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Solid solutions in disulfide systems Re(IV)S2–Ti(IV)S2, Re(IV)S2–Mo(IV)S2, and Re(IV)S2–W(IV)S2 二硫体系 Re(IV)S2-Ti(IV)S2、Re(IV)S2-Mo(IV)S2 和 Re(IV)S2-W(IV)S2 中的固溶体
Pub Date : 2024-07-06 DOI: 10.32362/2410-6593-2024-19-3-258-266
E. I. Efremova, M. Lazov, M. R. Kobrin, V. V. Fomichev
Objectives. Chalcogenides of transition elements with low oxidation states, as well as their substituted derivatives, remain a poorly studied class of chemical compounds. Rhenium disulfide has many distinctive features and great application potential as a new twodimensional semiconductor. This is due to its unusual structure and unique anisotropic properties. The presence of weak interlayer bonding and a unique distorted octahedral (1T) structure suggests the possibility of creating new phases on its basis. The aim of this work is to obtain and study phases in systems Re(IV)S2–Ti(IV)S2, Re(IV)S2–Mo(IV)S2, and Re(IV)S2–W(IV)S2.Methods. The samples were obtained by high-temperature solid-phase ampoule synthesis in a vacuum. The study was carried out using X-ray phase analysis and X-ray photoelectron spectroscopy.Results. The regions of existence of solid solutions, intercalates and two-phase regions in the resulting systems were established.Diffraction patterns were obtained for the new phases and the crystal lattice parameters were calculated. Based on data relating to the binding energies of core electrons with the nucleus, the study showed the valence states of the elements after synthesis. The study also confirmed that all phases obtained as a result of synthesis contain transition elements in the oxidation state (IV).Conclusions. Intercalated solid solutions are formed in areas rich in rhenium, while in areas close to titanium and molybdenum disulfides, intercalated phases are attained. In the ReS2–WS2 system there is a region of solid solutions, including 30, 50, and 70 mol % rhenium disulfide. Their structure is a polymorphic modification of the structure of the original components. The presence of rhenium, molybdenum, and tungsten in these phases in the oxidation state (+IV) was confirmed. The data obtained on phase formation in dichalcogenide systems can be practically used in the creation of materials with unique electronic, magnetic, and optical properties with a wide range of applications.
目的。低氧化态过渡元素的钙化物及其取代衍生物仍然是一类研究较少的化合物。作为一种新型二维半导体,二硫化铼具有许多独特的特征和巨大的应用潜力。这是因为它具有不同寻常的结构和独特的各向异性。二硫化铼存在弱层间键和独特的扭曲八面体(1T)结构,这表明有可能在其基础上产生新的相。这项工作的目的是获得并研究 Re(IV)S2-Ti(IV)S2、Re(IV)S2-Mo(IV)S2 和 Re(IV)S2-W(IV)S2 体系中的相。样品是在真空中通过高温固相安瓿合成获得的。研究使用了 X 射线相分析和 X 射线光电子能谱。确定了所得体系中固溶体、夹杂物和两相区的存在区域,获得了新相的衍射图样并计算了晶格参数。根据核心电子与原子核结合能的相关数据,研究显示了元素合成后的价态。研究还证实,合成后得到的所有相都含有氧化态(IV)的过渡元素。在富含铼的区域形成了插层固溶体,而在靠近二硫化钛和二硫化钼的区域则形成了插层相。在 ReS2-WS2 系统中,有一个固溶体区域,包括 30、50 和 70 摩尔%的二硫化铼。它们的结构是对原始成分结构的多晶型修正。在氧化态(+IV)的这些相中,铼、钼和钨的存在得到了证实。所获得的有关二钴化物体系中相形成的数据可实际用于制造具有独特电子、磁性和光学特性的材料,其应用范围十分广泛。
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引用次数: 0
Methylation of a group of microRNA genes as a marker for the diagnosis and prognosis of non-small cell lung cancer 一组微RNA基因的甲基化作为非小细胞肺癌诊断和预后的标志物
Pub Date : 2024-07-06 DOI: 10.32362/2410-6593-2024-19-3-232-239
V. Loginov, M. Gubenko, A. Burdennyy, I. Pronina, P. Postnikov, Yu. A. Efimova, F. V. Radus, E. S. Mochalova, T. Kazubskaya
Objectives. Lung cancer, representing a difficult-to-diagnose heterogeneous malignant neoplasm, is characterized by an asymptomatic course up to late stages, a high incidence of adverse outcomes, and a high probability of metastasis. Its most common form is non-small cell lung cancer (NSCLC). Recent studies have demonstrated a significant role of non-coding RNAs—in particular, microRNAs—in the development of NSCLC. MicroRNAs, which function as post-transcriptional regulators of the expression of protein-coding genes, including those associated with oncogenesis, are involved in the processes of cell proliferation, differentiation, and apoptosis. One of the approaches for regulating the expression of microRNAs themselves is to change the methylation of the CpG island adjacent to the microRNA gene or overlapping it. It has been shown that microRNA genes are several times more likely to undergo methylation than protein-coding genes. The aim of the present work is to study changes in the level of methylation of a number of microRNA genes and compile a potential panel of markers for the diagnosis and prognosis of NSCLC.Methods. Samples of NSCLC tumors were collected and clinically characterized at the Blokhin National Medical Research Center of Oncology, Ministry of Health of the Russian Federation, Moscow, Russia. High-molecular-weight DNA was isolated from tissues using a standard method. The level of methylation was analyzed using bisulfite conversion of DNA and quantitative methyl-specific polymerase chain reaction with real-time detection. The significance of differences between the studied groups was assessed by the nonparametric Mann–Whitney U test for independent samples. Differences were considered significant at p < 0.05.Results. The analysis of methylation levels of microRNA genes revealed a significant (p < 0.05) increase in the methylation level of eight microRNA genes: MIR124-1/2/3, MIR125В-1, MIR129-2, MIR137, MIR375, MIR1258, and MIR339 (p < 0.01, false discovery rate ≤ 0.25). On the basis of receiver operating characteristic analysis, a panel of markers is proposed for the diagnosis of NSCLC according to the nature of methylation of the studied microRNA genes in the tumor and in the normal tissue.Conclusions. Our results, which contribute to the understanding of molecular mechanisms involved in NSCLC development, can be used in the development of new diagnostic and prognostic approaches in clinical oncology.
目的。肺癌是一种难以诊断的异质性恶性肿瘤,其特点是晚期无症状、不良后果发生率高、转移概率高。其最常见的形式是非小细胞肺癌(NSCLC)。最近的研究表明,非编码 RNA(尤其是 microRNA)在 NSCLC 的发展过程中起着重要作用。微RNA是蛋白质编码基因(包括与肿瘤发生相关的基因)表达的转录后调节因子,参与细胞增殖、分化和凋亡过程。调节 microRNA 自身表达的方法之一是改变与 microRNA 基因相邻或重叠的 CpG 岛的甲基化。研究表明,microRNA 基因发生甲基化的几率是蛋白质编码基因的几倍。本研究的目的是研究一些 microRNA 基因甲基化水平的变化,并为 NSCLC 的诊断和预后编制一个潜在的标记物小组。NSCLC肿瘤样本由俄罗斯联邦卫生部布洛金国家肿瘤医学研究中心(位于俄罗斯莫斯科)收集并进行临床鉴定。采用标准方法从组织中分离出高分子量 DNA。利用 DNA 的亚硫酸氢盐转化和实时检测的定量甲基特异性聚合酶链反应分析甲基化水平。研究组间差异的显著性通过独立样本非参数曼-惠特尼 U 检验进行评估。P<0.05为差异显著。对 microRNA 基因甲基化水平的分析表明,8 个 microRNA 基因的甲基化水平显著增加(p < 0.05):MIR124-1/2/3、MIR125В-1、MIR129-2、MIR137、MIR375、MIR1258和MIR339(P<0.01,误发现率≤0.25)。在接受者操作特征分析的基础上,根据所研究的microRNA基因在肿瘤和正常组织中甲基化的性质,提出了一组用于诊断NSCLC的标记物。我们的研究结果有助于了解 NSCLC 发病的分子机制,可用于开发新的临床肿瘤学诊断和预后方法。
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引用次数: 0
Development of technology for culturing a cell line producing a single-domain antibody fused with the Fc fragment of human IgG1 开发培养产生与人类 IgG1 的 Fc 片段融合的单域抗体的细胞系的技术
Pub Date : 2024-07-06 DOI: 10.32362/2410-6593-2024-19-3-240-257
D. S. Polyansky, E. I. Ryabova, A. A. Derkaev, N. S. Starkov, I. S. Kashapova, D. Shcheblyakov, A. P. Karpov, I. Esmagambetov
Objectives. To develop an effective technology for the cultivation of Chinese hamster ovary (CHO) cells stably producing GamP2C5 antibody which is a component I of the GamCoviMab candidate drug for emergency prevention and therapy of  infection caused by SARS-CoV-2 virus; to select optimal cultivation parameters and to scale this technology in production.Methods. The study was performed on CHO GamP2C5 (clone 78) cell culture, producing a single-domain antibody fused to the Fc fragment of human IgG1 GamP2C5. Different culture media and supplements were used. Cells were cultured in Erlenmeyer flasks, Biostat® RM 20 wave-mixed bioreactor, Ambr® 250 mini bioreactors, STR 200 stirred-tank bioreactor.Results. Using molecular-genetic and biotechnological methods, a stable clone producer of CHO GamP2C5 antibody, clone 78, was obtained. Then a technique was worked out for the cultivation of the obtained clone producer on different culture media. The most suitable cultivation regimes, culture media, and optimal supplements were selected. This technology was tested in laboratory conditions in a 10-L reactor, and then successfully scaled up for production at the MedGamal Branch of the Gamaleya National Research Center for Epidemiology and Microbiology.Conclusions. This study demonstrates the fundamental feasibility of developing and scaling up a culture technology, in order to produce a drug based on a modified single-domain antibody with virus neutralizing activity against different strains of SARS-CoV-2 virus.
目的开发一种培养中国仓鼠卵巢(CHO)细胞稳定生产 GamP2C5 抗体的有效技术,该抗体是用于紧急预防和治疗 SARS-CoV-2 病毒感染的 GamCoviMab 候选药物的 I 组份;选择最佳培养参数并将该技术规模化生产。研究在 CHO GamP2C5(克隆 78)细胞培养物上进行,生产融合了人类 IgG1 GamP2C5 的 Fc 片段的单域抗体。使用了不同的培养基和补充剂。细胞在 Erlenmeyer 烧瓶、Biostat® RM 20 波混合生物反应器、Ambr® 250 迷你生物反应器和 STR 200 搅拌槽生物反应器中培养。利用分子遗传学和生物技术方法,获得了 CHO GamP2C5 抗体的稳定克隆生产者克隆 78。然后,研究了在不同培养基上培养克隆生产者的技术。选出了最合适的培养方案、培养基和最佳补充剂。这项技术在实验室条件下的 10 升反应器中进行了测试,然后在加马勒亚国家流行病学和微生物学研究中心的 MedGamal 分部成功地扩大了生产规模。这项研究证明了开发和扩大培养技术的基本可行性,以便生产出一种基于改良的单域抗体的药物,这种抗体具有中和病毒的活性,可抵抗不同的 SARS-CoV-2 病毒株。
{"title":"Development of technology for culturing a cell line producing a single-domain antibody fused with the Fc fragment of human IgG1","authors":"D. S. Polyansky, E. I. Ryabova, A. A. Derkaev, N. S. Starkov, I. S. Kashapova, D. Shcheblyakov, A. P. Karpov, I. Esmagambetov","doi":"10.32362/2410-6593-2024-19-3-240-257","DOIUrl":"https://doi.org/10.32362/2410-6593-2024-19-3-240-257","url":null,"abstract":"Objectives. To develop an effective technology for the cultivation of Chinese hamster ovary (CHO) cells stably producing GamP2C5 antibody which is a component I of the GamCoviMab candidate drug for emergency prevention and therapy of  infection caused by SARS-CoV-2 virus; to select optimal cultivation parameters and to scale this technology in production.Methods. The study was performed on CHO GamP2C5 (clone 78) cell culture, producing a single-domain antibody fused to the Fc fragment of human IgG1 GamP2C5. Different culture media and supplements were used. Cells were cultured in Erlenmeyer flasks, Biostat® RM 20 wave-mixed bioreactor, Ambr® 250 mini bioreactors, STR 200 stirred-tank bioreactor.Results. Using molecular-genetic and biotechnological methods, a stable clone producer of CHO GamP2C5 antibody, clone 78, was obtained. Then a technique was worked out for the cultivation of the obtained clone producer on different culture media. The most suitable cultivation regimes, culture media, and optimal supplements were selected. This technology was tested in laboratory conditions in a 10-L reactor, and then successfully scaled up for production at the MedGamal Branch of the Gamaleya National Research Center for Epidemiology and Microbiology.Conclusions. This study demonstrates the fundamental feasibility of developing and scaling up a culture technology, in order to produce a drug based on a modified single-domain antibody with virus neutralizing activity against different strains of SARS-CoV-2 virus.","PeriodicalId":12215,"journal":{"name":"Fine Chemical Technologies","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-07-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141672893","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
PROTAC® technology and potential for its application in infection control PROTAC® 技术及其在感染控制中的应用潜力
Pub Date : 2024-07-06 DOI: 10.32362/2410-6593-2024-19-3-214-231
M. A. Zakharova, M. Chudinov
Objectives. To describe the pharmaceutical technology of controlled degradation of protein molecules (PROTAC®, Proteolysis Targeting Chimera), approaches to the design of the PROTAC® molecule, methods of ligand and linker selection and synthesis, as well as the application of this technology in dealing with a variety of diseases and the possible limitations of its use.Results. The review covers 77 sources, mostly from 2020–2023. The review outlines the principle of PROTAC® technology: the construction of a chimeric molecule consisting of three fragments. One fragment specifically binds to the biotarget, another recruits the proteolytic system of the host cell, and the third binds them together. The main areas of the current development of the technology are described herein, as well as the opportunities and limitations of chimeric molecules in the fight against different types of infectious diseases.Conclusion. The potential to use PROTAC® technology to combat cancer as well as neurodegenerative, autoimmune, and infectious diseases is shown.
目的介绍蛋白质分子可控降解制药技术(PROTAC®,Proteolysis Targeting Chimera)、PROTAC® 分子的设计方法、配体和连接体的选择与合成方法,以及该技术在治疗各种疾病方面的应用和可能的局限性。该综述涵盖 77 个资料来源,大部分来自 2020-2023 年。综述概述了 PROTAC® 技术的原理:构建由三个片段组成的嵌合分子。一个片段与生物靶标特异性结合,另一个片段招募宿主细胞的蛋白水解系统,第三个片段将它们结合在一起。本文介绍了该技术目前发展的主要领域,以及嵌合分子在抗击不同类型传染病方面的机遇和局限性。利用 PROTAC® 技术防治癌症、神经退行性疾病、自身免疫性疾病和传染性疾病的潜力。
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引用次数: 0
L-Ornithine derivatives with structural hetaryl and alkyl moiety: Synthesis and antibacterial activity 具有结构性 hetaryl 和烷基的 L-鸟氨酸衍生物:合成与抗菌活性
Pub Date : 2024-07-05 DOI: 10.32362/2410-6593-2024-19-3-202-213
T. G. Bodrova, U. A. Budanova, Y. Sebyakin
Objectives. Cationic amphiphiles and antimicrobial peptidomimetics are widely investigated as antibacterial agents due to their membrane-active mechanism of action. Particular attention is focused on the rational design of compounds in this class to achieve high antimicrobial activity. The aim of the present work is to synthesize bivalent cationic amphiphiles with L-ornithine as a branching element and evaluate the effectiveness of their antibacterial action. The compounds differ in terms of hydrophobicity due to the variation of N-terminal aliphatic amino acids in the polar block and alternation of dialkyl and alkyl-hetaryl radicals in the lipophilic block.Methods. For the synthesis of nonpolar fragments of amphiphiles, methods for the alkylation of amines with alkyl bromides in the presence of carbonate salts were used. The formation of amide bonds of L-ornithine derivatives with amino acids was carried out using the carbodiimide method. For the reaction products recovery from the reaction mixture, column chromatography on silica gel and aluminum oxide activated Brockmann Grade II was used. The antimicrobial activity of the synthesized compounds against gram-positive B. subtilis 534 and gram-negative E. coli M17 bacterial strains was evaluated. Minimum inhibitory concentration (MIC) values were recorded using a serial microdilution method in a nutrient medium.Results. Developed schemes for the preparation of bivalent cationic amphiphiles based on L-ornithine derivatives are presented. Differences in the structure of aliphatic amino acids (glycine, β-alanine, γ-aminobutyric acid (GABA)), in the length of alkyl radicals (C8, C12), or in the presence of an indole moiety, were used in the design of target compounds. The high antibacterial activity of the synthesized compounds was demonstrated. The most active compounds were lipoamino acids with terminal GABA residues and asymmetrical non-polar block (tryptamyl–dodecylamine). The MIC values were 0.39 μg/mL for gram-positive bacteria and 1.56 μg/mL for gram-negative bacteria. A GABA derivative with a symmetrical lipophilic moiety based on dioctylamine demonstrated activity with an MIC of 0.78 μg/mL against B. subtilis and 3.12 μg/mL against E. coli.Conclusions. Nine new lipoamino acid cationic bivalent amphiphiles based on L-ornithine were synthesized. The structure of the obtained compounds was confirmed by nuclear magnetic resonance 1H spectroscopy and mass spectrometry data. Leading compounds in antimicrobial activity against both gram-positive and gram-negative strains of bacteria were determined. The influence of the degree of lipophilicity in the asymmetric nonpolar block on the level of exhibited antimicrobial activity is demonstrated.
目的。阳离子双亲化合物和抗菌拟肽化合物因其膜活性作用机制而被广泛研究用作抗菌剂。人们特别关注如何合理设计这类化合物,以获得高抗菌活性。本研究旨在合成以 L-鸟氨酸为分支元素的二价阳离子双亲化合物,并评估其抗菌作用的有效性。由于极性嵌段中 N 端脂肪族氨基酸的变化以及亲油嵌段中二烷基和烷基-芳香基的交替变化,这些化合物在疏水性方面存在差异。为了合成双亲化合物的非极性片段,采用了在碳酸盐存在下用烷基溴化物烷基化胺的方法。L- 鸟氨酸衍生物与氨基酸形成酰胺键的过程采用碳二亚胺法。为了从反应混合物中回收反应产物,采用了硅胶和氧化铝活化 Brockmann 二级柱色谱法。评估了合成化合物对革兰氏阳性枯草杆菌 534 和革兰氏阴性大肠杆菌 M17 菌株的抗菌活性。在营养培养基中采用序列微量稀释法记录最低抑菌浓度(MIC)值。介绍了基于 L-鸟氨酸衍生物的二价阳离子双亲化合物的制备方案。在设计目标化合物时,利用了脂肪族氨基酸(甘氨酸、β-丙氨酸、γ-氨基丁酸 (GABA))结构、烷基长度(C8、C12)或吲哚分子存在的差异。合成的化合物具有很高的抗菌活性。活性最强的化合物是具有 GABA 末端残基和不对称非极性嵌段(色胺-十二胺)的脂氨基酸。对革兰氏阳性菌的 MIC 值为 0.39 μg/mL,对革兰氏阴性菌的 MIC 值为 1.56 μg/mL。一种以二辛胺为基础、具有对称亲脂分子的 GABA 衍生物对枯草杆菌的 MIC 为 0.78 μg/mL,对大肠杆菌的 MIC 为 3.12 μg/mL。以 L-鸟氨酸为基础合成了九种新的脂氨基酸阳离子二价双亲化合物。核磁共振 1H 光谱和质谱数据证实了所获化合物的结构。测定了主要化合物对革兰氏阳性和革兰氏阴性菌株的抗菌活性。不对称非极性嵌段的亲脂程度对抗菌活性水平的影响得到了证实。
{"title":"L-Ornithine derivatives with structural hetaryl and alkyl moiety: Synthesis and antibacterial activity","authors":"T. G. Bodrova, U. A. Budanova, Y. Sebyakin","doi":"10.32362/2410-6593-2024-19-3-202-213","DOIUrl":"https://doi.org/10.32362/2410-6593-2024-19-3-202-213","url":null,"abstract":"Objectives. Cationic amphiphiles and antimicrobial peptidomimetics are widely investigated as antibacterial agents due to their membrane-active mechanism of action. Particular attention is focused on the rational design of compounds in this class to achieve high antimicrobial activity. The aim of the present work is to synthesize bivalent cationic amphiphiles with L-ornithine as a branching element and evaluate the effectiveness of their antibacterial action. The compounds differ in terms of hydrophobicity due to the variation of N-terminal aliphatic amino acids in the polar block and alternation of dialkyl and alkyl-hetaryl radicals in the lipophilic block.Methods. For the synthesis of nonpolar fragments of amphiphiles, methods for the alkylation of amines with alkyl bromides in the presence of carbonate salts were used. The formation of amide bonds of L-ornithine derivatives with amino acids was carried out using the carbodiimide method. For the reaction products recovery from the reaction mixture, column chromatography on silica gel and aluminum oxide activated Brockmann Grade II was used. The antimicrobial activity of the synthesized compounds against gram-positive B. subtilis 534 and gram-negative E. coli M17 bacterial strains was evaluated. Minimum inhibitory concentration (MIC) values were recorded using a serial microdilution method in a nutrient medium.Results. Developed schemes for the preparation of bivalent cationic amphiphiles based on L-ornithine derivatives are presented. Differences in the structure of aliphatic amino acids (glycine, β-alanine, γ-aminobutyric acid (GABA)), in the length of alkyl radicals (C8, C12), or in the presence of an indole moiety, were used in the design of target compounds. The high antibacterial activity of the synthesized compounds was demonstrated. The most active compounds were lipoamino acids with terminal GABA residues and asymmetrical non-polar block (tryptamyl–dodecylamine). The MIC values were 0.39 μg/mL for gram-positive bacteria and 1.56 μg/mL for gram-negative bacteria. A GABA derivative with a symmetrical lipophilic moiety based on dioctylamine demonstrated activity with an MIC of 0.78 μg/mL against B. subtilis and 3.12 μg/mL against E. coli.Conclusions. Nine new lipoamino acid cationic bivalent amphiphiles based on L-ornithine were synthesized. The structure of the obtained compounds was confirmed by nuclear magnetic resonance 1H spectroscopy and mass spectrometry data. Leading compounds in antimicrobial activity against both gram-positive and gram-negative strains of bacteria were determined. The influence of the degree of lipophilicity in the asymmetric nonpolar block on the level of exhibited antimicrobial activity is demonstrated.","PeriodicalId":12215,"journal":{"name":"Fine Chemical Technologies","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-07-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141676797","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
Effect of 2-hexanol and methanol on the one-pot process of dehydration and alkoxycarbonylation for the synthesis of esters 2- 己醇和甲醇对脱水和烷氧羰基化一步法合成酯的影响
Pub Date : 2024-07-05 DOI: 10.32362/2410-6593-2024-19-3-192-201
N. Sevostyanova, S. Batashev, A. S. Rodionova, D. K. Kozlenko
Objectives. To study the possibility of one-pot synthesis (combination of two processes in one reactor) for the following pairs of processes: (1) dehydration of 2-hexanol and isomerizing alkoxycarbonylation of the resulting 2-hexene, in order to obtain 2-hexyl heptanoate, and (2) dehydration of 2-hexanol and isomerizing methoxycarbonylation of the resulting 2-hexene, in order to obtain methyl esters of C7 carboxylic acids. To investigate the effect of the concentrations of 2-hexanol and methanol on the rate of the one-pot synthesis.Methods. One-pot synthesis was studied in a toluene medium in a steel batch reactor designed to operate at elevated pressure and equipped with a glass insert, a magnetic stirrer, a sampler, and gas input and discharge devices. Samples of the reaction mass were taken during the combined process and were analyzed by means of gas–liquid chromatography with a flame ionization detector.Results. The possibility of one-pot combination was demonstrated for 2-hexanol dehydration catalyzed by methanesulfonic acid, as well as for the isomerizing alkoxycarbonylation of the resulting 2-hexene with 2-hexanol and CO, catalyzed by the Pd(PPh3)2Cl2–XANTPHOS–methanesulfonic acid system. The dependencies of the rates of the dehydration of 2-hexanol and the formation of esters of C7 carboxylic acids on the concentration of 2-hexanol were shown to pass through a maximum. The possibility of the one-pot process was proved for the synthesis of esters from 2-hexanol, methanol, and CO with the predominant formation of heptanoic acid esters in the presence of the above catalytic system. The rates of dehydration of 2-hexanol and the formation of 2-hexyl esters of C7 carboxylic acids were found to decrease with increasing the concentration of methanol in the reaction mass. Under mild conditions (temperature 115°C, CO pressure 3 MPa) with the addition of methanol, the total fraction of 2-hexyl and methyl heptanoic acid esters among C7 carboxylic acid esters was determined to be 85.5%.Conclusions. The reactions of intramolecular acid–catalytic dehydration of 2-hexanol and isomerizing alkoxycarbonylation of the resulting 2-hexene, catalyzed by the Pd(PPh3)2Cl2–XANTPHOS–methanesulfonic acid system, can be performed as a one-pot process. Methanesulfonic acid simultaneously functions as a catalyst for the dehydration of 2-hexanol and a cocatalyst for the palladium–phosphine system for the alkoxycarbonylation of hexenes. In the presence of the Pd(PPh3) 2Cl2–XANTPHOS–methanesulfonic acid catalytic system, processes for the synthesis of heptanoic acid esters from 2-hexanol, methanol, and CO can be combined within one reactor. An increase in the methanol concentration negatively affects the rate of the dehydration of 2-hexanol and the formation of 2-hexyl esters of C7 carboxylic acids. A small amount of methanol in the reaction mass leads to an increase in the fraction of heptanoic acid esters among C7 carboxylic acid esters.
目标: 研究以下几种工艺的单锅合成(在一个反应器中结合两种工艺)的可能性研究以下几种工艺进行一次合成(在一个反应器中结合两种工艺)的可能性:(1) 2-己醇脱水,并对生成的 2-己烯进行异构化烷氧基羰基化反应,以获得庚酸 2-己酯;(2) 2-己醇脱水,并对生成的 2-己烯进行异构化甲氧基羰基化反应,以获得 C7 羧酸甲酯。研究 2-己醇和甲醇的浓度对单锅合成速率的影响。单锅合成是在甲苯介质中,在钢制间歇反应器中进行的,该反应器设计为在高压下运行,并配备了玻璃插件、磁力搅拌器、取样器以及气体输入和排放装置。在组合过程中对反应物进行取样,并通过带有火焰离子化检测器的气液相色谱法进行分析。甲磺酸催化的 2- 己醇脱水以及 Pd(PPh3)2Cl2-XANTPHOS-Methanesulfonic acid 系统催化的 2- 己烯与 2- 己醇和 CO 的异构化烷氧基羰基化反应都证明了单锅组合的可能性。结果表明,2-己醇的脱水速率和 C7 羧酸酯的生成速率与 2-己醇浓度的关系达到了最大值。在上述催化体系存在的情况下,证明了以 2-己醇、甲醇和 CO 为原料合成酯类的单锅工艺的可能性,并主要生成了庚酸酯。研究发现,随着反应物中甲醇浓度的增加,2-己醇的脱水率和 C7 羧酸 2-己酯的生成率都会降低。在加入甲醇的温和条件下(温度 115°C,CO 压力 3 兆帕),C7 羧酸酯中 2-己基和甲基庚酸酯的总比例为 85.5%。在 Pd(PPh3)2Cl2-XANTPHOS-甲磺酸体系的催化下,2-己醇的分子内酸催化脱水反应和生成的 2-己烯的异构化烷氧基羰基化反应可作为一锅工艺进行。甲磺酸既是 2-己醇脱水的催化剂,又是钯膦体系进行己烯烷氧基羰基化的助催化剂。在 Pd(PPh3) 2Cl2-XANTPHOS-Methanesulfonic acid 催化体系存在的情况下,从 2-己醇、甲醇和 CO 合成庚酸酯的过程可在一个反应器中进行。甲醇浓度的增加会对 2-己醇的脱水速率和 C7 羧酸 2-己酯的生成产生负面影响。反应物中少量甲醇会导致 C7 羧酸酯中庚酸酯的比例增加。
{"title":"Effect of 2-hexanol and methanol on the one-pot process of dehydration and alkoxycarbonylation for the synthesis of esters","authors":"N. Sevostyanova, S. Batashev, A. S. Rodionova, D. K. Kozlenko","doi":"10.32362/2410-6593-2024-19-3-192-201","DOIUrl":"https://doi.org/10.32362/2410-6593-2024-19-3-192-201","url":null,"abstract":"Objectives. To study the possibility of one-pot synthesis (combination of two processes in one reactor) for the following pairs of processes: (1) dehydration of 2-hexanol and isomerizing alkoxycarbonylation of the resulting 2-hexene, in order to obtain 2-hexyl heptanoate, and (2) dehydration of 2-hexanol and isomerizing methoxycarbonylation of the resulting 2-hexene, in order to obtain methyl esters of C7 carboxylic acids. To investigate the effect of the concentrations of 2-hexanol and methanol on the rate of the one-pot synthesis.Methods. One-pot synthesis was studied in a toluene medium in a steel batch reactor designed to operate at elevated pressure and equipped with a glass insert, a magnetic stirrer, a sampler, and gas input and discharge devices. Samples of the reaction mass were taken during the combined process and were analyzed by means of gas–liquid chromatography with a flame ionization detector.Results. The possibility of one-pot combination was demonstrated for 2-hexanol dehydration catalyzed by methanesulfonic acid, as well as for the isomerizing alkoxycarbonylation of the resulting 2-hexene with 2-hexanol and CO, catalyzed by the Pd(PPh3)2Cl2–XANTPHOS–methanesulfonic acid system. The dependencies of the rates of the dehydration of 2-hexanol and the formation of esters of C7 carboxylic acids on the concentration of 2-hexanol were shown to pass through a maximum. The possibility of the one-pot process was proved for the synthesis of esters from 2-hexanol, methanol, and CO with the predominant formation of heptanoic acid esters in the presence of the above catalytic system. The rates of dehydration of 2-hexanol and the formation of 2-hexyl esters of C7 carboxylic acids were found to decrease with increasing the concentration of methanol in the reaction mass. Under mild conditions (temperature 115°C, CO pressure 3 MPa) with the addition of methanol, the total fraction of 2-hexyl and methyl heptanoic acid esters among C7 carboxylic acid esters was determined to be 85.5%.Conclusions. The reactions of intramolecular acid–catalytic dehydration of 2-hexanol and isomerizing alkoxycarbonylation of the resulting 2-hexene, catalyzed by the Pd(PPh3)2Cl2–XANTPHOS–methanesulfonic acid system, can be performed as a one-pot process. Methanesulfonic acid simultaneously functions as a catalyst for the dehydration of 2-hexanol and a cocatalyst for the palladium–phosphine system for the alkoxycarbonylation of hexenes. In the presence of the Pd(PPh3) 2Cl2–XANTPHOS–methanesulfonic acid catalytic system, processes for the synthesis of heptanoic acid esters from 2-hexanol, methanol, and CO can be combined within one reactor. An increase in the methanol concentration negatively affects the rate of the dehydration of 2-hexanol and the formation of 2-hexyl esters of C7 carboxylic acids. A small amount of methanol in the reaction mass leads to an increase in the fraction of heptanoic acid esters among C7 carboxylic acid esters.","PeriodicalId":12215,"journal":{"name":"Fine Chemical Technologies","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-07-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141676850","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
Concentration of heavy metal ions from aqueous media under dynamic conditions using a composite sorbent based on chitosan and silica 使用基于壳聚糖和二氧化硅的复合吸附剂在动态条件下浓缩水介质中的重金属离子
Pub Date : 2024-07-05 DOI: 10.32362/2410-6593-2024-19-3-183-191
V. A. Gabrin, T. Nikiforova, V. Kozlov, P. Razgovorov
Objectives. The study set out to investigate the sorption, toxicological, and regeneration properties of a composite sorbent based on chitosan hydrogel and unsuspended silicon dioxide (chitosan–colloidal silica), which manifest themselves under dynamic conditions of purification of aqueous solutions, as a means of removing heavy metal ions.Methods. The total dynamic exchange capacity of a chitosan–colloidal silica composite sorbent was evaluated under dynamic sorption conditions by passing solutions containing Zn(II), Cd(II), Cu(II), and Cr(III) ions having a concentration of 240–251 mg/L through a fixed sorption bed. The method for determining acute toxicity using daphnia (Daphnia magna Straus) is based on the direct calculation of the mortality of daphnia exposed to toxic substances contained in the test aqueous extract in comparison with a reference culture in samples that do not contain toxic substances. The regeneration ability of the sorbent was assessed by counting the number of sorption–desorption cycles using 0.1 M NaOH and 0.1 M NaHCO3 eluents, as well as aqueous solutions of H2O2 (1 and 3%).Results. The effectiveness of the chitosan–colloidal silica composite sorbent in the process of dynamic purification of aqueous media to remove Cu(II), Zn(II), Cd(II), and Cr(III) ions was established. After determining the times of ion breakthrough and saturation of the developed sorbent, its dynamic exchange capacity was calculated by processing the kinetic curves of sorption of heavy metal ions under dynamic conditions. The results of regeneration of the sorbent were presented in the context of the possibility of its reuse. It is shown that the sorbent can withstand up to five sorption–desorption cycles while maintaining a level copper cation extraction above 90%.Conclusions. Analysis of the kinetic curves demonstrated that the driving force behind the removal of heavy metals from aqueous media by means of the obtained sorbent is the external diffusion mass transfer of ions from the mobile phase of the solution. Biotesting of samples showed that the developed chitosan-based sorbent does not have acute toxicity.
研究目的本研究旨在探究一种基于壳聚糖水凝胶和未悬浮二氧化硅(壳聚糖-胶体二氧化硅)的复合吸附剂在水溶液动态净化条件下的吸附、毒理学和再生特性,以此作为去除重金属离子的一种手段。在动态吸附条件下,将含有锌(II)、镉(II)、铜(II)和铬(III)离子的浓度为 240-251 毫克/升的溶液通过固定吸附床,评估壳聚糖-胶体二氧化硅复合吸附剂的总动态交换能力。利用水蚤(Daphnia magna Straus)测定急性毒性的方法是直接计算水蚤暴露于试验水提取物中的有毒物质后的死亡率,并与不含有毒物质的样品中的参考培养物进行比较。通过计算使用 0.1 M NaOH 和 0.1 M NaHCO3 洗脱液以及 H2O2(1% 和 3%)水溶液进行吸附-解吸循环的次数来评估吸附剂的再生能力。确定了壳聚糖-硅胶复合吸附剂在水介质动态净化过程中去除 Cu(II)、Zn(II)、Cd(II) 和 Cr(III) 离子的有效性。在确定了所开发吸附剂的离子突破时间和饱和时间后,通过处理动态条件下重金属离子吸附动力学曲线,计算了其动态交换容量。根据吸附剂的再利用可能性,介绍了吸附剂的再生结果。结果表明,吸附剂可以承受多达五次吸附-解吸循环,同时保持高于 90% 的阳离子铜萃取率。动力学曲线分析表明,利用所获得的吸附剂去除水介质中重金属的驱动力是溶液流动相中离子的外部扩散传质。样品的生物测试表明,所开发的壳聚糖基吸附剂没有急性毒性。
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引用次数: 0
Congratulations to Academician Ivan Aleksandrovich Novakov on his 75th birthday! 祝贺伊万-亚历山大罗维奇-诺瓦科夫院士 75 岁生日!
Pub Date : 2024-07-05 DOI: 10.32362/2410-6593-2024-19-3-181-182
A. Editorial
.
.
{"title":"Congratulations to Academician Ivan Aleksandrovich Novakov on his 75th birthday!","authors":"A. Editorial","doi":"10.32362/2410-6593-2024-19-3-181-182","DOIUrl":"https://doi.org/10.32362/2410-6593-2024-19-3-181-182","url":null,"abstract":"<jats:p>.</jats:p>","PeriodicalId":12215,"journal":{"name":"Fine Chemical Technologies","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-07-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141675476","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
Obtaining chitosan sulfate nanoparticles in an aqueous medium and their colloidal protection with polysaccharides 在水介质中获得硫酸壳聚糖纳米颗粒并用多糖对其进行胶体保护
Pub Date : 2024-05-04 DOI: 10.32362/2410-6593-2024-19-2-111-126
V. Erasov, Yu. O. Maltseva
Objectives. To develop a method to obtain a hydrosol of the salt of chitosan with sulfuric acid—chitosanium sulfate (ChS) hydrosol—and to study the effect of various water-soluble polysaccharides on its stability over time, as well as its resistance to indifferent and non-indifferent electrolytes.Methods. κ-Carrageenan, sodium alginate (SA), and xanthan were used as polymers which perform the function of colloidal protection for ChS nanoparticles. Capillary viscometry was used to study the viscosity of polymer solutions, their molecular weight, and their adsorption on ChS. The stability of the sols over time and their resistance to indifferent and non-indifferent electrolytes were evaluated photometrically. The hydrosol particle size was determined by means of dynamic light scattering.Results. On the surface of ChS, κ-carrageenan is adsorbed most strongly over a wide range of concentrations. The graphs of the dependencies of the relative change in the turbidity of sols with the addition of various polysaccharides on their weight concentration at a sol lifetime of 2 days have the shape of curves with a maximum. Sols with the addition of 0.0125% SA and κ-carrageenan in the range of 0.04% have the greatest stability over time. According to dynamic light scattering data, the average particle size of freshly prepared sols with the addition of the polymers to ensure their greatest stability over time are 10.8 nm and 14.6 nm, respectively. For freshly prepared sols without polysaccharides, this size is 24.8 nm. The hydrosol coagulation threshold with an indifferent electrolyte (NaCl) is 9.3 times higher than that with a non-indifferent electrolyte (Na2SO4). κ-Carrageenan and SA protect the hydrosol from coagulation with an indifferent electrolyte (NaCl) at all their used amounts. At the same polymer concentrations, no protection from coagulation with a non-indifferent electrolyte (Na2SO4) was observed.Conclusions. A method was developed to obtain ChS hydrosol with a positive particle charge. The stability of ChS sols over time was studied both without and with the addition of SA, κ-carrageenan, and xanthan. Sol coagulation thresholds with indifferent and non-indifferent electrolytes, as well as the protective numbers for κ-carrageenan and SA against the coagulation of hydrosols with these electrolytes, were established. The mechanism of stability of sols at certain concentrations of water-soluble polysaccharides was explained using data on the adsorption of these polysaccharides on the surface of chitosan treated with a solution of sulfuric acid. Based on the results of the work, it can be concluded that SA and κ-carrageenan can be used for the efficient stabilization of ChS hydrosols over time and for the colloidal protection of ChS from coagulation with sodium chloride.
研究目的采用κ-卡拉胶、海藻酸钠(SA)和黄原胶作为聚合物,对 ChS 纳米粒子进行胶体保护。使用毛细管粘度计研究了聚合物溶液的粘度、分子量及其对 ChS 的吸附。用光度计评估了溶胶的长期稳定性及其对无差异和非无差异电解质的耐受性。通过动态光散射法测定了水溶胶的粒度。在 ChS 表面,κ-卡拉胶在很大浓度范围内吸附力最强。在溶胶寿命为 2 天的情况下,加入各种多糖的溶胶浊度相对变化与重量浓度的关系曲线具有最大值曲线的形状。添加 0.0125% 的 SA 和 0.04% 的 κ 卡拉胶的溶胶随着时间的推移具有最大的稳定性。根据动态光散射数据,添加了聚合物以确保其最大稳定性的新制备溶胶的平均粒径分别为 10.8 nm 和 14.6 nm。而未添加多糖的新制备溶胶的平均粒径为 24.8 nm。在无差异电解质(NaCl)中,水溶胶的凝结阈值是非无差异电解质(Na2SO4)的 9.3 倍。在聚合物浓度相同的情况下,没有观察到它们能防止无差异电解质(Na2SO4)的凝结。开发出了一种获得带正电荷颗粒的 ChS 水溶液的方法。在不添加或添加 SA、κ-卡拉胶和黄原胶的情况下,研究了 ChS 溶胶随时间变化的稳定性。确定了溶胶在无差异和非无差异电解质下的凝结阈值,以及κ-卡拉胶和南非黄原胶对水溶液在这些电解质下凝结的保护数。利用这些多糖在用硫酸溶液处理过的壳聚糖表面的吸附数据,解释了溶胶在一定浓度的水溶性多糖中的稳定性机理。根据这项工作的结果,可以得出结论:SA 和 κ- 卡拉胶可用于长期有效地稳定 ChS 水溶液,并为 ChS 提供胶体保护,防止其与氯化钠发生凝结。
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引用次数: 0
Effect of leakage of volatile synthesis products on silicon carbide yield in an electrothermal fluidized bed reactor 电热流化床反应器中挥发性合成产物的泄漏对碳化硅产量的影响
Pub Date : 2024-05-04 DOI: 10.32362/2410-6593-2024-19-2-163-173
V. S. Kuzevanov, S. Zakozhurnikov, G. Zakozhurnikova
Objectives. To calculate the effect of leakage of volatile synthesis products on silicon carbide yield in an electrothermal fluidized bed reactor, as well as to develop a general model of the synthesis of finely divided silicon carbide. This will be achieved by particularizing a mathematical model of leakage of volatile products of chemical reactions from the reaction volume of the reactor with the fluidizing inert gas.Methods. As a method to produce silicon carbide, synthesis in an electrothermal fluidized bed was studied. The model of leakage of volatile products was validated by comparing the calculation results with existing experimental data on the SiC synthesis in a hightemperature fluidized bed reactor. The comparison parameters were: mass yield of silicon carbide, and the total synthesis time in a reactor with batch loading of silicon dioxide into the reaction volume.Results. The value of the parameter p in the general model of SiC synthesis in a fluidized bed was established. The parameter p is equal to the ratio of the number of carbon-containing particles involved in the formation of SiO, to the total number of silicon dioxide particles. It also characterizes the composition of stable complexes of particles of the charge at various operating temperatures of the fluidized bed. The discrepancy between the calculated and experimental values of the masses of the synthesized silicon carbide was shown not to exceed 15.5% at a high temperature of the fluidized bed (T = 1800°C) and decreases with a decrease in the operating temperature to 4.7% at T = 1450°C.Conclusions. The general computational model for silicon carbide synthesis with a built-in procedure for calculating the leakage of volatile products of chemical reactions enables the variants of SiC production in electrothermal fluidized bed reactors to be analyzed. In this case, it is important to establish an energy-efficient working cycle without preliminary expensive experimental studies.
目标: 计算电热流化床反应器中挥发性合成产物的泄漏对碳化硅产量的影响,并建立精细碳化硅合成的一般模型。计算电热流化床反应器中挥发性合成产物泄漏对碳化硅产量的影响,并建立精细碳化硅合成的一般模型。这将通过将化学反应的挥发性产物从反应器的反应容积中随流化惰性气体泄漏的数学模型具体化来实现。研究了在电热流化床中合成碳化硅的方法。通过将计算结果与现有的在高温流化床反应器中合成碳化硅的实验数据进行比较,验证了挥发性产物的泄漏模型。比较参数为:碳化硅的质量产率,以及在反应器中将二氧化硅分批装入反应容积的总合成时间。确定了流化床合成碳化硅一般模型中参数 p 的值。参数 p 等于参与形成氧化硅的含碳粒子数与二氧化硅粒子总数之比。它还表征了在流化床不同工作温度下电荷颗粒稳定复合物的组成。结果表明,在流化床温度较高(T = 1800°C)时,合成碳化硅质量的计算值与实验值之间的差异不超过 15.5%,而随着工作温度的降低,在 T = 1450°C时,差异降低到 4.7%。碳化硅合成的通用计算模型内置了计算化学反应挥发产物泄漏的程序,可以分析电热流化床反应器中碳化硅生产的变体。在这种情况下,重要的是在不进行昂贵的初步实验研究的情况下建立一个节能的工作循环。
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Fine Chemical Technologies
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