Sulfur-containing oligomers comprising C—S—C and C—S—S—C moieties were syntesized via the condensation of 1,2-dichloroethane with a mixture of potassium sulfide and disulfide. Cleavage of disulfide bonds in these oligomers with the hydrazine hydrate–KOH system led to the formation of α,ω-potassium dithiolates containing several ethylene sulfide S—C—C—S moieties in the chain. Alkylation of the dithiolates with iodomethane allowed obtaining compounds containing monosulfide moieties. Such compounds can be used as extractants, sorbents, and catalysts and can find applications in various fields, including microbiology, biotechnology, medicine, and agriculture.
The adsorption of nickel(II) ions by natural aluminosilicate modified with hydrochloric acid followed by immobilization of 1-(3-triethoxysilylpropyl)thiosemicarbazide (TSC) has been studied. The AS–HCl–TSC Series of adsorbents was obtained by treating AS–HCl with solutions TSC with a concentration of 0.5, 1.0, 1.8, 3.5, 4.5, 5.8 wt %. The adsorption capacity of the obtained samples was studied in relation to nickel(II) ions. The highest adsorption of nickel(II) ions, 165.7 mg/g, corresponds to the sample treated with a solution containing 1% TSC. A subsequent increase in the concentration of the modifier leads to a decrease in the amount of adsorption. It can be assumed that with an increase in the concentration of the modifier, the support surface is covered with a denser TSC layer. In this case, the internal volume of the carrier does not participate in exchange processes, which, in turn, contributes to a decrease in the adsorption value with an increase in the concentration of the modifier. The adsorption equilibrium corresponding to the constancy of the composition of the concentrations of metal ions in the adsorbate–aluminosilicate AS–HCl–TSC system was 90 min. For the AS–HCl–TSC adsorbents obtained, the adsorption kinetics of nickel(II) ions was studied. Kinetic equations of pseudofirst and pseudosecond orders are obtained. The values of the determination coefficients (0.98–0.99) indicate that the adsorption of nickel(II) ions by the AS–HCl–TSC adsorbent can be described by a pseudo-second-order equation. At concentration 1% TSC modifier, the initial adsorption rate of nickel(II) ions was 0.121 mmol/(g min). In this case, the value of the adsorption-rate constant is 0.082 g/(mmol min). For AS, AS–HCl, AS–TSC, and AS–HCl–TSC samples, the adsorption capacity was 5.9 mg/g (0.10 mmol/g), 11.6 mg/g (0.20 mmol/g), 16.6 mg/g (0.28 mmol/g), and 165.7 mg/g (2.8 mmol/g), respectively.
Исследована адсорбция ионов никеля(II) природным алюмосиликатом, модифицированным соляной кислотой с последующей иммобилизацией 1-(3-триэтоксисилилпропил)тиосемикарбазида (TSC). Серия адсорбентов AS-HCl-TSC получена обработкой AS–HCl растворами TSC с концентрацией 0.5, 1.0, 1.8, 3.5, 4.5, 5.8 мас. %. Адсорбционная способность полученных образцов исследована по отношении к ионам никеля(II). Наибольшая адсорбция ионов никеля(II) 165.7 мг/г соответствует образцу, обработанному раствором, содержащим 1% TSC. Последующее повышение концентрации модификатора приводит к снижению величины адсорбции. Можно предположить, что с увеличением концентрации модификатора, поверхность носителя покрывается более плотным слоем TSC. При этом внутренний объем носителя не участвует в обменных процессах, что в свою очередь способствует снижению величины адсорбции при увеличении концентрации модификатора. Адсорбционное равновесие, отвечающее постоянству составу концентраций ионов металлов в системе адсорбат-алюмосиликат AS–HCl–TSC, составило 90 мин. Для полученных адсорбентов AS–HCl–TSC исследована кинетика адсорбции ионов никеля(II). Получены кинетические уравнения псевдо-первого и псевдо-второго порядков. Значения коэффициентов детерминации (0.98–0.99) указывают на то, что адсорбция ионов никеля(II) адсорбентом AS–HCl–TSC может быть описана уравнением псевдо-второго порядка. При концентрации модификатора TSC 1% начальная скорость адсорбции ионов никеля(II) составила 0.121 ммоль/(г мин). При этом значение константы скорости адсорбции – 0.082 г/(ммоль мин). Для образцов АS, АS–HCl, АS–ТSC и AS–HCl–TSC адсорбционная емкость составила 5.9 мг/г (0.10 ммоль/г), 11.6 мг/г (0.20 ммоль/г) 16.6 мг/г (0.28 ммоль/г) и 165.7 мг/г (2.8 ммоль/г), соответственно.
Проведен анализ кристаллической структуры молекул (органил)трифторсиланов, содержащих атом кремния в пентакоординированном состоянии. Соединения химически безопасны. Рассмотрена одна из вероятных причин пентакоординации атома Si в них. Установлено, что длина координационной связи O‒Si, входящей в пятичленный гетероцикл, зависит от плоскостного состояния этого цикла. Впервые проанализирована слоистая упаковка молекул в кристаллах (циннамоилоксиметил)трифторсилана ‒ C6H4CH=CHCOOCH2SiF3. One of the probable causes of the pentacoordination of the silicon atom in the compounds (organyl)trifluorosilanes containing the atom in the pentacoordinated state has been established. The length of the O‒Si coordination bond included in a five-membered heterocycle depends on the planar state of this cycle. The layered packing of molecules of (cinnamoyloxymethyl)trifluorosilanes ‒ C6H4CH=CHCOOCH2SiF3 ‒ in its crystals was analyzed.
3-Aminopropyltriethoxysilane and -silatrane readily enter into the Michael aza reaction with various acrylates. Depending on the ratio of the reagents, Michael mono- or diadducts, containing functional groups (triethoxysilyl, carbonyl, nitrile, amino, etc.), are formed. These compounds have been characterized by IR and NMR spectroscopy, mass spectrometry, elemental and X-ray diffraction analyses. The siloxanes obtained from corresponding trialkoxysilanes form carbonyl and nitrile complexes with Ag, Cu, and Ni salts and comprise chemically and thermally stable promising sorbents (enterosorbents) of noble and heavy toxic metal ions. In silico calculations (Protos-II, PASS and Swiss ADMET programs) show that the synthesized silatranes are non-toxic and bioavailable compounds with a pronounced antitumor effect. The effect of silatranes on the growth of pathogenic bacteria (listeria, staphylococci, and plague bacilli) has been studied in vitro . It has been found that these silatranes in microconcentrations exhibit a significant stimulating effect and can be used as growth stimulators of bacterial biomass for rapid diagnosis of diseases caused by these and other pathogens.
Rhodococcus qingshengii VKM Ac-2784D isolated from the rhizosphere of Elytrigia repens, is a promising oil degrader. To increase its biotechnological potential, the effect of atranes (potential growth stimulants) on its growth and naphthalene degradation was studied. The effect of the studied atranes on R. qingshengii VKM Ac-2784D was shown to depend on the nature of the carbon source: addition of atranes had practically no effect on the growth rate of bacteria in the rich BTN medium; in the media 8E and 8E with glucose, it caused short-term activation of growth, characterized by a shorter lag phase. In the presence of naphthalene, atranes had a predominantly negative effect on the growth of R. qingshengii VKM Ac-2784D. The studied atranes had a negative effect on the rate of naphthalene decomposition by R. qingshengii VKM Ac-2784D, and also decreased the cell wall hydrophobicity and the synthesis of extracellular biosurfactants. It may therefore be assumed that the studied compounds will have a negative effect on the rate of naphthalene decomposition by this microorganism.
Modified adsorbents are obtained by the immobilization of 1-(3-triethoxysilylpropyl)thiosemicarbazide (TSC), 1-(3-triethoxysilylpropyl)-1-phenylthiosemicarbazide (1-FTSC), and 3-1-(3-triethoxysilylpropyl)-4-phenylthiosemicarbazide (4-FTSC) on the surface of natural microporous aluminosilicates (ASs). The morphology and elemental composition of the surface of the modified ASs are studied by scanning electron microscopy (SEM) and analysis of energy-dispersive X-ray spectra (EDXSs). The degree of silanization of ASs is determined by the structure of organosilicon thiosemicarbazides and decreases in the series AS–TSC > AS–4-FTSC > AS–1-FTSC. The presence of characteristic for TSC, 1-FTSC, and 4-FTSC structural groups in the composition of the modified samples is confirmed by IR spectroscopy. The AS–TSC, AS–1-FTSC, and AS–4-FTSC modified aluminosilicates are characterized as adsorbents for the extraction of Ni(II) ions from aqueous solutions. The time of establishment of adsorption equilibrium is 60 min in the AS–TSC adsorbent–adsorbate system and 120 min for the AS–1-FTSC adsorbent–adsorbate, AS–4-FTSC adsorbent–adsorbate, and AS adsorbent–adsorbate systems. The maximum values of adsorption of Ni(II) ions are 1.71 mmol/g (100.8 mg/g), 0.25 mmol/g (15.0 mg/g), 0.37 mmol/g (21.9 mg/g), respectively, for the samples of AS–TSC, AS–1-FTSC, and AS–4-FTSC. The obtained data on adsorption are in the best possible way described by the Langmuir and Freundlich models. Presumably, the adsorption of heavy metal ions on the surface of the AS–TSC, AS–1-FTSC, and AS–4-FTSC modified zeolites is accompanied by the formation of chelate complexes (with the 1 : 1 composition) formed due to the donor–acceptor interaction of the metal ions with the nitrogen and sulfur atoms of the thiosemicarbazide fragment.
New functionalized silatranes were synthesized by the reaction of 3-aminopropylsilatrane with urea, thiourea, guanidine, acetamide, acetylguanidine, and aminoguanidine. These silatranes were used to modify silica gel. The sorption activity of the modified silica gel towards the ions of the rare-earth elements Ce3+ and Tb3+ was studied.
New silatranyl–dihydropyran compound ( 3 ) is synthetized based on 1-(3-aminopropyl)silatrane ( 1 ) and 2,5-dibutylthio-2,3-dihydro-2-formyl-4 H -pyran, dibutyrine ( 2 ). Cd(II) and Cu(II) complexes ( 4 – 7 ), as well as samples of modified glass ( 8 ), are obtained from hybrid silatrane ( 3 ). Compounds ( 3 – 8 ) are characterized by elemental analysis and IR spectroscopy and 1 H and 13 C NMR spectroscopy. The antimicrobial properties of the obtained compounds are studied.
Paramagnetic complexes of hydrometallatranes with Co2+ and Ni2+ were studied by high-resolution 1H and 13C NMR spectroscopy. The paramagnetic shifts of the signals in the 1H NMR spectra by ∼100 ppm downfield with respect to their position in the spectra of uncoordinated ligands were observed. A similar upfield shift by ∼400 ppm was observed in the 13C NMR spectra. Analysis showed that paramagnetic shifts are caused by the contact hyperfine or electron-nucleus interactions between the unpaired electrons and the resonating nuclei of the ligand molecules. It was found that the preferred tridentate N,O,O-state of the ligand (triethanolamine) in aqueous solutions is accompanied by the intraligand exchange, in which two out of three oxygen centers compete for coordination. Triethanolamine was found to undergo substitution with 1-methylimidazole under mild conditions with the formation of complexes of the composition M(MIm)4X2 (M = Co, Ni; X = Cl, AcO). This causes a paramagnetic shift of the signals in the 13C NMR spectra as a result of the hyperfine interaction of the MIm nuclei with the unpaired spins of the coordinating ion.
At the A. E. Favorsky Irkutsk Institute of Chemistry, a series of silatrane-sulfonamide hybrids 1a-d and 2a-d was synthesized. The antibacterial activity of 1a, 1b, 1d, 2a, and 2b against test strains of bacteria Yersinia pestis EV NIIEG, Yersinia enterocolitica 628/1, Listeria monocytogenes 766, and Starhylococcus aureus ATCC 6538-P (FDA 209-Р) was evaluated. The minimum inhibitory concentration for silatrane-sulfonamide hybrids was 100-200 mg/liter. Silatrane-sulfonamide hybrid 1d was the most active against all tested strains: minimum inhibitory concentration 100 mg/liter. Exposure to silatrane-sulfonamide hybrids in a doses of 100-200 mg/liter inhibited culture growth by 50-75%.
The article studies the chemical compounds of a number of protatranes as biostimulants of the germination of wheat and triticale seeds after their long-term storage. The relevance of the study is determined by the need to restore the germination of unique samples of grain crops from the collection of the N.I. Vavilov All-Russian Institute of Plant Genetic Resources (VIR) (Saint Petersburg). The research objects were the seeds of different years of reproduction with various levels of original germination, as well as those with an initially high germination and subjected to accelerated aging. The experiments were conducted in the presence of the following physiologically active non-toxic protatranes 2-Me-C 6 H 4 OCH 2 COO - • HN + (CH 2 CH 2 OH) 3 ( 1 ) and 4-Cl-C 6 H 4 SCH 2 COO - •HN + (CH 2 CH 2 OH) 3 ( 2 ) across a wide range of concentrations (1•10 -2 – 1•10 -9 M). At the first stage, the effect of protatrane 1 on the germination of soft spring wheat was investigated. It was observed that, under the influence of protatrane 1 at concentrations from 10 -4 to 10 -9 M, the seed germination and the germination energy increased by 8.7-20.0% and 4.7-8.0%, respectively. The use of protatrane 1 at higher concentrations (10 -2 M) resulted in a decrease in germination. Subsequently, experiments were carried out on 3 samples of soft winter wheat seeds stored for 52 years and having the germination of 19-26%. The 20-hour exposure of seeds to water solutions of protatrane 1 at concentrations of 5 • 10 -7 -10 -9 M increased their germination by 3.7-10.0%. The best stimulating effect was achieved at a concentration of 5 • 10 -7 M. At the next stage, the seeds with a high original germination (86-96%) and subjected to accelerated aging were investigated. The treatment of such samples with protatrane 1 at concentrations of 10 -6 and 10 -4 M turned out to be less effective: the germination and its energy either remained the same or increased insignificantly (by 3.5% and 7.5%, respectively). The treatment of triticale seeds with pro-tatranes 1 and 2 at a concentration of 5 • 10 -7 M was carried out in a similar manner. It was shown that the action of protatranes 1 and 2 led to an increase in the germination by 3-7% and a significant increase in the germination energy by 7-45%. By further optimising the production process and selecting the most active protatranes, the described approach can provide for a significant recovery of seed germination.
Silatranes bearing the aryl(hetaryl)-substituted 1-azadienyl moiety ((Het)ArCH=C(YR) C(H)=N- (Y = O, S)) were synthesized by the reaction of 1-(3-aminopropyl)silatrane with 2-alkoxy- and 2-alkylthio-3-(het)arylpropenals. The structures and stereoisomeric compositions of the synthesized compounds were proved by elemental analysis, IR spectroscopy, 1D 1H, 13C, 15N, 29Si, and 2D NMR experiments, mass spectrometry, and DFT calculations. O-Containing compounds exist exclusively as the 1E,2Z isomers, while S-containing derivatives are the mixtures of the 1E,2Z and 1E,2E stereoisomers. Newly synthesized chalcogen-containing poly-functional compounds represent the promising building blocks for design and synthesis of advanced materials and pharmaceuticals.
Increased interest in carbofunctional organosilicon monomers (silanes) and polymers (silsesquioxanes) is associated with the fact that these compounds are promising reagents and building blocks, materials for micro-electronics, agriculture and medicine, complexones, catalysts, and efficient sorbents. Thus, functional polysilsesquioxanes surpass mineral and organic sorbents in sorption properties. Moreover, they have the highest chemical and thermal stability. Along with sorption activity carbofunctional organosilicon compounds of both monomeric and polymeric structures can possess metallochromic properties. All this paves the way for the large-scale development of analytical systems for the creation of new complex test methods for the determination, concentration and separation of metals from solutions. In the present study the functional monomer N-[3-(triethoxysilyl)propyl]acetylguanidine 1 was synthesized by the condensation reaction of 1-acetylguanidine and 3-triethoxysilyl-propylamine. Poly-N-[3-silsesquioxanyl) propyl]acetylguanidine 2 was obtained by hydrolytic polycondensation of compound 1. The composition and structure of compounds 1 and 2 were confirmed by IR and 1H NMR spectroscopy, as well as by elemental analysis. Polymer 2 was studied as a sorbent for ions of heavy metals, such as Hg (II), and noble metals Ag (I), Au (III), Rh (II), Pd (II), Pt (IV) from solutions of their salts in hydrochloric or nitric acid. For polymer 2, the values of static sorption capacities have been calculated. The latter depend on the nature of the metal and have values from 78 mg/g (for platinum) to 366 mg/g for rhodium. The graphs of the degree of metal extraction depending on the sorption time and acid concentration have been plotted. A sorption mechanism is proposed, which is realized due to the chelate interaction of the metal cation (M+) with the amide groups of compounds 1 and 2. The interaction of monomer 1, in the form of indicator paper, and polymer 2, in the powder form, with salts of the studied metals is accompanied by intense specific coloration (metallochromy). Color tables of the samples after their contact with the Ag (I), Au (III), Pd (II), Pt (IV), Rh (III), Hg (II) salts are given.
Background. Development of nutrient media ensuring the maximum growth rate of pathogens of dangerous infectious diseases while preserving their biological properties is extremely important. A promising direction in this area seems to be the use of synthetic microbial growth biostimulants.The aim of the work is to study the possibility of improving nutrient media for the cultivation of Listeria and Staphylococcus using a biologically active compound tris(2-hydroxyethyl)ammonium 4-chlorophenylsulfanylacetate.Materials and methods. The object of the study was experimental nutrient medium for the cultivation of Listeria used for the culturing of the test strain Listeria monocytogenes 766. As a comparison medium, commercial medium Fraser broth to which agar was added at a concentration of 1.5 %, was used. The test strain Staphylococcus aureus ATCC 6538-P (FDA 209-P) was cultivated on meat-peptone agar with 1% glucose. The compound tris(2-hydroxyethyl) ammonium (4-chlorophenyl)sulfanylacetate at a concentration of 10–4 wt. % was studied as a growth stimulator. A nutrient medium without a stimulant served as a control. The specific activity of nutrient media (germination rate, medium sensitivity, growth rate and stability of the main biological properties of microorganisms) was evaluated by the microbiological method.Results. Studies have shown that the addition of a growth stimulator to nutrient media contributes to the growth of colonies (by 10–50 %) and a decrease in the time of their development. When growth stimulator was added to the nutrient medium for the cultivation of Listeria, the initial growth of colonies of the L. monocytogenes 766 test strain after 12 hours of cultivation and growth of colonies of the test strain S. aureus ATCC 6538-P after 6 hours of cultivation on the meat-peptone agar with 1% glucose was observed.Conclusion. Thus, the addition of a growth biostimulator tris(2-hydroxyethyl)ammonium 4-chlorophenylsulfanyl acetate at a concentration of 10–4 wt. % in the nutrient medium accelerates the growth of Listeria and Staphylococcus, allows to reduce the time of issuance of the analysis result in half.
In the original international version of the article, the first Project No. was specified incorrectly.
Background. Development of nutrient media ensuring the maximum growth rate of pathogens of dangerous infectious diseases while preserving their biological properties is extremely important. A promising direction in this area seems to be the use of synthetic microbial growth biostimulants. The aim of the work is to study the possibility of improving nutrient media for the cultivation of Listeria and Staphylococcus using a biologically active compound tris(2-hydroxyethyl)ammonium 4-chlorophenylsulfanylacetate. Materials and methods . The object of the study was experimental nutrient medium for the cultivation of Listeria used for the culturing of the test strain Listeria monocytogenes 766. As a comparison medium, commercial medium Fraser broth to which agar was added at a concentration of 1.5 %, was used. The test strain Staphylococcus aureus ATCC 6538-P (FDA 209-P) was cultivated on meat-peptone agar with 1% glucose. The compound tris(2-hydroxyethyl) ammonium (4-chlorophenyl)sulfanylacetate at a concentration of 10–4 wt. % was studied as a growth stimulator. A nutrient medium without a stimulant served as a control. The specific activity of nutrient media (germination rate, medium sensitivity, growth rate and stability of the main biological properties of microorganisms) was evaluated by the microbiological method. Results . Studies have shown that the addition of a growth stimulator to nutrient media contributes to the growth of colonies (by 10–50 %) and a decrease in the time of their development. When growth stimulator was added to the nutrient medium for the cultivation of Listeria, the initial growth of colonies of the L. monocytogenes 766 test strain after 12 hours of cultivation and growth of colonies of the test strain S. aureus ATCC 6538-P after 6 hours of cultivation on the meat-peptone agar with 1% glucose was observed. Conclusion . Thus, the addition of a growth biostimulator tris(2-hydroxyethyl)ammonium 4-chlorophenylsulfanyl acetate at a concentration of 10–4 wt. % in the nutrient medium accelerates the growth of Listeria and Staphylococcus, allows to reduce the time of issuance of the analysis result in half.