Pub Date : 2023-01-19DOI: 10.18524/2304-0947.2022.3(83).271203
R. Y. Khoma
This paper is a brief report on the life journey and scientific insights of Inna Yosypivna Seyfullina, an outstanding scientist-chemist, Honoured Master of Science and Engineering of Ukraine, Doctor of Chemistry, Professor of the Department of Inorganic Chemistry and Chemical Education of Odesa I. I. Mechnikov National University.
{"title":"To the Anniversary of Seyfullina Inna Yosypivna - the Outstanding Scientist-Chemist, Professor of the Department of Inorganic Chemistry and Chemical Education of Odesa I. I. Mechnikov National University","authors":"R. Y. Khoma","doi":"10.18524/2304-0947.2022.3(83).271203","DOIUrl":"https://doi.org/10.18524/2304-0947.2022.3(83).271203","url":null,"abstract":"This paper is a brief report on the life journey and scientific insights of Inna Yosypivna Seyfullina, an outstanding scientist-chemist, Honoured Master of Science and Engineering of Ukraine, Doctor of Chemistry, Professor of the Department of Inorganic Chemistry and Chemical Education of Odesa I. I. Mechnikov National University.","PeriodicalId":19451,"journal":{"name":"Odesa National University Herald. Chemistry","volume":"40 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2023-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"91307300","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 : 2023-01-19DOI: 10.18524/2304-0947.2022.3(83).268769
O. Mariichak, A. Zakharchuk, G. M. Rozantsev, S. V. Radio
Conditions necessary for the formation of La(III)-containing polyoxotungstates in solutions of the system Na2WO4 – HNO3 – La(NO3)3 – H2O/Solvent (Solvent = acetone, acetonitrile, ethanol; 50/50 vol.% Н2О: Solvent ratio) acidified to acidity Z = ν(H+)/ν(WO42–) = 0.80 were elaborated. It was established that during salting out, the addition of an organic solvent leads to the crystallization of normal salts, Na9[La(W5O18)2]·nH2O (n = 32–35). Using FT-IR spectroscopy, it was shown that the anion [La(W5O18)2]9– in the composition of the isolated salts belongs to the Peacock–Weakley type of structure and the absence of solvent molecules in the composition of the crystalline product was established. Using the method of scanning electron microscopy, the single-phase nature of the synthesized salts was established (according to the uniform contrast of the surface of the samples during scanning in the backscattered electron mode and according to the results of energy dispersive X-ray microanalysis), and the grain sizes were determined (from 140–300 nm for the salt isolated from the H2O: acetone medium, to 300–450 nm for the salt isolated from the H2O: ethanol system). Microphotographs of powders of Na9[La(W5O18)2]·nH2O salts powders in characteristic X-ray emission do not show zones with different surface morphology, and demonstrate uniform distributions of Na, La, W, and O without segregation, which confirms the single–phase nature of the samples isolated from aqueous-organic solutions. The conducted research made it possible to expand the list of organic solvents that can be used for the synthesis of normal salts with a heteropoly anion with a Peacock–Weakley type of structure from aqueous-organic solutions. The use of acetonitrile and ethanol for Na9[La(W5O18)2 ]·nH2O isolating can be extended to the synthesis of salts with other lanthanide heteroatoms.
{"title":"Synthesis of lanthanum(III)-containing heteropoly compounds with a Peacock-Weakley type anion from aqueous-organic solutions","authors":"O. Mariichak, A. Zakharchuk, G. M. Rozantsev, S. V. Radio","doi":"10.18524/2304-0947.2022.3(83).268769","DOIUrl":"https://doi.org/10.18524/2304-0947.2022.3(83).268769","url":null,"abstract":"Conditions necessary for the formation of La(III)-containing polyoxotungstates in solutions of the system Na2WO4 – HNO3 – La(NO3)3 – H2O/Solvent (Solvent = acetone, acetonitrile, ethanol; 50/50 vol.% Н2О: Solvent ratio) acidified to acidity Z = ν(H+)/ν(WO42–) = 0.80 were elaborated. It was established that during salting out, the addition of an organic solvent leads to the crystallization of normal salts, Na9[La(W5O18)2]·nH2O (n = 32–35). Using FT-IR spectroscopy, it was shown that the anion [La(W5O18)2]9– in the composition of the isolated salts belongs to the Peacock–Weakley type of structure and the absence of solvent molecules in the composition of the crystalline product was established. Using the method of scanning electron microscopy, the single-phase nature of the synthesized salts was established (according to the uniform contrast of the surface of the samples during scanning in the backscattered electron mode and according to the results of energy dispersive X-ray microanalysis), and the grain sizes were determined (from 140–300 nm for the salt isolated from the H2O: acetone medium, to 300–450 nm for the salt isolated from the H2O: ethanol system). Microphotographs of powders of Na9[La(W5O18)2]·nH2O salts powders in characteristic X-ray emission do not show zones with different surface morphology, and demonstrate uniform distributions of Na, La, W, and O without segregation, which confirms the single–phase nature of the samples isolated from aqueous-organic solutions. The conducted research made it possible to expand the list of organic solvents that can be used for the synthesis of normal salts with a heteropoly anion with a Peacock–Weakley type of structure from aqueous-organic solutions. The use of acetonitrile and ethanol for Na9[La(W5O18)2 ]·nH2O isolating can be extended to the synthesis of salts with other lanthanide heteroatoms.","PeriodicalId":19451,"journal":{"name":"Odesa National University Herald. Chemistry","volume":"115 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2023-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"86202041","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 : 2023-01-19DOI: 10.18524/2304-0947.2022.3(83).268608
S. Bachinsky, N. Burenkova, Yu. V. Ishkov, V. Kravtsov
The purpose of this work is the synthesis of an annelated with pyrimidine system at position 2–3 of the diazepine cycle and the study of the affinity of the synthesized compound for the central benzodiazepine receptors (CBDR) and peripheral benzodiazepine receptors (PBDR) of the CNS, as well as, in the future, the study of pharmacological properties. The synthesis of 8-bromo‑11-methyl‑6-phenyl‑11-pyrimido[4,5-b][1,4]benzodiazepine II was carried out by heating 7-bromo‑1-methyl‑5-phenyl‑1,3-dihydro‑2Н‑1,4-benzodiazepin‑2-one I with formamide in a solution of phosphorus oxychloride. The structure of compound II was confirmed by mass spectrometry and 1H NMR spectroscopy, as well as by X‑ray diffraction analysis. 1Н NMR spectrum was recorded in ~2% solution of the compound in CDCl3 on the Bruker (300 MHz), internal standard TMS. Mass spectrum of the compound was obtained by electron impact on an mass spectrometer, “MX‑1321”, ionizing voltage 70 eV, ionizationchamber temperature 220 °C. The X‑ray diffraction study of the single crystal was carried out on a KUMA‑4CCD diffractometer using MoKa – radiation with ω-scanning at 100 K. The affinity of compound II to the central and peripheral benzodiazepine receptors of the CNS was studied by radioligand analysis. The experiment was carried out on nonpedigreed male rats with mass 180–220 g. The following radioligands were used: [3H]flumazenil (CBDR) and [3H]RK 11195 (PBDR). As a result of radioligand studies, it was found that compound II at a concentration of 1 10–6 M inhibits the specific binding of the radioligand [3H]flumazenil to CBDR by 43.7%, which indicates the presence of a moderate affinity for CBDR. It was also found that compound II at a concentration of 1 10–6 M inhibits the specific binding of the radioligand [3H]RK 11195 with PBDR by 3.7%, which indicates the practical absence of affinity for PBDR. The presence of a moderate affinity of compound II for CBDR and the selectivity of the binding of this compound to CBDR with respect to PBDR is of interest for further studies of this class of compounds as potential anxiolytics of a new type.
{"title":"SYNTHESIS, STRUCTURE AND AFFINITY TO CNS RECEPTORS 8-BROM-11-METHYL-6-PHENYL-11-PYRIMIDO[4,5-B][1,4]BENZO¬DIAZEPINE","authors":"S. Bachinsky, N. Burenkova, Yu. V. Ishkov, V. Kravtsov","doi":"10.18524/2304-0947.2022.3(83).268608","DOIUrl":"https://doi.org/10.18524/2304-0947.2022.3(83).268608","url":null,"abstract":"The purpose of this work is the synthesis of an annelated with pyrimidine system at position 2–3 of the diazepine cycle and the study of the affinity of the synthesized compound for the central benzodiazepine receptors (CBDR) and peripheral benzodiazepine receptors (PBDR) of the CNS, as well as, in the future, the study of pharmacological properties. The synthesis of 8-bromo‑11-methyl‑6-phenyl‑11-pyrimido[4,5-b][1,4]benzodiazepine II was carried out by heating 7-bromo‑1-methyl‑5-phenyl‑1,3-dihydro‑2Н‑1,4-benzodiazepin‑2-one I with formamide in a solution of phosphorus oxychloride. The structure of compound II was confirmed by mass spectrometry and 1H NMR spectroscopy, as well as by X‑ray diffraction analysis. 1Н NMR spectrum was recorded in ~2% solution of the compound in CDCl3 on the Bruker (300 MHz), internal standard TMS. Mass spectrum of the compound was obtained by electron impact on an mass spectrometer, “MX‑1321”, ionizing voltage 70 eV, ionizationchamber temperature 220 °C. The X‑ray diffraction study of the single crystal was carried out on a KUMA‑4CCD diffractometer using MoKa – radiation with ω-scanning at 100 K. The affinity of compound II to the central and peripheral benzodiazepine receptors of the CNS was studied by radioligand analysis. The experiment was carried out on nonpedigreed male rats with mass 180–220 g. The following radioligands were used: [3H]flumazenil (CBDR) and [3H]RK 11195 (PBDR). As a result of radioligand studies, it was found that compound II at a concentration of 1 10–6 M inhibits the specific binding of the radioligand [3H]flumazenil to CBDR by 43.7%, which indicates the presence of a moderate affinity for CBDR. It was also found that compound II at a concentration of 1 10–6 M inhibits the specific binding of the radioligand [3H]RK 11195 with PBDR by 3.7%, which indicates the practical absence of affinity for PBDR. The presence of a moderate affinity of compound II for CBDR and the selectivity of the binding of this compound to CBDR with respect to PBDR is of interest for further studies of this class of compounds as potential anxiolytics of a new type.","PeriodicalId":19451,"journal":{"name":"Odesa National University Herald. Chemistry","volume":"10 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2023-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"75818810","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 : 2023-01-19DOI: 10.18524/2304-0947.2022.3(83).268607
A. Kosinskaya, L. N. Ognichenko, T. A. Sidelnikova, Ya. F. Burdina, A. A. Shyrykalova, G. F. Stepanov, A. Grekova, I. R. Gridina, E. P. Lebed, V. Kuz'min
The aim of this work is to analyze the influence of the structure of organic compounds on their ability to penetrate the blood-brain barrier (BBB) using the values of LogPS (logarithm of the product of permeability and surface area of metabolism, which is a measure of the transfer of compounds from the blood to the brain and reflects the degree of penetration of the substance into the brain without relative binding to proteins). The study of the permeability of BBB is necessary both for the development of new drugs for which the CNS is a biointerference, and for the development of effective ways of treating diseases of the brain.
{"title":"2D QSAR ANALYSIS OF BLOOD-BRAIN BARRIER PERMEABILITY FOR ORGANIC COMPOUNDS","authors":"A. Kosinskaya, L. N. Ognichenko, T. A. Sidelnikova, Ya. F. Burdina, A. A. Shyrykalova, G. F. Stepanov, A. Grekova, I. R. Gridina, E. P. Lebed, V. Kuz'min","doi":"10.18524/2304-0947.2022.3(83).268607","DOIUrl":"https://doi.org/10.18524/2304-0947.2022.3(83).268607","url":null,"abstract":"The aim of this work is to analyze the influence of the structure of organic compounds on their ability to penetrate the blood-brain barrier (BBB) using the values of LogPS (logarithm of the product of permeability and surface area of metabolism, which is a measure of the transfer of compounds from the blood to the brain and reflects the degree of penetration of the substance into the brain without relative binding to proteins). The study of the permeability of BBB is necessary both for the development of new drugs for which the CNS is a biointerference, and for the development of effective ways of treating diseases of the brain.","PeriodicalId":19451,"journal":{"name":"Odesa National University Herald. Chemistry","volume":"47 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2023-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"76803324","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 : 2023-01-19DOI: 10.18524/2304-0947.2022.3(83).268690
E. Martsinko, I. Seifullina, E. Chebanenko, A. G. Pesaroglo
There were developed the novel methods for the synthesis of six mixed- metal and mixed-ligand complexes of germanium and rare earth metals (Pr, Nd, Dy, Ho, Tm, Lu) with 1-hydroxyethylidenediphosphonic acid and 2,2´-bipyridine. The compounds have been characterized using various research methods: elemental analysis, mass spectrometry, electrical conductivity, thermogravimetry, IR spectroscopy. It has proved that all complexes are crystal hydrates, belong to heterometallic mixed ligand compounds [Ln(H2O)4(bipy)2]2 [Ge(m-hedp) (m- OH)]6⸱nH2O, Ln=Pr (1); Nd (2); Dy (3); Ho (4); Tm (5); Lu (6); n = 22 (1, 2), 21 (3), 20 (4, 5), 19 (6). Their formation occurs due to the electrostatic interaction of complex cations [Ln(H2O)4(bipy)2]3+ with hexanuclear anions [Ge(m-hedp)(m- OH)]66-. According to the results of measuring the electrical conductivity of dimethylformamide solutions 1–6, it has been established that they belong to triionic electrolytes: λ (in Ohm-1∙сm2∙mol-1) for 1 = 131,3; 2 = 138,8; 3 = 145,8; 4 = 151,1; 5 = 158,3; 6 = 162,7. The cation-anionic type of complexes 1–6 has been confirmed as a result of the analysis of their mass spectrum. The analysis of the mass spectrum showed that the main decomposition direction of the complex is related to the formation of the complex cation fragment [Ln(H2O)4(bipy)2]3+, which corresponds to the most intense peak (m/z = 136, I = 55%). The thermal decomposition of compounds 1–6 includes dehydration, deaquatation, oxidative thermal destruction and the formation of final products as a mixture of Ln2O3 and GeP2O7. On the DTA curves in the interval 70–200 °C the first endothermic effect can be traced, which is accompanied by the removal of a certain number of crystallization and coordination water molecules into the gas phase. Absorption bands of the P-O bond have been detected at ~1053 and ~970 сm-1, that indicates the presence of the fully deprotonated PO32- groups in the composition of complexes. Furthermore, n(OH), ν(Ge–O), d(Ge–OH) bands characteristic for all the previously synthesized compounds with [Ge6(m-OH)6(m-hedp)6]6- anion have been detected in the IR spectra of 1–6. A set of the bands usual for the aromatic molecules n(C–C), das(CH3), ds(CH3), n(Сar=N) has been assigned with 2,2`-bipyridine in the structure of all compounds.
{"title":"MIXED-LIGAND GERMANIUM–LANTHANIDE COMPLEXES WITH 1-HYDROXYETHYLIDENEDIPHOSPHONIC ACID AND 2,2’-BIPYRIDINE","authors":"E. Martsinko, I. Seifullina, E. Chebanenko, A. G. Pesaroglo","doi":"10.18524/2304-0947.2022.3(83).268690","DOIUrl":"https://doi.org/10.18524/2304-0947.2022.3(83).268690","url":null,"abstract":"There were developed the novel methods for the synthesis of six mixed- metal and mixed-ligand complexes of germanium and rare earth metals (Pr, Nd, Dy, Ho, Tm, Lu) with 1-hydroxyethylidenediphosphonic acid and 2,2´-bipyridine. The compounds have been characterized using various research methods: elemental analysis, mass spectrometry, electrical conductivity, thermogravimetry, IR spectroscopy. It has proved that all complexes are crystal hydrates, belong to heterometallic mixed ligand compounds [Ln(H2O)4(bipy)2]2 [Ge(m-hedp) (m- OH)]6⸱nH2O, Ln=Pr (1); Nd (2); Dy (3); Ho (4); Tm (5); Lu (6); n = 22 (1, 2), 21 (3), 20 (4, 5), 19 (6). Their formation occurs due to the electrostatic interaction of complex cations [Ln(H2O)4(bipy)2]3+ with hexanuclear anions [Ge(m-hedp)(m- OH)]66-.\u0000According to the results of measuring the electrical conductivity of dimethylformamide solutions 1–6, it has been established that they belong to triionic electrolytes: λ (in Ohm-1∙сm2∙mol-1) for 1 = 131,3; 2 = 138,8; 3 = 145,8; 4 = 151,1; 5 = 158,3; 6 = 162,7. The cation-anionic type of complexes 1–6 has been confirmed as a result of the analysis of their mass spectrum. The analysis of the mass spectrum showed that the main decomposition direction of the complex is related to the formation of the complex cation fragment [Ln(H2O)4(bipy)2]3+, which corresponds to the most intense peak (m/z = 136, I = 55%).\u0000The thermal decomposition of compounds 1–6 includes dehydration, deaquatation, oxidative thermal destruction and the formation of final products as a mixture of Ln2O3 and GeP2O7. On the DTA curves in the interval 70–200 °C the first endothermic effect can be traced, which is accompanied by the removal of a certain number of crystallization and coordination water molecules into the gas phase.\u0000Absorption bands of the P-O bond have been detected at ~1053 and ~970 сm-1, that indicates the presence of the fully deprotonated PO32- groups in the composition of complexes. Furthermore, n(OH), ν(Ge–O), d(Ge–OH) bands characteristic for all the previously synthesized compounds with [Ge6(m-OH)6(m-hedp)6]6- anion have been detected in the IR spectra of 1–6. A set of the bands usual for the aromatic molecules n(C–C), das(CH3), ds(CH3), n(Сar=N) has been assigned with 2,2`-bipyridine in the structure of all compounds.","PeriodicalId":19451,"journal":{"name":"Odesa National University Herald. Chemistry","volume":"110 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2023-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"81738449","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 : 2023-01-19DOI: 10.18524/2304-0947.2022.3(83).268625
R. Khoma, T. Bienkovska, E. Y. Bugova, L. T. Osadchiy, S. Vodzinskii, S. Toporov
The study of data on acid-base properties of model systems SO2 – KOH – TrOOO – H2O and SO2 – Am – TrOOO – H2O (TrOOO – tropeoline OOO; Am – diethanolamine (DEA), triethanolamine (TEA), N‑methylmonoethanolamine (MMEA) and morpholine (Mf) at 293 K using pH-, spectrophotometry and colorimetry methods are presented. There is a pronounced isosbestic point at 415 nm in the electronic absorption spectra of the systems SO2– Am –TrOOO– H2O (Am = MMEA, MEA and TEA; pH ≤ 7.5; T = 293 K), which indicates the presence of a dynamic equilibrium between ion-molecular forms. According to the width of the absorption spectra, the bases in the region of 2.0 ≤ pH ≤ 8.0 can be arranged in the following row: MEA > Mf > KOH > DEA > TEA > MMEA. The bases can be arranged in the following rows for the effect on optical density at 490 nm: KOH > Mf ≥ MEA > DEA ≥ TEA (at 5.5 ≤ pH < 9.0); KOH = MEA = Mf > DEA = TEA (at pH < 6.0). According to the values of optical density at 360 nm in the region of 2.0 ≤ pH < 8.5, the bases can be arranged in the following row: Mf > KOH ≥ MEA ≥ DEA > MMEA > TEA. The total color difference (ΔE76) and specific color difference (SCD) values were calculated by colorimetric method as a function of pH. The acid–base dissociation constants in the SO2 – Am (KOH) – TrOOO – H2O systems significantly depend on the structure and physicochemical properties of the organic base and differ significantly from those in the HCl (HClO4, H2SO4) – MEA – TrOOO – H2O systems. The interrelation of colorimetric functions was established (total color difference and specific color difference) of SO2 – Am – TrOOO – H2O systems with molar refraction Am, empirical function pKa – lgPow, which combines the basicity and hydrophilicity of Am, formation constants of ammonium sulfites and hydrosulfites, pH- (dpH/dpQSO2), redox- (dЕ/dpQSO2) and conductometric (Dk) titration curves of Am aqueous solutions with gaseous sulfur dioxide.
{"title":"SO2 – Am (KOH) – TROPEOLIN OOO – H2O (Am – ETHANOLAMINES, MORPHOLINE) SYSTEMS ACID-BASE PROPERTIES","authors":"R. Khoma, T. Bienkovska, E. Y. Bugova, L. T. Osadchiy, S. Vodzinskii, S. Toporov","doi":"10.18524/2304-0947.2022.3(83).268625","DOIUrl":"https://doi.org/10.18524/2304-0947.2022.3(83).268625","url":null,"abstract":"The study of data on acid-base properties of model systems SO2 – KOH – TrOOO – H2O and SO2 – Am – TrOOO – H2O (TrOOO – tropeoline OOO; Am – diethanolamine (DEA), triethanolamine (TEA), N‑methylmonoethanolamine (MMEA) and morpholine (Mf) at 293 K using pH-, spectrophotometry and colorimetry methods are presented. There is a pronounced isosbestic point at 415 nm in the electronic absorption spectra of the systems SO2– Am –TrOOO– H2O (Am = MMEA, MEA and TEA; pH ≤ 7.5; T = 293 K), which indicates the presence of a dynamic equilibrium between ion-molecular forms. According to the width of the absorption spectra, the bases in the region of 2.0 ≤ pH ≤ 8.0 can be arranged in the following row: MEA > Mf > KOH > DEA > TEA > MMEA. The bases can be arranged in the following rows for the effect on optical density at 490 nm: KOH > Mf ≥ MEA > DEA ≥ TEA (at 5.5 ≤ pH < 9.0); KOH = MEA = Mf > DEA = TEA (at pH < 6.0).\u0000According to the values of optical density at 360 nm in the region of 2.0 ≤ pH < 8.5, the bases can be arranged in the following row: Mf > KOH ≥ MEA ≥ DEA > MMEA > TEA.\u0000The total color difference (ΔE76) and specific color difference (SCD) values were calculated by colorimetric method as a function of pH. The acid–base dissociation constants in the SO2 – Am (KOH) – TrOOO – H2O systems significantly depend on the structure and physicochemical properties of the organic base and differ significantly from those in the HCl (HClO4, H2SO4) – MEA – TrOOO – H2O systems.\u0000The interrelation of colorimetric functions was established (total color difference and specific color difference) of SO2 – Am – TrOOO – H2O systems with molar refraction Am, empirical function pKa – lgPow, which combines the basicity and hydrophilicity of Am, formation constants of ammonium sulfites and hydrosulfites, pH- (dpH/dpQSO2), redox- (dЕ/dpQSO2) and conductometric (Dk) titration curves of Am aqueous solutions with gaseous sulfur dioxide.","PeriodicalId":19451,"journal":{"name":"Odesa National University Herald. Chemistry","volume":"22 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2023-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"76473996","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 : 2023-01-19DOI: 10.18524/2304-0947.2022.3(83).268610
D. Snigur, V. V. Shapovalenko, O. Zhukovetska, O. Guzenko, T. M. Shcherbakova
In the current study, the peculiarities of the complexation of Hafnium(IV) with 6,7-dihyroxy‑4-carboxyl‑2-phenylbenzopyrylium salts (CDC) in binary systems and in the presence of cationic surfactants (Surf) were studied. The CDC was synthesized by condensation of pyrogallol A with benzoylpyruvic acid in an acetic acid medium in the presence of perchloric acid. To obtain KDC bromide and chloride, the synthesis was carried out in the presence of bromide acid or by sparging of dry hydrogen chloride, respectively. Using classical spectrophotometric methods of molar ratios and Bent-French, it was found that at pH 2.5 in binary system one complex with stoichiometry Hf(IV): CDC1:2 was formed. Molar absorptivity coefficient was calculated for Hf(IV) complex with CDC and it was equal 3,9⸱104. It was shown that in the presence of cetylpyridinium chloride or cetyltrimetrylammonium bromide complexes with a molar ratio of Hf(IV): CDC: Surf = 1:2:2 were formed. It is noted that the complexes were formed within 10–15 minutes, and the absorbance of the solutions remains constant for at least 2 hours. It was established that the nature of the anion, which is part of the reagent, does not significantly affect the characteristics of the analytical form. It is shown that in the presence of cationic surfactants, the optimal pH of complex formation shifts to a more acidic region. In addition, the introduction of cationic surfactants leads to a batachromic shift of the absorption band by 10–15 nm and an increase in the molar absorptivity to 5.8⸱104 and 6.4⸱104 when cetylpyridinium chloride or cetyltrimetrylammonium bromide were used respectively. It is noted that the found analytical forms can be used as a basis for the development of combined spectroscopic methods for determining trace amounts of Hafnium(IV).
{"title":"INTERACTION OF HAFNIUM(IV) WITH 6,7-DIHYDROXY‑4-CARBOXYL‑2- PHENYLBENZOPYRYLLIUM SALTS IN BINARY SYSTEMS AND IN THE PRESENCE OF CATIONIC SURFACTANTS","authors":"D. Snigur, V. V. Shapovalenko, O. Zhukovetska, O. Guzenko, T. M. Shcherbakova","doi":"10.18524/2304-0947.2022.3(83).268610","DOIUrl":"https://doi.org/10.18524/2304-0947.2022.3(83).268610","url":null,"abstract":"In the current study, the peculiarities of the complexation of Hafnium(IV) with 6,7-dihyroxy‑4-carboxyl‑2-phenylbenzopyrylium salts (CDC) in binary systems and in the presence of cationic surfactants (Surf) were studied. The CDC was synthesized by condensation of pyrogallol A with benzoylpyruvic acid in an acetic acid medium in the presence of perchloric acid. To obtain KDC bromide and chloride, the synthesis was carried out in the presence of bromide acid or by sparging of dry hydrogen chloride, respectively. Using classical spectrophotometric methods of molar ratios and Bent-French, it was found that at pH 2.5 in binary system one complex with stoichiometry Hf(IV): CDC1:2 was formed. Molar absorptivity coefficient was calculated for Hf(IV) complex with CDC and it was equal 3,9⸱104. It was shown that in the presence of cetylpyridinium chloride or cetyltrimetrylammonium bromide complexes with a molar ratio of Hf(IV): CDC: Surf = 1:2:2 were formed. It is noted that the complexes were formed within 10–15 minutes, and the absorbance of the solutions remains constant for at least 2 hours. It was established that the nature of the anion, which is part of the reagent, does not significantly affect the characteristics of the analytical form. It is shown that in the presence of cationic surfactants, the optimal pH of complex formation shifts to a more acidic region. In addition, the introduction of cationic surfactants leads to a batachromic shift of the absorption band by 10–15 nm and an increase in the molar absorptivity to 5.8⸱104 and 6.4⸱104 when cetylpyridinium chloride or cetyltrimetrylammonium bromide were used respectively. It is noted that the found analytical forms can be used as a basis for the development of combined spectroscopic methods for determining trace amounts of Hafnium(IV).","PeriodicalId":19451,"journal":{"name":"Odesa National University Herald. Chemistry","volume":"11 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2023-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"80179697","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 : 2023-01-19DOI: 10.18524/2304-0947.2022.3(83).268935
O. V. Shevchenko, K. Burenkova
Radical polymerization of methyl methacrylate with the addition of Cu(II), Ni(II), Co(II) 3-allylpentan-2,4-dione chelates was carried out. It is shown that in the case of the cobalt complex, the process occurs at rates comparable to those of the traditional radical initiator, benzoyl peroxide. The resulting polymethyl methacrylate has large molecular weights and contains fragments of β-diketonates in the polymer, which graft side chains. The branched structure of the polymer is proven based on the calculation of the Zimm-Stockmeier factor. It has been established that the branched polymethyl methacrylate obtained on the basis of chelates has a higher thermal stability compared to the sample obtained using benzoyl peroxide.
{"title":"CHELATES OF 3-ALLYLPENTAN-2,4-DIONE FOR THE SYNTHESIS OF BRANCHED THERMOSTABLE POLYMETHYL METHACRYLATE","authors":"O. V. Shevchenko, K. Burenkova","doi":"10.18524/2304-0947.2022.3(83).268935","DOIUrl":"https://doi.org/10.18524/2304-0947.2022.3(83).268935","url":null,"abstract":"Radical polymerization of methyl methacrylate with the addition of Cu(II), Ni(II), Co(II) 3-allylpentan-2,4-dione chelates was carried out. It is shown that in the case of the cobalt complex, the process occurs at rates comparable to those of the traditional radical initiator, benzoyl peroxide. The resulting polymethyl methacrylate has large molecular weights and contains fragments of β-diketonates in the polymer, which graft side chains. The branched structure of the polymer is proven based on the calculation of the Zimm-Stockmeier factor. It has been established that the branched polymethyl methacrylate obtained on the basis of chelates has a higher thermal stability compared to the sample obtained using benzoyl peroxide.","PeriodicalId":19451,"journal":{"name":"Odesa National University Herald. Chemistry","volume":"30 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2023-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"74611568","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 : 2023-01-19DOI: 10.18524/2304-0947.2022.3(83).268609
N. Blashko, O. Marchuk, O. Smitiukh, A. Fedorchuk
The samples of composition Pr3Ag4xGe1,25-xSe7 (x = 0,10; 0,15), weighing one gram, obtained by sintering elementary components in vacuumed quartz containers at a maximum temperature of 1150 °C. The diffraction patterns for X‑ray phase analysis were recorded at a DRON4–13 diffractometer for 2Q range of 10–100 ° (CuKα radiation, scan step 0,02 °, 20 s exposure in each point). For data processing and the determination of the crystal structure used WinCSD software package. Visualization of the crystal structure, stacking and coordination polyhedra was performed using VESTA program. The crystal structure of the quaternary compound Pr3Ag0,40Ge1,15Se7 (a = 1,06466(4) nm, с = 0,60552(3) nm, RI = 0,0511, Rp = 0,2455) and Pr3Ag0,60Ge1,10Se7 (a = 1,06556(2) nm, c = 0,60583(2) nm, RI = 0,0618, Rp = 0,2068) was investigated by powder X‑ray method. The structure of the compound belongs to the La3CuSiS7 structural type (space group P63, Pearsoncode hP24, a = 1,028 nm, c = 0,575 nm). In this structure, the Pr atom is located in the 6c site and, together with selenium atoms, form trigonal prisms with two additional atoms [Pr Se14Se23Se3] (CN = 8). The atoms of the statistical mixture M1 (0,15 Ge + 0,40 Ag) and M2 (0,10 Ge + 0,60 Ag) occupying one site 2a are located in triangles [M 3Se2] (CN = 3). The Ge atoms are localized in site 2b and have a tetrahedral surrounding of Selenium atoms [Gе Se13Se3] (CN = 4). Atoms Se1 (site 2b) and Se3 (site 6c) also have a tetrahedral surrounding. Se2 atoms (site 6c) are surrounded by five neighbors. Inter-atomic distances are consistent with the sum of the respective ionic radii. Germanium-containing Pr3Ag0,40Ge1,15Se7 and Pr3Ag0,60Ge1,10Se7 selenides based on praseodymium are promising chalcogenide phases on the basis of which materials for nonlinear optics can be created.
样品组成Pr3Ag4xGe1,25-xSe7 (x = 0,10;0,15)，重一克，由基本成分在真空石英容器中在1150°C的最高温度下烧结而成。在DRON4-13衍射仪上记录X射线相分析的衍射图，2Q范围为10-100°(CuKα辐射，扫描步长为0、02°，每个点曝光20 s)。采用WinCSD软件包进行数据处理和晶体结构的测定。利用VESTA程序对晶体结构、堆叠和配位多面体进行了可视化。用粉末X射线法研究了季元化合物pr3ag0,40ge1,15se7 (a = 1,06466(4) nm, r = 0,60552(3) nm, RI = 0,0511, Rp = 0,2455)和pr3ag0,60ge1,10se7 (a = 1,06556(2) nm, c = 0,60583(2) nm, RI = 0,0618, Rp = 0,2068)的晶体结构。化合物的结构属于La3CuSiS7结构类型(空间群P63, Pearsoncode hP24, a = 1,028 nm, c = 0,575 nm)。在这个结构中，Pr原子位于6c位点，与硒原子一起，与两个额外的原子[Pr Se14Se23Se3] (CN = 8)形成三角形棱镜。占据一个位点2a的统计混合物M1 (0,15 Ge + 0,40 Ag)和M2 (0,10 Ge + 0,60 Ag)的原子位于三角形[M 3Se2] (CN = 3)。Ge原子定位在位点2b并具有四面体包围硒原子[gfe Se13Se3] (CN = 4)。原子Se1(位点2b)和Se3(位点6c)也具有四面体包围。Se2原子(6c位)被5个相邻原子包围。原子间距离与各自离子半径之和一致。基于镨的含锗硒化物Pr3Ag0,40Ge1,15Se7和Pr3Ag0,60Ge1,10Se7是很有前途的硫系物，在此基础上可以制备非线性光学材料。
{"title":"CRYSTAL STRUCTURE OF THE Pr3Ag4xGe1,25-xSe7 (x = 0,10; 0,15)","authors":"N. Blashko, O. Marchuk, O. Smitiukh, A. Fedorchuk","doi":"10.18524/2304-0947.2022.3(83).268609","DOIUrl":"https://doi.org/10.18524/2304-0947.2022.3(83).268609","url":null,"abstract":"The samples of composition Pr3Ag4xGe1,25-xSe7 (x = 0,10; 0,15), weighing one gram, obtained by sintering elementary components in vacuumed quartz containers at a maximum temperature of 1150 °C.\u0000The diffraction patterns for X‑ray phase analysis were recorded at a DRON4–13 diffractometer for 2Q range of 10–100 ° (CuKα radiation, scan step 0,02 °, 20 s exposure in each point). For data processing and the determination of the crystal structure used WinCSD software package. Visualization of the crystal structure, stacking and coordination polyhedra was performed using VESTA program.\u0000The crystal structure of the quaternary compound Pr3Ag0,40Ge1,15Se7 (a = 1,06466(4) nm, с = 0,60552(3) nm, RI = 0,0511, Rp = 0,2455) and Pr3Ag0,60Ge1,10Se7 (a = 1,06556(2) nm, c = 0,60583(2) nm, RI = 0,0618, Rp = 0,2068) was investigated by powder X‑ray method. The structure of the compound belongs to the La3CuSiS7 structural type (space group P63, Pearsoncode hP24, a = 1,028 nm, c = 0,575 nm).\u0000In this structure, the Pr atom is located in the 6c site and, together with selenium atoms, form trigonal prisms with two additional atoms [Pr Se14Se23Se3] (CN = 8). The atoms of the statistical mixture M1 (0,15 Ge + 0,40 Ag) and M2 (0,10 Ge + 0,60 Ag) occupying one site 2a are located in triangles [M 3Se2] (CN = 3). The Ge atoms are localized in site 2b and have a tetrahedral surrounding of Selenium atoms [Gе Se13Se3] (CN = 4). Atoms Se1 (site 2b) and Se3 (site 6c) also have a tetrahedral surrounding. Se2 atoms (site 6c) are surrounded by five neighbors. Inter-atomic distances are consistent with the sum of the respective ionic radii. Germanium-containing Pr3Ag0,40Ge1,15Se7 and Pr3Ag0,60Ge1,10Se7 selenides based on praseodymium are promising chalcogenide phases on the basis of which materials for nonlinear optics can be created.","PeriodicalId":19451,"journal":{"name":"Odesa National University Herald. Chemistry","volume":"1 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2023-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"89119663","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 : 2022-11-16DOI: 10.18524/2304-0947.2022.2(82).264891
S. Y. Bachinskii, Yu. V. Ishkov, V. Kravtsov, S. Andronati
The aim of this work is the synthesis of a number of substituted E‑1-(2-amino‑5-R1-phenyl)-3-(4-R2-phenyl)prop‑2-en‑1-ones (2-aminochalcones) as precursors for obtaining new derivatives of 7-R1–5-[2-R2-phenylvinyl]-1,4-benzodiazepin‑2-ones. Starting 5-substituted 2-aminoacetophenones with bromo and nitro group were synthesized from 2-aminoacetophenone by bromination of the latter with N‑bromosuccinimide in acetonitrile and nitration of 2-acetaminoacetophenone with a nitrating mixture followed by removal of acetyl protection. 2-Aminochalcones were synthesized according to standard methods during the interaction of a number of 5-substituted 2-aminoacetophenones with para-substituted benzaldehydes under basic catalysis conditions. The target products turned out to be brightly colored compounds with low melting points, their isolation and purification did not cause any difficulties. According to the data of 1H NMR spectroscopy, all synthesized 2-aminochalcones were individual trans isomers, which was also confirmed by X‑ray structural analysis of one of the obtained 2-aminochalcones. A number of new substituted E‑1-(2-amino‑5R1-phenyl)-3-(4-R2-phenylprop‑2-en‑1-ones) were synthesized – compounds with amino and ketofunctions and are precursors for obtaining of a new series of 5-substituted 1,4-benzodiazepines with various arylvinyl groups. 2-aminoacetophenone, 2-amino‑5-bromoacetophenone, and 2-amino‑5-nitroacetophenone were selected as substrates for this series. The methyl groups of these acetophenones were condensed according to Claisen-Schmidt with parasubstituted benzaldehydes. Condensation was carried out under alkaline conditions in an aqueous solution. Yields of aminochalcones reached 60–85%. The methyl group of 2-aminoacetophenones smoothly reacted with aromatic aldehydes to form the corresponding 2-aminophenylchalcones. The structure of the obtained compounds was confirmed by mass spectrometry and 1H NMR spectroscopy. The structure of one of the chalcones was proved by X‑ray structural analysis. The obtained compounds can be used for the synthesis of 1,4-benzodiazepines with 5-arylvinyl substituents.
{"title":"SUBSTITUTED AMINOCHALCONES AS STARTING COMPOUNDS FOR RECEIVING NEW 1,4-BENZODIAZEPINES DERIVATIVES","authors":"S. Y. Bachinskii, Yu. V. Ishkov, V. Kravtsov, S. Andronati","doi":"10.18524/2304-0947.2022.2(82).264891","DOIUrl":"https://doi.org/10.18524/2304-0947.2022.2(82).264891","url":null,"abstract":"The aim of this work is the synthesis of a number of substituted E‑1-(2-amino‑5-R1-phenyl)-3-(4-R2-phenyl)prop‑2-en‑1-ones (2-aminochalcones) as precursors for obtaining new derivatives of 7-R1–5-[2-R2-phenylvinyl]-1,4-benzodiazepin‑2-ones. Starting 5-substituted 2-aminoacetophenones with bromo and nitro group were synthesized from 2-aminoacetophenone by bromination of the latter with N‑bromosuccinimide in acetonitrile and nitration of 2-acetaminoacetophenone with a nitrating mixture followed by removal of acetyl protection. 2-Aminochalcones were synthesized according to standard methods during the interaction of a number of 5-substituted 2-aminoacetophenones with para-substituted benzaldehydes under basic catalysis conditions. The target products turned out to be brightly colored compounds with low melting points, their isolation and purification did not cause any difficulties. According to the data of 1H NMR spectroscopy, all synthesized 2-aminochalcones were individual trans isomers, which was also confirmed by X‑ray structural analysis of one of the obtained 2-aminochalcones. A number of new substituted E‑1-(2-amino‑5R1-phenyl)-3-(4-R2-phenylprop‑2-en‑1-ones) were synthesized – compounds with amino and ketofunctions and are precursors for obtaining of a new series of 5-substituted 1,4-benzodiazepines with various arylvinyl groups. 2-aminoacetophenone, 2-amino‑5-bromoacetophenone, and 2-amino‑5-nitroacetophenone were selected as substrates for this series. The methyl groups of these acetophenones were condensed according to Claisen-Schmidt with parasubstituted benzaldehydes. Condensation was carried out under alkaline conditions in an aqueous solution. Yields of aminochalcones reached 60–85%. The methyl group of 2-aminoacetophenones smoothly reacted with aromatic aldehydes to form the corresponding 2-aminophenylchalcones. The structure of the obtained compounds was confirmed by mass spectrometry and 1H NMR spectroscopy. The structure of one of the chalcones was proved by X‑ray structural analysis. The obtained compounds can be used for the synthesis of 1,4-benzodiazepines with 5-arylvinyl substituents.","PeriodicalId":19451,"journal":{"name":"Odesa National University Herald. Chemistry","volume":"110 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2022-11-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"87673727","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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