Pub Date : 2023-02-24DOI: 10.33609/2708-129x.89.01.2023.46-59
Leon Shteinberg
Catalysis of the acylation of aniline with 3-hydroxy-2-naphthoic, 1-hydroxy-2-naphthoic, 2-hydroxy-1-naphthoic and 1-hydroxy-4-naphthoic acids by phosphorus P(III) and silicon Si(IV) compounds leads to the formation anilides of the corresponding hydroxynaphthoic acids under mild conditions (ortho-xylene, 146.5–147 °C) in almost quantitative yield. Among P(III) phosphorus trichloride and tribromide; phosphorous, 1-hydroxyethylidene-diphosphonic, pyrophosphorous and metaphosphorous acids; trimethyl-, dimethyl- and diethylphosphites; phosph(III)azan proved to be active catalysts; among Si(IV) – trichloro-(methyl)silane, dichloro(ethyl)silane, dichloro(dimethyl)silane, tetrachlorosilane and tetraethoxysilane are active. The catalysts were used in an amount of only 2% mole. from hydroxynaphthoic acid, which is 15–35 times less than the conventional use of the same compounds as condensing agents in the synthesis of carboxylic acid arylamides. P(V) compounds, thionyl chloride, and sulfuryl chloride practically do not exhibit catalytic activity. The presence of catalytic activity only in P(III) compounds, capable of forming phosphorous acid in the reaction mass, does not contradict to the previously proposed mechanism of P = O-nucleophilic catalysis for the reaction of substituted benzoic acids with aniline catalyzed by PCl3. In general, the use of P(III) and Si(IV) compounds as catalysts in the preparation of hydroxybenzoic and hydroxynaphthoic acid anilides successfully complements the range of catalysts, based on Ti(IV) compounds, previously used in the formation of substituted benzoic and naphthoic acid anilides (containing no aromatically bonded hydroxy group), allowing to create a universal method for their synthesis.
磷P(III)和硅Si(IV)化合物催化苯胺与3-羟基-2-萘酸、1-羟基-2-萘酸、2-羟基-1-萘酸和1-羟基-4-萘酸的酰化反应，在温和条件下(邻二甲苯，146.5-147℃)，以几乎定量产率生成相应的羟基-萘酸苯胺。在P(III)中，三氯化磷和三溴化物;磷、1-羟乙基- de - ne-二磷酸、焦磷酸和二磷酸;三甲基、二甲基和二乙基亚磷酸盐;磷酸(III)azan被证明是活性催化剂;硅(IV) -三氯-(甲基)硅烷、二氯(乙基)硅烷、二氯-(二甲基)硅烷、四氯硅烷和四氯-乙氧基硅烷具有活性。催化剂的用量仅为2%摩尔。从羟基萘酸中提取，这比常规使用相同化合物作为缩合剂合成羧酸芳酰胺少15-35倍。磷(V)化合物、亚硫酰氯和硫酰氯实际上不表现出催化活性。仅在反应质量中能形成磷酸的P(III)化合物中存在催化活性，这与先前提出的PCl3催化取代苯甲酸与苯胺反应的P = o -亲核催化机制并不矛盾。总的来说，使用P(III)和Si(IV)化合物作为催化剂制备羟基苯甲酸和羟基萘酸苯胺成功地补充了催化剂的范围，基于Ti(IV)化合物，以前用于形成取代苯甲酸和萘酸苯胺(不含芳香键合羟基)，允许创建一个通用的方法来合成它们。
{"title":"CATALYSIS BY PHOSPHORUS AND SILICON COMPOUNDS IN THE SYNTHESIS OF OXYNAPHTOIC ACID ANILIDES","authors":"Leon Shteinberg","doi":"10.33609/2708-129x.89.01.2023.46-59","DOIUrl":"https://doi.org/10.33609/2708-129x.89.01.2023.46-59","url":null,"abstract":"Catalysis of the acylation of aniline with 3-hydroxy-2-naphthoic, 1-hydroxy-2-naphthoic, 2-hydroxy-1-naphthoic and 1-hydroxy-4-naphthoic acids by phosphorus P(III) and silicon Si(IV) compounds leads to the formation anilides of the corresponding hydroxynaphthoic acids under mild conditions (ortho-xylene, 146.5–147 °C) in almost quantitative yield. \u0000Among P(III) phosphorus trichloride and tribromide; phosphorous, 1-hydroxyethylidene-diphosphonic, pyrophosphorous and metaphosphorous acids; trimethyl-, dimethyl- and diethylphosphites; phosph(III)azan proved to be active catalysts; among Si(IV) – trichloro-(methyl)silane, dichloro(ethyl)silane, dichloro(dimethyl)silane, tetrachlorosilane and tetraethoxysilane are active. \u0000The catalysts were used in an amount of only 2% mole. from hydroxynaphthoic acid, which is 15–35 times less than the conventional use of the same compounds as condensing agents in the synthesis of carboxylic acid arylamides. P(V) compounds, thionyl chloride, and sulfuryl chloride practically do not exhibit catalytic activity. The presence of catalytic activity only in P(III) compounds, capable of forming phosphorous acid in the reaction mass, does not contradict to the previously proposed mechanism of P = O-nucleophilic catalysis for the reaction of substituted benzoic acids with aniline catalyzed by PCl3. \u0000In general, the use of P(III) and Si(IV) compounds as catalysts in the preparation of hydroxybenzoic and hydroxynaphthoic acid anilides successfully complements the range of catalysts, based on Ti(IV) compounds, previously used in the formation of substituted benzoic and naphthoic acid anilides (containing no aromatically bonded hydroxy group), allowing to create a universal method for their synthesis.","PeriodicalId":23394,"journal":{"name":"Ukrainian Chemistry Journal","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-02-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"90267409","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-01-27DOI: 10.33609/2708-129x.88.12.2022.91-138
O. Trunova
The review article discusses the main issues of creating and using modern chelated microfertilizers based on trace elements in agricultural production. Issues of the role of microelements in the vital activity of living organisms and methods of overcoming the lack of microelements in plants are highlighted. An overview of coordination compounds of 3d-metals (Fe, Mn, Zn, Cu, Co, Ni, Mo) with different classes of complexons, features of their structure and properties is presented. It contains relevant material on the use of microelement complexes for the creation of modern chelated fertilizers. Attention is paid to the use of trace elements complexonates in areas contaminated with radionuclides (137Сs, 90Sr).
{"title":"THE ROLE OF CHELATE COORDINATION COMPOUNDS OF BIOGENIC METALS IN THE VITAL ACTIVITY OF PLANTS","authors":"O. Trunova","doi":"10.33609/2708-129x.88.12.2022.91-138","DOIUrl":"https://doi.org/10.33609/2708-129x.88.12.2022.91-138","url":null,"abstract":"The review article discusses the main issues of creating and using modern chelated microfertilizers based on trace elements in agricultural production. Issues of the role of microelements in the vital activity of living organisms and methods of overcoming the lack of microelements in plants are highlighted. An overview of coordination compounds of 3d-metals (Fe, Mn, Zn, Cu, Co, Ni, Mo) with different classes of complexons, features of their structure and properties is presented. It contains relevant material on the use of microelement complexes for the creation of modern chelated fertilizers. Attention is paid to the use of trace elements complexonates in areas contaminated with radionuclides (137Сs, 90Sr).","PeriodicalId":23394,"journal":{"name":"Ukrainian Chemistry Journal","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"84586035","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-01-27DOI: 10.33609/2708-129x.88.12.2022.189-198
Ivan Shcherbatiuk, Andrii Bazievskiy, Danylo Panchenko, Margaryta Gorobets, О. Potapenko, Кlym Vavilon, H. Potapenko, S. Kirillov, V. Zinin, S. Dubinevych, Оleksandr Golub
Due to the ability of LiFePO4 (LFP) to be charged with large currents, LFP batteries are widely used in household appliances and electric vehicles, so the recycling of spent LFP batteries becomes an urgent need. First, they contain toxic components of electrolyte that cannot be buried in landfills; secondly, the cost of lithium which contains in the electrode material continuously increases, and therefore its return to circulation is profitable and expedient. To achieve this goal, much attention is paid to hydrometallurgical processing based on the chemical extraction of Li2CO3 and FePO4 during the regeneration of the electrode material. Here we report on the wet chemistry recycling of used LFP batteries. The main task of the work was to simplify the LiFePO4 regeneration process by leaching with a solution of citric acid due to the elimination of the stage of isolation of Li2CO3 and FePO4, i.e. without selective separation of the filtrate components. The source of spent LiFePO4 was an industrial lithium iron phosphate battery failed due to an internal short circuit. It was found that using citric acid in the ratio H3Cit:LiFePO4=0.5:1, it is possible to efficiently and quickly separate the electrode material from the aluminum current collector. Further pyrolysis and heat treatment of the citrate solution makes it possible to obtain a high-purity LiFePO4/C composite material without extraneous impurities, except for amorphous carbon, which is formed during the pyrolysis of iron (II) and lithium citrates and the thermal decomposition of the binding material in an inert atmosphere. The specific capacity of the LiFePO4/C composite material recovered by the proposed method (145 mA∙h/g) insignificantly differs from that of commercial analogues. This, in our opinion, indicates good prospects of the lithium-iron phosphate regeneration method proposed in this paper.
{"title":"ELECTROCHEMICAL CHARACTERISTICS OF LiFePO4, RECOVERED AFTER BATTERY DEGRADATION","authors":"Ivan Shcherbatiuk, Andrii Bazievskiy, Danylo Panchenko, Margaryta Gorobets, О. Potapenko, Кlym Vavilon, H. Potapenko, S. Kirillov, V. Zinin, S. Dubinevych, Оleksandr Golub","doi":"10.33609/2708-129x.88.12.2022.189-198","DOIUrl":"https://doi.org/10.33609/2708-129x.88.12.2022.189-198","url":null,"abstract":"Due to the ability of LiFePO4 (LFP) to be charged with large currents, LFP batteries are widely used in household appliances and electric vehicles, so the recycling of spent LFP batteries becomes an urgent need. First, they contain toxic components of electrolyte that cannot be buried in landfills; secondly, the cost of lithium which contains in the electrode material continuously increases, and therefore its return to circulation is profitable and expedient. To achieve this goal, much attention is paid to hydrometallurgical processing based on the chemical extraction of Li2CO3 and FePO4 during the regeneration of the electrode material. Here we report on the wet chemistry recycling of used LFP batteries. The main task of the work was to simplify the LiFePO4 regeneration process by leaching with a solution of citric acid due to the elimination of the stage of isolation of Li2CO3 and FePO4, i.e. without selective separation of the filtrate components. The source of spent LiFePO4 was an industrial lithium iron phosphate battery failed due to an internal short circuit. It was found that using citric acid in the ratio H3Cit:LiFePO4=0.5:1, it is possible to efficiently and quickly separate the electrode material from the aluminum current collector. Further pyrolysis and heat treatment of the citrate solution makes it possible to obtain a high-purity LiFePO4/C composite material without extraneous impurities, except for amorphous carbon, which is formed during the pyrolysis of iron (II) and lithium citrates and the thermal decomposition of the binding material in an inert atmosphere. The specific capacity of the LiFePO4/C composite material recovered by the proposed method (145 mA∙h/g) insignificantly differs from that of commercial analogues. This, in our opinion, indicates good prospects of the lithium-iron phosphate regeneration method proposed in this paper.","PeriodicalId":23394,"journal":{"name":"Ukrainian Chemistry Journal","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"84865136","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-01-27DOI: 10.33609/2708-129x.88.12.2022.139-174
T. Maltseva, Y. Dzyazko
The review is devoted to the work, which were performed at the V.I. Vernadskii Institute of General and Inorganic Chemistry of the NAS of Ukraine according to the direction of the development of sorption naterials of wide functional purpose. All sorbents can be used in separation processes: due to their coarse dispersion and mechanical strength, they can be used as fillers for sorption columns.The direction of early works is the development of amorphous hydrophosphates and double hydrated oxides of multivalent metals, intended for the removal of toxic inorganic ions from water (arsenate-, chromate- and borate-anions, Cu2+, Pb2+, Cd2+cations etc.). Currently, attention is focused on the development of composite materials.The base of inorganic composites is hydrophosphate and oxide sorbents, and the modifiers are the advanced carbon materials, lithium-titanium and lithium-titanium-manganese spinels etc.Sorbents based on ion-exchange resins modified with inorganic ionites have also been developed.The combination of various components in composites makes it possible to obtain sorbents with improved properties (faster sorption, increased capacity and selectivity, sorption capacity in a wider pH range, easier regeneration) or multifunctional materials that sorb both inorganic and organic compounds, for example, pesticides. Prospective field of research is the development of technologies that include not only the extraction of toxic and valuable components from liquids of natural, technological and biogenic origin, but also the regeneration of the sorbent and processing of the concentrate to obtain commercial products.Thus, the integration of lithium sorption concentration into the process of reverse osmosis water desalination has been proposed. The processing of the solution formed during the regeneration of the sorbent includes the production of lithium carbonate and a complex fertilizer for acidic soils. Composites, the components of which are natural materials, are also in the focus of attention.Magnetic sorbents based on biopolymers, proposed for extraction of oil and oil products from water surfaces. Composites based on zeolites are used as containers for liquid fertilizers Another direction of research is the creation of composites - potential membrane modifiers for separation processes.
{"title":"DEVELOPMENT OF SORPTION MATERIALS OF WIDE FUNCTIONAL PURPOSE IN THE V.I. VERNADSKII INSTITUTE OF GENERAL AND INORGANIC CHEMISTRY OF THE NAS OF UKRAINE","authors":"T. Maltseva, Y. Dzyazko","doi":"10.33609/2708-129x.88.12.2022.139-174","DOIUrl":"https://doi.org/10.33609/2708-129x.88.12.2022.139-174","url":null,"abstract":"The review is devoted to the work, which were performed at the V.I. Vernadskii Institute of General and Inorganic Chemistry of the NAS of Ukraine according to the direction of the development of sorption naterials of wide functional purpose. All sorbents can be used in separation processes: due to their coarse dispersion and mechanical strength, they can be used as fillers for sorption columns.The direction of early works is the development of amorphous hydrophosphates and double hydrated oxides of multivalent metals, intended for the removal of toxic inorganic ions from water (arsenate-, chromate- and borate-anions, Cu2+, Pb2+, Cd2+cations etc.). Currently, attention is focused on the development of composite materials.The base of inorganic composites is hydrophosphate and oxide sorbents, and the modifiers are the advanced carbon materials, lithium-titanium and lithium-titanium-manganese spinels etc.Sorbents based on ion-exchange resins modified with inorganic ionites have also been developed.The combination of various components in composites makes it possible to obtain sorbents with improved properties (faster sorption, increased capacity and selectivity, sorption capacity in a wider pH range, easier regeneration) or multifunctional materials that sorb both inorganic and organic compounds, for example, pesticides. Prospective field of research is the development of technologies that include not only the extraction of toxic and valuable components from liquids of natural, technological and biogenic origin, but also the regeneration of the sorbent and processing of the concentrate to obtain commercial products.Thus, the integration of lithium sorption concentration into the process of reverse osmosis water desalination has been proposed. The processing of the solution formed during the regeneration of the sorbent includes the production of lithium carbonate and a complex fertilizer for acidic soils. Composites, the components of which are natural materials, are also in the focus of attention.Magnetic sorbents based on biopolymers, proposed for extraction of oil and oil products from water surfaces. Composites based on zeolites are used as containers for liquid fertilizers Another direction of research is the creation of composites - potential membrane modifiers for separation processes.","PeriodicalId":23394,"journal":{"name":"Ukrainian Chemistry Journal","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"89620655","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-01-27DOI: 10.33609/2708-129x.88.12.2022.175-188
T. Bienkovska, R. Khoma, Olena Vatral
The paper presents research results on the colorimetric behavior of impregnated fibrous chemisorbents (IFCS) of basic gases with visual identification of the dynamic absorption capacity “response” moment (IFCS-I) during the absorption of ammonia. Chemisorbents were obtained by impregnation of fibrous carriers with polybasic hydroxyl acid aqueous solutions with adding acid-base indicators (Ind). IFCS-I based on oxyethylenediphosphonic (IFCS-OEDPA-I), citric (IFCS-CA-I), and malic (IFCS-MA-I) acids were used. Azolithine (Az), lakmoid (LA), methyl orange (MO), methyl red (MR), Tropeolin OOO (TrOOO), Congo red (CoR), bromocresol green (BCG), broxylenol blue (BXB), bromophenol blue (BPB), bromophenol red (BPR), thymol blue (TB), xylenol orange (XO), and phenol red (PR) were used as acid-base indicators. The specificity of the changes in the colorimetric functions of IFCS-I during the absorption of NH3 by them was revealed. It was found that the color of the initial IFCS-I samples significantly depended not only on the structure of Ind, but also on the nature of the polybasic hydroxy acid being part of them. The colors of the samples based only on OEDPA (Ind = CoR, BCG, BPB), CA (Ind = CoR, TrOOO, BCG, BPB, BPR, XO) and some MA (TrOOO, BCG) are similar to the colors of aqueous solutions of Brönsted acids. The difference in the colors of the other samples from the colors of strong acid aqueous solutions with the same Ind is apparently due to specific interactions between hydroxy acid anions and neutral dye forms. During “response” to NH3 only some IFCS-I samples based on OEDPA (Ind: MO, TrOOO, Az and BPR), CA (Ind: CoR, MR, MO, TrOOO, BXB, BPR, TB, PR) and MA (Ind: LA, MR, MO, Az, BXB, XO, TB, PR) are discolored in contrast to the behavior of SO2 indicator chemisorbents.
{"title":"IMPREGNATED FIBROUS CHEMISORBENTS FOR THE COLORIMETRIC DETECTION OF AMMONIA","authors":"T. Bienkovska, R. Khoma, Olena Vatral","doi":"10.33609/2708-129x.88.12.2022.175-188","DOIUrl":"https://doi.org/10.33609/2708-129x.88.12.2022.175-188","url":null,"abstract":"The paper presents research results on the colorimetric behavior of impregnated fibrous chemisorbents (IFCS) of basic gases with visual identification of the dynamic absorption capacity “response” moment (IFCS-I) during the absorption of ammonia. Chemisorbents were obtained by impregnation of fibrous carriers with polybasic hydroxyl acid aqueous solutions with adding acid-base indicators (Ind). IFCS-I based on oxyethylenediphosphonic (IFCS-OEDPA-I), citric (IFCS-CA-I), and malic (IFCS-MA-I) acids were used. Azolithine (Az), lakmoid (LA), methyl orange (MO), methyl red (MR), Tropeolin OOO (TrOOO), Congo red (CoR), bromocresol green (BCG), broxylenol blue (BXB), bromophenol blue (BPB), bromophenol red (BPR), thymol blue (TB), xylenol orange (XO), and phenol red (PR) were used as acid-base indicators. The specificity of the changes in the colorimetric functions of IFCS-I during the absorption of NH3 by them was revealed. It was found that the color of the initial IFCS-I samples significantly depended not only on the structure of Ind, but also on the nature of the polybasic hydroxy acid being part of them. The colors of the samples based only on OEDPA (Ind = CoR, BCG, BPB), CA (Ind = CoR, TrOOO, BCG, BPB, BPR, XO) and some MA (TrOOO, BCG) are similar to the colors of aqueous solutions of Brönsted acids. The difference in the colors of the other samples from the colors of strong acid aqueous solutions with the same Ind is apparently due to specific interactions between hydroxy acid anions and neutral dye forms. During “response” to NH3 only some IFCS-I samples based on OEDPA (Ind: MO, TrOOO, Az and BPR), CA (Ind: CoR, MR, MO, TrOOO, BXB, BPR, TB, PR) and MA (Ind: LA, MR, MO, Az, BXB, XO, TB, PR) are discolored in contrast to the behavior of SO2 indicator chemisorbents.","PeriodicalId":23394,"journal":{"name":"Ukrainian Chemistry Journal","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"88851323","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2022-12-23DOI: 10.33609/2708-129x.88.11.2022.39-54
A. Nahornyi, Yulia Voloshanovska, Anatolii Omelchuk
This work presents the results of research of complex solid fluoride ion conducting phases based on lead and tin fluorides. Structure and conductive properties of solid solutions based on PbSnF4 were investigated. Series of samples were synthesized with replacement of lead cations with barium cations in structure of Pb0.86Sn1.14F4 in the concentration range of 0 ≤x ≤0.86. The barium cation has a larger radius and does not have a stereoactive lone pair of electrons, which can have a significant contribution to the conductivity of the synthesized phases and the characteristics of fluoride ion transportation in them. It was established that with partial or complete replacement of lead cations with barium cations in the fluoride ion conducting phases in Pb0.86Sn1.14F4 solid solutions of BaxPb0.86‑xSn1.14F4 , where x takes the values 0 ≤x ≤0.86 are formed. The symmetry of the crystal lattice of the synthesized phases in the concentration range of 0 ≤x ≤0.43 corresponds to the structural type of β-PbSnF4 (space group P4/ nmm). Farther increase in the content of barium fluoride cause their crystal lattice to rearrange and approach the structural type of BaSnF4 with preservation of the space group symmetry. The conductive properties of the synthesized phases were investigated. We register increase in conductivity of samples bound to increase of barium cation content in the range of 0 ≤x ≤0.43. After reaching peak in conductivity of samples it gradually lowers with increase of barium cation content in the range of 0.43 ≤x ≤0.86. The fluoride ion conducting phase Pb0.43Ba0.43Sn1.14F4, isostructural to β-PbSnF4, in comparison with the currently known fluoride-conducting phases has have the highest electrical conductivity in a wide temperature range. Its conductivity is almost two orders of magnitude higher than that of β-PbSnF4 and is 0.12 S/cm at 373 K. With 19FNMR method, it was determined that electrical conductivity is mainly provided by internodal fluorine anions, which are localized between layers of barium and stanium cations. The transfer numbers for fluorine anions in the synthesized phases correspond to the theoretical ones.
{"title":"CONDUCTIVITY OF SOLID FLUORIDE-CONDUCTING PHASES BaxPb0.86-xSn1.14F4","authors":"A. Nahornyi, Yulia Voloshanovska, Anatolii Omelchuk","doi":"10.33609/2708-129x.88.11.2022.39-54","DOIUrl":"https://doi.org/10.33609/2708-129x.88.11.2022.39-54","url":null,"abstract":"This work presents the results of research of complex solid fluoride ion conducting phases based on lead and tin fluorides. Structure and conductive properties of solid solutions based on PbSnF4 were investigated. Series of samples were synthesized with replacement of lead cations with barium cations in structure of Pb0.86Sn1.14F4 in the concentration range of 0 ≤x ≤0.86. The barium cation has a larger radius and does not have a stereoactive lone pair of electrons, which can have a significant contribution to the conductivity of the synthesized phases and the characteristics of fluoride ion transportation in them. \u0000It was established that with partial or complete replacement of lead cations with barium cations in the fluoride ion conducting phases in Pb0.86Sn1.14F4 solid solutions of BaxPb0.86‑xSn1.14F4 , where x takes the values 0 ≤x ≤0.86 are formed. The symmetry of the crystal lattice of the synthesized phases in the concentration range of 0 ≤x ≤0.43 corresponds to the structural type of β-PbSnF4 (space group P4/ nmm). Farther increase in the content of barium fluoride cause their crystal lattice to rearrange and approach the structural type of BaSnF4 with preservation of the space group symmetry. The conductive properties of the synthesized phases were investigated. \u0000We register increase in conductivity of samples bound to increase of barium cation content in the range of 0 ≤x ≤0.43. After reaching peak in conductivity of samples it gradually lowers with increase of barium cation content in the range of 0.43 ≤x ≤0.86. \u0000The fluoride ion conducting phase Pb0.43Ba0.43Sn1.14F4, isostructural to β-PbSnF4, in comparison with the currently known fluoride-conducting phases has have the highest electrical conductivity in a wide temperature range. Its conductivity is almost two orders of magnitude higher than that of β-PbSnF4 and is 0.12 S/cm at 373 K. With 19FNMR method, it was determined that electrical conductivity is mainly provided by internodal fluorine anions, which are localized between layers of barium and stanium cations. The transfer numbers for fluorine anions in the synthesized phases correspond to the theoretical ones.","PeriodicalId":23394,"journal":{"name":"Ukrainian Chemistry Journal","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2022-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"87227895","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2022-12-23DOI: 10.33609/2708-129x.88.11.2022.55-87
L. Zinko, Yelyzaveta Pletenets
The review presents different types of biosensors and their principles of operation that are currently used to detect heavy metals and lead. Biosensors are considered highly sensitive, specific, accurate, inexpensive and effective tools for the preliminary detection of one or more metals in sources of mixed pollution, especially in wastewater. The use of functional nanomaterials based on metal-organic frameworks and layered hydroxides allowed to miniaturize the design of biosensors and significantly improve their applicability for on-site analysis of target samples, which reduces the probability of any changes in the samples during transport to the laboratory. Also, these materials have long-term stability, improve the signal and response speed of electrochemical biosensors, and also increase their sensitivity and selectivity. An overview of the methods of manufacturing the active component of multilayer electrochemical sensors was conducted. The main methods of obtaining stable and sensitive to lead ions electrochemical systems are noted.Sensors and biosensors are powerful tools for accurate qualitative and quantitative analysis of a specific analyte and integration of biotechnology, microelectronics, and nanotechnology to fabricate miniaturized devices without loss of sensitivity, specificity, and control accuracy. The characteristic properties of biomolecule carriers significantly affect the sensitivity and selectivity of the device. The impact of carriers based on metal-organic frameworks and layered hydroxides on increasing the efficiency of modern lead biosensors due to the implementation of the enzyme inhibition mechanism was considered, and the methods of manufacturing the active component of multilayer electrochemical sensors were also reviewed. The perspective of using the coprecipitation method and the ion exchange method to obtain stable and sensitive lead ion electrochemical systems was noted. Thus, electrochemical biosensors can be considered as one of the most widely developed biosensors for the detection of lead ions, in which the presence of direct electron transfer from the recognition center to the electrode reduces the probability of unnecessary interference, which significantly increases their sensitivity and selectivity and enables the development of devices for in-mode monitoring real-time.
{"title":"ELECTROCHEMICAL BIOSENSORS FOR CONTROL OF LEAD CONTENT IN THE ENVIRONMENT. A REVIEW","authors":"L. Zinko, Yelyzaveta Pletenets","doi":"10.33609/2708-129x.88.11.2022.55-87","DOIUrl":"https://doi.org/10.33609/2708-129x.88.11.2022.55-87","url":null,"abstract":"The review presents different types of biosensors and their principles of operation that are currently used to detect heavy metals and lead. Biosensors are considered highly sensitive, specific, accurate, inexpensive and effective tools for the preliminary detection of one or more metals in sources of mixed pollution, especially in wastewater. The use of functional nanomaterials based on metal-organic frameworks and layered hydroxides allowed to miniaturize the design of biosensors and significantly improve their applicability for on-site analysis of target samples, which reduces the probability of any changes in the samples during transport to the laboratory. Also, these materials have long-term stability, improve the signal and response speed of electrochemical biosensors, and also increase their sensitivity and selectivity. An overview of the methods of manufacturing the active component of multilayer electrochemical sensors was conducted. The main methods of obtaining stable and sensitive to lead ions electrochemical systems are noted.Sensors and biosensors are powerful tools for accurate qualitative and quantitative analysis of a specific analyte and integration of biotechnology, microelectronics, and nanotechnology to fabricate miniaturized devices without loss of sensitivity, specificity, and control accuracy. The characteristic properties of biomolecule carriers significantly affect the sensitivity and selectivity of the device. The impact of carriers based on metal-organic frameworks and layered hydroxides on increasing the efficiency of modern lead biosensors due to the implementation of the enzyme inhibition mechanism was considered, and the methods of manufacturing the active component of multilayer electrochemical sensors were also reviewed. The perspective of using the coprecipitation method and the ion exchange method to obtain stable and sensitive lead ion electrochemical systems was noted. Thus, electrochemical biosensors can be considered as one of the most widely developed biosensors for the detection of lead ions, in which the presence of direct electron transfer from the recognition center to the electrode reduces the probability of unnecessary interference, which significantly increases their sensitivity and selectivity and enables the development of devices for in-mode monitoring real-time.","PeriodicalId":23394,"journal":{"name":"Ukrainian Chemistry Journal","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2022-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"82304397","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2022-12-23DOI: 10.33609/2708-129x.88.11.2022.3-10
B. Belan, M. Dzevenko, J. Stępień-Damm, R. Gladyshevskii
The structure of Pr3Co2Ge7.36 (Cmmm, a = 4.236 (1), b = 25.994(5), c = 4.272(1) Å, Z = 2) can be considered as a partly disordered derivative of the La3Co2Sn7 type. The Ge positions in the Pr4Ge8 cuboctahedra of the AuCu3-type slabs are conveniently described by two partly occupied sites, one of which is split. The Co and Ge atoms are characterized by square-antiprismatic, cubooctahedral, and trigonal-prismatic coordination.
Pr3Co2Ge7.36 (Cmmm, a = 4.236 (1)， b = 25.994(5)， c = 4.272(1) Å， Z = 2)的结构可以认为是La3Co2Sn7型的部分无序衍生物。在aucu3型板的Pr4Ge8立方体中，Ge的位置被方便地描述为两个部分占据的位置，其中一个是分裂的。Co和Ge原子具有方-反棱镜配位、三面体配位和三角-棱镜配位的特征。
{"title":"CRYSTAL STRUCTURE OF THE NEW GERMANIDE Pr3Co2Ge7.36","authors":"B. Belan, M. Dzevenko, J. Stępień-Damm, R. Gladyshevskii","doi":"10.33609/2708-129x.88.11.2022.3-10","DOIUrl":"https://doi.org/10.33609/2708-129x.88.11.2022.3-10","url":null,"abstract":"The structure of Pr3Co2Ge7.36 (Cmmm, a = 4.236 (1), b = 25.994(5), c = 4.272(1) Å, Z = 2) can be considered as a partly disordered derivative of the La3Co2Sn7 type. The Ge positions in the Pr4Ge8 cuboctahedra of the AuCu3-type slabs are conveniently described by two partly occupied sites, one of which is split. The Co and Ge atoms are characterized by square-antiprismatic, cubooctahedral, and trigonal-prismatic coordination.","PeriodicalId":23394,"journal":{"name":"Ukrainian Chemistry Journal","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2022-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"77394058","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2022-12-23DOI: 10.33609/2708-129x.88.11.2022.11-38
E. Trunova, Ganna Artamonova, M. Rusakova, O. Vasin, V. Glushakov
Two thio-containing complexones – S,S'-ethylenedithiodialanin (EDAL) and S,S'-carboxy-ethylenedithiodialanin (СEDAL) – were synthesized by the alkylation reaction of L-cysteine with dibromoethane. The developed technique has a number of advantages compared to those described in the literature: the absence of ammonia and metallic sodium as synthesis reagents, a decrease in the synthesis temperature and time, an increase in the yield of the final product to ~95%. The physicochemical properties of complesones were investigated using (1H, 13C) NMR, pH-potentiometry, UV-VIS, IR-spectroscopy, DTA and non-quantitative mass spectrometry. The acid dissociation constants of EDAL (pКN1=9.79; pКN2=8.79; pКCOO1=3.25) and СEDAL (pКN1=9.81; pКN2=8.17; pКCOO1=2.82; pКCOO2=3.34) were calculated and the scheme of protonation of complexons depending on pH was proposed. On the basis of NMR spectroscopy data, it is shown that the complexons have a folded structure, mobile along the S-CN2СНСООН and N–CH–COOH axes, in which betaine nitrogen atoms form two intramolecular five-membered glycine cycles due to the rapid exchange of labile protons of СООН groups. In addition, there is an intermolecular cycle in the molecule, which includes an ethylenethioamine fragment. DTA data show the presence of adsorbed and crystallization water in molecules of thio-complexons, which is eliminated at 100–170 0С. Intraspherical water molecules are located between molecular layers and form a branched system of hydrogen bonds. The final temperature of the decomposition of compounds is ~4600C. Probably, the end products of EDAL and СEDAL decomposition are non-stoichiometric sulfates or sulfides. Complex formation of thio-complexons with Mo(VI) and Cu(II) at their equimolar ratio was investigated in aqueous solutions in a wide pH range (1÷10). The formation of complexes of the composition MoO3CEDAL and CuEDAL in the range of pH 4–9 is shown and the structure of the complexes is proposed. The biological activity of carboxy-ethylenedithiodialanin and its complexes with Cu(II) was studied. It has been proven that the compounds exhibit fungistatic properties against pathogenic bacteria Candida spp. (main causative agents of fungal infections).
{"title":"SYNTHESIS AND COMPLEX-FORMING PROPERTIES OF THIO-CONTAINING COMPLEXONS: S,S'- ETHYLENEDITHIODIALANINE AND S,S'- CARBOXY- ETHYLENEDITHIODIALANINE","authors":"E. Trunova, Ganna Artamonova, M. Rusakova, O. Vasin, V. Glushakov","doi":"10.33609/2708-129x.88.11.2022.11-38","DOIUrl":"https://doi.org/10.33609/2708-129x.88.11.2022.11-38","url":null,"abstract":"Two thio-containing complexones – S,S'-ethylenedithiodialanin (EDAL) and S,S'-carboxy-ethylenedithiodialanin (СEDAL) – were synthesized by the alkylation reaction of L-cysteine with dibromoethane. The developed technique has a number of advantages compared to those described in the literature: the absence of ammonia and metallic sodium as synthesis reagents, a decrease in the synthesis temperature and time, an increase in the yield of the final product to ~95%. The physicochemical properties of complesones were investigated using (1H, 13C) NMR, pH-potentiometry, UV-VIS, IR-spectroscopy, DTA and non-quantitative mass spectrometry. The acid dissociation constants of EDAL (pКN1=9.79; pКN2=8.79; pКCOO1=3.25) and СEDAL (pКN1=9.81; pКN2=8.17; pКCOO1=2.82; pКCOO2=3.34) were calculated and the scheme of protonation of complexons depending on pH was proposed. On the basis of NMR spectroscopy data, it is shown that the complexons have a folded structure, mobile along the S-CN2СНСООН and N–CH–COOH axes, in which betaine nitrogen atoms form two intramolecular five-membered glycine cycles due to the rapid exchange of labile protons of СООН groups. In addition, there is an intermolecular cycle in the molecule, which includes an ethylenethioamine fragment. \u0000DTA data show the presence of adsorbed and crystallization water in molecules of thio-complexons, which is eliminated at 100–170 0С. Intraspherical water molecules are located between molecular layers and form a branched system of hydrogen bonds. The final temperature of the decomposition of compounds is ~4600C. Probably, the end products of EDAL and СEDAL decomposition are non-stoichiometric sulfates or sulfides. \u0000Complex formation of thio-complexons with Mo(VI) and Cu(II) at their equimolar ratio was investigated in aqueous solutions in a wide pH range (1÷10). The formation of complexes of the composition MoO3CEDAL and CuEDAL in the range of pH 4–9 is shown and the structure of the complexes is proposed. \u0000The biological activity of carboxy-ethylenedithiodialanin and its complexes with Cu(II) was studied. It has been proven that the compounds exhibit fungistatic properties against pathogenic bacteria Candida spp. (main causative agents of fungal infections).","PeriodicalId":23394,"journal":{"name":"Ukrainian Chemistry Journal","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2022-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"76766089","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2022-11-25DOI: 10.33609/2708-129x.88.10.2022.104-116
K. Pershina, O. Gayday, O. Boichuk, Alla Rak
A study of the accumulation of metal ions in the sludge of the bioenergy complex after burning the plant's raw materials was carried out. The value of the content of toxic metals (cadmium, lead, and mercury) is less than an order of magnitude than the MPC for soils. The presence of a complex of trace elements, iron, calcium, magnesium, and sodium in sludge makes them attractive for use as raw materials for production of organic-mineral fertilizers for the cultivation of a sufficiently wide range of agricultural and ornamental crops. It was studied that distribution of heavy metals in sludge of the filtration fields in different depths : 1 – from the surface (1–5 cm), 2 – from the middle (~500 cm) and 3 – from a depth > 1500 cm. The distribution of metal's ions accumulation established that the maximum content of cadmium and nickel observed in the surface layer of silt, lead in the middle layer, and manganese in the deep (more than 1500 m) layer. Such distribution of heavy metals shows, that the maximum concentration of cadmium and lead takes place in the surface layer of silt, lead in the middle layer , and manganese in the deep (more than 1500 m) layer. Thus, the deep layer is the safest to use as a raw material in production of fertilizers. But the presence of cadmium and lead, which have cumulative properties, in all layers of sludge is a risk factor for using sludge as fertilizers for crops that will be used for food purposes but can be use for growing technical crops and ornamental plants. Also, the presence of aluminum and titanium in the composition of the sludge requires a more detailed study. The final decision is possible only after conducting field tests, with subsequent analytical control of products and soil after harvesting.
{"title":"FEATURES OF THE ACCUMULATION OF METAL IONS IN SLUDGES OF THE BIOENERGY COMPLEX","authors":"K. Pershina, O. Gayday, O. Boichuk, Alla Rak","doi":"10.33609/2708-129x.88.10.2022.104-116","DOIUrl":"https://doi.org/10.33609/2708-129x.88.10.2022.104-116","url":null,"abstract":"A study of the accumulation of metal ions in the sludge of the bioenergy complex after burning the plant's raw materials was carried out. The value of the content of toxic metals (cadmium, lead, and mercury) is less than an order of magnitude than the MPC for soils. The presence of a complex of trace elements, iron, calcium, magnesium, and sodium in sludge makes them attractive for use as raw materials for production of organic-mineral fertilizers for the cultivation of a sufficiently wide range of agricultural and ornamental crops. It was studied that distribution of heavy metals in sludge of the filtration fields in different depths : 1 – from the surface (1–5 cm), 2 – from the middle (~500 cm) and 3 – from a depth > 1500 cm. The distribution of metal's ions accumulation established that the maximum content of cadmium and nickel observed in the surface layer of silt, lead in the middle layer, and manganese in the deep (more than 1500 m) layer. Such distribution of heavy metals shows, that the maximum concentration of cadmium and lead takes place in the surface layer of silt, lead in the middle layer , and manganese in the deep (more than 1500 m) layer. Thus, the deep layer is the safest to use as a raw material in production of fertilizers. But the presence of cadmium and lead, which have cumulative properties, in all layers of sludge is a risk factor for using sludge as fertilizers for crops that will be used for food purposes but can be use for growing technical crops and ornamental plants. Also, the presence of aluminum and titanium in the composition of the sludge requires a more detailed study. The final decision is possible only after conducting field tests, with subsequent analytical control of products and soil after harvesting.","PeriodicalId":23394,"journal":{"name":"Ukrainian Chemistry Journal","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2022-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"89436397","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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