Vol 89, No 2 (2019)
- Year: 2019
- Articles: 30
- URL: https://journals.rcsi.science/1070-3632/issue/view/13707
Article
Physico-Chemical Bases of BaBiO3 Perovskite Synthesis
Abstract
The physico-chemical basis of optimal conditions for synthesis of BaBiO3 oxide, free from impurities of BaBiO3 and BaBiO3−x oxygen-deficient phases, is given. The reduction of time of the melt contact with a crucible makes it possible to obtain BaBiO3 samples minimum polluted by a crucible material. It was found that an abnormal behavior of BaBiO3 in the course of long-time annealing in air at 450°C is caused by the interaction with CO2.
Solubility of Ozone in Organic Solvents
Abstract
The possibility of using spectrophotometric method for the evaluation of ozone solubility in highly concentrated solutions by measuring absorption in the Chappuis band directly in the liquid phase has been demonstrated. The solubilities of ozone in various organic solvents have been determined, and its limiting solubility has been calculated. The molar absorption coefficient in the long-wavelength band of ozone has been found to depend on the solvent nature.
Study of Kinetics and Mechanism of Heterogenous Catalytic Hydrazinolysis of Oleic Acid
Abstract
Kinetics and mechanism of the hydrazinolysis of oleic acid in the presence of a highly basic anionexchange resin AV-17-8 have been studied for the first time. The first reaction rate order has been found. The values of activation energy and entropy of the process have been determined. A plausible reaction mechanism involving a fixed resin cation has been proposed basing on the kinetic and IR spectroscopy data.
Kinetics of Thermal Decomposition of 3,7-Dinitro-1,3,5,7-tetraazabicyclo[3.3.1]nonane
Abstract
The kinetics of thermal decomposition of 3,7-dinitro-1,3,5,7-tetraazabicyclo[3.3.1]nonane has been studied in solid phase and in solution. The mechanism, kinetic parameters of decomposition, and activation parameters of the rate-limiting step have been determined.
Structure and Conformational Analysis of 5,5-Bis(bromomethyl)-2-methyl-2-phenyl-1,3-dioxane
Abstract
The structure of 5,5-bis(bromomethyl)-2-methyl-2-phenyl-1,3-dioxane 1 has been studied by means of 1H and 13C NMR spectroscopy as well as X-ray diffraction analysis. The molecules of compound 1 exist in the chair conformation with the axially oriented phenyl group. The computer simulation using DFT approximation at the PBE/3ξ level has revealed the route of interconversion of the ring and the optimal conformation of the phenyl group corresponding to the data of X-ray diffraction analysis.
Catalytic Aminomethylation of Aminobenzamides with Bis(N,N-dimethylamino)methane and Carbamides
Abstract
An effective method was developed for the synthesis of acyclic aniline derivatives bearing carbamide fragments by the reaction of carbamides with ortho-, meta-, and para-aminobenzamides and bis(N,N-dimethylamino) methane in the presence of NiCl2·6H2O and SmCl3·6H2O as catalysts.
Isomeric Bisdicyanomethylene-Substituted 1,3- and 1,2-Pyrilo-4-squaraines: Synthesis, Molecular, and Crystal Structure
Abstract
Isomeric biscyanomethylene-substituted 1,3- and 1,2-pyrilo-4-squaraines have been synthesized. The formation of a dye, derivative of 1,2-squarate, from the derivative of 1,3-squarate has been demonstrated for the first time. Electronic absorption spectra of the synthesized dyes have been studied. The molecular and crystal structure has been investigated by X-ray diffraction analysis. Both isomeric dyes exist in the cis-conformation.
Reactions of (E)-(3-Aryl-3-oxoprop-1-en-1-yl)triphenylphosphonium Bromides with Arylhydrazines
Abstract
(E)-(3-Aryl-3-oxoprop-1en-1-yl)triphenylphosphonium bromides reacted with arylhydrazines in an acidic medium to form hydrazones, the intramolecular heterocyclization of which led to the formation of (2,5- diaryl-2,3-dihydro-1H-pyrazol-3-yl)triphenylphosphonium bromides. Under the action of hydrobromic acid, the resulting quaternary phosphonium salts produced saturated (3-aryl-3-oxopropyl)triphenylphosphonium salts.
Synthesis and Structure of Disodium 1,2-Bis(2-oxocycloalkylidene)ethane-1,2-diolates and Disodium 4-Alkoxy-4-oxo-1-(2-oxocycloalkylidene)but-2-ene-1,2-diolates
Abstract
Two-stage condensation of cycloalkyl ketones with dimethyl oxalate or alkyl acetates with dialkyl oxalates and cycloalkyl ketones produced disodium 1,2-bis(2-oxocycloalkylidene)ethane-1,2-diolates and disodium 4-alkoxy-4-oxo-1-(2-oxocycloalkylidene)but-2-ene-1,2-diolates, respectively. The structural features of the obtained compounds were discussed on the basis of their IR, 1H NMR spectroscopy, and mass spectrometry data.
Pyrazine-2-carbohydrazone of Pyridoxal 5′-Phosphate: Synthesis, Stability, Formation Kinetics, and Interaction with DNA
Abstract
(5-Hydroxy-6-methyl-4-{(E)-[2-oxo-2-(pyrazin-2-yl)ethyl]hydrazinylidenemethyl}pyridin-3-yl)- methyl phosphate has been synthesized via the interaction of pyridoxal-5-phosphate and pyrazin-2- carbohydrazide. Its stability constants in an aqueous solution at pH = 1.9, 6.6, 7.0, and 7.4 have been determined. The kinetics of formation and hydrolysis of the hydrazone has been studied, and rate constants of the direct and reverse reactions have been calculated from the electronic absorption spectroscopy data. The interaction of the obtained hydrazone and its Cu(II) complex with calf thymus DNA has been investigated.
Bis[2-(4-pyridyl)ethyl](2-cyanoethyl)phosphine Oxide: Synthesis and Reactions with 1,4-Dihalobutanes
Abstract
Bis[2-(4-pyridyl)ethyl]phosphine reacts with acrylonitrile under mild conditions to form bis[2-(4- pyridyl)ethyl](2-cyanoethyl)phosphine which is readily oxidized in air to the corresponding bis[2-(4-pyridyl)- ethyl](2-cyanoethyl)phosphine oxide. The latter compound reacts with 1,4-dihalobutanes according the scheme of polyquaternization with practically quantitative formation of high-molecular cationic compounds (ionenes) bearing phosphine oxide groups and pyridinium cycles in the main chain. The thus obtained ionenes enter the intermolecular interaction with anionic polyelectrolytes (polyacrylic acid, heparin). They were also found to exhibit antibacterial activity.
Thermodynamics of Complexation Reactions of Pr3+ and Sm3+ Ions with Glycylglycine in an Aqueous Solution
Abstract
Enthalpies of complexation of diglycine (HL±) with Pr3+ and Sm3+ ions at 303.15 K and I = 0.5 (KNO3) have been determined by means of calorimetry. The thermodynamic parameters of the formation of diglycine complexes with Pr3+ and Sm3+ ions have been calculated at different molar ratios between metal and the ligand.
Spectrophotometric Study of Acid-Base Properties of Sulfonated Derivatives of 5,10,15,20-Tetraphenyl-21-thiaand 5,10,15,20-Tetraphenyl-21-oxoporphyrins in the Ethanol–Sulfuric Acid System
Abstract
Spectral and basic properties of heterosubstituted porphyrins of anionic type have studied by means of spectrophotometric titration in comparison with their structural analog — tetraphenylporphine tetrasulfonic acid. The parameters of electronic absorption spectra and concentration ranges of existence of the mono- and diprotonated forms of the studied ligands as well as the constants of basic dissociation have been determined. Comparative analysis of the effect of the reactive site modification and the medium composition on the basicity of the compounds has been performed.
Zinc(II) Complexes with Tetrafluoroterephthalic and Octafluorobiphenyl-4,4′-dicarboxylic Acid Anions and 1,10-Phenanthroline
Abstract
Zinc(II) complexes with 1,10-phenanthroline and tetrafluoroterephthalate and octafluorobiphenyl 4,4′-dicarboxylate anions have been synthesized. According to the IR spectral data, the complexation involves coordination of the metal ion to the nitrogen atoms of phenanthroline and carboxylate oxygen atom of the acid anion. The complexes show photoluminescence in the visible region of the spectrum. The structure of the complex salt [Zn(H2O)6][Zn(H2O)4(L2)2] · H2O, where L2 is octafluorobiphenyl-4,4′-dicarboxylate anion (monodentate ligand), has been determined by X-ray analysis.
Redox Processes Involving Quinones on Poly-3,4-ethylenedioxythiophene-Modified Glassy Carbon Surface
2,3,9,10,16,17,23,24-Octakis-[(4-phenoxy)phenoxy]phthalocyanine and Its Erbium Complexes. Synthesis, Spectral, and Luminescent Properties, Self-Association
Abstract
4,5-bis[(4-phenoxy)phenoxy]phthalonitrile was obtained by the reaction of 4,5-dichlorophthalonitrile with 4-phenoxyphenol. On its basis 2,3,9,10,16,17,23,24-octakis-[(4-phenoxy)phenoxy]phthalocyanine and its single- and double-decked complexes with erbium were synthesized. Spectral-luminescent properties of resulting phthalocyanines were studied. The tendency of phthalocyanines to association in dichloromethane depends on the structure of their molecules.
Synthesis and Structure of Platinum Diethyl Sulfoxide Complexes
Abstract
The reaction of tetraorganylphosphonium and tetraethylammonium chlorides with hexachloroplatinic acid hydrate in a mixture of acetonitrile and diethyl sulfoxide produced [Ph3PEt][PtCl5(deso-S)] and [Et4N][PtCl5(deso-S)] complexes containing tetrahedral tetraorganylphosphonium or tetraethylammonium cations and octahedral diethylsulfoxidopentachloroplatinate anions.
Classification and Prediction of Sodium and Potassium Coronates Stability in Aqueous-Organic Media by Exploratory Data Analysis Methods
Abstract
Linear Fisher classification functions, canonical linear discriminant functions, and trees (rules) for classification and prediction of the stability of sodium (18-crown-6Na+) and potassium coronates (18-crown-6K+) from the properties of aqueous-organic solvents (water—methanol, water—propan-2-ol, and water—acetonitrile) have been obtained basing on multivariate exploratory analysis. The proposed approach to prediction of the coronates stability has been verified using independent experimental data on the stability constants of sodium and potassium coronates in water—dioxane and water—acetone mixtures. The constructed classification functions and rules have possessed high predictive potential.
Synthesis of Mono- and Disaccharide 4-[(ω-Sulfanylalkyl)oxy]benzoylhydrazones as Potential Glycoligands for Noble Metal Nanoparticles
Abstract
A procedure has been developed for the synthesis of previously unknown aldose 4-[(ω-sulfanylalkyl) oxy]benzoylhydrazones (where alkyl is hexyl or decyl and aldoses are D-glucose, D-galactose, D-maltose, and D-lactose) that a repromising glycoligands for noble metal nanoparticles. According to the 1H and 13C NMR data, 4-[(ω-sulfanylalkyl)oxy]benzoylhydrazones derived from D-glucose, D-maltose, and D-lactose in crystal and in DMSO-d6 solution have exclusively the cyclic pyranose structure (α- and β-anomers). D-Galactose 4-[(ω-sulfanylalkyl)oxy]benzoylhydrazones in DMSO-d6 solution exist as tautomeric mixtures of cyclic pyranose and open-chain acylhydrazone structures.
Synthesis of Gold Glyconanoparticles Based on Thiol-Containing d-Hexose Acylhydrazones and Their Modification by Thiolated Poly(2-deoxy-2-methacryloylamino-D-glucose)
Abstract
A procedure has been developed for the synthesis of gold glyconanoparticles with an average particle size of 15–30 nm and a low polydispersity index on the basis of natural hexose (d-glucose, d-galactose, d-mannose) sulfanylacetyl-, 3-sulfanylpropanoyl-, and 2-sulfanylbenzoylhydrazones and thiolated poly(2-deoxy-2-methacryloylamino-d-glucose).
Synthesis of Bimetallic Pt-W Particles in Autoclave
Abstract
A possibility of obtaining bimetallic Pt-W particles in an autoclave at 190°C in an alkaline solution was shown. Structure of the obtained particles was studied by dynamic light scattering and X-ray phase analysis. A possible route for the reduction of platinum and tungsten in the selected conditions to the metallic state with ammonia in statu nascendi was proposed.
An Efficient Microwave Assisted Synthesis and Antimicrobial Activty of 1,2,3-Triazolyl-pyrrolidinyl-quinolinolines
Abstract
A novel series of 1,2,3-triazolyl-pyrrolidinyl-quinolinolines are synthesised by the Click reaction of alkynes with aromatic azides catalysed by CuI under microwave assisted and conventional conditions. All synthesized 1,2,3-triazoles are screened for their in vitro antimicrobial activity against different bacterial and fungal pathogens. Majority of the synthesized compounds demonstrate moderate to good inhibition zones compared to the standard drugs.
Synthesis and Antibacterial Assay of Some New Pyrenyl Pyridine Candidates
Abstract
Novel polycyclic compounds, 1-pyrene-based pyridone derivatives, are synthesized by treatment of pyrenyl acetohydtazide with several arylidenemalononitriles and acetylacetone. Intramolecular cyclization furnishes the functionalized substituted pyridine-2-ones with high yields. Structures of the products are elucidated from the spectral data. Tests on antibacterial activity of the products reveal their high antibacterial effect.
Synthesis and Anticancer Activity of Amide Derivatives of 1,2-Isoxazole Combined 1,2,4-Thiadiazole
Abstract
A series of amide derivatives of 1,2-isoxazole combined with 1,2,4-thiadiazole are synthesized 11a–11j. Their chemical structures are confirmed by 1H and 13C NMR, and mass spectra. The products are tested for their anticancer activity against four types of human cancer cell lines, including MCF-7 (breast), A549 (lung), Colo-205 (colon), and A2780 (ovarian). Etoposide is used as a positive control. Most of the compounds show good anticancer activity. The compounds 11b, 11c, 11d, 11e, 11g, and 11j demonstrate more potent activity than etoposide.
Structural Characterization and Second-Order Nonlinear Optical Behavior of Metal Complexes of Ferrocene Derivative
Abstract
In this manuscript, a ferrocene-linked vic-dioxime ligand (LH2) and its metal complexes [Ni(LH)2, Cu(LH)2, Co(LH)2(H2O)2, Cd(LH)(H2O)(Cl), and Zn(LH)(H2O)(Cl)] are synthesized, and their structures are studied by spectral methods. Redox behavior of the compounds is studied by cyclic voltammetry (CV). For approaching microscopic second-order nonlinear optical (NLO) behavior of the synthesized ligand and its diamagnetic Cd(II), Zn(II), Ni(II) complexes, the electric dipole moment μ, static dipole polarizability α, and first hyperpolarizability β values are computed using ab-initio quantum chemical procedure [finite field (FF)]. The accumulated data indicate that the compounds exhibit non-zero quadratic hyperpolarizability tensor components, implying microscopic NLO phenomena. The HOMOs, LUMOs and the HOMO—LUMO band gaps for first and second frontier orbitals of LH2 ligand and its Cd(II), Zn(II), Ni(II) complexes are evaluated by means of the Hartree-Fock (HF) method.
Pyrazole and Nicotinonitrile Derivatives Synthesized from Sulfa Drugs, and Their Antibacterial Activity
Abstract
Utility of sulfadiazine and sulfaguanidine in synthesis of new series of pyrazoles and 2-pyridones is described. Diazotization of sulfadiazine that results in formation of diazonium salt 2 followed by coupling of the latter with active methylene compounds leads to hydrazinyl derivatives 3a–3d. Heterocyclization of compounds 3a–3c with hydrazine derivatives gives to a series of pyrazole derivatives 4–6. Similarly, a series of pyrazole derivatives 12–14 is developed from sulfaguanidine. Condensation of hydrazinyl derivatives 3a–3c with cyanoacetamide in the presence of a catalytic amount of piperidine gives 2-oxonicotinonitriles 15a–15c. Tests of the new synthesized compounds against four pathogenic gram (+ve) and gram (−ve) bacteria demonstrate their activity higher than that of the standard Amoxicillin.
Synthesis of New 1,3,4-Oxadiazole-benzimidazole Derivatives as Potential Antioxidants and Breast Cancer Inhibitors with Apoptosis Inducing Activity
Abstract
Synthesis of new compounds combining benzimidazole with 1,3,4-oxadiazole functionalized by various alkyl and heterocyclic moieties is studied. The new hybrids were evaluated as DPPH radical scavengers and antioxidants. The most active compounds 1, 2, 3a, 3c, and 5d were tested as anticancer agents against MCF-7 and MDA-MB-231 breast cancer cells. The biological study demonstrated significant sensitivity of both types of cancer cells towards the synthesized compounds in comparison with erlotinib used as a reference drug. Cell cycle and apoptosis analysis indicated compound 5d as the one inducing G2/M phase arrest and apoptosis in MCF-7 and MDA-MB-231 cancer cells, in addition to its upregulation of caspases-3 and caspases-9.
Synthesis and Antitumor Evaluation of Novel Alkylated Hydantoin and Thiohydantoin Derivatives
Abstract
New alkylated hydantoin as well as 2-thiohydantoins were synthesized for broadening the library of compounds screened for antitumor activity. Antitumor activity of the new compounds was evaluated against breast cancer cell line (MCF-7) and demonstrated moderate to good activity.
Letters to the Editor
Methyl Trifluoropyruvate Pyrazin-2-ylimine in Cyclocondensation and Cycloaddition Reactions
Abstract
The transformations of methyl trifluoropyruvate pyrazin-2-ylimine in the cyclocondensation reactions with 2-aminothiazoline, amidines, aminocrotonitrile and aza-Diels—Alder reactions with cyanamines, leading to five- and six-membered trifluoromethyl-containing heterocycles, were studied. The possibility of using 4-(pyrazin-2-ylamino)-1-(prop-2-yn-1-yl)-4-(trifluoromethyl)-1H-imidazol-5(4H)-one, the product of methyl trifluoropyruvate pyrazin-2-ylimine cyclocondensation, for modification of phenothiazine by copper-catalyzed alkyne-azide 1,3-dipolar cycloaddition was shown.