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BIOLOGICAL ACTIVITY OF N-{3-[(4-METHYLBENZENE-1- SULFONYL)IMINO]-6-OXOCYCLOHEXA-1,4-DIEN-1-YL}ARYLAMIDES AND THEIR DERIVATIVES n -{3-[(4-甲基苯-1-磺酰)亚胺]-6-氧环己-1,4-二烯-1-基}芳基酰胺及其衍生物的生物活性
Pub Date : 2021-07-27 DOI: 10.18524/2304-0947.2021.1(77).226136
S. Konovalova, A. Avdeenko, V. Lubenets, O. Komarovska-Porokhnyavets, I. Yakymenko, E. Lysenko
N-{3-[(4-Methylbenzene-1-sulfonyl)imino]-6-oxocyclohexa-1,4-dien-1-yl}arylamides and their derivatives were synthesized by the reaction of the corresponding N-(4-oxocyclohexa-2,5-dien-1-ylidene)arylsulfonamides with N-chloramides. The biological activity of the synthesized compounds was studied on test cultures of Escherichia coli 67, Staphylococcus aureus 209-p, Mycobacterium luteum VKM B-868 and fungi Candida tenuis VKM Y-70, Aspergillus niger VKM F-1119 by the method of diffusion of substances into agar on a solid nutrient medium. The degree of activity of the test compounds was determined by the diameter of the zones of inhibition of growth of test cultures of microorganisms. The minimum inhibitory, bactericidal and fungicidal concentrations were determined by the method of serial dilutions of the substance in a liquid nutrient medium. At the studied concentration, the method of diffusion of substances into agar on a solid nutrient medium has shown that these compounds have low activity against bacteria Escherichia coli, Staphylococcus aureus, Mycobacterium luteum and fungi Candida tenuis, Aspergillus niger. The diameters of the zones of inhibition of growth of test cultures of microorganisms were less than 15 mm. In research by the method of serial dilutions of the substance in a liquid nutrient medium, they have been found to have bactericidal and fungicidal activity. The minimum inhibitory concentration of N-{2-hydroxy-5-[(4-methylbenzene-1-sulfonyl)amino]phenyl}benzamide was 31.2 μg/ml against bacteria Mycobacterium luteum. The minimum inhibitory concentration of N-{2-hydroxy-3-methyl-5-[(4-methylbenzene-1-sulfonyl)amino]phenyl}benzamide against fungi Aspergillus niger was 31.2 μg/ml. The minimum bactericidal concentration of N-{2-hydroxy-5-[(4-methylbenzene-1-sulfonyl)amino]phenyl}benzamide was 62.5 μg/ml against bacteria Mycobacterium luteum. Minimum fungicidal concentration of N-{3-[(4-methylbenzene-1-sulfonyl)imino]-6-oxocyclohexa-1,4-dien-1-yl}benzamide and N-{2-hydroxy-3-methyl-5-[(4-methylbenzene-1-sulfonyl)amino]phenyl}benzamide was 62.5 μg/ml in action to mold fungi Aspergillus niger.
N-{3-[(4-甲基-1-磺酰)亚胺]-6-氧环己-1,4-二烯-1-基}芳基酰胺及其衍生物是由相应的N-(4-氧环己-2,5-二烯-1-基)芳基磺酰胺与N-氯酰胺反应合成的。采用固体营养培养基上琼脂扩散法对大肠杆菌67、金黄色葡萄球菌209-p、黄体分枝杆菌VKM B-868和假丝酵母菌VKM Y-70、黑曲霉VKM F-1119进行了生物活性研究。试验化合物的活性程度由微生物生长抑制区直径决定。通过在液体营养培养基中连续稀释该物质的方法确定了最低抑菌、杀菌和杀真菌浓度。在研究的浓度下,将物质扩散到固体营养培养基上的琼脂中的方法表明,这些化合物对细菌大肠杆菌、金黄色葡萄球菌、黄体分枝杆菌和真菌假丝酵母、黑曲霉的活性较低。试验培养的微生物生长抑制带直径小于15mm。通过在液体营养培养基中对该物质进行连续稀释的方法研究,发现它们具有杀菌和杀真菌的活性。N-{2-羟基-5-[(4-甲基苯-1-磺酰)氨基]苯基}苯甲酰胺对黄体分枝杆菌的最低抑菌浓度为31.2 μg/ml。N-{2-羟基-3-甲基-5-[(4-甲基-1-磺酰)氨基]苯基}苯酰胺对黑曲霉的最低抑菌浓度为31.2 μg/ml。N-{2-羟基-5-[(4-甲基苯-1-磺酰)氨基]苯基}苯甲酰胺对黄体分枝杆菌的最低杀菌浓度为62.5 μg/ml。N-{3-[(4-甲基苯-1-磺酰基)亚胺]-6-氧环己-1,4-二烯-1-基}苯酰胺和N-{2-羟基-3-甲基-5-[(4-甲基苯-1-磺酰基)氨基]苯基}苯酰胺对霉菌黑曲霉的最小杀真菌浓度为62.5 μg/ml。
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引用次数: 0
SPECTROSCOPIC STUDY OF SALT MELTS OF THE SmF3-CeF3-NaCl-KCl SYSTEM SmF3-CeF3-NaCl-KCl体系盐熔体的光谱研究
Pub Date : 2021-07-27 DOI: 10.18524/2304-0947.2021.1(77).226135
V. Zinchenko, O. Ieriomin, I. Stoianova, G. Volchak, N. Chivireva, P. Doga, O. V. Stamikosto
Redox interactions between the components of the SmF3-CeF3 and SmF3-CeF3-NaCl-KCl systems have been established by IR transmission spectroscopy, diffuse reflectance electron spectroscopy and luminescence spectroscopy. A significant decrease in the transparency in the IR range of the spectrum was found when passing from the first of the systems to the second, which is explained by an increase in scattering by ultramicrodispersed particles of fluorides in the salt melt. In both systems, the formation of a significant amount of Sm (II) and a decrease in the content of Sm (III) are observed. The change in the valence state of Samarium both during solid-phase heat treatment (1100 °C) and during holding in a salt melt at 700 °C is manifested in the disappearance of some absorption bands, the appearance of new bands, and a gypsochromic shift of the remaining bands. The luminescence spectra exhibit high-intensity emission bands in the 640–740 nm range, which correspond to 5d‑4f electronic transitions in Sm2+ ions. At the same time, the highest intensity is observed in the band corresponding to intracenter 5d‑4f electronic transitions in Ce3+ ions. Apparently, the Ce(IV) compound, formed as a result of the exchange reaction of complex fluoride with a salt melt, volatilizes with subsequent decomposition and does not affect the character of luminescence. On the whole, the luminescence intensity after treatment in the molten salt increases by several tens of times, which indicates a significant change in the radiation mechanism. The mechanism of redox reactions in the solid-phase state, as well as exchange processes in the salt melt and after its crystallization, is discussed. A significant role of solvation shells around particles of lanthanide fluorides in luminescence processes is assumed.
利用红外透射光谱、漫反射电子能谱和发光能谱等方法建立了SmF3-CeF3和SmF3-CeF3- nacl - kcl体系组分之间的氧化还原相互作用。当从第一个系统过渡到第二个系统时,发现红外光谱范围内的透明度显著降低,这是由于盐熔体中超微分散的氟化物颗粒散射增加所致。在这两种体系中,观察到大量Sm (II)的形成和Sm (III)含量的减少。在1100℃固相热处理和700℃盐液保温过程中,钐的价态发生变化,表现为部分吸收带消失,新吸收带出现,其余吸收带发生石膏色移。发光光谱在640 ~ 740 nm范围内呈现高强度发射带,对应于Sm2+离子中的5d - 4f电子跃迁。同时,在Ce3+离子中心内5d - 4f电子跃迁对应的波段中观察到最高的强度。显然,由配合氟化物与盐熔体交换反应形成的Ce(IV)化合物随后续分解挥发,不影响发光特性。总体上看,熔盐中处理后的发光强度增加了几十倍,表明辐射机理发生了显著变化。讨论了固相氧化还原反应的机理,以及盐熔体和结晶后的交换过程。假设了镧系氟化物粒子周围的溶剂化壳在发光过程中的重要作用。
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引用次数: 0
CATALYTIC PROPERTIES OF SYNTHETIC HAUSMANNITE IN THE OZONE DECOMPOSITION REACTION 合成豪斯曼铁矿在臭氧分解反应中的催化性能
Pub Date : 2021-07-27 DOI: 10.18524/2304-0947.2021.1(77).226025
A. Truba, T. L. Rakitskaya
Samples of IS-Mn and IIS-Mn were synthesized and characterized by X-ray diffraction, IR spectroscopy and pH-metry. The X-ray diffraction method revealed both samples to be crystalline and single-phase. IS-Mn sample contains a phase of gausmannite (Mn3O4) with the parameters of the crystal lattice of tetragonal symmetry and the crystallites sized 43 nm. IIS-Mn sample, obtained by calcination of Mn3O4 sample in air under the condition of 600 oC for 4 hours, contains a phase of bixbyite Mn2O3 with a cubic crystal lattice and the crystallites sized 66 nm. The spectra of the Mn3O4 and Mn2O3 samples are particularly different in the region of Mn-OH and Mn-O valence vibrations. For gausmannite, the absorption band for Mn2+ in Td-coordination at 631 cm-1 and the absorption band for Mn3+ in Oh-coordination at 523 and 407cm-1 were clearly shown. In the IR spectrum of bixbyite, several intense absorption bands were observed at 674; 658; 606 and 542 cm-1, which correlate with the literature data and correspond to the valence oscillations of Mn-O in Mn2O3. The pH measurement of the aqueous suspension of the synthesized samples showed that Mn3O4 forms an alkaline medium, and Mn2O3 –weakly acidic upon contact with water molecules. Testing of Mn3O4 and Mn2O3 samples in the ozone decomposition reaction at the initial concentration of 100 mg/m3 showed that the kinetic curves profiles were determined by the phase composition. The testing of the samples was completed and it was established that the same degree of ozone decomposition, namely 50%, was achieved. For hausmannite, the values of the ozone half-life (t1/2) and the amount of ozone (Qexp), which reacted at the end of the experiment, are greater than Mn2O3 sample. The presence of manganese in two oxidation states Mn2+ and Mn3+ in the Mn3O4 structure promotes the redox process, and the alkaline medium contributes to the radical-chain reaction, which affects values t1/2 of and Qexp, which reacted.
合成了IS-Mn和IS-Mn样品,并用x射线衍射、红外光谱和ph法对其进行了表征。x射线衍射法显示两种样品均为晶体和单相。IS-Mn样品中含有一种高斯锰矿相(Mn3O4),其晶格参数为四方对称,晶粒尺寸为43 nm。Mn3O4样品在空气中600℃下煅烧4小时得到的IIS-Mn样品含有立方晶格的bixbyite Mn2O3相,晶粒尺寸为66 nm。Mn3O4和Mn2O3样品在Mn-OH和Mn-O价振动区域的光谱差异较大。在631 cm-1的td配位上Mn2+的吸收带,在523和407cm-1的oh配位上Mn3+的吸收带清晰可见。在碳化物的红外光谱中,674处有多条强吸收带;658;606和542 cm-1,与文献数据相关,对应于Mn2O3中Mn-O的价态振荡。合成样品的水悬浮液pH值测定表明,Mn3O4与水分子接触后形成碱性介质,Mn2O3 -弱酸性介质。对初始浓度为100 mg/m3的臭氧分解反应中Mn3O4和Mn2O3样品的动力学曲线分布进行了测试,结果表明,动力学曲线分布由相组成决定。样品的测试已完成,并确定臭氧分解程度相同,即50%,达到。豪斯曼尼体的臭氧半衰期(t1/2)和实验结束时发生反应的臭氧量(Qexp)均大于Mn2O3样品。Mn3O4结构中锰以Mn2+和Mn3+两种氧化态的存在促进了氧化还原过程,碱性介质有利于自由基链反应,影响了反应的t1/2和Qexp值。
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引用次数: 0
HYDROGEN BONDS IN THE FORMATION OF COPPER(II) 1,10-PHENANTHROLINE HYDROXYCARBOXYLATOGERMANATE CRYSTALS USING HIRSHFELD SURFACE ANALYSIS 用hirshfeld表面分析法研究1,10-邻菲罗啉羟基羧酸铜晶体形成过程中的氢键
Pub Date : 2021-07-27 DOI: 10.18524/2304-0947.2021.1(77).226142
E. Chebanenko, O. Buchko, E. Afanasenko, I. Seifullina, E. Martsinko
This article is dedicated to the investigation of crystalline structure in the complex cation-anionic compounds Cu(Phen)2Cl]2[Ge(HCit)2]⋅6H2O (I), [Cu(Phen)3]2[Ge2(OH)(HTart)(μ-Tart)2]·11H2O (II), [CuCl(Phen)2]4[{Ge2(OH)2(μ-Tart)2}Cl2]·4Н2О (III), [Cu(Phen)3]2[(OH)2Ge2(μ-HXylar)4Ge2(μ-OH)2]·8H2O (IV), [CuCl(Phen)2]4[(OH)2Ge2(μ-HXylar)4Ge2(μ-OH)2]·8H2O (V) using Hirshfeld surface analysis. This method has showed itself as an effective tool for analysis of intermolecular interactions, such as hydrogen bonds or weaker C…H and С…Н…p connections. Three-dimensional picture of close interactions in the crystal was built for each of the compounds I–V, where short connections are red-colored, while others – weaker and shorter – are light areas and small spots. It was established that in the structures of all compounds different types of hydrogen bonds are presented: bifurcate connections, symmetrical О-Н…О, С-Н…С and asymmetrical ones with water molecules. Two-dimensional histograms – 2D-fingerprint plots, allowed to evaluate quantitively connections in the crystals and establish that H…O/O…H and H…H interactions make the biggest contribution to the total surface area. The presence of the big number of crystallization water molecules is determinant for the formation of complex system of hydrogen bonds and strengthening of the structure, that otherwise would be unstable because of the big size of cations and anions. Due to the fact, that all compounds have the same complexing agent Ge(IV), structure of the anion is determined by polydentate ligand. Obtained results are important for the further development of the water role in the processes of crystallization, crystal formation, electrical dissociation and, especially, dissolving of coordination compounds in biological systems.
本文采用Hirshfeld表面分析方法研究了正阴离子络合物Cu(Phen)2Cl]2[Ge(HCit)2]·6H2O (I)、[Cu(Phen)3]2[Ge2(OH)(HTart)(μ-Tart)2]·11H2O (II)、[CuCl(Phen)2]4[{Ge2(OH)2(μ-Tart)2}Cl2]·4Н2О (III)、[Cu(Phen)3]2[(OH)2Ge2(μ-HXylar)4Ge2(μ-OH)2]·8H2O (IV)、[CuCl(Phen)2]4[(OH)2Ge2(μ-HXylar)4Ge2(μ-OH)2]·8H2O (V)的晶体结构。该方法已被证明是分析分子间相互作用的有效工具,如氢键或较弱的C…H和С…Н…p连接。为每一种化合物I-V建立了晶体中密切相互作用的三维图像,其中短连接是红色的,而其他较弱和较短的连接是浅色区域和小点。在所有化合物的结构中都存在不同类型的氢键:分叉连接,对称的О-Н…О, С-Н…С和与水分子不对称的氢键。二维直方图-二维指纹图,可以定量评估晶体中的连接,并确定H…O/O…H和H…H相互作用对总表面积的贡献最大。大量结晶水分子的存在是形成复杂氢键体系和加强结构的决定因素,否则由于阳离子和阴离子的大尺寸而不稳定。由于所有化合物具有相同的络合剂Ge(IV),阴离子的结构由多齿配体决定。所得结果对于进一步研究水在结晶、晶体形成、电解离,特别是在生物系统中配位化合物溶解过程中的作用具有重要意义。
{"title":"HYDROGEN BONDS IN THE FORMATION OF COPPER(II) 1,10-PHENANTHROLINE HYDROXYCARBOXYLATOGERMANATE CRYSTALS USING HIRSHFELD SURFACE ANALYSIS","authors":"E. Chebanenko, O. Buchko, E. Afanasenko, I. Seifullina, E. Martsinko","doi":"10.18524/2304-0947.2021.1(77).226142","DOIUrl":"https://doi.org/10.18524/2304-0947.2021.1(77).226142","url":null,"abstract":"This article is dedicated to the investigation of crystalline structure in the complex cation-anionic compounds Cu(Phen)2Cl]2[Ge(HCit)2]⋅6H2O (I), [Cu(Phen)3]2[Ge2(OH)(HTart)(μ-Tart)2]·11H2O (II), [CuCl(Phen)2]4[{Ge2(OH)2(μ-Tart)2}Cl2]·4Н2О (III), [Cu(Phen)3]2[(OH)2Ge2(μ-HXylar)4Ge2(μ-OH)2]·8H2O (IV), [CuCl(Phen)2]4[(OH)2Ge2(μ-HXylar)4Ge2(μ-OH)2]·8H2O (V) using Hirshfeld surface analysis. This method has showed itself as an effective tool for analysis of intermolecular interactions, such as hydrogen bonds or weaker C…H and С…Н…p connections. Three-dimensional picture of close interactions in the crystal was built for each of the compounds I–V, where short connections are red-colored, while others – weaker and shorter – are light areas and small spots. It was established that in the structures of all compounds different types of hydrogen bonds are presented: bifurcate connections, symmetrical О-Н…О, С-Н…С and asymmetrical ones with water molecules. Two-dimensional histograms – 2D-fingerprint plots, allowed to evaluate quantitively connections in the crystals and establish that H…O/O…H and H…H interactions make the biggest contribution to the total surface area. The presence of the big number of crystallization water molecules is determinant for the formation of complex system of hydrogen bonds and strengthening of the structure, that otherwise would be unstable because of the big size of cations and anions. Due to the fact, that all compounds have the same complexing agent Ge(IV), structure of the anion is determined by polydentate ligand. Obtained results are important for the further development of the water role in the processes of crystallization, crystal formation, electrical dissociation and, especially, dissolving of coordination compounds in biological systems.","PeriodicalId":19451,"journal":{"name":"Odesa National University Herald. Chemistry","volume":"159 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2021-07-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"80068296","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}
引用次数: 3
QSPR MODELS FOR ZETA-POTENTIAL OF NANO-OXIDES PREDICTION 纳米氧化物ζ电位预测的QSPR模型
Pub Date : 2021-06-27 DOI: 10.18524/2304-0947.2021.2(78).239101
Stelmakh Stelmakh, V. Kuz'min, L. M. Ognichenko
Nano-QSPR modeling often requires considering variety of factors, if neglected, may lead to erroneous result of the study. Frequently, the data turned out to be inaccurate, incomplete, or fragmentary. Obviously, the quality of experimental data directly depends on many factors: laboratory equipment, organization of internal regulations, skills of researchers, and so on. As a result of violations of algorithms and protocols of initial data streams processing – there are errors and distortions of data, that is why performing a solid multistep data-curation process is crucial for such procedures. Data curation procedure was performed and approximately 60% was rejected (due to various errors, incomplete or absent records for physicochemical parameters or conditions of performed experiment), followed up by using zeta-potential value dataset for 37 various sizes nanoparticles of 14 metal oxides for calculation of 1D SiRMS descriptors as well as «liquid drop» model cross-descriptors. An efficient consensus model was built (R2 = 0.88, R2test = 0.81). Predictive power (R2 = 0.84) of the model was tested using an external set of 5 nano-oxides and the possibility of satisfactory zeta-potential prediction was shown. Prediction of zeta-potential value within domain applicability of obtained QSPR model confirmed using a Williams plot. The interpretation of the final model was carried out and it was found that the contribution of descriptors was distributed between individual descriptors and cross-descriptors by 46% and 54% respectively. The contribution 1D SiRMS descriptors was 59%, the second group – 41% (liquid drop model descriptors – 29%, descriptors characterizing the metal atom – 12%). It was found that the most influential parameters are the characteristics that reflect the nature of the oxides. The parameters of electrostatic interactions have the highest contribution.
纳米qspr建模往往需要考虑多种因素,如果忽视,可能会导致错误的研究结果。这些数据往往是不准确的、不完整的或零碎的。显然,实验数据的质量直接取决于许多因素:实验室设备、内部法规的组织、研究人员的技能等等。由于违反了初始数据流处理的算法和协议-存在数据的错误和扭曲,这就是为什么执行可靠的多步骤数据管理过程对于此类过程至关重要。执行数据管理程序,大约60%的数据被拒绝(由于各种错误,物理化学参数或实验条件的不完整或缺失记录),随后使用14种金属氧化物的37种不同尺寸纳米颗粒的ζ电位值数据集计算1D SiRMS描述符以及“液滴”模型交叉描述符。建立了有效的共识模型(R2 = 0.88, R2test = 0.81)。使用5种纳米氧化物对模型的预测能力(R2 = 0.84)进行了测试,表明该模型有可能实现令人满意的ζ电位预测。利用Williams图对所得QSPR模型在域适用性范围内的ζ势值进行了预测。对最终模型进行了解释,发现描述符的贡献分布在单个描述符和交叉描述符之间,分别为46%和54%。1D SiRMS描述符的贡献为59%,第二组为41%(液滴模型描述符为29%,表征金属原子的描述符为12%)。结果表明,反映氧化物性质的特性是影响性能的主要参数。静电相互作用参数的贡献最大。
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引用次数: 0
SYNTHESIS AND STRUCTURE OF BINUCLEAR GERMANIUM(IV)-THULIUM(III) COMPLEX WITH 1,3-DIAMINO-2-PROPANOLTETRAACETIC ACID 1,3-二氨基-2-丙醇四乙酸双核锗(iv)-铥(iii)配合物的合成与结构
Pub Date : 2020-11-21 DOI: 10.18524/2304-0947.2020.4(76).216921
E. Martsinko, E. Chebanenko, I. Seifullina, V. Dyakonenko, S. Shishkina
New heteronuclear Germanium(IV)- Thulium (III) complex with 1,3-diamino-2-pro- panoltetraacetic acid (H 5 hpdta) was synthesized for the first time. Comparative analysis of IR-spectrum of complex and ligand proved the absence of free COOH-groups in the structure of compound – there are no ν(СООН) absorption bands in the IR-spectra of complex. The significant shift of the ν(С-N) absorption band (about 45 cm -1 ), ν(СН) (about 5 cm -1 ) and presence of ν(Ge-N) and ν(Tm-N) bands evidences that protonized nitrogen atoms form coordination bonds with metals. Two pairs of ν as (СОО) and ν s (СОО) absorption bands of carboxylate ions together with stretching vibrations of Ge-O and Tm-O bonds confirm their coordination to metals. There are also presented ν as (Ge-O-Tm), ν s (Ge-O-Tm), δ (OH міст ) and δ (Ge-OH) absorption bands in the IR-spectrum of complex that indicates the bridging nature of deprotonated hydroxy and hydroxyl group of ligand and also hydrolyzed form of germanium in the structure of compound. During thermal decomposition of the complex in the temperature range of 90-150 ° С as a result of the endothermic effect, two molecules of crystallization water are removed into the gas phase. The further endoeffects at around 150-220° C are seen with the removal of three coordinated water molecules. The oxidative destruction of the complexes is accompanied by the three exoeffects in temperature range 220-800 ° С. The products of final thermal destruction at 1000°C are GeO 2 and Tm 2 O 3 . According to the X-Ray diffraction data of complex [Ge(ОН)( µ -hpdta)( µ -OH) Tm(H 2 O) 3 ] ⋅ 2H 2 O, the six-coordinated atom of Germany and octa-coordinated atom of Thulium are bound by the bridging oxygen atom of hydroxyl group and hydroxyl-anion. The coordination polyhedron of Ge(1) atom is a distorted octahedron formed by three O atoms of deprotonated carboxyl and hydroxyl groups, the nitrogen atom of the hpdta 5– and two O atoms of two hydroxyl-anions. The coordination polyhedron of octa-coordinated atom of Thulium is formed by of the O atoms of deprotonated carboxyl, deprotonated hydroxyl groups of the hpdta 5– , the bridging oxygen atom of hydroxyl-anion, three O atoms of coordinated water molecules and one N-atom of the hpdta 5– .
首次合成了新的杂核锗(IV)-铥(III)与1,3-二氨基-2-原聚四乙酸(h5 hpdta)配合物。配合物与配体的红外光谱对比分析表明,配合物的红外光谱中没有ν(СООН)吸收带,结构中不存在游离cooh基团。ν(С-N)吸收带(约45 cm -1)和ν(СН)吸收带(约5 cm -1)的显著位移以及ν(Ge-N)和ν(Tm-N)吸收带的存在证明质子化的氮原子与金属形成配位键。羧酸盐离子的两对ν as (СОО)和ν s (СОО)吸收带以及Ge-O和Tm-O键的伸缩振动证实了它们与金属的配位。配合物红外光谱中还存在ν as (Ge-O-Tm)、ν s (Ge-O-Tm)、δ (OH міст)和δ (Ge-OH)吸收带,说明配体的去质子化羟基与羟基的桥接性质以及锗在化合物结构中的水解形式。在90-150°С温度范围内的热分解过程中,由于吸热效应,两分子结晶水被移到气相中。在150-220°C左右,随着三个配位水分子的去除,可以看到进一步的内效应。在220 ~ 800°С温度范围内,配合物的氧化破坏伴随着三种外效应。在1000℃时最终热破坏的产物是geo2和tm2o3。根据配合物[Ge(ОН)(µ-hpdta)(µ-OH) Tm(h2o) 3]·2h2o的x射线衍射数据,德国的六配位原子和铥的八配位原子是由羟基和羟基阴离子的桥接氧原子结合的。Ge(1)原子的配位多面体是由去质子化羧基和羟基的3个O原子、hpdta5 -的氮原子和2个羟基阴离子的2个O原子组成的畸变八面体。铥的八配位原子的配位多面体是由去质子化羧基的1个O原子、去质子化的hpdta5 -羟基、羟基阴离子的桥接氧原子、配位水分子的3个O原子和hpdta5 -的1个n原子组成的。
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引用次数: 0
SOLVATOCHROMISM OF SOME FOOD AZO DYES 某些食品偶氮染料的溶剂致色性
Pub Date : 2020-11-21 DOI: 10.18524/2304-0947.2020.4(76).216933
K. Bevziuk, Y. Bazel, A. Chebotarev, D. Snigur
In the current study the solvatochromic properties of such food azo dyes as tartrazine, sunset yellow FCF and carmoisine were described. It was shown that with an increase in the dielectric permittivity of the solvent, a bathochromic shift of the absorption band maxima of azo dyes is observed, which corresponds to the π → π* electronic transition. It has been established that the values of the molar absorptivities of the dominant acid-base form of azo dyes in organic solvents almost linearly (R≈0.90-0.92) increase with an increase in their dielectric permittivity. It is noted that there is a weak correlation (R = 0.70-0.80) between the position of the absorption maximum of the dye and the value of the Hansen parameter.
本文研究了酒黄石、日落黄FCF和胭脂红等食品偶氮染料的溶剂致变色性能。结果表明,随着溶剂介电常数的增大,偶氮染料的吸收带最大值发生了色移,对应于π→π*电子跃迁。在有机溶剂中,优势酸碱型偶氮染料的摩尔吸收率随其介电常数的增加几乎呈线性增加(R≈0.90 ~ 0.92)。值得注意的是,染料吸收最大值的位置与汉森参数的值之间存在弱相关性(R = 0.70-0.80)。
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引用次数: 0
SYNTHESIS, FT–IR SPECTROSCOPY AND SURFACE MICROMORPHOLOGY OF Ho(III)–CONTAINING POLYOXOTUNGSTATES 含Ho(III)多氧化钨酸盐的合成、红外光谱及表面微观形貌
Pub Date : 2020-09-11 DOI: 10.18524/2304-0947.2020.3(75).211723
O. Mariichak, Y. Oleksii, G. M. Rozantsev, S. V. Radio
nm. The technique developed in this work for the preparation of sodium decatungstoholmiate(ІІІ) is new and differs in that it allows one to synthesize a normal salt, which can be used for the synthesis of other normal salts of sodium heteropoly decatungstolanthanidates(ІІІ). As a result of attempts to synthesize salts by the interaction of holmium(III) nitrate with aqueous solutions of sodium tungstate acidified to Z = 1.17 and 1.29, X-ray amorphous solids were obtained, which most likely are mixtures of paratungstate B and holmium heptatungstate. Using the methods of chemical analysis and FTIR spectroscopy, the conditions for the formation of a sodium-holmium double salt with lacunar undecatungstate anion, derived from Keggin structure Na 2 Ho 2 [Нo 2 (H 2 O) 10 W 22 O 72 ( OH) 2 ]·46H 2 O are established. Procedure for the synthesis of holmium(III) paratungstate B Ho 10 [W 12 O 40 (OH) 2 ] 3 ·54H 2 O by the exchange reaction of holmium(ІІІ) nitrate with sodium paratungstate B was elaborated, and by the method of scanning electron microscopy it is proved to be single–phase. It was found that the grain size of the sample is in the range 200–450 nm. The absence of sodium(I) ions in the composition of the synthesized salt was proved by atomic absorption spectroscopy and EDX. Microphotographs of the salt powders Na 9 [Но(W 5 O 18 ) 2 ]·23H 2 O and Ho 10 [W 12 O 40 (OH) 2 ] 3 ·54H 2 O in the characteristic X–ray radiation show no zones with different surface morphologies, and show uniform distribution of Na, Ho, W, O is observed without segregation, which confirms the single–phase nature of the products.
nm。这项工作中开发的制备十钨酸钠(ІІІ)的技术是新的,不同之处在于它可以合成一种正常的盐,这种盐可以用于合成十钨酸杂多钠的其他正常盐(ІІІ)。通过硝酸钬(III)与酸化至Z = 1.17和1.29的钨酸钠水溶液相互作用合成盐,得到了x射线无定形固体,很可能是仲钨酸B和七钨酸钬的混合物。采用化学分析和红外光谱分析的方法,确定了Keggin结构Na 2 Ho 2 [Нo 2 (h2o) 10 W 22 O 72 (OH) 2]·46h2o生成具有腔隙十一钨酸盐阴离子的钠-钬双盐的条件。阐述了硝酸钬(ІІІ)与仲钨酸钠B交换反应合成仲钨酸钬(III) bho 10 [w12 o40 (OH) 2] 3·54 h2o的工艺过程,并通过扫描电镜方法证实其为单相反应。结果表明,样品的晶粒尺寸在200 ~ 450 nm之间。通过原子吸收光谱和EDX验证了合成盐中不存在钠离子。盐粉Na 9 [Но(w5 O 18) 2]·23H 2o和Ho 10 [w12 O 40 (OH) 2] 3·54H 2o在特征x射线下的显微照片没有显示出不同的表面形貌区,Na、Ho、W、O分布均匀,没有偏析,证实了产物的单相性质。
{"title":"SYNTHESIS, FT–IR SPECTROSCOPY AND SURFACE MICROMORPHOLOGY OF Ho(III)–CONTAINING POLYOXOTUNGSTATES","authors":"O. Mariichak, Y. Oleksii, G. M. Rozantsev, S. V. Radio","doi":"10.18524/2304-0947.2020.3(75).211723","DOIUrl":"https://doi.org/10.18524/2304-0947.2020.3(75).211723","url":null,"abstract":"nm. The technique developed in this work for the preparation of sodium decatungstoholmiate(ІІІ) is new and differs in that it allows one to synthesize a normal salt, which can be used for the synthesis of other normal salts of sodium heteropoly decatungstolanthanidates(ІІІ). As a result of attempts to synthesize salts by the interaction of holmium(III) nitrate with aqueous solutions of sodium tungstate acidified to Z = 1.17 and 1.29, X-ray amorphous solids were obtained, which most likely are mixtures of paratungstate B and holmium heptatungstate. Using the methods of chemical analysis and FTIR spectroscopy, the conditions for the formation of a sodium-holmium double salt with lacunar undecatungstate anion, derived from Keggin structure Na 2 Ho 2 [Нo 2 (H 2 O) 10 W 22 O 72 ( OH) 2 ]·46H 2 O are established. Procedure for the synthesis of holmium(III) paratungstate B Ho 10 [W 12 O 40 (OH) 2 ] 3 ·54H 2 O by the exchange reaction of holmium(ІІІ) nitrate with sodium paratungstate B was elaborated, and by the method of scanning electron microscopy it is proved to be single–phase. It was found that the grain size of the sample is in the range 200–450 nm. The absence of sodium(I) ions in the composition of the synthesized salt was proved by atomic absorption spectroscopy and EDX. Microphotographs of the salt powders Na 9 [Но(W 5 O 18 ) 2 ]·23H 2 O and Ho 10 [W 12 O 40 (OH) 2 ] 3 ·54H 2 O in the characteristic X–ray radiation show no zones with different surface morphologies, and show uniform distribution of Na, Ho, W, O is observed without segregation, which confirms the single–phase nature of the products.","PeriodicalId":19451,"journal":{"name":"Odesa National University Herald. Chemistry","volume":"2012 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2020-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"86424617","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}
引用次数: 0
AMPHOTERICITY OF OXIDE COMPOUNDS AS A CRITERION AND THE BASIS FOR THE CREATION OF FILM-FORMING MATERIALS 氧化物的两性性是形成成膜材料的标准和基础
Pub Date : 2020-09-11 DOI: 10.18524/2304-0947.2020.3(75).211721
V. Zinchenko, V. V. Menchuk
The question of the quantitative determination of the amphotericity of oxides by the values of their electronegativity is considered. The approximate boundaries of the electronegativity of amphoteric oxides from 1.6 to 2.2 eВ 1/2 /О 2- are established according to the concept of acidity- basicity of Lux-Flood. The possibility of the manifestation of amphoteric properties with a different ratio of acid and basic functions for oxides of the composition MO, M 2 O 3 , MO 2 , M 2 O 5 and MO 3 is analyzed, and the oxides of the composition M 2 O 3 , exhibit the most balanced ratio. The limit values of electronegativity for acid and basic functions are established, which differ by 0.3-0.4 eВ 1/2 /О 2- . The influence of the binary oxide form (oxo-, ortho-, meta-, etc.) on the value of the electronegativity of simple oxides, which they manifest during acid-base interaction, is explained. The influence of the acid-base interaction on the electronegativity of binary oxides at the formation of ternary oxides (complex sulfates, silicates and phosphates) of metals with their equalization and the acquisition of amphoteric properties is shown. The relationship between the electronegativity of simple oxides and their thermal characteristics (melting and boiling points) characterizing the strength of crystal lattices is established. It has been shown that amphoteric oxides having a predominantly covalent crystalline structure have higher thermal parameters than oxides of a predominantly ionic or molecular nature, i.e., basic or acidic oxides. On the other hand, having the most stable crystalline structure, they are less able to chemically interact with environmental components, that is, they have higher climatic stability compared to acidic or basic oxides. This indicates the possible ways of choosing simple oxides as the basis of film-forming materials, as well as creating binary and ternary oxides with the acquisition of amphoteric properties.
本文讨论了用氧化物的电负性值定量测定其两性性的问题。根据Lux-Flood的酸碱度概念,建立了两性氧化物的电负性在1.6 ~ 2.2 eВ 1/2 /О 2-范围内的近似边界。分析了MO、m2o3、m2o3、m2o3、m2o3、m2o3和m2o3的氧化物在酸碱功能不同比例下表现两性性质的可能性,其中m2o3的氧化物表现出最平衡的比例。确定了酸碱函数的电负性极限值,其差值为0.3 ~ 0.4 eВ 1/2 /О 2-。解释了二元氧化物形式(氧-、邻-、间-等)对简单氧化物在酸碱相互作用中表现出的电负性值的影响。研究了在金属三元氧化物(络合硫酸盐、硅酸盐和磷酸盐)形成过程中,酸碱相互作用对二元氧化物电负性的影响及其均衡化和两性性质的获得。建立了简单氧化物的电负性与其表征晶格强度的热特性(熔点和沸点)之间的关系。研究表明,具有主要共价晶体结构的两性氧化物比具有主要离子或分子性质的氧化物(即碱性或酸性氧化物)具有更高的热参数。另一方面,它们具有最稳定的晶体结构,与环境成分的化学相互作用能力较弱,也就是说,与酸性或碱性氧化物相比,它们具有更高的气候稳定性。这表明选择简单的氧化物作为成膜材料的基础,以及创造具有两性性质的二元和三元氧化物的可能方法。
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引用次数: 1
INTERACTION OF 2,4- AND 3,4-BIS(TRIFLUOROACETOXY)BENZOATES WITH SULFUR TETRAFLUORIDE IN ANHYDROUS HYDROGEN FLUORIDE SOLUTION 在无水氟化氢溶液中2,4-和3,4-双(三氟乙酰氧基)苯甲酸酯与四氟化硫的相互作用
Pub Date : 2020-05-30 DOI: 10.18524/2304-0947.2020.2(74).204384
I. I. Gaidarzhy, L. A. Motnyak, B. V. Kunshenko
Interaction of methyl 3,4-bis(trifluoroacetoxy)benzoate, methyl and ethyl 2,4-bis( trifluoroacetoxy)benzoates with sulfur tetrafluoride in anhydrous hydrogen fluoride solution has been investigated. On the first stage methyl 3,4-dihydroxybenzoate, methyl 2,4-dihydroxybenzoate and ethyl 2,4-dihydroxybenzoate were obtained by esterification of appropriate acids with respective alcohols using concentrated sulfuric acid as a catalyst. On the second stage obtained dihydroxybenzoates were treated with excess of trifluoroacetic anhydride in autoclave at 150 °C for 5 hours. Then, obtained 2,4- and 3,4-bis(trifluoroacetoxy)benzoates were treated with sulfur tetrafluoride in anhydrous hydrogen fluoride solution at 35 °C for 7 hours under continuous stirring. In such conditions methyl 3,4-bis(trifluoroacetoxy)benzoate transforms into methyl 3,4-bis(pentafluoroethoxy)benzoate with high yield. Unexpectedly, methyl and ethyl 2,4-bis(trifluoroacetoxy)benzoate didn’t undergo similar transformations when treated the same way. Instead of respective bis(pentafluoroethoxy)benzoates, methyl and ethyl 2-hydroxy-4-pentafluoroethoxybenzoates were isolated from the reaction mixture. Obviously, fluorination of trifluoroacetoxy group in the 2 position of benzene ring didn’t take place because of the steric hindrance made by ester group, so 4-pentafluoroethoxy-2- trifluoroacetoxy benzoates were formed. The last compounds were turned to 2-hydroxy-4- pentafluoroethoxybenzoates after quenching the reaction mixture with water. Hydrolysis of obtained methyl 3,4-bis(pentafluoroethoxy)benzoate and methyl and ethyl 2-hydroxy-4-pentafluoroethoxybenzoates with water-alcohol alkaline solution and further acidification of reaction mixture with concentrated hydrochloric acid led to the formation of firstly prepared 3,4-bis(pentafluoroethoxy)benzoic and 2-hydroxy-4-pentafluoroethoxybenzoic acids, respectively. The last one is new fluorine-containing analogue of salicylic acid. The molecular mass of the compounds subject to this study was confirmed by EI-MS and GC/ MS analysis.
研究了甲基3,4-二(三氟乙酰氧基)苯甲酯、甲基和乙基2,4-二(三氟乙酰氧基)苯甲酯与四氟化硫在无水氟化氢溶液中的相互作用。在第一阶段,以浓硫酸为催化剂,通过适当的酸与相应的醇酯化反应得到3,4-二羟基苯甲酸甲酯、2,4-二羟基苯甲酸甲酯和2,4-二羟基苯甲酸乙酯。在第二阶段,得到的二羟基苯甲酸酯用过量的三氟乙酸酐在150℃的高压灭菌器中处理5小时。然后,将得到的2,4-和3,4-双(三氟乙酰氧基)苯甲酸酯在无水氟化氢溶液中,在35℃连续搅拌下,用四氟化硫处理7小时。在这种条件下,3,4-二(三氟乙酰氧基)苯甲酸甲酯转化为3,4-二(五氟乙氧基)苯甲酸甲酯,收率高。出乎意料的是,甲基和乙基2,4-二(三氟乙酰氧基)苯甲酸酯在相同的处理方式下没有发生类似的转化。从反应混合物中分离出2-羟基-4-五氟乙氧基苯甲酸甲酯和乙基苯甲酸甲酯,而不是各自的双(五氟乙氧基)苯甲酸酯。很明显,由于酯基的位阻作用,苯环2位的三氟乙氧基没有发生氟化,所以形成了4-五氟乙氧基-2-三氟乙氧基苯甲酸酯。将反应混合物用水淬急后,得到2-羟基-4-五氟乙氧基苯甲酸酯。将得到的3,4-二(五氟乙氧基)苯甲酸甲酯和2-羟基-4-五氟乙氧基苯甲酸甲酯和乙基苯甲酸甲酯用水-醇碱性溶液水解,并用浓盐酸进一步酸化反应混合物,分别得到首次制备的3,4-二(五氟乙氧基)苯甲酸和2-羟基-4-五氟乙氧基苯甲酸。最后一种是新的含氟水杨酸类似物。通过EI-MS和GC/ MS分析确定了化合物的分子质量。
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引用次数: 1
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Odesa National University Herald. Chemistry
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