Pub Date : 2023-08-25DOI: 10.33609/2708-129x.89.07.2023.26-39
Oleg Posilskyi, Ganna Artamonova, Elena Trunova
In the work, the qualitative composition and differentiation of 43 samples of ballpoint pen pastes of different colors was investigated (blue-violet – 29 samples, pink-violet – 3 samples, blue – 3 samples, black – 5 samples, green – 1 sample and red –2 samples) by the method of electronic absorption spectroscopy. The results of the study showed that each paste can be distinguished by studying the nature of their absorption spectra, which arises due to the presence of different functional groups. It was established that most of the analyzed paste samples contain pigments based on triarylmethane, phthalocyanine, xanthene dyes or their mixture. Certain absorption maxima correspond to each type of dyes. The broad and most intense band at λ~590 nm, which was detected for all samples, corresponds to triarylmethane dyes. The band at λ~670 nm corresponds to phthalocyanine dyes. The presence of absorption bands in the green range (λ~520–560 nm) indicates the presence of xanthene dyes in the composition of the pastes. Using the method of photoluminescence spectroscopy upon excitation of IR luminescence in the green region of the spectrum (λ=530 nm) it is shown that 11 blue-violet, 5 black and one red pastes exhibit bright luminescence due to the presence of crystal violet and some other triarylmethane dyes in their composition. Weak luminescence was detected for three blue pastes. No luminescence response was observed for the other tested pastes, which is due to the presence of phthalocyanine dyes in these pastes, the absorption of which overlaps with the luminescence spectra of triarylmethane dyes. The obtained data can be used to create a reference base for identifying and differentiating the composition of ballpoint pen pastes of modern manufacturers and establishing their classification and identification differences.
{"title":"IDENTIFICATION OF TRIARYLMETHANE, PHTHALOCYANINE AND XANTHENE IN A MIXTURE OF DYES BY ELECTRON ABSORPTION SPECTROSCOPY","authors":"Oleg Posilskyi, Ganna Artamonova, Elena Trunova","doi":"10.33609/2708-129x.89.07.2023.26-39","DOIUrl":"https://doi.org/10.33609/2708-129x.89.07.2023.26-39","url":null,"abstract":"In the work, the qualitative composition and differentiation of 43 samples of ballpoint pen pastes of different colors was investigated (blue-violet – 29 samples, pink-violet – 3 samples, blue – 3 samples, black – 5 samples, green – 1 sample and red –2 samples) by the method of electronic absorption spectroscopy. The results of the study showed that each paste can be distinguished by studying the nature of their absorption spectra, which arises due to the presence of different functional groups. It was established that most of the analyzed paste samples contain pigments based on triarylmethane, phthalocyanine, xanthene dyes or their mixture. Certain absorption maxima correspond to each type of dyes. The broad and most intense band at λ~590 nm, which was detected for all samples, corresponds to triarylmethane dyes. The band at λ~670 nm corresponds to phthalocyanine dyes. The presence of absorption bands in the green range (λ~520–560 nm) indicates the presence of xanthene dyes in the composition of the pastes. Using the method of photoluminescence spectroscopy upon excitation of IR luminescence in the green region of the spectrum (λ=530 nm) it is shown that 11 blue-violet, 5 black and one red pastes exhibit bright luminescence due to the presence of crystal violet and some other triarylmethane dyes in their composition. Weak luminescence was detected for three blue pastes. No luminescence response was observed for the other tested pastes, which is due to the presence of phthalocyanine dyes in these pastes, the absorption of which overlaps with the luminescence spectra of triarylmethane dyes. The obtained data can be used to create a reference base for identifying and differentiating the composition of ballpoint pen pastes of modern manufacturers and establishing their classification and identification differences.
","PeriodicalId":498014,"journal":{"name":"Ukraïnsʹkij hìmìčnij žurnal","volume":"49 1","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"2023-08-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"134983279","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 : 2023-08-25DOI: 10.33609/2708-129x.89.07.2023.8-25
Leon Shteinberg
Arylamides of 3-hydroxy-2-naphthoic acid are widely used in the synthesis of dyes and pigments, as pesticides and medicines. Therefore, the development of new methods for their synthesis is an urgent task.
It has been found that catalysis by phosphorus trichloride and/or phosphorous acid (2 mol %) of acylation in refluxing ortho-xylene or ortho-chlorotoluene of arylamines with 3-hydroxy-2-naphthoic acid leads to the formation of the corresponding arylamides with a high, and often almost quantitatively yield. Substituted anilines, containing electron-bearing and electron-withdrawing substituents in ortho-, meta- and para-positions, successfully enter the reaction in an air atmosphere. The catalytic reaction of 1-naphthylamine and 5-aminobenzimidazolone with 3-hydroxy-2-naphthoic acid makes it possible to obtain in high yield, respectively, 1-naphthylamide of 3-hydroxy-2-naphthoic acid and 5-(2'-hydroxy-3'-naphthoylamido)-2-benzimidazolone only in a nitrogen atmosphere.
Based on the yield of 3-hydroxy-2-naphthoic acid arylamides over a certain time in the reaction catalyzed by phosphorous acid in ortho-xylene, the average initial amidation rates were calculated at a semi-quantitative level and their dependence on pKa of the corresponding arylamines was plotted in logarithmic coordinates, according to the Bronsted equation. The graph is a curved line with two maxima and one minimum, while arylamines containing electronwithdrawing substituents (4-Br; 3-F; 3-Br; 3-Cl) are the most reactive, and the most strongly basic 4-anisidine and weakly basic 3-nitroaniline are the least reactive.
Based on these data, as well as the results of the earlier interaction of substituted anilines with benzoic acid, catalyzed by polybutoxytitanates, and substituted benzoic acids and 3-hydroxy-2-naphthoic acid with aniline, catalyzed by phosphorus trichloride and phosphorous acid, under comparable conditions, a mechanism of amidation was proposed. It includes the formation in the first minutes of the reaction in situ of arylamine phosphite, which can act as a P=O–oxygennucleophilic catalyst, which forms the corresponding phosphite upon interaction with 3-hydroxy-2-naphthoic acid, which is subsequently attacked by a free arylamine molecule to obtain arylamide 3-hydroxy-2-naphthoic acid. In addition to the basicity of arylamine at the stage of nucleophilic attack, the reaction rate can be affected by its oxidation as such and the phosphite formed by it with atmospheric oxygen, unproductive binding of arylamine into a salt or H-complex with 3-hydroxy-2-naphthoic acid, participation of the final target product in amido-imide rearrangement with further inhibition of catalysis by the resulting imide form.
3-羟基-2-萘酸芳酰胺类化合物广泛用于染料和色素的合成、农药和医药等方面。因此,开发合成它们的新方法是一项紧迫的任务。
已经发现,在3-羟基-2-萘酸的催化下,三氯化磷和(或)磷酸(2 mol %)对芳胺的邻二甲苯或邻氯甲苯回流的酰化反应,可生成相应的芳胺,而且产量很高,通常几乎是定量的。取代苯胺,在邻位,间位和对位上含有电子和吸电子取代基,成功地在空气气氛中进入反应。1-萘胺和5-氨基苯并咪唑酮与3-羟基-2-萘酸的催化反应使得仅在氮气气氛下即可高产得3-羟基-2-萘酸的1-萘酰胺和5-(2'-羟基-3'-萘酰胺)-2-苯并咪唑酮。
根据磷酸在邻二甲苯中催化反应一定时间内3-羟基-2-萘酸芳酰胺的产率,在半定量水平上计算了平均初始酰胺化率,并根据Bronsted方程在对数坐标下绘制了其与相应芳胺pKa的依赖关系。该图是一条有两个最大值和一个最小值的曲线,而芳胺含有吸电子取代基(4-Br;3 f;三室;碱性最强的4-茴香胺和碱性较弱的3-硝基苯胺反应最弱。
在此基础上,结合较早前用聚丁氧钛酸酯催化取代苯胺与苯甲酸的相互作用,以及用三氯化磷和磷酸催化取代苯甲酸和3-羟基-2-环烷酸与苯胺在相似条件下的相互作用的结果,提出了酰胺化的机理。它包括在反应的最初几分钟内原位形成芳胺亚磷酸酯,它可以作为P= o -氧亲核催化剂,与3-羟基-2-环烷酸相互作用形成相应的亚磷酸酯,随后被游离芳胺分子攻击得到芳胺- 3-羟基-2-环烷酸。除了芳胺在亲核攻击阶段的碱度外,反应速率还受其氧化及其与大气氧形成的亚磷酸盐、芳胺与3-羟基-2-环烷酸形成盐或h配合物的非生产结合、最终目标产物参与酰胺-亚胺重排并进一步抑制由此产生的亚胺形式的催化裂解等因素的影响。
{"title":"CATALYSIS BY PHOSPHORUS (III) COMPOUNDS IN THE SYNTHESIS OF ARYLAMIDES OF 3-OXY-2-NAPH-THOIIC ACID","authors":"Leon Shteinberg","doi":"10.33609/2708-129x.89.07.2023.8-25","DOIUrl":"https://doi.org/10.33609/2708-129x.89.07.2023.8-25","url":null,"abstract":"Arylamides of 3-hydroxy-2-naphthoic acid are widely used in the synthesis of dyes and pigments, as pesticides and medicines. Therefore, the development of new methods for their synthesis is an urgent task.
 It has been found that catalysis by phosphorus trichloride and/or phosphorous acid (2 mol %) of acylation in refluxing ortho-xylene or ortho-chlorotoluene of arylamines with 3-hydroxy-2-naphthoic acid leads to the formation of the corresponding arylamides with a high, and often almost quantitatively yield. Substituted anilines, containing electron-bearing and electron-withdrawing substituents in ortho-, meta- and para-positions, successfully enter the reaction in an air atmosphere. The catalytic reaction of 1-naphthylamine and 5-aminobenzimidazolone with 3-hydroxy-2-naphthoic acid makes it possible to obtain in high yield, respectively, 1-naphthylamide of 3-hydroxy-2-naphthoic acid and 5-(2'-hydroxy-3'-naphthoylamido)-2-benzimidazolone only in a nitrogen atmosphere.
 Based on the yield of 3-hydroxy-2-naphthoic acid arylamides over a certain time in the reaction catalyzed by phosphorous acid in ortho-xylene, the average initial amidation rates were calculated at a semi-quantitative level and their dependence on pKa of the corresponding arylamines was plotted in logarithmic coordinates, according to the Bronsted equation. The graph is a curved line with two maxima and one minimum, while arylamines containing electronwithdrawing substituents (4-Br; 3-F; 3-Br; 3-Cl) are the most reactive, and the most strongly basic 4-anisidine and weakly basic 3-nitroaniline are the least reactive.
 Based on these data, as well as the results of the earlier interaction of substituted anilines with benzoic acid, catalyzed by polybutoxytitanates, and substituted benzoic acids and 3-hydroxy-2-naphthoic acid with aniline, catalyzed by phosphorus trichloride and phosphorous acid, under comparable conditions, a mechanism of amidation was proposed. It includes the formation in the first minutes of the reaction in situ of arylamine phosphite, which can act as a P=O–oxygennucleophilic catalyst, which forms the corresponding phosphite upon interaction with 3-hydroxy-2-naphthoic acid, which is subsequently attacked by a free arylamine molecule to obtain arylamide 3-hydroxy-2-naphthoic acid. In addition to the basicity of arylamine at the stage of nucleophilic attack, the reaction rate can be affected by its oxidation as such and the phosphite formed by it with atmospheric oxygen, unproductive binding of arylamine into a salt or H-complex with 3-hydroxy-2-naphthoic acid, participation of the final target product in amido-imide rearrangement with further inhibition of catalysis by the resulting imide form.","PeriodicalId":498014,"journal":{"name":"Ukraïnsʹkij hìmìčnij žurnal","volume":"165 1","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"2023-08-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"134983280","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 : 2023-08-25DOI: 10.33609/2708-129x.89.07.2023.40-60
Oleg Ryabokin
On the basis of the conducted critical review of modern physical models of the porous electrode, it сan be stated that under the conditions of non-uniform mass transfer taking into account the depth of the electrode, it is possible not only to develop new porous electrodes for a certain application, but also to control the state of electrochemical systems as a whole using the non-destructive method of electrochemical impedance spectroscopy. The presence of a macroscopic model of porous electrode allows one to use the integration of parameters over the surface of the electrode and obtain the average values of current, resistance and capacity within the electrode using the method of averaging in the volume element within the electrode, where porosity is the volume fraction of the void within the element, which is filled with electrolyte solution. This is the theoretical basis for using electrochemical impedance spectroscopy to assess the state of electrodes in electrochemical current sources. To take into account the influence of the aqueous electrolyte, it is possible to use a model taking into account the area of the effective wetted surface, which makes it possible to relate the wetting of the electrode pores with the electrolyte solution to the change in electrical conductivity and polarization of the electrode surface. In this case, when usingelectrochemical impedance spectroscopy, it is possible to obtain information about the following changes in primary current sources: 1– the effect of temperature, which leads to a decrease in the areas of the electrode wetted by the electrolyte, which affect the value of the capacity of the DEL, 2 – chemical processes that lead to the destruction of hydrophilic pores and pores with hydrophilic-hydrophobic walls, an increase in the hydrophobic component on the surface of the electrode, 3 – mechanical destruction of the electrodes. The use of models that take into account the geometry of pores makes it possible to obtain correct data for the analysis of the porous surface in the presence of an electrolyte and in cases of gas phase adsorption in presence of closed pores, as well as to use the value of the capacity on the surface of electrodes to assess the state of their performance.
{"title":"THEORETICAL BASICS OF MONITORING THE CONDITION OF THE ELECTRODES OF CHEMICAL CURRENT SOURCES BY THE METHOD OF ELECTROCHEMICAL IMPEDANCE SPECTROSCOPY","authors":"Oleg Ryabokin","doi":"10.33609/2708-129x.89.07.2023.40-60","DOIUrl":"https://doi.org/10.33609/2708-129x.89.07.2023.40-60","url":null,"abstract":"On the basis of the conducted critical review of modern physical models of the porous electrode, it сan be stated that under the conditions of non-uniform mass transfer taking into account the depth of the electrode, it is possible not only to develop new porous electrodes for a certain application, but also to control the state of electrochemical systems as a whole using the non-destructive method of electrochemical impedance spectroscopy. The presence of a macroscopic model of porous electrode allows one to use the integration of parameters over the surface of the electrode and obtain the average values of current, resistance and capacity within the electrode using the method of averaging in the volume element within the electrode, where porosity is the volume fraction of the void within the element, which is filled with electrolyte solution. This is the theoretical basis for using electrochemical impedance spectroscopy to assess the state of electrodes in electrochemical current sources. To take into account the influence of the aqueous electrolyte, it is possible to use a model taking into account the area of the effective wetted surface, which makes it possible to relate the wetting of the electrode pores with the electrolyte solution to the change in electrical conductivity and polarization of the electrode surface. In this case, when usingelectrochemical impedance spectroscopy, it is possible to obtain information about the following changes in primary current sources: 1– the effect of temperature, which leads to a decrease in the areas of the electrode wetted by the electrolyte, which affect the value of the capacity of the DEL, 2 – chemical processes that lead to the destruction of hydrophilic pores and pores with hydrophilic-hydrophobic walls, an increase in the hydrophobic component on the surface of the electrode, 3 – mechanical destruction of the electrodes. The use of models that take into account the geometry of pores makes it possible to obtain correct data for the analysis of the porous surface in the presence of an electrolyte and in cases of gas phase adsorption in presence of closed pores, as well as to use the value of the capacity on the surface of electrodes to assess the state of their performance.","PeriodicalId":498014,"journal":{"name":"Ukraïnsʹkij hìmìčnij žurnal","volume":"8 1","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"2023-08-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"134983278","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 : 2023-06-26DOI: 10.33609/2708-129x.89.05.2023.13-25
Vitalii SMOKAL, Dmytro KHOMENKO, Roman DOROSHCHUK, Oksana KHARCHENKO
The development of modern technologies are constantly requires seeking new low-cost, efficient materials and establish new technical methods for application these materials. Synthesis of polymers with predicted and expected properties on the one hand and using specific features of interaction light with photoactive fragments in polymers, on the other hand, opens new prospects of application for new materials based on these polymers. The side chain methacrylic polymers with different active functional group have been well studied and widely applied in many fields, such as optoelectronics, nonlinear optics, optical storage materials, biochemicals, and medicine.
The present work focused on synthesis new azostyrylcontaining methacrylic monomers and copolymers with methylmetacrylate (MMA) based on these monomers. The present study is a first reported notice of the synthesis and photochemical properties of methacrylic polymers with 6-azo-phenylquinoline fragments in side chain. Moreover in this work the features of syntheses have been described in detail for monomers and polymers based on new azocompounds. Absorption spectroscopic properties for new quinoline polymers with azo fragment were investigated with UV-Visible spectrophotometry in THF solutions. All studied polymers show a strong absorption band in the range of 300–375 nm resulting from π-π* electronic transition and a weak absorption band in the range of 400–490 nm assigned to n-π* transitions. Electron donating and electron withdrawing substituents at quinoline moity of azo-quinoline polymer solutions lead to bathochromic shift of the π-π*absorption band which agrees well with the result of work. We found that this red-shift increases with an increase of electron donating strength of the substituent as well as with an increase of electron withdrawing strength of the substituent. Based on of the result achieved we can suppose that irradiation of polymers with azo fragment lead to photoinduced trans-cis-isomerization.
From the obtained and presented results one can conclude that novel quinoline polymers with azo fragment can be considered as promising materials for applications requiring photosensitivity in certain of range of wavelength.
{"title":"SYNTHESIS AND PHOTOCHEMICAL PROPERTIES OF NOVEL AZOQUINOLINE CONTAINING POLYMERS","authors":"Vitalii SMOKAL, Dmytro KHOMENKO, Roman DOROSHCHUK, Oksana KHARCHENKO","doi":"10.33609/2708-129x.89.05.2023.13-25","DOIUrl":"https://doi.org/10.33609/2708-129x.89.05.2023.13-25","url":null,"abstract":"The development of modern technologies are constantly requires seeking new low-cost, efficient materials and establish new technical methods for application these materials. Synthesis of polymers with predicted and expected properties on the one hand and using specific features of interaction light with photoactive fragments in polymers, on the other hand, opens new prospects of application for new materials based on these polymers. The side chain methacrylic polymers with different active functional group have been well studied and widely applied in many fields, such as optoelectronics, nonlinear optics, optical storage materials, biochemicals, and medicine.
 The present work focused on synthesis new azostyrylcontaining methacrylic monomers and copolymers with methylmetacrylate (MMA) based on these monomers. The present study is a first reported notice of the synthesis and photochemical properties of methacrylic polymers with 6-azo-phenylquinoline fragments in side chain. Moreover in this work the features of syntheses have been described in detail for monomers and polymers based on new azocompounds. Absorption spectroscopic properties for new quinoline polymers with azo fragment were investigated with UV-Visible spectrophotometry in THF solutions. All studied polymers show a strong absorption band in the range of 300–375 nm resulting from π-π* electronic transition and a weak absorption band in the range of 400–490 nm assigned to n-π* transitions. Electron donating and electron withdrawing substituents at quinoline moity of azo-quinoline polymer solutions lead to bathochromic shift of the π-π*absorption band which agrees well with the result of work. We found that this red-shift increases with an increase of electron donating strength of the substituent as well as with an increase of electron withdrawing strength of the substituent. Based on of the result achieved we can suppose that irradiation of polymers with azo fragment lead to photoinduced trans-cis-isomerization.
 From the obtained and presented results one can conclude that novel quinoline polymers with azo fragment can be considered as promising materials for applications requiring photosensitivity in certain of range of wavelength.","PeriodicalId":498014,"journal":{"name":"Ukraïnsʹkij hìmìčnij žurnal","volume":"384 1","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"2023-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"134958832","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}