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DEVELOPMENT AND VALIDATION OF SPECTROPHOTOMETRIC METHOD FOR DETERMINATION OF FABOMOTIZOLE DIHYDROCHLORIDE FOR STUDY OF DISSOLUTION PROFILES 分光光度法测定盐酸法莫替唑溶出度的建立与验证
Pub Date : 2022-06-05 DOI: 10.18524/2304-0947.2022.1(81).255834
A. Yegorova, Y. Scrypynets, I. Leonenko, D. Aleksandrova, S. M. Kashutskуy, I. V. Umetskaya
Establishing the biopharmaceutical equivalence of generic drugs is a necessary component of the  relevant drug dossier. Determination of in vitro  equivalence is a test designed to assess the equivalence of the dissolution profiles of the study  and reference drugs in three dissolution media with  pH values of 1.2; 4.5 and 6.8. A value of f2 in the  range from 50 to 100 guarantees the similarity or equivalence of the two profiles and the equivalence  of the pharmacological action of the test drug and  the reference drug. A method for the quantitative  determination of the fabomotizole dihydrochloride  by spectrophotometric method has been developed,  which is suitable for studying the dissolution profiles of BAFAZOL IC tablets, 10 mg tablets. Measure the absorbance of the test solution and the reference  solution in a 1 cm cell relative to the compensation  solution at wavelength: 302 nm for 0.1 M  hydrochloric acid solution and 296 nm for acetate  buffer pH 4.5 and phosphate buffer pH 6 8. The method was validated on the parameters of specificity, accuracy, correctness, linearity in the  studied range of concentrations. Excipients do not  interfere on the determination of the fabomotizole  dihydrochloride. The absorption spectra of the test  solution and the reference solution coincide in nature and position of the maximum. This also confirms the specificity of the method. Linearity was investigated on model mixtures in different dissolution media inthe range of 10. – 130%. The coefficients of linear  dependences in the studied concentration ranges  correspond to the allowable values. The stability of the tested solutions and reference solutions in the  case of their storage at room temperature for 8  hours was confirmed. The release of more than 85%  of fabomotizole dihydrochloride in 15 min in all  dissolution media indicates the similarity of the  dissolution profiles and does not require the  calculation of the similarity factor f2.
建立仿制药的生物等效性是相关药品档案的必要组成部分。体外等效性测定是评价研究药物和参比药物在3种pH值为1.2的溶出介质中溶出谱的等效性的试验;4.5和6.8。在50 ~ 100范围内f2的值保证了两个谱图的相似性或等效性,以及试验药物和参比药物的药理作用的等效性。建立了分光光度法测定盐酸法莫替唑含量的方法,该方法适用于巴法唑IC片(10mg片)溶出度的测定。测量测试溶液和参考溶液相对于补偿溶液在1厘米的电池中的吸光度:波长为302 nm的0.1 M盐酸溶液和296 nm的醋酸缓冲液pH 4.5和磷酸盐缓冲液pH 6.8。在研究浓度范围内对该方法的特异性、准确性、正确性、线性等参数进行了验证。辅料对盐酸法莫替唑的测定无干扰。试验溶液和参比溶液的吸收光谱在性质和最大值位置上是一致的。这也证实了该方法的特殊性。在10的范围内考察了模型混合物在不同溶解介质中的线性关系。- 130%。研究浓度范围内的线性相关系数与允许值相符。在室温下保存8小时的情况下,测试溶液和参考溶液的稳定性得到了证实。在所有溶出介质中,15 min内法莫替唑的释放量大于85%,说明溶出谱相似,不需要计算相似因子f2。
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引用次数: 0
SPECTROPHOTOMETRIC DETERMINATION OF BISMUTH (III) WITH 6,7-DIHYDROXY‑4-CARBOXYL‑2-PHENYLBENZOPYRILIUM PERCHLORATE 6,7-二羟基- 4-羧基- 2-苯基苯并吡啶高氯酸盐分光光度法测定铋(iii)
Pub Date : 2022-06-05 DOI: 10.18524/2304-0947.2022.1(81).255832
D. Snigur, D. Barbalat, O. Zhukovetska, O. Guzenko, T. M. Scherbakova, O. M. Chebotarev
In the current study, the peculiarities of the complexation of Bi(III) with 6,7-dihyroxy‑4-carboxyl‑2-phenylbenzopyrylium perchlorate (CDC) in binary systems and in the presence of cationic surfactants (Surf) were studied. Using classical spectrophotometric methods of molar ratios and equilibrium shift, it was found that in two systems two complexes with stoichiometry Bi(III): CDC are formed: 1:2 and 1:3 at pH 2.0 and pH 4.5, respectively. Molar light absorption coefficients were calculated for Bi(III) complexes with CDC, which are 1.4⸱104 and 1.0⸱104, respectively. It is shown that in the presence of cetylpyridinium chloride or cetyltrimetrylammonium bromide complexes with a molar ratio of Bi(III): CDC: Surf =1:3:3 are formed. In the presence of cationic surfactants there is no shift in the optimal pH of complexation, but there is an increase in the number of coordinated reagent molecules due to the loosening of the hydrate shell of the ion Bi(III) due to hydrophobic hydration of the complex. In addition, the introduction of cationic surfactants leads to a batochromic shift of the absorption band by 10–15 nm and an increase in the molar absorption coefficient to 3.1⸱104 and 4.1⸱104 when using cetylpyridinium chloride or cetyltrimetrylammonium bromide, respectively. Methods of spectrophotometric determination of Bi(III) with the use of analytical forms based on complexes of 1:2 and ternary complex 1:3:3 were developed, which were tested in the analysis of pharmaceuticals, alloys and model solutions. It is noted that the proposed methods are characterized by satisfactory reproducibility and are not inferior in sensitivity to known analogues.
本文研究了Bi(III)与6,7-二羟基- 4-羧基- 2-苯基苯并吡啶高氯酸盐(CDC)在二元体系和阳离子表面活性剂(Surf)存在下的络合特性。采用经典的摩尔比和平衡位移分光光度法,发现在pH 2.0和pH 4.5下,两种体系形成了两个化学计量比为Bi(III): CDC的配合物,分别为1:2和1:3。Bi(III)配合物与CDC的摩尔光吸收系数分别为1.4⸱104和1.0⸱104。结果表明,在氯化十六烷基吡啶或十六烷基三甲基溴化铵存在下,形成了摩尔比为Bi(III): CDC: Surf =1:3:3的配合物。在阳离子表面活性剂存在的情况下,络合的最佳pH值没有变化,但由于配合物的疏水水合作用,离子Bi(III)的水合壳松动,配位试剂分子的数量增加。此外,阳离子表面活性剂的引入使得十六烷基氯吡啶和十六烷基三甲基溴化铵的吸收带发生了10-15 nm的色移,摩尔吸收系数分别提高到3.1⸱104和4.1⸱104。建立了以1:2配合物和1:3:3三元配合物为分析形式的分光光度法测定Bi(III)的方法,并在药物、合金和模型溶液中进行了试验。值得注意的是,所提出的方法具有令人满意的再现性,并且对已知类似物的灵敏度不差。
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引用次数: 0
DOUBLE Ge(IV)-Co(ІІ) COMPLEXES WITH 1-HYDROXYETHYLIDENEDIPHOSPHONIC ACID AND 2,2-BIPYRIDINE 双Ge(IV)-Co(ІІ)配合物与1-羟乙基二膦酸和2,2-联吡啶
Pub Date : 2022-06-05 DOI: 10.18524/2304-0947.2022.1(81).255828
І. Мечникова, вул. Дворянська
The novel developed synthesis methods allowed to obtain three Ge(IV)-Co(II) coordination compounds  with 1- hydroxyethylidenediphosphonic acid and 2,2`-bipyridine [{Co(bipy)3}2{Co(bipy)(H2O)4}2][{Ge(μ-OH)(μ-hedp)}6Cl2]∙2H2O (1), [Co(bipy)3]4[{Ge(μ-OH)(μ-hedp)}6Cl2]∙30H2O (2), [Co(bipy)3]3[{Ge(μ-OH)(μ-hedp)}6]⋅20Н2О⋅2CH3COOH (3). Complexes are characterized by the methods of elemental analysis, IR-, Diffuse Reflectance spectroscopy,  thermogravimetric analysis. All absorption bands presented in the IR-spectra of compounds 1-3 are highlighted in the Table 2. Absorption bands of the P-O bond are 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–Ophosph), d(Ge–OH)  bands characteristic for all the previously synthesized compounds with [Ge6(m-OH)6(m-hedp)6]6-anion is detected in the IR spectra of 1-3. Presence of the crystal water molecules is confirmed by the ν(OH) at 3400 сm-1. A set of the bands usual for the aromatic molecules (n(C–Harom), n(C–Carom), das(CH3),  ds(CH3), n(С–N)) is assigned with 2,2`-bipyridine in  the structure of all compounds. A special feature of the IR-spectra of 1 is presence of COOH absorption band at 1700 сm-1, that indicates the location of  solvated acetic acid. Complex 1 also contains coordination water molecules, confirmed by the d(H2O) at 1642 сm-1 in its IR-spectrum. Absorption bands of Co–N and Со-О bonds evidence that 2,2`-bipyridine and H2O molecules are coordinated to the cobalt atom. Thermal decomposition of 1-3 differs a lot. Variable interval and temperature of the first  endoeffect is explained by the different nature of  water in them – crystal (1-3) and coordinated (1). In the diffuse reflection spectra of compounds 1-3, two bands corresponding to the following transitions are observed: 4T1g(F)→ 4T2g (1 – 7250, 2 – 7100, 3 – 7300 сm-1), 4T1g(F)→ 4T1g(P) (1 – 13800, 2 – 14200, 3 – 14000 сm-1). Such results confirm an octahedral  configuration of cobalt atom. There was also established, how composition and structure of the  synthesized compounds depend from the molar ratio of the reagents and anion of the initial Co(II) salt (chloride, acetate).
新开发的合成方法可以得到三个Ge(IV)-Co(II)配位化合物与1-羟乙基二膦酸和2,2 ' -联吡啶[{Co(bipy)3}2{Co(bipy)(H2O)4}2][{Ge(μ-OH)(μ-hedp)}6Cl2]∙2H2O (1), [Co(bipy)3]4[{Ge(μ-OH)(μ-hedp)}6Cl2]∙30H2O (2), [Co(bipy)3]3[{Ge(μ-OH)(μ-hedp)}6]⋅20Н2О⋅2CH3COOH(3)。配合物通过元素分析,IR-, Diffuse refltance spectroscopy, thermo重量分析等方法进行了表征。化合物1-3红外光谱中的所有吸收带均在表2中突出显示。在~1053和~970 μ m-1处检测到P-O键的吸收带,表明在配合物的组成中存在完全去质子化的PO32-基团。此外,在1-3的红外光谱中还检测到所有含有[Ge6(m-OH)6(m-hedp)6]6阴离子的化合物的n(OH)、ν(Ge-Ophosph)、d(Ge-OH)特征带。晶体水分子的存在是由3400 сm-1的ν(OH)确定的。在所有化合物的结构中,芳香分子(n(C-Harom), n(C-Carom), das(CH3), ds(CH3), n(С-N))通常的一组带与2,2 ' -联吡啶配位。1的红外光谱的一个特殊特征是在1700 μ m-1处存在COOH吸收带,这表明溶剂化乙酸的位置。配合物1也含有配位水分子,其红外光谱的d(H2O)为1642 μ m-1。Co-N和Со-О键的吸收带证明2,2 ' -联吡啶和H2O分子与钴原子配位。热分解1-3差别很大。在化合物1-3的漫反射光谱中,观察到4T1g(F)→4T2g(1- 7250、2 - 7100、3 - 7300 μ m-1)、4T1g(F)→4T1g(P)(1- 13800、2 - 14200、3 - 14000 μ m-1)两个对应跃迁的波段。这些结果证实了钴原子的八面体构型。同时还确定了合成化合物的组成和结构如何取决于初始Co(II)盐(氯化物、醋酸盐)的试剂和阴离子的摩尔比。
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引用次数: 0
MONO- AND BIFUNCTIONAL IMPREGNATED FIBER CHEMOSORBENTS FOR RESPIRATORY PURPOSE 呼吸用单功能和双功能浸渍纤维化学吸附剂
Pub Date : 2022-04-29 DOI: 10.18524/2304-0947.2022.1(81).248297
A. Ennan, R. Khoma, R. Dlubovskii, Y. Zakharenko, T.S. Benkovska, I. M. Knysh
This paper summarizes the data on the development of import-substituting impregnated This paper summarizes the data on the development of import-substituting impregnated fibrous chemisorbents (IFCS) intended for equipping gas cleaning equipment and personal respiratory protection equipment against gaseous toxicants of various chemical nature. To obtain IFCS of the basic gases (ammonia, organic amines), aqueous solutions of polybasic acids (citric, tartaric and hydroxyethylenediphosphonic) are used as impregnating reagents. IFCS absorb toxicants due to neutralization reactions. The absorption of ammonia and amines of IFCS obtained by impregnation of fibrous carriers (FC) with aqueous solutions of 3d-metals (Ni2+, Co2+ and Cu2+) salts occurs due to complex formation reactions. To obtain IFCS of acidic gases, aqueous solutions of sodium carbonate and urotropine (HMTA) containing structuring additives were used. Impregnating aqueous solutions based on monoethanolamine (MEA) and polyethylenepolyamine (PEPA) have also been developed using their non-volatile derivatives with a higher molar mass. A significant improvement of the IFCS protective characteristics was achieved by introducing of various modifying additives – promoters into the composition of these solutions. Single-layer IFCS -ampholytes (IFCS-A) for respiratory purposes have been developed, which depending on the circumstances are able to absorb both acidic and basic gases (vapours), for example SO2 and NH3. Impregnation solutions include complex compounds of 3d-metals (Ni2+, Co2+ and Cu2+) with MEA, ethylenediamine, HMTA and PEPA at various molar ratios of components or buffer mixtures based on polybasic acids and organic bases (MEA and PEPA) of medium strength salts. Chemisorbents for acidic and/or basic gases (IFCS-I, IFCS-AI) have been developed, the moment of “response” of the dynamic absorption capacity of which can be visually determined by the change in color of the gas mask elements during the “breakthrough” of the sorbate, obtained by impregnating of FC with solutions containing acid-base indicators.
本文综述了进口替代浸渍纤维化学吸附剂(IFCS)的发展情况,该纤维浸渍剂用于装备气体净化设备和个人呼吸防护设备,以防止各种化学性质的气体毒物。为了获得碱性气体(氨、有机胺)的IFCS,用多碱性酸(柠檬酸、酒石酸和羟乙基二膦酸)的水溶液作为浸渍试剂。IFCS通过中和反应吸收有毒物质。纤维载体(FC)与3d金属(Ni2+, Co2+和Cu2+)盐的水溶液浸渍所得IFCS的氨和胺的吸收是由于复杂的形成反应而发生的。为了获得酸性气体的IFCS,使用碳酸钠和含有结构添加剂的乌洛托品(HMTA)水溶液。基于单乙醇胺(MEA)和聚乙烯多胺(PEPA)的浸渍水溶液也被开发出来,使用它们的非挥发性衍生物具有更高的摩尔质量。通过在这些溶液的组成中引入各种改性添加剂-促进剂,IFCS的保护特性得到了显著改善。用于呼吸目的的单层IFCS-两性电解质(IFCS- a)已被开发出来,它根据具体情况能够吸收酸性和碱性气体(蒸气),例如二氧化硫和氨。浸渍溶液包括3d金属(Ni2+, Co2+和Cu2+)与MEA,乙二胺,HMTA和PEPA以不同摩尔比的组分或基于多碱性酸和中等强度盐的有机碱(MEA和PEPA)的缓冲混合物的复合化合物。已开发出用于酸性和/或碱性气体的化学吸附剂(IFCS-I, IFCS-AI),其动态吸收能力的“响应”时刻可以通过含有酸碱指示剂的溶液浸渍FC得到的山梨酸“突破”时防毒面具元件的颜色变化来直观地确定。
{"title":"MONO- AND BIFUNCTIONAL IMPREGNATED FIBER CHEMOSORBENTS FOR RESPIRATORY PURPOSE","authors":"A. Ennan, R. Khoma, R. Dlubovskii, Y. Zakharenko, T.S. Benkovska, I. M. Knysh","doi":"10.18524/2304-0947.2022.1(81).248297","DOIUrl":"https://doi.org/10.18524/2304-0947.2022.1(81).248297","url":null,"abstract":"This paper summarizes the data on the development of import-substituting impregnated This paper summarizes the data on the development of import-substituting impregnated fibrous chemisorbents (IFCS) intended for equipping gas cleaning equipment and personal respiratory protection equipment against gaseous toxicants of various chemical nature. To obtain IFCS of the basic gases (ammonia, organic amines), aqueous solutions of polybasic acids (citric, tartaric and hydroxyethylenediphosphonic) are used as impregnating reagents. IFCS absorb toxicants due to neutralization reactions. The absorption of ammonia and amines of IFCS obtained by impregnation of fibrous carriers (FC) with aqueous solutions of 3d-metals (Ni2+, Co2+ and Cu2+) salts occurs due to complex formation reactions. To obtain IFCS of acidic gases, aqueous solutions of sodium carbonate and urotropine (HMTA) containing structuring additives were used. Impregnating aqueous solutions based on monoethanolamine (MEA) and polyethylenepolyamine (PEPA) have also been developed using their non-volatile derivatives with a higher molar mass. A significant improvement of the IFCS protective characteristics was achieved by introducing of various modifying additives – promoters into the composition of these solutions. Single-layer IFCS -ampholytes (IFCS-A) for respiratory purposes have been developed, which depending on the circumstances are able to absorb both acidic and basic gases (vapours), for example SO2 and NH3. Impregnation solutions include complex compounds of 3d-metals (Ni2+, Co2+ and Cu2+) with MEA, ethylenediamine, HMTA and PEPA at various molar ratios of components or buffer mixtures based on polybasic acids and organic bases (MEA and PEPA) of medium strength salts. Chemisorbents for acidic and/or basic gases (IFCS-I, IFCS-AI) have been developed, the moment of “response” of the dynamic absorption capacity of which can be visually determined by the change in color of the gas mask elements during the “breakthrough” of the sorbate, obtained by impregnating of FC with solutions containing acid-base indicators.","PeriodicalId":19451,"journal":{"name":"Odesa National University Herald. Chemistry","volume":"2020 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2022-04-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"74296998","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: 1
SPECTROPHOTOMETRIC DETERMINATION OF COPPER (II) AFTER DISPERSIVE LIQUID-LIQUID EXTRACTION OF ITS COMPLEX WITH 6,7-DIHYDROXY-4-METHYL-2-PHENYLBENZOPYRYLIUM CHLORIDE 6,7-二羟基-4-甲基-2-苯基苯并吡氯铵分散液-液萃取络合物分光光度法测定铜(ii)
Pub Date : 2021-12-29 DOI: 10.18524/2304-0947.2021.4(80).248296
D. Snigur
The specificity of the dispersive liquid-liquid semi-microextraction of Copper (II) complex with 6,7-dihydroxy-4-methyl-2-phenylbenzopyryl chloride has been studied. It is noted that the transition to semi-microextraction technology can significantly reduce the toxic organic solvents consumption, and the use of dispersion solvent can intensify the complex extraction of Сopper (II) complex with 6,7-dihydroxy-4-methyl-2-phenylbenzopyryl chloride. Optimal conditions for spectrophotometric determination of Сopper (II) after dispersive liquid-liquid semi-microextraction of its complex with 6,7-dihydroxy-4-methyl-2-phenylbenzopyrylium chloride were found to be: 1.5 mL of chloroform, 1.5 mL of methanol, pH 4.5, λmax = 535 nm, l = 1 cm. The main analytical characteristics of the developed dispersive liquid-liquid semi-microextraction-spectrophotometric method are calculated: the calibration graph is linear in the wide range of concentrations of 17-480 μg/L, and the limit of detection and limit of determination are 5 and 17 μg/L, respectively. The molar ratios Copper (II) : interferer, in which there is no effect on the quantitative determination of Copper(II) by the proposed dispersive liquid-liquid semi-microextraction-spectrophotometric method have been established. The proposed method for Copper (II) spectrophotometric quantification after preconcentration via dispersive liquid-liquid semi-microextraction as a complex with 6,7-dihydroxy-4-methyl-2-phenylbenzopyrilium chloride was tested in the analysis of model solutions and water samples. The accuracy of the developed dispersive liquid-liquid semi-microextraction-spectrophotometric method was checked by the "spiked-found" method and the relative standard deviation does not exceed 3.9%. The proposed technique is simple, sensitive and environmentally friendly.
研究了6,7-二羟基-4-甲基-2-苯基苯并吡氯分散液-液半微萃取铜(II)配合物的特异性。注意到过渡到半微萃取技术可以显著减少有毒有机溶剂的消耗,并且使用分散溶剂可以强化与6,7-二羟基-4-甲基-2-苯基苯并吡氯配合物Сopper (II)的配合物萃取。采用6,7-二羟基-4-甲基-2-苯基苯并氯吡啶对其配合物进行分散液-液半微萃取,测定Сopper (II)的最佳工艺条件为:氯仿1.5 mL,甲醇1.5 mL, pH 4.5, λmax = 535 nm, l = 1 cm。计算了所建立的分散液-液半微萃取-分光光度法的主要分析特性:在17 ~ 480 μg/L的浓度范围内,标定图呈线性关系,检出限为5,测定限为17 μg/L。建立了铜(II)与干扰物的摩尔比,该摩尔比对分散液-液半微萃取-分光光度法测定铜(II)的含量无影响。以6,7-二羟基-4-甲基-2-苯基苯并氯化吡啶为络合物,采用分散液-液半微萃取法对铜(II)进行预富集,并对模型溶液和水样进行了分析。建立的分散液-液半微萃取-分光光度法的准确度经“尖峰发现”法检验,相对标准偏差不超过3.9%。该技术简单、灵敏、环保。
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引用次数: 0
EFFECT OF ACETYL ACETONE ON RADICAL POLYMERIZATION OF VINYL MONOMERS INITIATED BY BENZOYL PEROXIDE 乙酰丙酮对过氧化苯甲酰引发乙烯基单体自由基聚合的影响
Pub Date : 2021-12-29 DOI: 10.18524/2304-0947.2021.4(80).248293
O. V. Shevchenko, K. Burenkova
The radical polymerization of styrene and methyl methacrylate (MMA) initiated by benzoyl peroxide (BР) with the addition of 10, 20, 50, and 80% of acetylacetone (AA) mixed with a monomer was studied. It was found that the rate of the polymerization process increases in the presence of a certain amount of AA in the system (³ 50% of the monomer). This is due to the fact that AA accelerates the decomposition of BP, while removing it from the system in the form of non-radical products, and the initiating function is performed by acetylacetonate radicals, which are formed upon interaction with BP. The incorporation of acac fragments into the polymer chain has been proved by IR and 1H NMR spectroscopy. It was found that these groups in the composition of the polymer interact with the p-system of benzene rings of polystyrene. The second reason for the accelerating action is the formation of complexes between the monomer and AA, in which the additive has an acceptor effect, leading to the facilitation of the breaking of double bonds in the monomer. It was shown that MMA has a stronger effect on AA polymerization, because forms stronger complexes with the enol form of AA, which requires a longer time for the radical to leave the complex. In this regard, during its polymerization, induction periods are observed, the duration of which is directly proportional to the concentration of AA in a mixture with MMA. It was revealed that another feature of the effect of AA on radical polymerization is its participation in chain transfer reactions, which does not decrease the rate of the process, but only leads to a decrease in the molecular weight of the products. This makes it an effective regulator of polymer molecular weights. The paper proposes a scheme for the polymerization of vinyl monomers, initiated by BP with the addition of AA.
研究了过氧化苯甲酰(BР)在10%、20%、50%和80%的乙酰丙酮(AA)与单体混合的条件下引发苯乙烯与甲基丙烯酸甲酯(MMA)的自由基聚合反应。研究发现,当体系中存在一定量的AA(单体的50%³)时,聚合过程的速率提高。这是因为AA加速了BP的分解,同时以非自由基产物的形式将其从系统中清除,而启动功能是由乙酰丙酮自由基完成的,乙酰丙酮自由基是与BP相互作用形成的。通过红外光谱和核磁共振氢谱证实了acac片段与聚合物链的结合。结果表明,这些基团与聚苯乙烯苯环的p系相互作用。加速作用的第二个原因是单体与AA之间形成配合物,其中添加剂具有受体作用,导致单体双键断裂的促进作用。结果表明,MMA对AA聚合的影响更大,因为它与烯醇形式的AA形成更强的配合物,这需要更长的时间自由基离开配合物。因此,在其聚合过程中观察到诱导期,诱导期的持续时间与MMA混合物中AA的浓度成正比。结果表明,AA对自由基聚合影响的另一个特点是参与链转移反应,但不降低聚合速率,只导致产物分子量降低。这使它成为聚合物分子量的有效调节剂。本文提出了一种由BP引发AA聚合乙烯基单体的方案。
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引用次数: 0
SYNTHESIS AND STRUCTURE OF HETEROMETALLIC – MIXED-LIGAND Ge(IV) – 3d-METAL COMPLEXES WITH GALLIC ACID AND 1,10-PHENANTHROLINE 杂金属混合配体锗(IV) -没食子酸- 1,10-邻菲罗啉的三维金属配合物的合成与结构
Pub Date : 2021-12-29 DOI: 10.18524/2304-0947.2021.4(80).248288
E. Martsinko, E. Chebanenko, I. Seifullina
Authors have developed optimal conditions and synthetic methods in water-organic solutions for ten heterometallic – mixed-ligand complexes of germanium(IV) and 3d-metals with gallic acid (Н2Gal) and 1,10-phenanthroline (phen), their composition and structure [M(phen)3][Ge(H2O)(HGal)2]∙nH2O (M = Mn (1), Co (2), Ni (3), Zn(5)); [CuCl(phen)2]2[Ge(H2O)(HGal)2]∙2H2O (4). Comparative analysis of their IR-spectra and spectra gallic acid and 1,10-phenanthroline with involvement diffuse reflection spectra allowed to establish coordination sphere of germanium and 3-metals. IR-spectra of complexes 1-5 are similar, therefore coordination of ligands in them is the same. Comparatively to the IR-spectrum of gallic acid, there are absent valence absorption bands of free carboxylic groups while two bands of asymmetric and symmetric oscillation of C-O groups in carboxylate ions CОО- appear in the spectra of complexes. Deformation bands d(Сarom-О-Н) are shifted to the low-frequency region for 50-40 cm-1, which indicates deprotonation and binding to the complexing agent of OH-groups from gallic acid. Appearance of deformation bands d(H2О) at 1625 сm-1 is characteristic for the coordination water in composition of complexes. Presence of coordination and crystalline water as well as unbonded OH-group are confirmed with the band n(Ge-О) at 620 сm-1. Thermal decomposition of mixed-metal complexes starts with an endothermic effect in the temperature range 80-160°С where elimination of certain number of water molecules takes place: two – for 1 and 4, three – for 2 and 5, four – for 3. On the thermogravigrams of all compounds one more endoeffect in the temperature range 160-220°С is presented, where removal of one coordination water molecule happens. It was established, that coordination polyhedron of germanium was formed by five oxygen atoms of deprotonated hydroxyl groups from two molecules of gallic acid and one water molecule in all compounds. Second ligand – 1,10-phenanthroline is coordinated to 3d-metal through heterocyclic nitrogen atoms with formation of cations with different composition [M(phen)3]2+ (M = Mn, Co, Ni, Zn) та [CuCl(phen)2]+. 
作者开发了十种锗(IV)和3d金属与没食子酸(Н2Gal)和1,10-菲罗啉(phen)的杂金属混合配体配合物在水-有机溶液中的最佳合成条件和方法,它们的组成和结构[M(phen)3][Ge(H2O)(HGal)2]∙nH2O (M = Mn (1), Co (2), Ni (3), Zn(5));[CuCl(phen)2]2[Ge(H2O)(HGal)2]∙2H2O(4).对它们的红外光谱与没食子酸和1,10-菲罗啉的光谱进行了对比分析,建立了锗与3金属的配位球。配合物1-5的红外光谱相似,说明其配位相同。与没食子酸的红外光谱相比,配合物的光谱中没有游离羧基的价吸收带,而羧酸离子中C-O基的不对称和对称振荡带CОО-出现。变形带d(Сarom-О-Н)在50-40 cm-1范围内移至低频区,表明没食子酸的oh -基团脱质子并与络合剂结合。变形带d(H2О)在1625 -1处的出现是配合物中配位水的特征。在620 μ m-1的n(Ge-О)波段证实了配位和结晶水以及未键oh基团的存在。混合金属配合物的热分解始于80-160°С温度范围内的吸热效应,在此温度范围内,一定数量的水分子被消除:2 -用于1和4,3 -用于2和5,4 -用于3。在所有化合物的热重图上,在160-220°С温度范围内出现了一个内效应,其中一个配位水分子发生了去除。确定了锗的配位多面体是由两个没食子酸分子和一个水分子的去质子化羟基的5个氧原子构成的。第二配体- 1,10-菲罗啉通过杂环氮原子与三维金属配位,形成不同组成的阳离子[M(phen)3]2+ (M = Mn, Co, Ni, Zn) та [CuCl(phen)2]+。
{"title":"SYNTHESIS AND STRUCTURE OF HETEROMETALLIC – MIXED-LIGAND Ge(IV) – 3d-METAL COMPLEXES WITH GALLIC ACID AND 1,10-PHENANTHROLINE","authors":"E. Martsinko, E. Chebanenko, I. Seifullina","doi":"10.18524/2304-0947.2021.4(80).248288","DOIUrl":"https://doi.org/10.18524/2304-0947.2021.4(80).248288","url":null,"abstract":"Authors have developed optimal conditions and synthetic methods in water-organic solutions for ten heterometallic – mixed-ligand complexes of germanium(IV) and 3d-metals with gallic acid (Н2Gal) and 1,10-phenanthroline (phen), their composition and structure [M(phen)3][Ge(H2O)(HGal)2]∙nH2O (M = Mn (1), Co (2), Ni (3), Zn(5)); [CuCl(phen)2]2[Ge(H2O)(HGal)2]∙2H2O (4). Comparative analysis of their IR-spectra and spectra gallic acid and 1,10-phenanthroline with involvement diffuse reflection spectra allowed to establish coordination sphere of germanium and 3-metals. IR-spectra of complexes 1-5 are similar, therefore coordination of ligands in them is the same. Comparatively to the IR-spectrum of gallic acid, there are absent valence absorption bands of free carboxylic groups while two bands of asymmetric and symmetric oscillation of C-O groups in carboxylate ions CОО- appear in the spectra of complexes. Deformation bands d(Сarom-О-Н) are shifted to the low-frequency region for 50-40 cm-1, which indicates deprotonation and binding to the complexing agent of OH-groups from gallic acid. Appearance of deformation bands d(H2О) at 1625 сm-1 is characteristic for the coordination water in composition of complexes. Presence of coordination and crystalline water as well as unbonded OH-group are confirmed with the band n(Ge-О) at 620 сm-1. Thermal decomposition of mixed-metal complexes starts with an endothermic effect in the temperature range 80-160°С where elimination of certain number of water molecules takes place: two – for 1 and 4, three – for 2 and 5, four – for 3. On the thermogravigrams of all compounds one more endoeffect in the temperature range 160-220°С is presented, where removal of one coordination water molecule happens. It was established, that coordination polyhedron of germanium was formed by five oxygen atoms of deprotonated hydroxyl groups from two molecules of gallic acid and one water molecule in all compounds. Second ligand – 1,10-phenanthroline is coordinated to 3d-metal through heterocyclic nitrogen atoms with formation of cations with different composition [M(phen)3]2+ (M = Mn, Co, Ni, Zn) та [CuCl(phen)2]+.\u0000 ","PeriodicalId":19451,"journal":{"name":"Odesa National University Herald. Chemistry","volume":"1 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2021-12-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"75070728","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
HOCH2CH2NH2 – TROPEOLIN OOO – H2O SYSTEM ACID-BASIC PROPERTIES IN THE PRESENCE OF HCl, HClO4, H2SO4 AND SO2H2O 在HCl、HClO4、H2SO4和SO2存在下的酸碱性质
Pub Date : 2021-12-29 DOI: 10.18524/2304-0947.2021.4(80).248292
R. Khoma, A. Ennan, T. S. Ben’kovs’ka, E. Y. Bugova, L. T. Osadchiy, E. M. Menchuk
The influence of hydrochloric, chloric, sulfuric and sulfurous acids (HCl, HClO4, H2SO4 and SO2×H2O, respectively) on protolytic equilibria in the system monoethanolamine (MEA) – tropeolin OOO (TrOOO) – water (CMEA = 0.1 M; pH = 1.0 ÷ 9.5) was studied by pH-metric, spectrophotometric and colorimetric methods.The acid-base behavior of the HOCH2CH2NH2 – TrOOO – H2O system was investigated at CTrOOO = 1,12 ×10-4 М, CMEA = 1,0×10-4  ÷ 1,0 М (pH = 8,25 ÷ 12,05), T = 293 K. TrOOO in this system exists in two tautomeric forms due to acid-base dissociation of the 4-OH group and associates formed by H-bonding with MEA molecules. There is a direct ratio between the pH values ​​of solutions and the total color difference (ΔE76), in contrast to the specific color difference (SCD). The difference in the behavior of the H2SO4 – HOCH2CH2NH2 – TrOOO – H2O system from the systems with HCl and HClO4 is due to the fact that the interaction of the first acid with MEA (8,0 £ pH) forms an ionic associate [HOCH2СH2NH3]2(SO4), which is more stable than ionic pairs [[HOCH2СH2NH3](HSO4), [HOCH2СH2NH3](ClO4), [HOCH2СH2NH3]Cl и [HOCH2СH2NH3](O3S-C­10H6-N=N-C6H4-SO3)[H3NCH2СH2OH]. Acid-base dissociation constants in systems significantly depend on the structure and physicochemical parameters of the mineral acid. In the electronic absorption spectra of the SO2 – MEA – TrOOO – H2O system (pH £ 7,5), there is a pronounced isobestic point at 415 nm, due to the dynamic equilibrium between ion-molecular forms. The coincidence of the maxima on the curves ΔE76 = f(pH) and SCD = f(pH) for the indicated system, in contrast to others studied in this work, was stated. The difference between the spectrophotometric and colorimetric behavior of the SO2 – MEA – TrOOO – H2O system from behavior of the systems with HCl, HClO4, and H2SO4 systems is due to the sulfur(IV)oxyanions with an azo indicator redox interaction.
盐酸、氯酸、硫酸和亚硫酸(HCl、HClO4、H2SO4和SO2×H2O)对单乙醇胺(MEA) - tropeolin OOO (TrOOO) -水(CMEA = 0.1 M;pH = 1.0 ÷ 9.5),分别用pH法、分光光度法和比色法研究。在CTrOOO = 1,12 ×10-4 М, CMEA = 1,0×10-4 ÷ 1,0 М (pH = 8,25 ÷ 12,05), T = 293 K条件下,研究了HOCH2CH2NH2 - TrOOO - H2O体系的酸碱行为。该体系中的TrOOO以两种互变异构形式存在,这是由于4-OH基团的酸碱解离和与MEA分子的氢键形成的结合。溶液的pH值与总色差(ΔE76)成正比,而不是特定色差(SCD)。H2SO4 - HOCH2CH2NH2 - TrOOO - H2O体系与HCl和HClO4体系的行为差异是由于第一种酸与MEA(8,0£pH)相互作用形成离子缔合物[HOCH2СH2NH3]2(SO4),该离子缔合物比离子对[[HOCH2СH2NH3](HSO4), [HOCH2СH2NH3](ClO4), [HOCH2СH2NH3]Cl * [HOCH2СH2NH3](O3S-C-10H6-N =N-C6H4-SO3)[H3NCH2СH2OH]更稳定。体系中的酸碱解离常数在很大程度上取决于矿物酸的结构和物理化学参数。在SO2 - MEA - TrOOO - H2O体系(pH = 7,5)的电子吸收光谱中,由于离子-分子形态之间的动态平衡,在415 nm处存在明显的等容点。与本工作中研究的其他系统相比,所指示系统的曲线ΔE76 = f(pH)和SCD = f(pH)上的最大值是重合的。SO2 - MEA - TrOOO - H2O体系的分光光度和比色行为与HCl、HClO4和H2SO4体系的不同是由于硫(IV)氧离子与偶氮指示剂氧化还原相互作用。
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引用次数: 1
SYNTHESIS AND PROPERTIES OF IMIDATION PRODUCTS OF MONOSUBSTITUTED AND DISUBSTITUTED NAPHTHALIC ANHYDRIDES WITH P-AMINOBENZOIC ACID 对氨基苯甲酸单取代和二取代萘酸酐酰化产物的合成及性能研究
Pub Date : 2021-12-29 DOI: 10.18524/2304-0947.2021.4(80).248290
N. Fedko, V. F. Anikin, V. V. Veduta, V. V. Stankevich, A. V. Balatska
4-Monosubstituted and 4,5-disubstituted halogeno- and nitro- N-(4-carboxyphenylnaphthalimides) were synthesized by imidation of the corresponding 4-monosubstituted and 4,5-disubstituted naphthalic anhydrides with para-aminobenzoic acid using acetic acid as solvent with 75-85% yields. 4-Amino-N- (4-carboxyphenyl)naphthalimide and 4,5-diamino-N-(4-carboxyphenyl)naphthalimide were obtained by reduction of corresponding nitrosubstituted N-(4-carboxyphenyl)naphthalimides using sodium dithionite as reducing agent in mixed ethanol-water solvent. The completion of reaction was monitored by thin layer chromatography with disappearance of the spot of the corresponding starting naphthalic anhydride. Starting 4-monosubstituted and 4,5-disubstituted naphthalic anhydrides were obtained by oxidation of corresponding substituted acenaphthenes with sodium dichromate in acetic acid. The synthesized N-carboxyphenylnaphthalimides with chlorine and bromine in positions 4 or 4 and 5 are yellow crystal substances with blue fluorescence; 4-nitro- and 4,5-dinitro-N-carboxyphenylnaphthalimides are orange crystal substances without fluorescence; 4-amino-, 4-dimethylamino and 4,5-diamino-N-carboxyphenylnaphthalimides are orange crystal substances with orange fluorescence. The structure of all the synthesized products was confirmed by IR and NMR 1H spectroscopy. The results of computer screening of the synthesized compounds using the PASS Online Internet service confirm a wide range of biological activity of N-carboxyphenylnaphthalimides, which makes them promising substances for further biological testing.
以对氨基苯甲酸为溶剂,以4-单取代和4- 5-二取代萘酸酐为原料,合成了4-单取代和4,5-二取代卤化萘和硝基N-(4-羧基苯基萘酰亚胺),产率为75 ~ 85%。以二亚硫酸钠为还原剂,在乙醇-水混合溶剂中还原相应的硝基取代N-(4-羧基苯基)萘酰亚胺,得到4-氨基-N-(4-羧基苯基)萘酰亚胺和4,5-二氨基-N-(4-羧基苯基)萘酰亚胺。用薄层色谱法监测反应的完成情况,相应的萘酸酐起始点消失。用重铬酸钠在乙酸中氧化取代萘,得到4-单取代萘和4,5-二取代萘酸酐。合成的4位氯和5位溴的n -羧基苯基萘酰亚胺为黄色晶体物质,荧光为蓝色;4-硝基和4,5-二硝基-n -羧基苯基萘酰亚胺为无荧光的橙色晶体物质;4-氨基,4-二甲胺和4,5-二胺- n -羧基苯基萘酰亚胺是具有橙色荧光的橙色晶体物质。所有合成产物的结构均经红外光谱和核磁共振1H谱证实。利用PASS在线互联网服务对合成化合物进行计算机筛选的结果证实了n -羧基苯基萘酰亚胺具有广泛的生物活性,这使它们成为进一步生物学测试的有希望的物质。
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引用次数: 0
SURFACE TENSION AND ASSOCIATION IN AQUEOUS SOLUTION SURFACTANTS IN THE PRESENCE OF POLYACRYLAMIDE 聚丙烯酰胺存在下,表面活性剂在水溶液中的表面张力和结合力
Pub Date : 2021-12-26 DOI: 10.18524/2304-0947.2021.4(80).250930
E. Streltsova, O. Voliuvach, E. Bondar’
The surface tension of aqueous solutions of cationic (dodecylammonium and dodecylpyridinium chlorides) and anionic (sodium dodecylsulfate) surfactants was measured in the presence of polyacrylamide in the solution.  A synergistic effect of reducing the surface tension of mixed solutions of cationic surfactants, in the region of sufficiently high concentrations of mixed solutions of sodium dodecyl sulfate, with polyacrylamide in the range of molar ratios of the mixture components - n (Surfactants : PAA) = 1: 1; 1: 0.25 was established. The values ​​of the maximum adsorption, the values ​​of the area per molecule or associate of surfactants in the adsorption layer, as well as the standard Gibbs free energy of adsorption of surfactant - PAA associates are calculated. In accordance with Rosen's model, the composition of mixed adsorption layers at the solution-air interface is calculated, as well as the parameter of intermolecular interaction in adsorption layers between molecules, cationic and anionic ions surfactants and PAA. The values ​​of the critical micelle concentration (CMC) of individual surfactants in aqueous solutions exceed the CMC of the studied surfactants in the presence of PAA, which promotes micelle formation.
在聚丙烯酰胺存在的情况下,测定了阳离子(十二烷基铵和十二烷基吡啶氯化物)和阴离子(十二烷基硫酸钠)表面活性剂水溶液的表面张力。在十二烷基硫酸钠混合溶液浓度足够高的区域内,阳离子表面活性剂与聚丙烯酰胺的混合溶液的摩尔比在混合物组分- n(表面活性剂:PAA) = 1:1的范围内具有降低表面张力的协同效应;1:0 .25成立。计算了最大吸附量、表面活性剂在吸附层中每分子或伴生物的面积以及表面活性剂- PAA伴生物的标准吉布斯自由能。根据Rosen的模型,计算了溶液-空气界面混合吸附层的组成,以及吸附层中分子、阳离子、阴离子表面活性剂与PAA之间的分子间相互作用参数。PAA存在时,水溶液中单个表面活性剂的临界胶束浓度(CMC)超过所研究表面活性剂的临界胶束浓度,促进了胶束的形成。
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引用次数: 0
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Odesa National University Herald. Chemistry
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