Russian Journal of Inorganic Chemistry最新文献

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Size-Focusing Synthetic Process and Properties of [Au25Cu8(S-Adam)19(PPh3)5]+ Nanocluster 尺寸聚焦合成[Au25Cu8(S-Adam)19(PPh3)5]+ 纳米团簇的过程与性质

IF 2.1 3区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Russian Journal of Inorganic Chemistry

Pub Date : 2024-03-28 DOI: 10.1134/s0036023623603148

Fu Xuemei, Xiao Zuoyi, Yang Qianyu, Li Zhonghai, Li Yixuan, Zhang Qiang, Liu Songgang

Abstract

Compared with nanoparticles, nanoclusters have some unique properties, such as definite structure, surface effect, and quantum size effect. In this work, AuCu nanocluster protected by triphenylphosphine and adamantane mercaptan is synthesized and it is formulated to [Au₂₅Cu₈(S-Adam)₁₉(PPh₃)₅]⁺. With the characterization of UV-Vis absorption spectrum and Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF), the synthesis of [Au₂₅Cu₈(S-Adam)₁₉(PPh₃)₅]⁺ nanocluster is demonstrated to be a size-focusing process: polydisperse Au_mCu_n(S-Adam)_x(PPh₃)_y precursor with a size ranging from 900 Da to 2000 Da generates firstly and it transforms into [Au₂₅Cu₈(S-Adam)₁₉(PPh₃)₅]⁺ nanocluster in 3 days. TEM image demonstrates it is monodisperse distributing between 0.84 and 2.0 nm with an average size of 1.4 nm. TG shows a weight loss of 38.70% with ligands continuously breaking down between 200 and 330°C. Thermal stability test shows that it keeps well thermal stability at 40°C: the peaks of UV-Vis absorption spectrum gradually get weaken at 6 h and completely become a decaying curve at 8 h. This work provides a simple method to prepare AuCu nanocluster and affords new ideas for preparing Au-based alloy nanoclusters.

摘要与纳米颗粒相比，纳米团簇具有结构确定、表面效应和量子尺寸效应等独特性质。本研究合成了由三苯基膦和金刚烷硫醇保护的金铜纳米团簇，并配制成[Au25Cu8(S-Adam)19(PPh3)5]+。通过紫外-可见吸收光谱和基质辅助激光解吸电离飞行时间质谱（MALDI-TOF）的表征，证明了[Au25Cu8(S-Adam)19(PPh3)5]+ 纳米团簇的合成是一个尺寸聚焦过程：首先生成尺寸为 900 Da 至 2000 Da 的多分散 AumCun(S-Adam)x(PPh3)y 前驱体，然后在 3 天内将其转化为[Au25Cu8(S-Adam)19(PPh3)5]+ 纳米团簇。TEM 图像显示它是单分散的，分布在 0.84 至 2.0 nm 之间，平均尺寸为 1.4 nm。TG 显示，配体在 200 至 330°C 之间不断分解，重量损失为 38.70%。热稳定性测试表明，其在 40°C 下保持良好的热稳定性：紫外可见吸收光谱的峰值在 6 小时后逐渐减弱，在 8 小时后完全变成衰减曲线。

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引用次数: 0

Binding Studies of Novel Manganese Complexes to DNA 新型锰配合物与 DNA 的结合研究

IF 2.1 3区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Russian Journal of Inorganic Chemistry

Pub Date : 2024-03-28 DOI: 10.1134/s0036023623603033

B. Wang, X. Y. Ma, W. Yao, S. Y. Wu, Y. Zhang, W. Liu, E. J. Gao

Abstract

A new Mn(II) complex was designed and synthesized in hydrothermal conditions using phenylmalonic acid and phosphine as raw materials. The effective characterization method was single-crystal X-ray diffraction. Besides, the interaction with FS-DNA (fish sperm DNA) and the DNA binding constants of the complex were determined by UV spectroscopy. The results showed that it was a significant apoptotic effect on cancer cells; therefore, the synthesized Mn(II) complex is important for the treatment of cancer.

摘要以苯基丙二酸和膦为原料，在水热条件下设计并合成了一种新的锰(II)配合物。单晶 X 射线衍射是有效的表征方法。此外，还利用紫外光谱测定了复合物与 FS-DNA（鱼精 DNA）的相互作用以及 DNA 结合常数。结果表明，该复合物对癌细胞有明显的凋亡作用，因此对治疗癌症有重要意义。

引用次数: 0

Increasing the Water Solubility of N-Acyl-Substituted Amino Acid Esters as Inhibitors of the Replication of Modern Influenza A Virus Strains In Vitro by Zinc(II) Complexation 通过锌（II）络合增加 N-酰基取代的氨基酸酯作为现代甲型流感病毒株体外复制抑制剂的水溶性

IF 2.1 3区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Russian Journal of Inorganic Chemistry

Pub Date : 2024-03-28 DOI: 10.1134/s0036023623603495

T. M. Garaev, I. I. Yudin, N. V. Breslav, T. E. Savochkina, A. S. Krepkaya, T. V. Grebennikova, S. E. Nikiforova, I. I. Myshletsov, V. V. Avdeeva, E. A. Malinina

Abstract

This article proposes carbocyclic derivatives of N-acylated esters of L-amino acids with aromatic carboxylic acids as antiviral small-molecule agents. To increase the water solubility of inhibitors that are insoluble in aqueous solutions, the target compounds were used as zinc(II) complexes. It has been shown that hydrophobic organic compounds in the form of zinc(II)-coordinated ligands are capable of suppressing the replication of the influenza A virus strain resistant to adamantane-type drugs. Zinc(II) chloride at the concentration used does not have antiviral or toxic effects in experiments in vitro.

摘要本文提出将 L-氨基酸与芳香族羧酸的 N-酰化酯的碳环衍生物作为抗病毒小分子药物。为了增加不溶于水溶液的抑制剂的水溶性，目标化合物被用作锌（II）配合物。研究表明，锌（II）配位体形式的疏水性有机化合物能够抑制对金刚烷类药物有抗药性的甲型流感病毒株的复制。在体外实验中，所使用浓度的氯化锌（II）没有抗病毒或毒性作用。

引用次数: 0

Determination of Optimal Conditions for Template Sol-Gel Synthesis for the Formation of Antibacterial Materials 确定模板溶胶-凝胶合成形成抗菌材料的最佳条件

IF 2.1 3区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Russian Journal of Inorganic Chemistry

Pub Date : 2024-03-28 DOI: 10.1134/s003602362460028x

E. A. Lantsova, M. A. Bardina, E. A. Saverina, O. A. Kamanina

Abstract

One of the current global problems is the increasing resistance of microorganisms to antibacterial agents and the emergence of associated infections. Therefore, the synthesis of new hybrid materials capable of resisting bacteria is necessary. In this work, loading platforms for antibacterial material based on tetraethoxysilane were formed using yeast cells Ogataea polymorpha VKM Y-2559 and Cryptococcus curvatus VKM Y-3288 as templates under conditions of acid and alkaline hydrolysis. Using scanning electron microscopy, it was shown that an alkaline environment is most optimal when using yeast cells as templates for the formation of a porous material. The surface-active properties of a number of quaternary ammonium compounds were studied using the tensometry method to select the optimal template for the production of antibacterial materials in one stage.

摘要当前的全球性问题之一是微生物对抗菌剂的耐药性不断增强，并出现了相关的感染。因此，合成具有抗菌能力的新型杂化材料十分必要。在这项工作中，以酵母细胞 Ogataea polymorpha VKM Y-2559 和隐球菌 Curvatus VKM Y-3288 为模板，在酸性和碱性水解条件下形成了基于四乙氧基硅烷的抗菌材料装载平台。扫描电子显微镜显示，以酵母细胞为模板形成多孔材料时，碱性环境最为理想。利用张量测定法研究了一些季铵盐化合物的表面活性特性，从而为一步法生产抗菌材料选择了最佳模板。

引用次数: 0

Study of the Reversible Hawthorne Rearrangement between Isomeric Forms of the Octadecahydroeicosaborate Anion Using Dynamic 11B NMR Spectroscopy 利用动态 11B NMR 光谱研究十八氢硼酸阴离子异构体之间的可逆霍桑重排作用

IF 2.1 3区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Russian Journal of Inorganic Chemistry

Pub Date : 2024-03-28 DOI: 10.1134/s0036023624600345

O. S. Dontsova, E. Yu. Matveev, E. A. Eshtukova-Shcheglova, A. I. Nichugovskii, A. V. Golubev, V. I. Privalov, V. V. Avdeeva, E. A. Malinina, K. Yu. Zhizhin, N. T. Kuznetsov

Abstract

The process of rearrangement of the octadecahydroeicosaborate anion [trans-B₂₀H₁₈]^2– → [iso-B₂₀H₁₈]^2– in organic solvents (acetonitrile, DMF, DMSO) under UV irradiation has been studied using ¹¹B NMR spectroscopy in dynamics. It has been shown that the time of complete isomeric transition depends on the solvent used. In acetonitrile, complete conversion of the [trans-B₂₀H₁₈]^2– anion to the iso form is achieved in 1 h; in DMF, the process takes about 2 h; in DMSO, it takes about 3 h. The reverse process of rearrangement of the macropolyhedral borohydride anion [iso-B₂₀H₁₈]^2– → [trans-B₂₀H₁₈]^2– has been studied under the influence of temperature in DMF; it has been shown that an increase in the reaction time and temperature of the reaction solution is accompanied by degradation of the boron cluster.

摘要使用 11B NMR 光谱动态研究了十八氢硼酸阴离子 [trans-B20H18]2- → [iso-B20H18]2- 在有机溶剂（乙腈、DMF、DMSO）中紫外线照射下的重排过程。研究表明，同分异构体完全转变的时间取决于所使用的溶剂。在乙腈中，[反式-B20H18]2- 阴离子完全转化为异构形式需要 1 小时；在 DMF 中，这一过程需要约 2 小时；在 DMSO 中，则需要约 3 小时。在 DMF 中，研究了温度对大分子硼氢化阴离子 [iso-B20H18]2- → [trans-B20H18]2- 的反向重排过程的影响；结果表明，反应时间和反应溶液温度的增加伴随着硼簇的降解。

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引用次数: 0

Derivatives of (2-Carbamoylethyl)diphenylphosphine Oxides: Synthesis and Extraction Properties toward Actinides and Lanthanides (2-氨基甲酰乙基)二苯基氧化膦的衍生物：合成及对锕系元素和镧系元素的萃取特性

IF 2.1 3区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Russian Journal of Inorganic Chemistry

Pub Date : 2024-03-11 DOI: 10.1134/s0036023623602751

Abstract

A series of (2-carbamoylethyl)diphenylphosphine oxides (CEPO) has been synthesized from commercially available reagents: chlorodiphenylphosphine and acrylamides. Effect of coordinating fragments Ph₂P(O)(CH₂)₂C(O), nature of oligoyl group that binds these fragments, and the presence of additional coordinating centers in CEPO on extraction properties toward actinides and lanthanides has been studied. It has been found that N,N′-methylene-bis[3-(diphenylphosphoryl)propionamide] (III) containing two diphenylphosphorylpropionyl fragments bound by rigid HNCH₂NH linker shows the highest efficiency in extraction of actinides (recovery extent is ∼73% for U(VI) and ~85% for Th(IV)), whereas ligand V containing the maximum number of such phosphorylcarbonyl groups in conformationally non-rigid nitrogen heterocyclic matrix and CEPO (II) containing additional C=O group in the alkyl fragment at the nitrogen atom of carbamoyl fragment exhibit considerable preference in the extraction of lanthanides (extraction of gadolinium with this compound is close to 92%). Obtained data display that highly efficient and selective extractants for both 4f and 5f elements can be constructed on the basis of (2-carbamoylethyl)diphenylphosphine oxides.

摘要利用市售试剂氯二苯基膦和丙烯酰胺合成了一系列（2-氨基甲酰基乙基）二苯基膦氧化物（CEPO）。研究了配位片段 Ph2P(O)(CH2)2C(O)、结合这些片段的低聚酰基的性质以及 CEPO 中附加配位中心的存在对锕系元素和镧系元素萃取特性的影响。研究发现，N,N′-亚甲基双[3-（二苯基磷酰）丙酰胺]（III）含有两个二苯基磷酰丙酰基片段，并通过刚性 HNCH2NH 链接结合，在萃取锕系元素时效率最高（对铀（VI）的回收率为 73%，对钍（IV）的回收率为 85%）、而在构象非刚性氮杂环基质中含有最多此类磷酰羰基的配体 V 和在氨基甲酰基片段的氮原子上的烷基片段中含有额外 C=O 基团的 CEPO (II) 则在镧系元素的萃取中表现出相当大的优势（该化合物对钆的萃取率接近 92%）。所获得的数据表明，可以在（2-氨基甲酰基乙基）二苯基膦氧化物的基础上构建出对 4f 和 5f 元素具有高效选择性的萃取剂。

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引用次数: 0

Determination of the Eutectic to Peritectic Fold Transition in the Cu(Ni)–Fe–S System by Directional Crystallization of Melts 通过熔体定向结晶确定 Cu（Ni）-Fe-S 体系中从共晶到包晶的褶皱转变

IF 2.1 3区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Russian Journal of Inorganic Chemistry

Pub Date : 2024-03-11 DOI: 10.1134/s0036023623602660

E. F. Sinyakova, I. G. Vasilyeva

Abstract

This paper is concerned with theoretical analysis of the quasi-equilibrium directional crystallization of three-component melts. How the phase composition changes at each site of the sample and how the phase compositions change for various types of phase reactions are considered. It is shown that the eutectic reaction can change to a peritectic reaction as temperature lowers during directional crystallization. A 29.96 Fe + 21.55 Cu + 2.01 Ni + 46.49 S (at %) melt was directionally crystallized. Since nickel is present in the ingot in the form of impurities dissolved in the phases of the Cu–Fe–S system, the behavior of the melt belonging to this three-component system could be involved in data interpretation. As a result, a sample has been obtained with three zones changing one another: single-phase Fe_zS_{1 ± δ} (Poss), a Poss + (Cu,Fe)_{1 + x}S (Iss) two-phase eutectic mixture, and then single-phase Iss. The average composition of the solid phase changes from one discrete value to another in going to the next zone, while the melt and solid solutions in the neighboring zones have their compositions changing continuously. These results are consistent with theoretical ideas.

摘要本文涉及三组分熔体准平衡定向结晶的理论分析。研究了样品各部位的相组成如何变化，以及各种相反应的相组成如何变化。研究表明，随着定向结晶过程中温度的降低，共晶反应会转变为包晶反应。对 29.96 Fe + 21.55 Cu + 2.01 Ni + 46.49 S（%）的熔体进行了定向结晶。由于镍以溶解在 Cu-Fe-S 系统相中的杂质形式存在于铸锭中，因此属于这种三组份系统的熔体的行为可能涉及数据解释。因此，得到的样品具有三个相互变化的区域：单相 FezS1 ± δ (Poss)、Poss + (Cu,Fe)1 + xS (Iss) 两相共晶混合物，然后是单相 Iss。在进入下一个区域时，固相的平均成分从一个离散值变为另一个离散值，而相邻区域的熔体和固溶体的成分则不断变化。这些结果与理论观点一致。

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引用次数: 0

Synthesis and Properties of Asymmetrically Substituted Mn(III)-Nitro-Phenylporphyrins 不对称取代的 Mn(III)-Nitro-Phenyl卟啉的合成及其性质

IF 2.1 3区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Russian Journal of Inorganic Chemistry

Pub Date : 2024-03-11 DOI: 10.1134/s0036023623602775

N. V. Chizhova, S. V. Zvezdina, A. E. Likhonina, N. Zh. Mamardashvili, O. I. Koifman

Abstract

Mn(III)-5-(4-nitrophenyl)-10,15,20-triphenylporphyrin and Mn(III)-5,10,15-tri(4-nitrophenyl)-20-phenylporphyrin were synthesized by complex formation reactions of the specified porphyrins and by metal exchange of Cd porphyrin complexes with MnCl₂ in dimethylformamide. The products were identified by mass spectrometry and UV-Vis, IR, and ¹H NMR spectroscopy. Partial reduction of Mn(III) to Mn(II) takes place upon dissolution of manganese(III) complexes in DMF. The addition of solid NaOH to a solution in DMF or ethanolamine gives unstable Mn(II) porphyrins. The photochemical stability and oxidative degradation of Mn(III) porphyrins were studied in chloroform and in a chloroform–hydrogen peroxide mixture. The metal exchange reaction between asymmetrically substituted Cd(II) porphyrins and MnCl₂ in DMF was studied. The kinetic parameters of the reaction were calculated. The influence of substituents and the nature of the salt on the kinetic parameters of the metal exchange reaction was identified.

摘要通过特定卟啉的络合物形成反应以及镉卟啉络合物与氯化锰在二甲基甲酰胺中的金属交换反应，合成了锰(III)-5-(4-硝基苯基)-10,15,20-三苯基卟啉和锰(III)-5,10,15-三(4-硝基苯基)-20-苯基卟啉。通过质谱法、紫外-可见光谱法、红外光谱法和 1H NMR 光谱法对产物进行了鉴定。在 DMF 中溶解锰（III）络合物时，锰（III）会部分还原成锰（II）。在 DMF 或乙醇胺溶液中加入固体 NaOH 会产生不稳定的锰（II）卟啉。研究了 Mn（III）卟啉在氯仿和氯仿-过氧化氢混合物中的光化学稳定性和氧化降解。研究了不对称取代镉（II）卟啉与氯化锰在 DMF 中的金属交换反应。计算了反应的动力学参数。确定了取代基和盐的性质对金属交换反应动力学参数的影响。

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引用次数: 0

Low-Temperature One-Pot Synthesis of Tin(II) Sulfide Nanocrystalline Thin Films 硫化亚锡（II）纳米晶薄膜的低温一锅法合成

IF 2.1 3区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Russian Journal of Inorganic Chemistry

Pub Date : 2024-03-11 DOI: 10.1134/s0036023623602738

N. S. Kozhevnikova, L. N. Maskaeva, A. N. Enyashin, O. A. Lipina, A. P. Tyutyunnnik, I. O. Selyanin, I. V. Baklanova, M. V. Kuznetsov, V. F. Markov

Abstract

Photosensitive semiconducting p-type tin(II) sulfide thin films with a band gap of 1.03 ± 0.09 eV have been manufactured in compliance with green chemistry principles using the one-pot approach. To extend the range of sulfidizers suitable for chemical deposition of thin nanostructured SnS films, the efficiency of using sodium thiosulfate solutions has been shown. It has been found that thin SnS films with good adhesion to a dielectric substrate and a coherent scattering region size of ⁓30 nm can be synthesized through hydrolytic decomposition of thiosulfate ions. The conditions for synthesis of SnS have been justified by thermodynamic analysis of ionic equilibria. Quantum-chemical calculations have shown that the p-type conductivity of the synthesized SnS films is most likely due to tin vacancies.

摘要利用一锅法，按照绿色化学原理制造出了带隙为 1.03 ± 0.09 eV 的光敏对型硫化锡（II）半导体薄膜。为了扩大适用于纳米结构 SnS 薄膜化学沉积的硫化剂范围，研究人员展示了使用硫代硫酸钠溶液的效率。研究发现，通过水解分解硫代硫酸根离子，可以合成与介电基底有良好附着力、相干散射区尺寸为 ⁓30 nm 的 SnS 薄膜。离子平衡的热力学分析证明了合成 SnS 的条件。量子化学计算表明，合成的 SnS 薄膜的 p 型导电性很可能是由于锡空位造成的。

引用次数: 0

Thermodynamic Modeling of the CVD Process in the Ni–Si–C–H System 镍-硅-碳-氢体系中 CVD 过程的热力学建模

IF 2.1 3区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Russian Journal of Inorganic Chemistry

Pub Date : 2024-03-11 DOI: 10.1134/s0036023623602441

V. A. Shestakov, M. L. Kosinova

Abstract

Oxygen-free ceramics are promising for use in various technologies owing to their unique properties. Additions of metals or metal compounds significantly expand the application range of the ceramics. Therefore, methods for the synthesis of such composites are being actively developed. One way to manufacture such films is chemical vapor deposition (CVD). Thermodynamic modeling offers a means to choose the process parameters. In this work, thermodynamic modeling of the CVD process in the Ni–Si–C–H system, where nickelocene and silane were precursors, was carried out. The results can be useful for film materials design based on SiC and nickel-containing phases.

摘要无氧陶瓷因其独特的性能而有望用于各种技术。金属或金属化合物的添加大大扩展了陶瓷的应用范围。因此，人们正在积极开发合成这种复合材料的方法。化学气相沉积（CVD）是制造此类薄膜的一种方法。热力学建模为选择工艺参数提供了一种方法。在这项工作中，对以二茂镍和硅烷为前驱体的 Ni-Si-C-H 系统中的 CVD 过程进行了热力学建模。研究结果有助于基于碳化硅和含镍相的薄膜材料设计。

引用次数: 0

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