Effect of Phosphorus Precursor, Reduction Temperature, and Support on the Catalytic Properties of Nickel Phosphide Catalysts in Continuous-Flow Reductive Amination of Ethyl Levulinate

Levulinic acid and its esters (e.g., ethyl levulinate, EL) are platform chemicals derived from biomass feedstocks that can be converted to a variety of valuable compounds. Reductive amination of levulinates with primary amines and H2 over heterogeneous catalysts is an attractive method for the synthesis of N-alkyl-5-methyl-2-pyrrolidones, which are an environmentally friendly alternative to the common solvent N-methyl-2-pyrrolidone (NMP). In the present work, the catalytic properties of the different nickel phosphide catalysts supported on SiO2 and Al2O3 were studied in a reductive amination of EL with n-hexylamine to N-hexyl-5-methyl-2-pyrrolidone (HMP) in a flow reactor. The influence of the phosphorus precursor, reduction temperature, reactant ratio, and addition of acidic diluters on the catalyst performance was investigated. The Ni2P/SiO2 catalyst prepared using (NH4)2HPO4 and reduced at 600 °C provides the highest HMP yield, which reaches 98%. Although the presence of acid sites and a sufficient hydrogenating ability are important factors determining the pyrrolidone yield, the selectivity also depends on the specific features of EL adsorption on active catalytic sites

Pharmacologic and toxicologic properties of lyophilic extract Achillea setacea Waldst. et Kit.

Infusions based on Achillea setacea Waldst. et Kit. are traditionally used as antiinflammatory, hepatic, appetizing, spasmolytic agents, they are used as well in hemorrhages of different etiology, thrombophlebitis and varicose ulcers. Diverse pharmacologic properties are due to the presence of essential oils, proazulene, sesquiterpenic lactones, hydroxycinnamomic acids, flavonoids, vitamin K1 in medicinal raw materials. In using infusion phylloquinone, ascorbinic acid, flavonoids, hydroxycinnamomic acids, Calcium salts, tannins, achileine contribute to regulation of blood coagulation. It is very timely to assess hemostatic activity for lyophilic plant extracts which are perfectly soluble in water and have high biologic availability. The aim of research is to assess the degree of acute toxicity and hemostatic activity for lyophilic extract of herb Achillea setacea Waldst. et Kit. Materials and methods. Lyophilic extracts based on infusion of herb Achillea setacea Waldst. et Kit. obtained by dry sublimation have been used for the research. Lyophilic extracts obtained have been standardized for available vitamin K1 and have been studied for acute toxicity and hemostatic activity. Studying blood coagulation system has been carried out in animals with experimental toxic hepatitis for the following indices: blood coagulation time, prothrombin time, fibrin concentration in the blood. Results. Lyophilic extract based on Achillea setacea Waldst. et Kit. is friable amorphous light yellow mass with bitter taste, containing phylloquinone in concentration 5.79 ± 0.05 %. When studying acute toxicity median lethal dose for lyophilic extracts of Achillea setacea Waldst. et Kit. was above 2000 mg/ml (practically nontoxic ones). Course therapy of extract Achillea setacea Waldst. et Kit. and solution of “Vikasol” for animals with toxic hepatitis led to decreasing hypocoagulation: decreasing prothrombin time and clotting time, increasing fibrin concentration in the blood up to 14.2 ± 1.2 mg/ml. Conclusions. Studying lyophilic extracts of Achillea setacea Waldst. et Kit. standardized on vitamin K1 for acute toxicity allows to attribute them to VI class of toxicity. Administration of lyophilic extract Achillea setacea Waldst. et Kit. in dose 100 mg/ml resulted in decreasing hypocoagulation displaying in decreasing clotting time, in decreasing prothrombin time and increasing available fibrin in the blood. These indices exceeded by its activity reference medicine “Vikasol” (6 mg/kg)

Research of Sex-role Stereotypes of Cruelty of Teenagers

The relevance of this study is caused by the dramatic picture of the psychological theory of the development of the modern teenager in modern science. Rapidly changing social conditions at the beginning of the third Millennium need scientific understanding of possible future prospects of development of the period of childhood and adolescence. The efforts of those responsible for the training of educators, teachers, child psychologists, support for the institution of the family, conducting comprehensive studies of the modern teenager are needed.  Of particular importance for the future of the theory and practice of upbringing of the teenager deserves the study of phenomenology for the development of a modern teenager, the rejection of rigid social stereotypes that are the choice of positive strategies in the relations with teenagers.  Before the reader is an article in which the authors comprehend the existence of social stereotypes on the issue of gender differences in the manifestation of cruel behavior by teenagers. The authors presented a brief analysis of the scientific problem of cruelty.   The problem field of empirical research is defined in the identification of sexual differences in the manifestation of types of cruelty and sexual differences in the attitude to cruel behavior. The study sample is correctly formed, the author's methods of ideographic type are presented, which have passed the stage of approbation in numerous studies. This study belongs to the category of point quasi-experiments.  The stages of research are consistently presented. Qualitative analysis of empirical data is based on evidence-based methods of statistical thesaurus.  The main conclusions of the study allow us to comprehend the existing social stereotypes of types of cruelty and attitudes to violence on a gender basis

Фармако-токсикологічні властивості ліофільного екстракту Achillea setacea Waldst. et Kit.

Infusions based on Achillea setacea Waldst. et Kit. are traditionally used as antiinflammatory, hepatic, appetizing, spasmolytic agents, they are used as well in hemorrhages of different etiology, thrombophlebitis and varicose ulcers. Diverse pharmacologic properties are due to the presence of essential oils, proazulene, sesquiterpenic lactones, hydroxycinnamomic acids, flavonoids, vitamin K1 in medicinal raw materials. In using infusion phylloquinone, ascorbinic acid, flavonoids, hydroxycinnamomic acids, Calcium salts, tannins, achileine contribute to regulation of blood coagulation. It is very timely to assess hemostatic activity for lyophilic plant extracts which are perfectly soluble in water and have high biologic availability.The aim of research is to assess the degree of acute toxicity and hemostatic activity for lyophilic extract of herb Achillea setacea Waldst. et Kit.Materials and methods. Lyophilic extracts based on infusion of herb Achillea setacea Waldst. et Kit. obtained by dry sublimation have been used for the research. Lyophilic extracts obtained have been standardized for available vitamin K1 and have been studied for acute toxicity and hemostatic activity. Studying blood coagulation system has been carried out in animals with experimental toxic hepatitis for the following indices: blood coagulation time, prothrombin time, fibrin concentration in the blood.Results. Lyophilic extract based on Achillea setacea Waldst. et Kit. is friable amorphous light yellow mass with bitter taste, containing phylloquinone in concentration 5.79 ± 0.05 %. When studying acute toxicity median lethal dose for lyophilic extracts of Achillea setacea Waldst. et Kit. was above 2000 mg/ml (practically nontoxic ones). Course therapy of extract Achillea setacea Waldst. et Kit. and solution of “Vikasol” for animals with toxic hepatitis led to decreasing hypocoagulation: decreasing prothrombin time and clotting time, increasing fibrin concentration in the blood up to 14.2 ± 1.2 mg/ml.Conclusions. Studying lyophilic extracts of Achillea setacea Waldst. et Kit. standardized on vitamin K1 for acute toxicity allows to attribute them to VI class of toxicity. Administration of lyophilic extract Achillea setacea Waldst. et Kit. in dose 100 mg/ml resulted in decreasing hypocoagulation displaying in decreasing clotting time, in decreasing prothrombin time and increasing available fibrin in the blood. These indices exceeded by its activity reference medicine “Vikasol” (6 mg/kg).Настой из травы Achillea setacea Waldst. еt Kit. традиционно используют как противовоспалительное, аппетитное, гепатопротекторное, спазмолитическое средство, применяют для остановки кровотечений различной этиологии,  тромбофлебитах и варикозных язвах. Многогранные фармакологические свойства обусловлены наличием в лекарственном сырье эфирных масел, проазулена, сесквитерпеновых лактонов, гидроксикоричных кислот, флавоноидов, витамина К1. В процессе регуляции свертывания крови при использовании настоя принимают участие филлохинон, аскорбиновая кислота, флавоноиды, гидроксикоричные кислоты, соли кальция, дубильные вещества, ахилеин. Актуальным является определение гемостатической активности лиофильных экстрактов растения, которые хорошо растворимы в воде и имеют высокую биологическую доступность.Цель работы – определение острой токсичности и гемостатической активности лиофильного экстракта травы тысячелистника щетинистого.Материалы и методы. Для проведения исследования использовали лиофильные экстракты, полученные из настоя травы тысячелистника щетинистого методом сублимационной сушки. Полученные лиофильные экстракты стандартизировали по содержанию витамина К1 и исследовали на острую токсичность и гемостатическую активность. Исследование свертывающей системы крови проводили у животных с экспериментальным токсическим гепатитом по таким показателям, как время свертывания крови, протромбиновое время и концентрация фибрина в крови.Результаты. Полученный лиофильный экстракт тысячелистника щетинистого представляет собой рыхлую аморфную массу светло-желтого цвета с горьким вкусом, содержащий филлохинон в концентрации 5,79 ± 0,05 %. При исследовании острой токсичности, средняя смертельная доза для исследуемых лиофильных экстрактов тысячелистника щетинистого составляла свыше 2000 мг/кг (практически не токсичные). Курсовое назначение животным с токсическим гепатитом экстракта тысячелистника и раствора викасола приводило к уменьшению проявлений гипокоагуляции: уменьшению протромбинового времени и времени свертывания крови, повышению концентрации фибрина в крови до 14,2 ± 1,2 мг/мл.Выводы. Исследование стандартизированных по витамину К1 лиофильных экстрактов тысячелистника щетинистого на острую токсичность позволило отнести их к VI классу токсичности. Назначение животным с токсическим гепатитом лиофильного экстракта тысячелистника щетинистого в дозе 100 мг/кг приводило к уменьшению проявлений гипокоагуляции, которое проявлялось в уменьшении времени свертывания крови, протромбинового времени, а также увеличении содержания фибрина в крови в значениях, превышающих по своей активности референс-препарат викасол (6 мг/кг).Настій із трави Achillea setacea Waldst. еt Kit. традиційно використовують як протизапальний, апетитний, гепатопротекторний, спазмолітичний засіб, застосовують для зупинки кровотеч різної етіології, при тромбофлебітах і варикозних виразках. Багатогранні фармакологічні властивості зумовлені наявністю в лікарській сировині ефірних олій, проазулену, сесквітерпенових лактонів, гідроксикоричних кислот, флавоноїдів, вітаміну К1. У процесі регуляції згортання крові під час використання настою беруть участь філохінон, аскорбінова кислота, флавоноїди, гідроксикоричні кислоти, солі кальцію, дубильні речовини, ахілеїн. Актуальним є визначення гемостатичної активності ліофільних екстрактів рослини, що добре розчинні у воді та мають високу біологічну доступність.Мета роботи – визначення гострої токсичності та гемостатичної активності ліофільного екстракту трави деревію щетинистого.Матеріали та методи. Для дослідження використовували ліофільні екстракти, що отримали з настою трави деревію щетинистого методом сублімаційного сушіння. Отримані ліофільні екстракти стандартизували за вмістом вітаміну К1 і досліджували на гостру токсичність і гемостатичну активність. Дослідження системи згортання крові проводили у тварин з експериментальним токсичним гепатитом за такими показниками, як-от: час згортання крові, протромбіновий час і концентрація фібрину у крові.Результати. Ліофільний екстракт деревію щетинистого, котрий отримали, являє собою пухку аморфну масу світло-жовтого кольору з гірким смаком, що містить філохінон у концентрації 5,79 ± 0,05 %. При дослідженні гострої токсичності середня смертельна доза для досліджуваних ліофільних екстрактів деревію щетинистого становила понад 2000 мг/кг (практично не токсичні). Курсове призначення тваринам із токсичним гепатитом екстракту деревію та розчину вікасолу призводило до зменшення проявів гіпокоагуляції: зменшення протромбінового часу та часу згортання крові, підвищення концентрації фібрину в крові до 14,2 ± 1,2 мг/мл.Висновки. Дослідження на гостру токсичність стандартизованих по вітаміну К1 ліофільних екстрактів деревію щетинистого дало можливість віднести їх до VI класу токсичності. Призначення тваринам із токсичним гепатитом ліофільного екстракту деревію щетинистого в дозі 100 мг/кг призводило до зменшення проявів гіпокоагуляції, яке виявлялось у зменшенні часу згортання крові, протромбінового часу, а також збільшення вмісту фібрину у крові в значеннях, що перевищують за своєю активністю референс-препарат вікасол (6 мг/кг)

Study of the High-Coercivity Material Based on ε-Fe2O3 Nanoparticles in the Silica Gel Matrix

Текст статьи не публикуется в открытом доступе в соответствии с политикой журнала.We report the results of investigations of ε-Fe2O3 magnetic nanoparticles obtained by incipient wetness impregnation of silica gel. It was established that the obtained samples with an iron content of 12‒16% mass % containing ε-Fe2O3 nanoparticles with an average size of 10 nm on the silica gel surface exhibit a room-temperature coercivity of about 10 kOe. Along with fabrication simplicity, this fact makes the prepared samples promising for application as a magnetically hard material

Study of the High-Coercivity Material Based on ε-Fe2O3 Nanoparticles in the Silica Gel Matrix

Текст статьи не публикуется в открытом доступе в соответствии с политикой журнала.We report the results of investigations of ε-Fe2O3 magnetic nanoparticles obtained by incipient wetness impregnation of silica gel. It was established that the obtained samples with an iron content of 12‒16% mass % containing ε-Fe2O3 nanoparticles with an average size of 10 nm on the silica gel surface exhibit a room-temperature coercivity of about 10 kOe. Along with fabrication simplicity, this fact makes the prepared samples promising for application as a magnetically hard material

Size effects in the magnetic properties of ε-Fe2O3 nanoparticles

Текст статьи не публикуется в открытом доступе в соответствии с политикой журнала.We report the results of comparative analysis of magnetic properties of the systems based on ε-Fe2O3, nanoparticles with different average sizes (from ∼3 to 9 nm) and dispersions. The experimental data for nanoparticles higher than 6–8 nm in size are consistent with the available data, specifically, the transition to the magnetically ordered state occurs at a temperature of ∼500 K and the anomalies of magnetic properties observed in the range of 80–150 K correspond to the magnetic transition. At the same time, Mőssbauer and ferromagnetic resonance spectroscopy data as well as the results of static magnetic measurements show that at room temperature all the investigated samples contain ε-Fe2O3 particles that exhibit the superparamagnetic behavior. It was established that the magnetic properties of nanoparticles significantly change with a decrease in their size to ∼6 nm. According to high-resolution electron microscopy and Mőssbauer spectroscopy data, the particle structure can be attributed to the ε–modification of trivalent iron oxide; meanwhile, the temperature of the magnetic order onset in these particles is increased, the well-known magnetic transition in the range of 80–150 K does not occur, the crystallographic magnetic anisotropy constant is significantly reduced, and the surfacemagnetic anisotropy plays a decisive role. This is apparently due to redistribution of cations over crystallographic positions with decreasing particle size, which was established using Mössbauer spectra. As the particle size is decreased and the fraction of surface atoms is increased, the contribution of an additional magnetic subsystem formed in a shell of particles smaller than ∼4 nm becomes significant, which manifests itself in the static magnetic measurements as paramagnetic contributio

Size effects in the magnetic properties of ε-Fe2O3 nanoparticles

Текст статьи не публикуется в открытом доступе в соответствии с политикой журнала.We report the results of comparative analysis of magnetic properties of the systems based on ε-Fe2O3, nanoparticles with different average sizes (from ∼3 to 9 nm) and dispersions. The experimental data for nanoparticles higher than 6–8 nm in size are consistent with the available data, specifically, the transition to the magnetically ordered state occurs at a temperature of ∼500 K and the anomalies of magnetic properties observed in the range of 80–150 K correspond to the magnetic transition. At the same time, Mőssbauer and ferromagnetic resonance spectroscopy data as well as the results of static magnetic measurements show that at room temperature all the investigated samples contain ε-Fe2O3 particles that exhibit the superparamagnetic behavior. It was established that the magnetic properties of nanoparticles significantly change with a decrease in their size to ∼6 nm. According to high-resolution electron microscopy and Mőssbauer spectroscopy data, the particle structure can be attributed to the ε–modification of trivalent iron oxide; meanwhile, the temperature of the magnetic order onset in these particles is increased, the well-known magnetic transition in the range of 80–150 K does not occur, the crystallographic magnetic anisotropy constant is significantly reduced, and the surfacemagnetic anisotropy plays a decisive role. This is apparently due to redistribution of cations over crystallographic positions with decreasing particle size, which was established using Mössbauer spectra. As the particle size is decreased and the fraction of surface atoms is increased, the contribution of an additional magnetic subsystem formed in a shell of particles smaller than ∼4 nm becomes significant, which manifests itself in the static magnetic measurements as paramagnetic contributio

Synergetic Effect of Ni2P/SiO2 and γ-Al2O3 Physical Mixture in Hydrodeoxygenation of Methyl Palmitate

The Ni2P/SiO2 catalyst, which was prepared by in situ temperature-programmed reduction and in the mixture with the inert (SiC, SiO2) or acidic (γ-Al2O3) material was studied in methyl palmitate hydrodeoxygenation (HDO). Methyl palmitate HDO was carried out at temperatures of 270–330 °C, H2/feed volume ratio of 600 Nm3/m3, and H2 pressure of 3.0 MPa. Ni2P/SiO2 catalyst, diluted with γ-Al2O3 showed a higher activity than Ni2P/SiO2 catalyst diluted with SiC or SiO2. The conversion of methyl palmitate increased significantly in the presence of γ-Al2O3 most probably due to the acceleration of the acid-catalyzed reaction of ester hydrolysis. The synergism of Ni2P/SiO2 and γ-Al2O3 in methyl palmitate HDO can be explained by the cooperation of the metal sites of Ni2P/SiO2 and the acid sites of γ-Al2O3 in consecutive metal-catalyzed and acid-catalyzed reactions of HDO. The obtained results let us conclude that the balancing of metal and acid sites plays an important role in the development of the efficient catalyst for the HDO of fatty acid esters over supported phosphide catalysts

Support Effect on the Performance of Ni2P Catalysts in the Hydrodeoxygenation of Methyl Palmitate

The effect of support nature, SiO2 and γ-Al2O3, on physicochemical and catalytic properties of nickel phosphide catalysts in methyl palmitate hydrodeoxygenation (HDO) has been considered. Firstly, alumina-supported nickel phosphide catalysts prepared by temperature-programmed reduction method starting from different precursors (phosphate–Ni(NO3)2 and (NH4)2HPO4 or phosphite–Ni(OH)2 and H3PO3) were compared using elemental analysis, N2 physisorption, H2-TPR, XRD, TEM, NH3-TPD, 27Al and 31P MAS NMR techniques and catalytic experiments. The mixture of nickel phosphide phases was produced from phosphate precursor on alumina while using of phosphite precursor provides Ni2P formation with the higher activity in methyl palmitate HDO. Besides, the comparative study of the performances of Ni2P/SiO2 and Ni2P/Al2O3 catalysts demonstrates the apparent superiority of alumina-supported Ni2P in the methyl palmitate hydrodeoxygenation. Considering the tentative scheme of methyl palmitate transformation, we proposed that cooperation of Ni2P and acid sites on the surface of alumina provides the enhanced activity of alumina-supported Ni2P through the acceleration of acid-catalysed hydrolysis