo secondary photolysis by the mechanism similar to initial TRI with the formation of products of acetic group elimination, sequential substitution of chlorine atoms to hydroxyl groups and, finally, oxidation and opening of the pyridine ring. Obtained results can be important for understanding the fate of pyridine herbicides in the processes of UVC disinfection and in natural waters under action of the sunlight.
- Published
- 2021
33. Synthesis, Structure, and Spectroscopic Study of Redox-Active Heterometallic Cluster-Based Complexes [Re
- Author
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Viktoria K, Muravieva, Ivan P, Loginov, Taisiya S, Sukhikh, Maxim R, Ryzhikov, Vadim V, Yanshole, Vladimir A, Nadolinny, Vincent, Dorcet, Stéphane, Cordier, and Nikolay G, Naumov
- Abstract
The heterometallic cluster-based compound K
- Published
- 2021
34. Metabolomic profiling of biological fluids of patients with lymphedema
- Author
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Vadim V. Yanshole, Ekaterina A. Zelentsova, Lyudmila V. Yanshole, Vadim Nimaev, Rustam Khapaev, and Yuri P. Tsentalovich
- Subjects
Breast cancer ,Lymphatic system ,Metabolomics ,Lymphedema ,Blood serum ,Interstitial space ,Interstitial fluid ,business.industry ,medicine ,Disease ,medicine.disease ,business ,Bioinformatics - Abstract
Lymphedema is a congenital or acquired pathology which appears as an accumulation of a protein-rich fluid in the interstitial space, the limbs swelling, and subsequently fibrous changes in the skin and subcutaneous tissue due to functional disorders of the lymphatic bed. In our days, the use of conservative and surgical treatment can only stanch symptoms, slow down the progress of the disease and prevent complications. But, even in this case, the patient’s quality of life deteriorates. This makes the search for new and effective methods for the early diagnosis and treatment of lymphedema extremely urgent. This is especially important for patients after complex treatment of breast cancer. One of the main objectives of the paper is to identify changes in the metabolomic profiles of human biological fluids, such as blood serum and interstitial fluid. This work is aimed at identifying metabolomic markers - lymphedema precursors in the blood serum of patients in the early stages of the disease development. Metabolomic analysis allows to establishing the molecular mechanisms of lymphedema. The simultaneous use of high-field NMR spectroscopy and high-performance liquid chromatography with optical and mass spectrometric detection is sufficient for quantitative metabolomic profiling of biological fluids. The use of a metabolomic approach to the study of changes in the human lymphatic system functioning will contribute to both a better understanding of the mechanisms of the onset and development of lymph outflow dysfunction, and the development of new tools for early diagnosis and personalized treatment of lymphedema of various origins.
- Published
- 2021
35. Coordination capacity of Keggin anions as polytopic ligands: case study of [VNb
- Author
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Anna A, Mukhacheva, Victoria V, Volcheck, Dmitry G, Sheven, Vadim V, Yanshole, Nikolay B, Kompankov, Mohamed, Haouas, Pavel A, Abramov, and Maxim N, Sokolov
- Abstract
Reaction of Na9H4[VNb12O40{NbO(CO3)}2] with [(C6H6)RuCl2]2 (molar ratio {VNb12} : {(C6H6)Ru} = 1 : 4) in aqueous solution gives a mixture of [α-{(C6H6)Ru}4VNb12O40]7- and [α-{(C6H6)Ru}3VNb12O40]9-. Direct acetone diffusion into mother liquor leads to crystallization of Na6H[α-{(C6H6)Ru}4VNb12O40]·41.25H2O (1), characterized by single crystal X-ray diffraction (SCXRD). This anion has four organometallic fragments coordinated to the α-Keggin type [VNb12O40]15- backbone in different manner. Three {(C6H6)Ru}2+ groups cap triangular faces and one group a rectangular face of [VNb12O40]15-. Equilibrated mixture of [α-{(C6H6)Ru}4VNb12O40]7- and [α-{(C6H6)Ru}3VNb12O40]9- was studied by 1H DOSY NMR, HPLC-ICP-AES and HPLC-ESI-MS combined techniques. Direct chromatographic separation of these complexes results in unexpected transformation of both species into [α-{(C6H6)Ru}5VNb12O40]5-, isolated and characterized as Na5[α-{(C6H6)Ru}5VNb12O40]·16H2O (2). This anion contains five coordinated organometallic groups occupying both triangular and rectangular faces.
- Published
- 2021
36. Stabilization of Re
- Author
-
Spartak S, Yarovoy, Yakov M, Gayfulin, Anton I, Smolentsev, Vadim V, Yanshole, and Yuri V, Mironov
- Abstract
The interaction of rhenium(III) halides Re
- Published
- 2021
37. A previously unknown way of heme detoxification in the digestive tract of cats
- Author
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Yuri P. Tsentalovich, Vadim V. Yanshole, Petr S. Sherin, O. I. Sinitsyna, Sergey L. Veber, S. I. Baiborodin, and Alexandr B. Duzhak
- Subjects
0301 basic medicine ,ADSORPTION ,02 engineering and technology ,Matrix (biology) ,Biochemistry ,TOXICITY ,chemistry.chemical_compound ,Feces ,Heme ,Multidisciplinary ,CATS ,Gastric Juice ,Hemozoin ,IRON ,MIDGUT ,Gastroenterology ,021001 nanoscience & nanotechnology ,Chemical biology ,Multidisciplinary Sciences ,medicine.anatomical_structure ,TARGET ,Inactivation, Metabolic ,Medicine ,Science & Technology - Other Topics ,0210 nano-technology ,BONE ,Science ,Article ,Excretion ,03 medical and health sciences ,Detoxification ,medicine ,Animals ,Science & Technology ,RED ,Animal Feed ,In vitro ,Small intestine ,Diet ,Gastrointestinal Tract ,030104 developmental biology ,CARBONATED HYDROXYAPATITE ,Durapatite ,chemistry ,Cats ,Nanoparticles ,HEMOZOIN - Abstract
Free heme is a highly toxic molecule for a living organism and its detoxification is a very important process, especially for carnivorous animals. Here we report the discovery of a previously unknown process for neutralizing free heme in the digestive tract of domestic cats. The cornerstone of this process is the encapsulation of heme into carbonated hydroxyapatite nanoparticles, followed by their excretion with faeces. This way of heme neutralization resembles the formation of insoluble heme-containing particles in the digestive tracts of other hematophagous species (for example, the formation of insoluble hemozoin crystals in malaria-causing Plasmodium parasites). Our findings suggest that the encapsulation of heme molecules into a hydroxyapatite matrix occurs during the transition from the acidic gastric juice to the small intestine with neutral conditions. The formation of these particles and their efficiency to include heme depends on the bone content in a cat’s diet. In vitro experiments with heme-hydroxyapatite nanoparticles confirm the proposed scenario.
- Published
- 2021
38. Direct UVC photodegradation of imipramine in aqueous solutions: a mechanistic study
- Author
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Vadim V. Yanshole, Vyacheslav P. Grivin, Ekaterina D. Mordvinova, Victoria A. Salomatova, Olga A. Snytnikova, and Ivan P. Pozdnyakov
- Subjects
Aqueous solution ,010405 organic chemistry ,Chemistry ,Photodissociation ,Quantum yield ,General Chemistry ,Photoionization ,Molar absorptivity ,010402 general chemistry ,Photochemistry ,01 natural sciences ,0104 chemical sciences ,Radical ion ,Flash photolysis ,Photodegradation - Abstract
Mechanism of direct UVC photolysis of dibenzazepine-type drug imipramine (IMI) was revealed by the combination of laser flash photolysis for the detection of short lived intermediates and steady-state photolysis coupled with LC-MS for identification of final products. Both quantum yield of IMI photoionization and molar absorption coefficient of IMI radical cation were determined for the first time.
- Published
- 2020
39. Water-soluble Re6-clusters with aromatic phosphine ligands – from synthesis to potential biomedical applications
- Author
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Noboru Kitamura, Michael A. Shestopalov, Anastasiya O. Solovieva, Dmitry I. Konovalov, Natalia V. Kuratieva, Kamil Lang, Vadim V. Yanshole, L. V. Shestopalova, Anton A. Ivanov, Anatoly R. Melnikov, Tatiana N. Pozmogova, Kaplan Kirakci, Svetlana N. Cheltygmasheva, Yuri V. Mironov, and Konstantin A. Brylev
- Subjects
Photoluminescence ,medicine.medical_treatment ,Photodynamic therapy ,Combinatorial chemistry ,Inorganic Chemistry ,chemistry.chemical_compound ,chemistry ,Excited state ,Amphiphile ,medicine ,Cluster (physics) ,Cytotoxicity ,Luminescence ,Phosphine - Abstract
The development of water-soluble hexanuclear cluster complexes of low toxicity is a promising task due to their potential biomedical applications such as bioimaging and photodynamic therapy. Herein, we present the syntheses of two new water-soluble hexarhenium cluster complexes with terminal amphiphilic phosphine ligands, and delineate their photoluminescence and X-ray excited optical luminescence (XEOL) properties. These cluster complexes, namely [{Re6Q8}(PPh2CH2CH2COO)6]4− (Q = S (1); Se, (2)), have the least cytotoxicity among all the tested hexanuclear metal-clusters, are capable of penetrating into cells and exhibit moderate photodynamic toxicity toward Hep-2 cells.
- Published
- 2019
40. Photoinduced inhibition of DNA repair enzymes and the possible mechanism of photochemical transformations of the ruthenium nitrosyl complex [RuNO(β-Pic)2(NO2)2OH]
- Author
-
Gennadiy A. Kostin, Daria V. Petrova, Vladislav A. Nichiporenko, Vjacheslav P. Grivin, Darya V. Khantakova, Vadim V. Yanshole, Artem A. Mikhailov, Victor F. Plyusnin, Evgeni M. Glebov, and Inga R. Grin
- Subjects
0301 basic medicine ,030102 biochemistry & molecular biology ,DNA repair ,Chemistry ,Photodissociation ,Metals and Alloys ,Biophysics ,chemistry.chemical_element ,Covalent Interaction ,Photochemistry ,Mass spectrometry ,Cleavage (embryo) ,Biochemistry ,Ruthenium ,Biomaterials ,Solvent ,03 medical and health sciences ,030104 developmental biology ,Chemistry (miscellaneous) ,DNA glycosylase - Abstract
In this work we have demonstrated that the ruthenium nitrosyl complex [RuNO(β-Pic)2(NO2)2OH] is suitable for investigation of the inactivation of DNA repair enzymes in vitro. Photoinduced inhibition of DNA glycosylases such as E. coli Endo III, plant NtROS1, mammalian mNEIL1 and hNEIL2 occurs to an extent of ≥90% after irradiation with the ruthenium complex. The photophysical and photochemical processes of [RuNO(β-Pic)2(NO2)2OH] were investigated using stationary and time-resolved spectroscopy, and mass spectrometry. A possible mechanism of the photo-processes was proposed from the combined spectroscopic study and DTF calculations, which reveal that the photolysis is multistage. The primary and secondary photolysis stages are the photo-induced cleavage of the Ru–NO bond with the formation of a free nitric oxide and RuIII complex followed by ligand exchange with solvent. For E. coli Endo III, covalent interaction with the photolysis product was confirmed by UV-vis and mass spectrometric methods.
- Published
- 2019
41. A novel method of sample homogenization with the use of a microtome-cryostat apparatus
- Author
-
Ekaterina A. Zelentsova, Vadim V. Yanshole, and Yuri P. Tsentalovich
- Subjects
Cryostat ,Materials science ,Chromatography ,Sample Weight ,General Chemical Engineering ,Sample (material) ,02 engineering and technology ,General Chemistry ,010402 general chemistry ,021001 nanoscience & nanotechnology ,01 natural sciences ,0104 chemical sciences ,law.invention ,law ,Heat generation ,Microtome ,Sample preparation ,0210 nano-technology ,Homogenization (biology) - Abstract
Quantitative metabolomics places high demands on sample preparation, including a high degree of metabolite extraction and controlled sample weight. In respect to elastic collagen-rich tissues, the existing methods of sample homogenization poorly fit these demands due to incomplete homogenization, sample material loss, or metabolite degradation. Herein, a novel method based on the use of a microtome-cryostat apparatus is proposed. The performance of the cryotome method is compared with the results obtained with the use of a vortex bead beating. NMR-based metabolomic analysis shows that the extraction efficiency and the data scattering for both methods of sample preparation are similar. However, the heat generation during the bead beating causes the destruction of thermally-unstable compounds; besides, it may cause protein hydrolysis, leading to an artificial increase in the amino acid level. The cryotome method of sample homogenization does not cause sample heating, and it seems to be ideal for elastic tissues.
- Published
- 2019
42. Niobium uptake by a [P8W48O184]40−macrocyclic polyanion
- Author
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Vadim V. Yanshole, Nikolay B. Kompankov, Victoria V. Volchek, Maxim N. Sokolov, Nicolas P. Martin, May Nyman, Alexandra A. Shmakova, and Pavel A. Abramov
- Subjects
Thermogravimetric analysis ,Aqueous solution ,Small-angle X-ray scattering ,Niobium ,chemistry.chemical_element ,02 engineering and technology ,General Chemistry ,010402 general chemistry ,021001 nanoscience & nanotechnology ,01 natural sciences ,Catalysis ,0104 chemical sciences ,Crystallography ,chemistry ,Elemental analysis ,Inductively coupled plasma atomic emission spectroscopy ,Materials Chemistry ,0210 nano-technology ,Single crystal ,Natural bond orbital - Abstract
Reactions of inorganic macrocyclic polytungstate cavitands K28Li5H7[P8W48O184]·92H2O or Li17(NH4)21H2[P8W48O184]·85H2O with (NH4)[NbO(C2O4)2(H2O)2]·3H2O (Nb–Ox) in aqueous solution lead to incorporation of up to five {NbO(H2O)}3+ units into the {P8W48} cavity. The most stable species contain four {NbO(H2O)}3+ units. The uptake of {NbO(H2O)}3+ was determined by corroborative methods including single crystal XRD, inductively coupled plasma atomic emission spectroscopy (ICP-AES), 31P and 13C nuclear magnetic resonance (NMR), C–H–N elemental analysis (EA) and thermal gravimetric analysis (TGA). Solution speciation of the Nb-encapsulating macrocycles was studied by HPLC-ICP-AES and small angle X-ray scattering (SAXS).
- Published
- 2019
43. Reactions of [Ru(NO)Cl5]2− with pseudotrilacunary {XW9O33}9− (X = AsIII, SbIII) anions
- Author
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Enrico Benassi, Anna A. Mukhacheva, Artem L. Gushchin, Vadim V. Yanshole, Alexandra A. Shmakova, Victoria V. Volchek, Pavel A. Abramov, Dmitri G Sheven, Nikolay B. Kompankov, Maxim N. Sokolov, and Tamara E. Romanova
- Subjects
chemistry.chemical_classification ,Quantum chemical ,010405 organic chemistry ,chemistry.chemical_element ,Salt (chemistry) ,010402 general chemistry ,01 natural sciences ,Medicinal chemistry ,0104 chemical sciences ,Ion ,Inorganic Chemistry ,chemistry ,Antimony ,Polyoxometalate ,Arsenic - Abstract
Reactions of [Ru(NO)Cl5]2- with pseudotrivacant B-α-[XW9O33]9- (X = AsIII, SbIII) at 160 °C result in the rearrangement of polyoxometalate backbones into {XM18} structures. In the case of arsenic, oxidation of AsIII to AsV takes place with the formation of a mixture of plenary and monosubstituted Dawson [As2W18O62]6- and [As2W17Ru(NO)O61]7- anions, of which the latter was isolated as Me2NH2+ (DMA-1a and DMA-1b) and Bu4N+ (Bu4N-1) salts and fully characterized. Both α1 and α2 isomers of [As2W17Ru(NO)O61]7- were present in the reaction mixture; pure [α2-As2W17Ru(NO)O61]7- was isolated as the Bu4N+ salt. In the case of antimony, [SbW9O33]9- is converted into a mixture of [SbW18O60]9- and [SbW17{Ru(NO)}O59]10-. The formation of trisubstituted [SbW15{Ru(NO)}3O57]12- as a minor byproduct was detected by HPLC-ICP-AES. The monosubstituted [SbW17{Ru(NO)}O59]10- anion was isolated as DMAH+ (DMA-2) and mixed inorganic cation (CsKNa-2) salts and characterized by XRD, HPLC-ICP-AES, EA and TGA techniques. X-ray analysis shows the presence of the {Ru(NO)}-group in the 6-membered ("equatorial") belt of the Sb-free hemisphere. The experimental findings were confirmed and interpreted by means of quantum chemical calculations.
- Published
- 2019
44. From Photoinduced to Dark Cytotoxicity through an Octahedral Cluster Hydrolysis
- Author
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Darya V. Evtushok, Olga A. Efremova, Ali M. Adawi, J. S. Bouillard, Anton A. Ivanov, Michael A. Shestopalov, Svetlana M. Miroshnichenko, Yuri V. Mironov, Vadim V. Yanshole, Yuri A. Vorotnikov, Maria S. Fufaeva, Charlotte J. Eling, Ilia V. Eltsov, Ekaterina V. Svezhentseva, Natalia V. Kuratieva, L. V. Shestopalova, Anastasiya O. Solovieva, and Tatiana N. Pozmogova
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Models, Molecular ,Octahedral cluster ,Light ,Cell Survival ,chemistry.chemical_element ,Nanoparticle ,Antineoplastic Agents ,02 engineering and technology ,Tungsten ,010402 general chemistry ,Photochemistry ,01 natural sciences ,Catalysis ,Hydrolysis ,Drug Stability ,Cell Line, Tumor ,Neoplasms ,Humans ,Solubility ,Molybdenum ,Photosensitizing Agents ,Endoplasmic reticulum ,Organic Chemistry ,Hep G2 Cells ,General Chemistry ,Photochemical Processes ,021001 nanoscience & nanotechnology ,0104 chemical sciences ,chemistry ,Octahedron ,0210 nano-technology - Abstract
Octahedral molybdenum and tungsten clusters have potential biological applications in photodynamic therapy and bioimaging. However, poor solubility and hydrolysis stability of these compounds hinder their application. The first water-soluble photoluminescent octahedral tungsten cluster [{W6 I8 }(DMSO)6 ](NO3 )4 was synthesised and demonstrated to be at least one order of magnitude more stable towards hydrolysis than its molybdenum analogue. Biological studies of the compound on larynx carcinoma cells suggest that it has a significant photoinduced toxicity, while the dark toxicity increases with the increase of the degree of hydrolysis. The increase of the dark toxicity is associated with the in situ generation of nanoparticles that clog up the cisternae of rough endoplasmic reticulum.
- Published
- 2018
45. Probing reactions between imipramine and hydroxyl radical with the photolysis of iron(III) oxalate: Implications for the indirect photooxidation of tricyclic antidepressants in waters
- Author
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Vadim V. Yanshole, Jing Xu, V.P. Grivin, Roman G. Fedunov, Olga A. Snytnikova, Semen E. Erokhin, Victor F. Plyusnin, Ivan P. Pozdnyakov, Feng Wu, and Mikhail V. Novikov
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General Chemical Engineering ,Radical ,General Physics and Astronomy ,General Chemistry ,Potassium persulfate ,Photochemistry ,Persulfate ,Oxalate ,chemistry.chemical_compound ,Reaction rate constant ,chemistry ,Flash photolysis ,Hydroxyl radical ,Photodegradation - Abstract
Photodegradation of imipramine (IMI), a widely used tricyclic antidepressant, in the presence of Fe(III) oxalate and potassium persulfate (PS) was studied for the first time by combination of steady state and laser flash photolysis. It was demonstrated that Fe(III) oxalate system exhibits an effective photooxidation of IMI due to the formation of reactive oxygen species (ROS) with a very high quantum yield, φROS(308 nm) ∼0.3. The quantum yield of the most important ROS, hydroxyl radical, was also measured for the first time (φOH(308 nm) = 0.25 ± 0.02) as well as the rate constant of the reaction between •OH radical and IMI (kOH = (1.5 ± 0.1) ×1010 M−1s−1). Nature and spectral properties of short lived organic radicals formed in this reaction were also determined experimentally and proved by quantum-chemical calculations. At a IMI concentration of less than 10 µM it is possible to achieve full disappearance of the initial compound in Fe(III)-oxalate system. Main aromatic by-products of the IMI oxidation are connected with its consequent hydroxylation and elimination of aliphatic substituent. Complete degradation of both IMI and all aromatic byproducts needs joint application of Fe(III) oxalate and PS, as additional oxidizing agent. Combined Fe(III) oxalate – PS system demonstrates high photoactivity under UV irradiation and could be used for the effective degradation of IMI and its close analogues in aqueous media.
- Published
- 2022
46. The {Re
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Aleksei S, Pronin, Yakov M, Gayfulin, Anton I, Smolentsev, Svetlana G, Kozlova, Vadim V, Yanshole, and Yuri V, Mironov
- Abstract
A reaction between ReI
- Published
- 2020
47. Water-Soluble Rhenium Clusters with Triazoles: The Effect of Chemical Structure on Cellular Internalization and the DNA Binding of the Complexes
- Author
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Masoomeh Bazzar, Jean-Sebastien G. Bouillard, Vadim V. Yanshole, Louis Plunkett, Tatiana S. Frolova, Michael A. Shestopalov, Dmitry I. Konovalov, Ali M. Adawi, Ilia V. Eltsov, Yakov M. Gayfulin, Olga A. Efremova, S. I. Baiborodin, Anton A. Ivanov, Natalia V. Kuratieva, and Olga I. Sinitsyna
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Luminescence ,media_common.quotation_subject ,Chemical structure ,chemistry.chemical_element ,010402 general chemistry ,Ligands ,01 natural sciences ,Catalysis ,Cell Line ,HeLa ,chemistry.chemical_compound ,Coordination Complexes ,Humans ,Internalization ,Cytotoxicity ,media_common ,Benzotriazole ,biology ,010405 organic chemistry ,Organic Chemistry ,Water ,General Chemistry ,DNA ,Rhenium ,Fibroblasts ,Triazoles ,biology.organism_classification ,Combinatorial chemistry ,0104 chemical sciences ,chemistry ,Cell culture - Abstract
Here we explore the effect of the nature of organic ligands in rhenium cluster complexes [Re6 Q8 L6 ]4- (where Q=S or Se, and L=benzotriazole, 1,2,3-triazole or 1,2,4-triazole) on the biological properties of the complexes, in particular on the cellular toxicity, cellular internalization and localization. Specifically, the study describes the synthesis and detailed characterization of the structure, luminescence and electrochemical properties of the four new Re6 clusters with 1,2,3- and 1,2,4-triazoles. Biological assays of these complexes are also discussed in addition to those with benzotriazole using cervical cancer (HeLa) and immortalized human fibroblasts (CRL-4025) as model cell lines. Our study demonstrates that the presence of hydrophobic and π-bonding rich units such as the benzene ring in benzotriazole significantly enhances cellular internalization of rhenium clusters. These ligands facilitate binding of the clusters to DNA, which results in increased cytotoxicity of the complexes.
- Published
- 2020
48. Easy Ligand Activation in the Coordination Sphere of Ru inside the [PW11O39]7– Backbone
- Author
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Maksim N. Sokolov, Vadim V. Yanshole, Artem L. Gushchin, Anna A. Mukhacheva, and Pavel A. Abramov
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Azides ,Spectrometry, Mass, Electrospray Ionization ,Coordination sphere ,Pharmaceutical Science ,chemistry.chemical_element ,Ligands ,Article ,Analytical Chemistry ,lcsh:QD241-441 ,chemistry.chemical_compound ,lcsh:Organic chemistry ,Coordination Complexes ,Drug Discovery ,polyoxometalate ,azide ,Physical and Theoretical Chemistry ,ruthenium ,Molecular Structure ,Ligand ,Photoelectron Spectroscopy ,Organic Chemistry ,Tungsten Compounds ,Ruthenium ,HR-ESI-MS ,Crystallography ,chemistry ,Chemistry (miscellaneous) ,Product (mathematics) ,Polyoxometalate ,Molecular Medicine ,CV ,Azide - Abstract
Irradiation of the Keggin-type [PW11O39{Ru(NO)}]4&minus, (Ru-NO) polyoxometalate in CH3CN results in rapid NO ligand elimination with the formation of [PW11O39{RuIII(CH3CN)}]4&minus, (Ru-CH3CN). This complex offers an easy entry into the Ru-based chemistry of the {PW11Ru} complex. Attempts to substitute N3&minus, for CH3CN in the presence of an NaN3 excess lead a variety of products: (i) [PW11O39{RuIII(N3)}]4&minus, (Ru-N3), (ii) [PW11O39{RuIII(N4HC-CH3)}]4&minus, (Ru-Tz) as a click-reaction product, and (iii) [PW11O39{RuII(N2)}]5&minus, (Ru-N2). UV-VIS, CV, and HR-ESI-MS techniques were used for the reaction monitoring and characterization of the products.
- Published
- 2020
49. Is It Possible To Prepare a Heterometal Anderson-Evans Type Anion?
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Nikolay B. Kompankov, Anna A. Mukhacheva, Artem L. Gushchin, Victoria V. Volchek, Vadim V. Yanshole, Maxim N. Sokolov, Enrico Benassi, and Pavel A. Abramov
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Inorganic Chemistry ,010405 organic chemistry ,Chemistry ,Physical and Theoretical Chemistry ,Type (model theory) ,010402 general chemistry ,01 natural sciences ,Medicinal chemistry ,0104 chemical sciences ,Ion - Abstract
Reaction of [SbW9O33]9- with [Pt(H2O)2(OH)4] results in the first example of the mixed addenda Anderson-Evans type PtIV{SbV(OH)2}WVI5O22]7- anion, isolated and characterized as K6Na2[Pt{Sb(OH)2}W5O22](NO3)0.1(OH)0.911H2O (1).
- Published
- 2020
50. Mixed-metal clusters with a {Re3Mo3Se8} core: from a polymeric solid to soluble species with multiple redox transitions
- Author
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Dmitry A. Piryazev, Nikolay G. Naumov, Yakov M. Gayfulin, Denis G. Samsonenko, Maxim R. Ryzhikov, Vadim V. Yanshole, Viktoria K. Muravieva, Igor N. Novozhilov, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Novosibirsk State University (NSU), 16-33-00085, RFBR, Russian Foundation for Basic Research, Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)
- Subjects
Chemistry ,02 engineering and technology ,Electronic structure ,Crystal structure ,010402 general chemistry ,021001 nanoscience & nanotechnology ,01 natural sciences ,0104 chemical sciences ,Ion ,Inorganic Chemistry ,Crystallography ,Paramagnetism ,Salt metathesis reaction ,Cluster (physics) ,[CHIM]Chemical Sciences ,Cyclic voltammetry ,0210 nano-technology ,Valence electron - Abstract
Cluster compounds based on a new {Re3Mo3Se8}n core were obtained and studied. The polymeric solid K6[Re3Mo3Se8(CN)4(CN)2/2] (1) containing 24 cluster valence electrons (CVE) was isolated as a result of high-temperature reaction. Water-soluble salts K5[Re3Mo3Se8(CN)6]·11H2O (2) and Cs5[Re3Mo3Se8(CN)6]·H2O (3) were prepared from compound 1. Crystal structures of the diamagnetic compounds 2 and 3 contain a cluster anion [Re3Mo3Se8(CN)6]5- with a 22-electronic core {Re3Mo3Se8}+. Metathesis reaction followed by recrystallization from CH3CN yielded paramagnetic salt (Ph4P)4[Re3Mo3Se8(CN)6]·2CH3CN (4) containing the {Re3Mo3Se8}2+ core with 21 CVE. Cyclic voltammetry of the solution of 4 displayed three quasi-reversible waves with E1/2 = -0.325, -0.818 and -1.410 V vs. Ag/AgCl electrode indicating the presence of [Re3Mo3Se8(CN)6]4-/5-/6-/7- transitions. Electronic structure calculations showed that both mer- and fac-isomers of [Re3Mo3Se8(CN)6]n- clusters undergo great distortion when the number of CVE decreases.
- Published
- 2018
Catalog
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