статье приведены итоги синтеза и исследования структуры металл-полимерных комплексов на основе полиэтилен(пропилен)гликольмалеинатов с акриловой кислотой и металлами п-ЭГМ:АК/Ag, п-ЭГМ:АК/Ni, п-ЭГМ:АК/Аg-Ni, п-ПГМ:АК/Ag, п-ПГМ:АК/Ni, п-ПГМ:АК/Аg-Ni с применением методов микроскопии, спектроскопии и термогравиметрии. Полученные нанокомпозиты содержат изолированные наночастицы Аg0 диаметром 60±10 нм преимущественно сферической формы и металлического Ni0, размером 70±10 нм, кубической формы равномерно распределенные в полимерной матрице, агломераты на поверхности полимерной матрицы в пределах 150-200 нм. Синтезированные нанокомпозиты обладают термической стабильностью до ~900 ºС. Исследована антимикробная активность металл-полимерного комплекса п-ПГМ/AК-Ag, который показал высокую эффективность в отношении стандартных штаммов Pseudomonas aeruginosa, Escherichia coli, Staphylococcus aureus.
Thermal decomposition of the copolymer of polyethylene glycol fumarate with acrylic acid (p-EGF:AA) of two different compositions synthesized earlier was studied in the present work. TG and DTG curves prove that decomposition takes place in several stages. According to thermogravimetric curves it has been found out that for the copolymer with higher content of acrylic acid the decomposition of the copolymer’s sample is started at higher temperatures. It has been shown the shift of the temperature of decomposition’s start to the higher area with the increase of heating rate which is necessary for the detorsion of macromolecular coil. Experimental data processed using graphical methods of Kissinger–Akahira–Sunose and Friedman allowed us to calculate the activation energy of the thermal decomposition process. It has been established that the copolymer with the composition of 21.03:78.97 mass.% has lower meaning of activation energy than the one with the composition of 68.96:31.04 mass.%. As a result of calculation one can see that the meanings found out using these methods depend slightly on conversion. Using Achar-Brindley-Sharp method and the method of invariant kinetic parameters the kinetic triplet of the decomposition process has been found which was used to build the calculated curve. The dependences of g(α) on α using these parameters showed a satisfactory agreement of calculated curves with the experimental ones. One can conclude that the decomposition process of the copolymer of polyethylene glycol fumarate with acrylic acid is well described with of D3 (three-dimensional diffusion) model.
The article presents the results of the synthesis and study of the structure of metal-polymer complexes p-EGM: АА/Ag, p-EGM: АА/Ni, p-EGM:АА/Ag-Ni, p-PGM:АА/Ag, p-PGM:АА/Ni, p-PGM:АА/Ag-Ni based on copolymers of polyethylene(propylene)glycolmaleates with acrylic acid and metals, which have been characterized using microscopy, spectroscopy and thermogravimetry. The antimicrobial activity of a new metal-polymer nanocomposite p-PGM/АА-Ag was studied, which is showing high efficiency against standard strains of Pseudomonas aeruginosa, Escherichia coli, Staphylococcus aureus.
The thermal decomposition of polyethylene glycol fumarate–acrylic acid copolymer is investigated at different rates of heating. It is shown that increasing the rate of heating raises the temperature of the onset of decomposition. The kinetic parameters of decomposition are calculated using the integral Kissinger–Akahira–Sunose procedure. It is found that at different degrees of conversion, the activation energies are very close: E = 205–227 kJ/mol. The effect the composition of the copolymer has on the results from kinetic calculations is shown. The Coates–Redfern approach is used to determine the pre-exponential factor and the model of thermal decomposition. Calculated thermogravimetric curves are constructed and compared to experimental ones.
The present work aimed at encapsulation of fat-soluble vitamin Aevit (vitamins A and E, oil) with β-cyclodextrin. Inclusion complex of vitamins A and E with β-cyclodextrin was prepared in an aqueous alcohol medium by ultrasonic treatment. The surface morphology of the resulting clathrate inclusion complexes was described using a scanning electron microscope. The results of thermographic measurements on a differential scanning calorimeter are presented. The spectral properties of the inclusion complex are characterized by 1H and 13C NMR spectroscopy data. The experimental results confirmed the existence of a complex of inclusion of β-cyclodextrin with vitamin Aevit (2:1). The activation energy of the thermooxidation destruction reaction of the clathrate complex β-cyclodextrin:vitamin Aevit was calculated, kinetic parameters of thermal destruction of clathrate were determined. These parameters were determined based on the Freeman-Carroll, Sharpe-Wentworth, Ahar and Coates-Redfern methods. The use of the above models made it possible to graphically establish the thermodynamic parameters of the thermal decomposition of β-cyclodextrin and its clathrate with vitamin. The data of thermographic measurements on a differential scanning calorimeter showed that the thermal destruction of the Aevite clathrate with β-cyclodextrin begins with the removal of water molecules from the β-cyclodextrin cavity, then the “guest” substance and the cyclic oligosaccharide are destroyed.
Metal-polymer composites based on copolymers of polypropylene glycol maleate phthalate with acrylic acid and metallic nickel and silver were synthesized for the first time. The objects obtained were characterized by infrared (IR) and Raman spectroscopies, thermogravimetry, a scanning electron microscope with energy dispersive spectroscopy, and atomic emission spectrometry. The catalytic activity of new metal-polymer composites that exhibited a rather high efficiency in the reactions of electrocatalytic hydrogenation of pyridine was studied. It is shown that nanoparticles of metals are evenly distributed in the volume of the polymer matrix; more than 80% of nanoparticles are in the range from 25 to 40 nm and have spherical and rhombic shapes. The reusability of the obtained composites is shown.
In this work, the thermal decomposition of copolymers based on polyethylene glycol fumarate with the acrylic acid using various ratios of initial monomers has been studied for the first time. The samples were studied in air and nitrogen. According to the thermograms analysis, it was found that the copolymer sample decomposition begins at higher temperatures for a copolymer with high content of polyester resin. The copolymer is vigorously oxidized by the oxygen when heated in air, and one can observe almost complete sample decomposition, whereas it decomposes with a residue of ~ 15% in an inert medium. The activation energies for copolymers with different compositions were estimated using the differential methods of Freeman-Carroll, Achar and Sharpe-Wentworth. The activation energy values found by the three methods demonstrated a good convergence. It was shown that, the activation energy values are higher (~ 200 kJ/mol in the inert medium, and ~ 95 kJ/mol in the oxygen atmosphere) for a copolymer with a lower composition of polyester resin, and the activation energy is ~180 and ~85 kJ/mol for a copolymer with a greater composition of p-EGF-AA. The copolymer is more thermostable in the nitrogen atmosphere according to the kinetic parameters. Additionally, there were determined the thermodynamic characteristics, such as the Gibbs energy (∆G) and the entropy (∆S). They also confirm the destruction process dependence on the components ratio in the synthesized copolymer.
Poly(propylene fumarate phthalate) and acrylic acid radical copolymerization in dioxane solution at various molecular ratios of original monomeric mixture was studied in this work for the first time. An unsaturated polyester resin was obtained using the polycondensation reaction. The composition of the obtained poly(propylene fumarate phthalate) was determined according to elemental analysis. The studied copolymers are promising for further study due to their swelling ability, antioxidant activity, and biodegradable ability. Copolymerization reaction kinetics has been studied. The composition of the copolymers was determined using chromatemass spectrometry. Radical copolymerization constants and parameters have been calculated by Mayo-Lewis integral method. Based on the copolymerization constants the Q-e parameters was calculated according to the Alfrey-Price equation. It was proved that non-solvable polymers of a net-shaped structure are formed in the whole range of the researched comonomer ratios during the radical copolymerization of p-PFF with A.. Based on the results presented in the article, we can say that all copolymer compounds based on poly(propylene fumarate phthalate) and acrylic acid demonstrate the ability to control physical and chemical properties. This in turn will allow to create new materials with a pre-defined behavior program. It was found that the unsaturated polyester resin is characterized by a lower reactivity in case of acrylic acid and poly(propylene fumarate phthalate) copolymerization.
The article is devoted to the research of the influence of external factors on copolymers based on poly (propylene fumarate phthalate) and acrylic acid. In this paper, the effect of organic solvents and pH of the medium on the rate of swelling of synthesized copolymers is studied. The rate of polymer swelling depends on many factors, including: the nature of the polymer and the solvent, the presence of electrolytes, changes in pH and ambient temperature, the molecular weight of the polymer, and so on. It is assumed that the polymer network of copolymers consists mostly of unsaturated polyester resin links. Research results show that the ratio of monomer units in the copolymer significantly affects the susceptibility of the polymer gel to the pH of the medium and the presence of organic solvents (DMSO, DMFA, ethanol). It is proved that changing the properties of the comonomer allows you to obtain hydrogels that can swell or collapse due to changes in the ionic strength or thermodynamic quality of the solution. By varying the ratio of comonomers of the links was adjusted by the intervals of the swelling and compression of the polymer networks. The molecular weight of poly (propylene fumarate phthalate)was determined by gel-penetrating chromatography. The identification and composition of copolymers were determined by IR spectroscopy and HPLC, respectively.
The article presents the results of a study by the authors of the article on the development of new ways of synthesis and study of the biological activity of hydrazide derivatives of o-hydroxybenzoic acid. Methods for the preparation of hydrazone, oxadiazole, thiosemicarbazide, 1,2,4-triazole-3-thionic derivatives and methods for their further modification are described. The condensation reaction of hydroxybenzoic acid hydrazides with 1-deoxy-2,3,4,6-tetra-O-acetyl-D-glucopyranosyl isothiocyanate synthesized their corresponding acetylated glycosyl-contai-ning thiosemicarbazide derivatives. The structures of the synthesized compounds were studied by 1H and 13C NMR spectroscopy, as well as by the data of two-dimensional spectra of COSY (1H-1H) and HMQC (1H-13C). The values of chemical shifts, multiplicity, and integrated intensity of 1H and 13C signals in one-dimensional NMR spectra were determined. Using spectra in the formats COSY (1Н-1Н) and HMQC (1Н-13С), homo- and heteronuclear interactions were established, confirming the structure of the compounds under study. The results of evaluating their antimicrobial, anti-inflammatory and cytotoxic activity (in vitro) on cultures of human monocytic cell lines MonoMac-6 and THP-1Blue are described.
This article provides results of evaluation of synthesized biologically active substances 1-4 antiradical activity according to their ability to interact with the 2,2- diphenyl-1-picrylhydrazyl radical (DPPH center dot). It was found that all synthesized compounds 1-4 have antiradical activity. Pronounced antiradical activity was shown by Nethyl-2-(2-hydroxybenzoyl)hydrazine-carbothioamide (1) (IC50(DPPH) = 12.5 mu Mu) and N-ethyl-2-(4-hydroxybenzoyl)hydrazine-carbothioamide (2) (IC50(DPPH) = 16.7 mu Mu) samples under the conditions of this test system. Activity of N-ethyl-2-(2-hydroxybenzoyl) hydrazinecarbothioamide (1) and N-ethyl-2-(4-hydroxybenzoyl)hydrazinecarbothioamide (2) samples are comparable to activity of known antioxidants. Studied substances 1 and 2 are promising for further advanced research of their antioxidant properties and other types of biological activity. Results of PASS computer system applicability estimation for prediction of biological activity using structural formula as a part of pre-experimental screening are provided. Expected activity of chemical compounds combines physiological activity of initial hydrazides of o- and p-hydroxybenzoic acids as well as components of structural molecule. According to bioprediction data analysis, all compounds can act as inhibitors with a high degree of probability.
The antimicrobial and antioxidant activity of synthesized biologically active compounds have been evaluated in comparison with the standard antioxidant, ascorbic acid. The antioxidant activity of the compounds has been studied by their ability to interact with the 2,2-diphenyl-1-picrylhydrazyl radical ($${\text{DPP}}{{{\text{H}}}^{\centerdot }}$$). The proposed test system has revealed the pronounced antiradical activity of 2-(2-hydroxybenzoyl)-N-phenylhydrazinecarbothioamide (1) (IC50(DPPH) = 15.5 μM) and 2-(4-hydroxybenzoyl)N-phenylhydrazinecarbothiamide (2) (IC50(DPPH) = 31.7 μM). A weak antibacterial activity of these compounds has been shown against gram-positive and gram-negative test strains.
In the present work, the binary radical copolymerization of poly(propylene glycol) fumarate with acrylic acid in a dioxane medium was investigated for the first time at various mole ratios of the initial monomer mixture. The kinetics of the copolymerization reaction was studied. Kinetic curves show that with increasing mole fraction of acrylic acid in solution, the reaction rate and sorption capacity of copolymers also increase. The synthesized copolymers composition was determined by chromatography-mass spectrometry. The constants and parameters of radical copolymerization were calculated using the integral methods of Mayo-Lewis, Fineman-Ross and Kelen-Tudos. The Q-e parameters were calculated by the Alfray-Price equation on the basis of copolymerization constants. A lower reactivity characterization of poly(propylene glycol) fumarate was found at copolymerization of it with acrylic acid. The relative activity r(1) in the p-PGF-AA system is less than one. This suggests that the p-PGF ability to copolymerize with other monomers is higher than homopolymerization. Direct proportionality of the unsaturation degree of copolymers to the content of poly(propylene glycol) fumarate in the composition of the initial monomer mixture was shown. Thus, the results of this study show that the synthesized polymers based on PGPP have good characteristics and can be used in various fields of science.
The thermal decomposition of copolymers based on polyethylene glycol fumarate with acrylic acid in oxygen and nitrogen were studied. The activation energies at different degrees of conversion were evaluated by the Friedman and Flynn–Ozawa–Wall kinetic methods. It was found, using the nonparameteric kinetic methods, that the reaction rate depends on the temperature and degree of conversion in air and inert media.
New mono- and bimetallic polymer nanocomposites based on polyethylene( propylene) glycol maleates with acrylic acid and silver and nickel metals were prepared and studied. Metal particles were immobilized into copolymer supports by reduction of Ag+ and Ni2+ ions from solution of their nitrates to Ag-0 and Ni-0 in the presence of a catalyst, a solution of silver chloride in aqueous ammonia. The structure and composition of the complexes were determined by spectroscopy, calorimetry, microscopy, and chromatography. The catalytic activity was studied using pyridine hydrogenation as a model reaction.
The article is devoted to the study of the spatial structure of 4-ethyl-5-(2-hydroxyphenyl)-1,2,4-triazole-3-thione. The molecular and crystalline structure was determined by x-ray diffraction analysis. Data on the spatial structure and crystal packing of the molecule are presented. It is established that phenyl and triazole rings are flat. Due to hydrogen bonds, the molecules in the crystal form three-dimensional networks. The results of an X-ray diffraction study were deposited at the Cambridge Center for Crystal Structural Data. The structure of the synthesized 1,2,4-triazole was studied by 1H NMR spectroscopy. When analyzing the 1H NMR spectrum of the compound, characteristic signals of the protons of the aromatic ring are observed. The value of the chemical shift and the integrated signal intensity are determined. A quantum chemical study of 4-ethyl-5-(2-hydroxyphenyl)-1,2,4-triazole-3-thione was carried out by the DFT method using the B3LYP exchange-correlation functional in combination with the Danning basic set cc-pVDZ. The molecular characteristics of the compound, such as total electron energy, rotational constants, dipole moment and contributions, and thermodynamic functions, are predicted. The equilibrium geometric parameters of the 4-ethyl-5-(2-hydroxyphenyl)-1,2,4-triazole-3-thione molecule were determined. The performed analysis of the spatial configuration and molecular parameters showed a qualitative correspondence between the crystalline and gas-phase structures of the molecule, while it was noted that the main difference is observed in the relative orientation of six-and five-membered cycles.
In the result of reaction of free radical copolymerization of poly(ethylene glycol) fumarate and methacrylic acid insoluble copolymers of different weight composition were obtained. Influence of ionic strength of the solution, organic solvents on the level of swelling of synthesized copolymers was studied. According to the result of the research, it is possible to make the conclusion that ratio of monomeric units in copolymer, as well as concentration of low-molecular components in the solution significantly influence the perceptivity of polymeric gels to the presence of low-molecular salts (NaCl and CaCl2), organic solvents (DMSO, DMF, and ethanol). When the share of methacrylic acid is decreased in copolymer, the perceptivity of gels to admixtures of low-molecular salts and organic solvents is decreased. This is conditioned both by increase of the content of carboxyl groups in the macrochain, and density decrease of polymer network. Observed influence of ionic strength confirms contribution of both electrostatic and hydrophobic interactions in process of swelling-collapse of samples examined. It is shown that changing the nature of comonomer, we can obtain the hydrogels with the ability to turgesce or collapse at change of ionic strength, thermodynamic quality of the solution, and with variation of ratio of comonomer units it is possible to regulate the intervals of swelling and compression of polymer networks. As well, results of X-ray energy-dispersive microanalysis show that examined polymeric systems based on copolymers p-EGF - MAA might be in demand as sorbent agents in purification and beneficiation technologies.