Vol 89, No 3 (2019)

Properties of homologous increments of gas chromatographic retention indices have been examined, i_RI = RI − 100int(M/14), where M is molecular weight and RI is retention index. Comparing to the characteristics of other organic substances (normal boiling points, permittivity, dipole moments, retention indices and their differences for standard polar and nonpolar phases, indices of boiling points, molecular masses, molar refractions, and their differences), it has been shown that the i_RI value can be used as an additional characteristic of polarity.

The reaction of 1-(2-oxocyclohexyl)ethane-1,1,2,2-tetracarbonitrile with crotonic aldehyde, cinnamic aldehyde, 2-furylacrolein, 3-phenyl-2-propinal, 3-butyl-2-propinal, and R-(−)-myrtenal have been investigated. It has been shown that these reactions proceed through the stage of the formation of 8a-hydroxyhexahydro-2H-chromene-3,3,4,4-tetracarbonitrile, followed by the formation of 10-iminotetrahydro-8a,4-(epoxymethane)chromene-3,3,4(2H,4aH-tricarboritrile. The X-ray diffraction data have suggested that the stereochemical features of the target products are determined by the reaction path.

A significant effect of the steric factor on the activity of 3,5-dimethyl-1H-pyrazolide as an acylating agent has been found using the example of acylation of camphane-type monoamines. The predominant contribution of the catalytic hydrogenation as a component of the Schwenk-Papa reaction has been confirmed by the synthesis of 4-chlorobenzoyl derivatives.

Indolyl(thienyl)maleimides with terpyridine receptor in the bridge part have been synthesized. Irradiation of their toluene solutions with light at λ = 436 nm has led to the formation of cyclic isomers. The reverse ring opening reaction has occurred during the photolysis with visible light (λ > 500 nm). 1-(4-([2,2′:6′,2″-Terpyridin]-4′-yl)phenyl)derivatives have exhibited the properties of chromogenic naked-eye sensors to Fe²⁺ cations in acetonitrile solution, changing the solution color from bright-orange to red.

The ecdysteroid 3-epi-2-deoxyecdysone has been isolated from the aerial part of Acanthophyllum gypsophiloides Regel. The complexes formation of the ecdysteroid with α-, β-, λ-, and 2-hydroxypropyl-β-cyclodextrins has been studied by means of NMR spectroscopy. Anti-inflammatory activity of the obtained 3-epi-2-deoxyecdysone complexes with cyclodextrins has been investigated.

Coordination compounds of terbium(III) and gadolinium(III) with some hydroxybenzoic acids were electrochemically synthesized. Structure and spectral properties of the obtained compounds were confirmed by IR and luminescent spectroscopy, as well as by thermogravimetry data.

Cross-coupling of 4,5-diphenoxyphthalonitrile or 4,5-bis(phenylsulfanyl)phthalonitrile (component A) with imide of anthraquinone-2,3-dicarboxylic acid (component B) in the presence of urea, nickel acetate, ammonium chloride, and molybdate has afforded metal complexes of the corresponding low-symmetry phthalocyanines of the A₃B, AABB, and ABAB type. Investigation of their spectral properties has shown that the complexes are associated in chloroform, the type of association depending on the dipole moment of the molecule.

2,3,7,8,12,13,17,18-Ocatbromo-5,10,15,20-tetra-(4-chloroprienyl)porphyrin and 2,3,7,8,12,13,17,18-octachloro-5,10,15,20-tetra-(4-bromophenyl)porphyrin have been synthesized. The obtained compounds have been identified by electronic absorption and ¹H NMR spectroscopy as well as mass spectrometry. The complex-forming properties of the synthesized porphyrins in the zinc acetate (II)-acetonitrile system at 278–298 K have been studied. Kinetic parameters of the formation of the corresponding zinc complexes in acetonitrile have been determined.

Thermodynamic properties of NaNO₃-KNO₃ melts have been studied by high-temperature mass spectrometry. The activities of the components of the condensed phase have been determined and the changes in the chemical potentials and Gibbs energies of the binary system have been calculated.

Barium-doped nanocrystalline lanthanum ferrite was synthesized by the method of co-precipitation and subsequent annealing at 1000°C. The maximum degree of doping of La_1−xBa_xFeO_3−x (x = 0.1) was established before the appearance of other phases. The introduction of Ba²⁺ cations leads to an increase in the average crystallite size from 25±4 nm for x = 0 to 42±4 nm for x = 0.1. The formation of particles characterized by a complex magnetic structure combining two types of magnetic ordering was found. The synthesized samples of (1−x)LaFeO₃: xBa²⁺ (x = 0, 0.075, 0.1, 0.15, 0.2, 0.25) are magnetically hard materials.

A new series of coupled benzofuran derivatives that contain the trifluoromethyl group and pyrazole moiety is synthesized for evaluation of their anti-inflammatory and analgesic activities. Their synthesis proceeds via cyclocondensation of 2-hydroxy-4-(trifluoromethyl)benzaldehyde with chloroacetone with formation of 2-acetylbenzofuran, which upon treatment with different aldehydes via the Claisen-Schmidt condensation gives the corresponding chalcones. Cyclization of chalcones with hydrazine hydrate leads to pyrazoline derivatives, that exhibit significant anti-inflammatory and analgesic activities. Docking modelling of selected active compounds are correlated well with their anti-inflammatory tests data.

A series of ellipticine derivatives 8a–8j containing oxadiazole structural block are synthesized and evaluated for their anticancer activity on human cancer cell lines (Colo-205, MCF-7, A-549, and KB). Among those, the products 8b, 8c, 8d, 8i exhibit potent cytotoxic activity with GI50 values ranging from <0.1 to 23.6 µM. The positive control etoposide GI₅₀ values are ranging from 0.13 to 3.08 µM.

Manganese forms a big number of complexes with Schiff bases that are extensively used as catalysts of oxidation, epoxidation, decarboxylation, coupling reactions, decomposition, urease inhibitory, catalase activity, anticancer activity, antibacterial activity, and many more. To the best of our knowledge, though some catalytic applications of such complexes are reported but hardly as independent reviews. The presented below review deals with various catalytic applications of novel Schiff base Mn(H,HI) complexes.

The behavior of bovine serum albumin as a function of the pH of the medium and the presence in the test systems of symmetrical and asymmetrical hydrophobic porphyrins was investigated. It was established that 4-[(tert-butoxycarbonylamino)acetamido]phenyl group favors stronger protein binding to porphyrin, and this effect enhances in an alkaline medium. Solubilization of protein by porphyrins leads to the fact that the particles are spherical in solution, the hydrodynamic radius of the protein globule reduced in an alkaline medium but in neutral medium, in contrast, increases. By IR spectroscopy it was shown that beta-structuring and the proportion of disordered coils of the polypeptide chain in an alkaline medium increases, because the complexability of the protein towards porphyrin is changes.

The stationary phase for gas chromatography on the basis of the chiral R(+)-1′,7′,7′-trimethylbicyclo-[2.2.1]heptano[2′,3′-b]-2,3-dicyanopyrazine (10.4 wt %) and a liquid crystalline 4,4′-dihexyloxyazoxybenzene was studied. The phase transition temperatures of the binary mixture were measured by polarizing microscopy. It was shown that the chiral camphor-substituted 2,3-dicyanopyrazine induces formation of an enantiotropic chiral helically coiled nematic phase in the achiral liquid crystal over a wide temperature range. The gas chromatographic retention times of organic compounds on this sorbents were measured. The structural and chiral selectivity of the stationary phase on the basis of a liquid crystal and camphor-substituted 2,3-dicyanopyrazine was determined. The retention volumes, activity coefficients, and sorption enthalpies and entropies were calculated and analyzed.

The results of investigation of the interrelation between the geometric structure and coordination, acid, and spectral properties of a series of porphyrins with different systems of meso and β substituents are presented. The geometry of polysubstituted porphyrins was optimized at the DFT B3LYP/6-311G level of theory using Gaussian 09. It was shown that the dianionic forms of dodecasubstituted porphyrins hold promise for the development of highly efficient liquid sensors for metal cations.

The supramolecular self-assembly in mixed low-concentrated aqueous solutions of chitosan and sulfonated metallophthalocyanines was examined by spectroscopic and dynamic light scattering techniques. The research subjects were Cu(II) and Co(II) tetrasulfophthalocyaninates, as well as Cu(II) phthalocyaninate containing sulfonate groups and a vinylsulfonic substituent. The resulting supramolecular complexes were characterized by a reproducible stoichiometric composition, as well as by the ability to move slowly into a colloidal-dispersed state. Phase separation was preceded by a metastable state with unchanging spectral characteristics, for which the size and ζ-potential of the primary supramolecular particles were determined.

Synthetic methods for preparation of novel 3-acyl-substituted 1-hydroxyindole-5,6-dicarboxylic acids and 1-hydroxy-pyrrolo[3,4-f]indole-5,7-diones from 4-(2-substituted-2-oxoethyl)-5-nitrophthalonitriles via successive Vilsmeier-Haack and reductive cyclization reactions were developed.

The reactions of alkyl 3-bromo-3-nitroacrylates with aliphatic alcohols at reflux led to the formation of O-adducts—alkyl 2-alkoxy-3-bromo-3-nitropropanoates isolated as mixtures of diastereomers; their structure was proved using ¹H, ¹³C-{¹H} NMR, and IR spectroscopy methods.

Stereoselective synthesis of N-2,4-enyne cyclic amines was performed by one-pot animation of individual isomers of 1,3-dichloropropene and the subsequent Pd-Cu-catalyzed cross-coupling of the formed vinyl chlorides with terminal alkynes.

Co(II), Ni(II), and Cu(II) complexes with N-(2-hydroxybenzamido)phthalimide (LH₂) were synthesized and studied by IR, electron absorption, EPR spectroscopy, and thermogravimetry. In the case of Cu(II) ions, binuclear Cu₂L₂ complexes are formed, in which the ligand acts as a dianion, while Co(II) and Ni(II) ions form M(LH)₂ complexes.

The electronic structure of SO₃H functional groups in Nafion and Aquivion monomers was calculated. The effect of charge states of the functional group atoms on the proton mobility was studied.

The row in the table on p. 1802 for compound 8a should be as follows: