IF 2.4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2024-10-28 DOI: 10.1016/j.poly.2024.117278

A series of four new bis(imino)phosphine [NPN] ligands PhP(C₆H₄-2-HC=NAr)₂ (Ar = 4-OMeC₆H₄ (L¹, 1), 4-ClC₆H₄ (L², 2), 4-BrC₆H₄ (L³, 3), 2,6-iPr₂C₆H₃ (L⁴, 4)) were synthesized and structurally characterized. Their reactions with Cu(I) halides CuX (X = Cl, Br, I) were explored for the assembly of coordination complexes LⁿCuX, and the effects of substituent (Ar) and anion (X) were also investigated in a comparative manner. It was found that the reaction of methoxy substituted L¹ (Ar = 4-OMeC₆H₄) with CuX gave the mononuclear Cu(I) complexes L¹CuX (X = Cl (1a), Br (1b), I (1c)) with isostructural feature. In contrast, when halogen-substituted ligands L^2-3 (4-ClC₆H₄, 4-BrC₆H₄) were applied, their reactions with CuCl afforded the formation of tetranuclear dimer [Lⁿ(CuCl)₂]₂ (n = 2 (2a), 3 (3a)) bridged by the Cu₂Cl₂ square, regardless of the composition of the reactants. On the other hand, reactions of L^2-3 with CuBr and CuI generated the mononuclear Cu(I) complexes LⁿCuX (n = 2, X = Br (2b), I (2c); n = 3, X = Br (3b), I (3c)) again. In all these cases above, L^1-3 ligands played the tridentate role by biting the copper(I) centers through NPN sites. When the bulky L⁴ (Ar = 2,6-iPr₂C₆H₃) was involved, the binuclear dimer (L⁴CuI)₂ (4c) bridged by iodide anions was obtained, where each L⁴ ligand coordinated the copper center using the bidentate P^N mode with another imino arm pendant. In further exploration, 1,10-o-phenanthroline (denoted as phen) was introduced to produce the heteroleptic complex L¹CuCl(phen) (1d), where both imino arms in L¹ were pendent. The obtained ligand (L^1-4) and Cu(I) complexes were characterized by melting point, elemental analysis, FT-IR, UV–Vis, NMR, and single crystal X-ray diffraction.

合成了一系列四种新的双(亚氨基)膦[NPN]配体 PhP(C6H4-2-HC=NAr)2（Ar = 4-OMeC6H4 (L1, 1)、4-ClC6H4 (L2, 2)、4-BrC6H4 (L3, 3)、2,6-iPr2C6H3 (L4, 4)），并对其进行了结构表征。探讨了它们与 Cu（I）卤化物 CuX（X = Cl、Br、I）的反应，以组装配位配合物 LnCuX，并比较研究了取代基（Ar）和阴离子（X）的影响。研究发现，甲氧基取代的 L1（Ar = 4-OMeC6H4）与 CuX 反应生成具有等结构特征的单核 Cu（I）配合物 L1CuX（X = Cl (1a)、Br (1b)、I (1c)）。相反，当使用卤素取代配体 L2-3（4-ClC6H4、4-BrC6H4）时，无论反应物的组成如何，它们与 CuCl 反应都会形成由 Cu2Cl2 方桥连接的四核二聚体 [Ln(CuCl)2]2 （n = 2 (2a)、3 (3a)）。另一方面，L2-3 与 CuBr 和 CuI 反应再次生成单核 Cu（I）配合物 LnCuX（n = 2，X = Br (2b)，I (2c)；n = 3，X = Br (3b)，I (3c)）。在上述所有情况中，L1-3 配体通过 NPN 位点咬合铜(I)中心，发挥了三位一体的作用。当涉及到大块 L4（Ar = 2,6-iPr2C6H3）时，就得到了由碘阴离子桥接的双核二聚体 (L4CuI)2 (4c)，其中每个 L4 配体都通过双齿 P^N 模式与另一个亚氨基臂悬垂配位铜中心。在进一步的探索中，引入了 1,10-邻菲罗啉（表示为 phen），生成了异极配合物 L1CuCl(phen)（1d），其中 L1 中的两个亚氨基臂都是悬垂的。获得的配体（L1-4）和 Cu（I）配合物通过熔点、元素分析、傅立叶变换红外光谱、紫外可见光谱、核磁共振和单晶 X 射线衍射进行了表征。

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引用次数: 0

Bis(4-aminopyridinium) and bis(2-amino-6-methylpyridinium) cations stabilised by [MS4]2− anions: Synthesis, crystal structures, Hirshfeld surface analysis and sulfur transfer reactions 由 [MS4]2- 阴离子稳定的双(4-氨基吡啶)和双(2-氨基-6-甲基吡啶)阳离子：合成、晶体结构、Hirshfeld 表面分析和硫转移反应

IF 2.4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2024-10-28 DOI: 10.1016/j.poly.2024.117272

Four new organic ammonium tetrasulfidometallates: (4-aminopyridinium)₂[MoS₄]·H₂O 1, (4-aminopyridinium)₂[WS₄]·H₂O 2, (2-amino-6-methylpyridinium)₂[MoS₄] 3, and (2-amino-6-methylpyridinium)₂[WS₄] 4 have been synthesized by a well-known base promoted cation exchange method. All compounds were characterized by elemental analysis, IR/Raman/UV–Vis spectroscopy, thermogravimetric analysis, and X-ray crystallography. The structures of 1 and 2 consist of unique tetrahedral [MoS₄]²⁻ and [WS₄]²⁻ dianions, which are charge-balanced by crystallographically independent 4-aminopyridinium monocations. Additionally, both have a lattice water molecule, which contributes to the overall stability of their structures. In compounds 3 and 4, 4-aminopyridinium of 1 and 2 are replaced by 2-amino-6-methylpyridinium cation and lack lattice water. The different H-bonding interactions viz NH⋯S, CH⋯S, NH⋯O and OH⋯O are observed in 1 and 2, which are reduced to two viz. NH⋯S and CH⋯S in 3 and 4. The weak interactions (NH⋯O and OH⋯O) originating from lattice water further interlink cations with [MoS₄]²⁻ and [WS₄]²⁻ anions forming extended networks in 1 and 2. To understand the importance of intermolecular interactions in the structures of 1–4, the Hirshfeld surface analyses were performed. The enrichment ratio (E) in the structures of compounds 1–4 was obtained. Compounds 1–4 were tested for their sulfur transfer ability. Only compound 1 showed a predominant disulfide product formation in reaction with 1,3-dibromopropane.

采用著名的碱促进阳离子交换法合成了四种新的有机四硫代金铵盐：(4-氨基吡啶鎓)2[MoS4]-H2O 1、(4-氨基吡啶鎓)2[WS4]-H2O 2、(2-氨基-6-甲基吡啶鎓)2[MoS4] 3 和 (2-氨基-6-甲基吡啶鎓)2[WS4] 4。所有化合物都通过元素分析、红外/拉曼/紫外-可见光谱、热重分析和 X 射线晶体学进行了表征。1 和 2 的结构由独特的四面体 [MoS4]2- 和 [WS4]2- 二价离子组成，它们通过晶体学上独立的 4-aminopyridinium 单价离子实现电荷平衡。此外，这两种化合物都有一个晶格水分子，这有助于提高其结构的整体稳定性。在化合物 3 和 4 中，1 和 2 中的 4-氨基吡啶鎓被 2-氨基-6-甲基吡啶鎓阳离子取代，并且缺少晶格水。在 1 和 2 中观察到不同的 H 键相互作用，即 NH⋯S、CH⋯S、NH⋯O 和 OH⋯O，而在 3 和 4 中则减少为两种，即 NH⋯S 和 CH⋯S。在 1 和 2 中，源自晶格水的弱相互作用（NH⋯O 和 OH⋯O）进一步将阳离子与 [MoS4]2- 和 [WS4]2- 阴离子相互连接，形成扩展网络。为了了解分子间相互作用在 1-4 结构中的重要性，我们进行了 Hirshfeld 表面分析。得出了 1-4 号化合物结构中的富集比（E）。测试了化合物 1-4 的硫转移能力。只有化合物 1 在与 1,3-二溴丙烷反应时形成了主要的二硫产物。

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引用次数: 0

Synthesis of pyrazolopyrano pyrimidines via one-pot solvent free greener approach utilizing lanthanum trifluoroacetate and trichloroacetate Lewis acids supported on mesoporous silica: An experimental and DFT studies 利用介孔二氧化硅支撑的三氟乙酸镧和三氯乙酸路易斯酸，通过无溶剂绿色方法合成吡唑并吡喃嘧啶：实验和 DFT 研究

IF 2.4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2024-10-24 DOI: 10.1016/j.poly.2024.117273

Herein, an economic, environment-benign and sustainable greener protocol was developed for the production of pyrazolopyrano pyrimidines utilizing water competent Lanthanum trifluoroacetate and trichloroacetate Lewis acids based over silica via one-pot reaction involving aromatic aldehydes, ethyl acetoacetate, hydrazine hydrate and barbituric acid. The capability to incorporate a broad spectrum of functional groups, fast reaction times, best product yield, gentle reaction medium, solvent-free synthesis and the easy recoverability and multiple-time reusability of catalysts are notable advantages of the present synthetic approach. Furthermore, DFT studies was employed to study the pyrazolopyrano pyrimidines (5a-l), highlighting role of computational methods in predicting and understanding reactivity. Consequently, the integration of DFT studies with synthesis has proven to be a potent strategy for creating the current synthesis method.

在此，研究人员开发了一种经济、环保和可持续的绿色方法，利用基于二氧化硅的水性三氟乙酸镧和三氯乙酸路易斯酸，通过芳香醛、乙酰乙酸乙酯、水合肼和巴比妥酸的一锅反应生产吡唑并吡喃嘧啶。本合成方法的显著优点包括：可加入多种官能团、反应时间快、产品收率高、反应介质温和、无溶剂合成以及催化剂易于回收和可多次重复使用。此外，在研究吡唑并吡喃嘧啶（5a-l）时还采用了 DFT 研究，这凸显了计算方法在预测和理解反应性方面的作用。因此，将 DFT 研究与合成相结合被证明是创造当前合成方法的有效策略。

引用次数: 0

Conjugated 1,3-diketone calix[4]arenes: synthesis, complexation and structure-dependent sensitizing of Eu3+-luminescence 共轭 1,3-二酮钙[4]烯：Eu3+ 发光的合成、复合和结构致敏

IF 2.4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2024-10-23 DOI: 10.1016/j.poly.2024.117271

This work presents new type of bis-1,3-diketone calix[4]arene derivatives, in which the chelate groups are directly conjugated through the carbonyl carbon atom with aromatic fragments of calix[4]arene, and their lower rims bear four propoxy groups or pairs of hydroxy and propoxy groups. Tetrapropoxy-calix[4]arene is synthesized by acylation of magnesium enolates of a calix[4]arene ketone with 1-benzoylbenzotriazoles, and the dipropoxy analogue is obtained by bromination of bis(chalcone)-calix[4]arene, followed by methanolysis and hydrolysis. Significant conjugation of 1,3-diketo groups with the π-system of calix[4]arene is revealed for calixarenes of both types. Analysis of complexes formed by the ligands using the UV–Vis and NMR diffusion methods in combination with DFT calculations makes it possible to identify differences in the modes of complex formation of di- and tetrapropoxy- substituted ligands. It is demonstrated that a more enhanced sensibilization of Eu³⁺-luminescence in complexes with dipropoxy-calix[4]arene compared to that for complexes with tetrapropoxy-counterpart correlates with the formation of a tetrameric structure, in which the binding of Eu³⁺ ions does not disturb the conjugation of 1,3-diketonate moieties with aromatic calix[4]arene fragments. This is quite different from the significant disturbance of conjugation during intramolecular bis-chelation of Eu³⁺ ion by 1,3-diketo groups of tetraalkyl substituted ligand.

本研究提出了新型双-1,3-二酮钙[4]炔衍生物，其中的螯合基团通过羰基碳原子与钙[4]炔的芳香族片段直接共轭，其下缘带有四个丙氧基基团或一对羟基和丙氧基基团。四丙氧基钙[4]炔是通过钙[4]炔酮的烯醇化镁与 1-苯甲酰基苯并三唑酰化合成的，而二丙氧基类似物则是通过溴化双（查尔酮）-钙[4]炔，然后进行甲醇分解和水解得到的。在这两种类型的钙烯烃中，1,3-二酮基团与钙[4]炔的π-系统发生了显著的共轭。利用紫外可见光和核磁共振扩散方法以及 DFT 计算分析配体形成的络合物，可以发现二丙氧基和四丙氧基取代配体形成络合物的模式存在差异。研究表明，与四丙氧基配体相比，二丙氧基萼[4]炔配体的 Eu3+ 发光敏感性更强，这与四聚体结构的形成有关，在四聚体结构中，Eu3+ 离子的结合不会干扰 1,3-二酮酸分子与芳香族萼[4]炔片段的共轭。这与四烷基取代配体的 1,3-二酮基团在分子内双螯合 Eu3+ 离子时严重干扰共轭作用的情况截然不同。

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引用次数: 0

Synthesis, characterization, and cytotoxicity studies of diimine derivatives and their ruthenium(II)-p-cymene complexes 二亚胺衍生物及其对伞花烃钌(II)配合物的合成、表征和细胞毒性研究

IF 2.4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2024-10-23 DOI: 10.1016/j.poly.2024.117269

The reaction of five di-imines obtained by condensation of etilendiamine with 4-hydroxybenzaldehyde (L¹), 2,4-dihydroxibenzaldehyde (L²) and 1-(2,4-dihydroxyphenyl)ethan-1-one (L³) or, condensations of glyoxal with 4-aminophenol (L⁴) and 4-amino-3-fluorphenol (L⁵) with [Ru₂(Cl)₄(η⁶-p-cymene)₂] was studied. In absence of silver salts, four cationic complexes of formula [RuCl(η⁶-p-cymene)(Lⁿ)]X where n = 1, 3, 4 and X = Cl and, n = 5 and X = PF₆ could be isolated as pure solid materials. The complexes were characterized by different spectroscopic techniques and the X-ray structures of the L¹ hydrate and its complex [RuCl(η⁶-p-cymene)(L¹)]Cl were also determined. These studies confirm the N,N’-bidentate nature of the ligand L¹ and the pseudo-octahedral geometry of the ruthenium coordination environment in the complex. Furthermore, the complex derived from L³, shows a potent cytotoxic activity against tumor cell line A549.

研究了乙烯二胺与 4-羟基苯甲醛 (L1)、2,4-二羟基苯甲醛 (L2) 和 1-(2,4-二羟基苯基)乙-1-酮 (L3) 缩合，或乙二醛与 4-氨基苯酚 (L4) 和 4-氨基-3-氟苯酚 (L5) 缩合而得的五种二亚胺与 [Ru2(Cl)4(η6-对-苯)2]的反应。在没有银盐的情况下，可以分离出四种式为[RuCl(η6-对伞花烃)(Ln)]X 的阳离子配合物，其中 n = 1、3、4 和 X = Cl，n = 5 和 X = PF6 为纯固体材料。通过不同的光谱技术对这些配合物进行了表征，并确定了 L1 水合物及其配合物 [RuCl(η6-对-亚甲基)(L1)]Cl 的 X 射线结构。这些研究证实了配体 L1 的 N,N'-配位性质以及配合物中钌配位环境的假八面体几何形状。此外，由 L3 衍生的复合物对肿瘤细胞株 A549 具有很强的细胞毒活性。

{"title":"Synthesis, characterization, and cytotoxicity studies of diimine derivatives and their ruthenium(II)-p-cymene complexes","authors":"","doi":"10.1016/j.poly.2024.117269","DOIUrl":"10.1016/j.poly.2024.117269","url":null,"abstract":"<div><div>The reaction of five di-imines obtained by condensation of etilendiamine with 4-hydroxybenzaldehyde (L1), 2,4-dihydroxibenzaldehyde (L2) and 1-(2,4-dihydroxyphenyl)ethan-1-one (L3) or, condensations of glyoxal with 4-aminophenol (L4) and 4-amino-3-fluorphenol (L5) with [Ru2(Cl)4(η6-p-cymene)2] was studied. In absence of silver salts, four cationic complexes of formula [RuCl(η6-p-cymene)(Ln)]X where n = 1, 3, 4 and X = Cl and, n = 5 and X = PF6 could be isolated as pure solid materials. The complexes were characterized by different spectroscopic techniques and the X-ray structures of the L1 hydrate and its complex [RuCl(η6-p-cymene)(L1)]Cl were also determined. These studies confirm the N,N’-bidentate nature of the ligand L1 and the pseudo-octahedral geometry of the ruthenium coordination environment in the complex. Furthermore, the complex derived from L3, shows a potent cytotoxic activity against tumor cell line A549.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":null,"pages":null},"PeriodicalIF":2.4,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142531347","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Promising catalysts for aquatic pollutants degradation via persulfate activation: Insight into MOFs materials based on category, preparation and application 通过过硫酸盐活化降解水生污染物的前景广阔的催化剂：根据类别、制备和应用深入了解 MOFs 材料

IF 2.4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2024-10-22 DOI: 10.1016/j.poly.2024.117267

Deep purification of toxic pollutants in water requires more selective and efficient catalytic materials, when heterogeneous catalysis process is the first choice. Metal-Organic Frameworks (MOFs) have demonstrated high efficiency in catalysis due to their unique properties, including a large specific surface area, numerous active sites, and easily adjustable structure. These characteristics greatly improve the degradation efficiency of pollutants in water. A thorough understanding of the regulation methods for MOFs materials, the mechanisms of oxidant activation, and the influence of reaction parameters is crucial for improving their catalytic performance as heterogeneous catalysts. This study systematically investigates, for the first time, the potential of catalysts derived from MOFs in the degradation of water pollutants through persulfate activation, with a particular focus on various types of MOF composites. In contrast to previous research, this article presents an innovative approach by proposing the application of MOFs in both single-atom and multi-atom catalytic systems. This review discusses the various types of MOFs used as heterogeneous catalysts and the synthesis and regulation methods for different types of catalysts. It summarizes the applications of MOFs in environmental catalysis, with a particular focus on persulfate (PS) activation systems, elucidates the mechanisms by which MOFs activate PS, and examines the effects of reaction parameters on MOFs catalysts. Furthermore, it anticipates future research trends and highlights potential challenges and opportunities for MOFs as catalysts.

深度净化水中的有毒污染物需要选择性更强、效率更高的催化材料，而异相催化过程则是首选。金属有机框架（MOFs）具有独特的性能，包括比表面积大、活性位点多、结构易于调节等，因此在催化过程中表现出很高的效率。这些特性大大提高了水中污染物的降解效率。深入了解 MOFs 材料的调节方法、氧化剂活化机理以及反应参数的影响，对于提高其作为异相催化剂的催化性能至关重要。本研究首次系统地探讨了 MOFs 催化剂通过过硫酸盐活化降解水污染物的潜力，尤其关注各种类型的 MOF 复合材料。与以往的研究不同，本文提出了一种创新方法，建议在单原子和多原子催化系统中应用 MOFs。这篇综述讨论了用作异相催化剂的各种类型的 MOF，以及不同类型催化剂的合成和调节方法。综述总结了 MOFs 在环境催化中的应用，尤其关注过硫酸盐 (PS) 活化体系，阐明了 MOFs 活化 PS 的机理，并探讨了反应参数对 MOFs 催化剂的影响。此外，该书还预测了未来的研究趋势，并强调了 MOFs 作为催化剂可能面临的挑战和机遇。

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引用次数: 0

Development of tripeptide-cyclotriphosphazene derivatives: In vitro cytotoxicity, genotoxicity studies and molecular docking analysis within ovarian and prostate cancer cell line receptors 开发三肽-环三磷酸嗪衍生物：卵巢癌和前列腺癌细胞系受体的体外细胞毒性、遗传毒性研究和分子对接分析

IF 2.4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2024-10-22 DOI: 10.1016/j.poly.2024.117261

Peptide-phosphazene compounds are important compounds of growing interest in biomedical research and have potential therapeutic effects. The tripeptide-cyclotriphosphazenes conjugates were synthesized and analyzed for their molecular docking analysis, visualizing their binding profiles within various cancer cell line receptors and tested in vitro cytotoxic and genotoxic properties. Determining in vitro cytotoxic studies of obtained compounds displayed cytotoxic effect against two selected human cancer cell lines, including ovarian (A2780) and prostate (PC-3), cancer cells. The compound DTAP demonstrated significantly higher efficacy at 100 µM in the PC-3 cancer cell line compared to the reference drug docetaxel at 50 µM. Among the tripeptide-phosphazene conjugtates, DTGG demonstrates the most promising anticancer activity with a logIC₅₀ of 1.23 µM, forming five hydrogen bonds and a favorable salt bridge interaction, along with several hydrophobic interactions, thereby stabilizing its binding within the human ovarian tumor domain based on molecular docking analysis. The derivative DTGP emerges as the most potent among the DTG derivatives, achieving a ΔG model value of −108 kcal/mol, primarily due to a π-cationic interaction with the LYS204 amino acid in chain C, which significantly enhances its binding affinity. Additionally, DNA damage studies on human ovarian and prostate cancer cell lines determined that cell death due to DNA damage was the basis of the decrease in cell viability. These results support the evaluation of the compounds as potential drug candidates.

肽-膦氮化合物是生物医学研究中越来越受关注的重要化合物，具有潜在的治疗作用。我们合成了三肽-环三膦烯共轭物，并对其进行了分子对接分析，观察了它们在各种癌细胞系受体中的结合情况，并对其进行了体外细胞毒性和基因毒性测试。所获化合物的体外细胞毒性研究显示，它们对两种选定的人类癌细胞系（包括卵巢癌细胞系（A2780）和前列腺癌细胞系（PC-3））具有细胞毒性作用。与参考药物多西他赛（50 µM）相比，化合物 DTAP 在 PC-3 癌细胞系中 100 µM 的药效明显更高。根据分子对接分析，在三肽-膦氮化合物共轭物中，DTGG 的抗癌活性最高，其对数半数致死浓度（logIC50）为 1.23 µM，形成了五个氢键和一个有利的盐桥相互作用，以及若干疏水相互作用，从而稳定了其在人类卵巢肿瘤结构域内的结合。衍生物 DTGP 是 DTG 衍生物中最有效的一种，其 ΔG 模型值为 -108 kcal/mol，这主要是由于它与 C 链中的 LYS204 氨基酸发生了 π 阳离子相互作用，从而显著增强了其结合亲和力。此外，对人类卵巢癌和前列腺癌细胞系进行的 DNA 损伤研究确定，DNA 损伤导致的细胞死亡是细胞活力下降的基础。这些结果支持将这些化合物作为潜在候选药物进行评估。

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引用次数: 0

A hexanuclear Iridium(III) cluster for histidine-induced singlet oxygen and superoxide radicals generation 组氨酸诱导单线态氧和超氧自由基生成的六核铱(III)团簇

IF 2.4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2024-10-22 DOI: 10.1016/j.poly.2024.117264

Photosensitizers (PSs) play key roles in photodynamic therapy (PDT). PDT is typically reliant on the local concentration of oxygen. A big challenge for PSs is to develop oxygen-independent photosensitizers, which can work well in hypoxic tumor microenvironment. In this piece of work, a hexanuclear Ir(III) cluster (Ir6) is highly selective towards histidine and histidine-rich (His-rich) proteins to form mononuclear Ir(III) complexes of [Ir(bpy)₂(His)]. After the selective response to histidine or his-rich proteins, [Ir(bpy)₂(His)] generates both singlet oxygen(¹O₂) and superoxide (O₂⁻). This work opens an avenue for the potential application of Ir6 for type Ι and ΙΙ synergic photodynamic therapy.

光敏剂（PSs）在光动力疗法（PDT）中发挥着关键作用。光动力疗法通常依赖于局部的氧气浓度。光敏剂面临的一大挑战是开发不依赖氧气的光敏剂，这种光敏剂能在缺氧的肿瘤微环境中发挥良好作用。在这项研究中，六核 Ir(III) 簇（Ir6）对组氨酸和富含组氨酸（His-rich）的蛋白质具有高度选择性，形成 [Ir(bpy)2(His)] 的单核 Ir(III) 复合物。在对组氨酸或富含组氨酸的蛋白质产生选择性反应后，[Ir(bpy)2(His)] 会产生单线态氧（1O2）和超氧（O2-）。这项工作为 Ir6 在Ι型和ΙΙ型协同光动力疗法中的潜在应用开辟了一条途径。

引用次数: 0

Predictive calculation of the stability constants of silver(I) ion with pyridine and 2,2′-bipyridyl in a solvent environment 银（I）离子与吡啶和 2,2′-联吡啶在溶剂环境中的稳定常数的预测计算

IF 2.4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2024-10-22 DOI: 10.1016/j.poly.2024.117265

In the present study, the stability constants of silver(I) coordination compounds with 2,2′-bipyridyl (bpy, L) in mixed methanol–acetonitrile solvents (MeOH-AN, χ_AN = 0.0 ÷ 1.0 mol fr.) were determined by the potentiometric method at 25.0 °C. The influence of reagents solvation on the change in stability of [Ag(bpy)]⁺ and [Ag(bpy)₂]⁺ complexes upon changing the composition of the solvent MeOH→(MeOH-AN) was analyzed. It has been established that the determining factor in the shift of the complex formation equilibrium along the first and second steps of coordination with a change in the composition of the solvent is the contribution from the central ion resolvation. The obtained results and data on the thermodynamics of complex formation reactions of Ag⁺ with bpy and pyridine (py, L) in a few binary non-aqueous solvents were compared. The possibility of carrying out an estimated calculation of the stability constants of [Ag(L)]⁺ in non-aqueous solvents was confirmed.

本研究采用电位法测定了 2,2′-联吡啶（bpy，L）与银（I）配位化合物在甲醇-乙腈混合溶剂（MeOH-AN，χAN = 0.0 ÷ 1.0 mol fr.）中于 25.0 ℃下的稳定性常数。分析了试剂溶解度对改变溶剂 MeOH→（MeOH-AN）组成时 [Ag(bpy)]+ 和 [Ag(bpy)2]+ 复合物稳定性变化的影响。结果表明，随着溶剂成分的改变，络合物形成平衡在第一步和第二步配位过程中发生变化的决定因素是中心离子解析的贡献。我们比较了 Ag+ 与铋和吡啶（py, L）在一些二元非水溶剂中形成络合物反应的热力学结果和数据。证实了对非水溶剂中[Ag(L)]+ 的稳定常数进行估计计算的可能性。

引用次数: 0

Investigation of the homonuclear and polynuclear complexes of FeIII of pentadentate dipodal s-triazine Schiff base ligand 五正齿二极 s-三嗪希夫碱配体的 FeIII 同核和多核配合物研究

IF 2.4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2024-10-22 DOI: 10.1016/j.poly.2024.117268

An efficient synthesis of a new class of “Dipodal s-triazine Schiff base ligand” has been developed based on high-yielding amines substitutions of 2-vinyl-4,6-diamino-1,3,5-triazine (acryloguanamine) (VDAT) by salicylaldehyde. A new compound characterized by a dipodal s-triazine pentadentate Schiff base with 2-vinyl-4,6-N,N’-bis(2,4-dihydroxybenzylidine)-1,3,5-triazine [VDAT24] has been developed. The obtained [VDAT24] was polymerized to obtain poly(2-vinyl-4,6-N,N’-bis(2,4-dihydroxybenzylidine)-1,3,5-triazine) [PVDAT24]. Subsequently, s-Triazine-centered Fe(III) homonuclear complexes [VDAT24Fe], and polynuclear complexes [PVDAT24Fe] were obtained derived. As a result, the ligand obtained by elemental analysis, ICP-AES, TGA, FTIR, ¹H NMR and ¹³C NMR. Isolated ligand complex, FTIR, TGA, and were illuminated structures on the magnetic susceptibility. The resulting two different polymeric ligands and certain complexes of FTIR, TGA, and Ostwald Viscometer elucidated the structures of magnetic susceptibility.

基于水杨醛对 2-乙烯基-4,6-二氨基-1,3,5-三嗪（丙烯酰胍胺）（VDAT）的高产胺取代，开发了一种新型 "二极 s-三嗪希夫碱配体 "的高效合成方法。我们开发出了一种新化合物，其特征是 2-乙烯基-4,6-N,N'-双（2,4-二羟基苄基啶）-1,3,5-三嗪与 2-乙烯基-4,6-N,N'-双（2,4-二羟基苄基啶）-1,3,5-三嗪形成了二极 s-三嗪五价席夫碱[VDAT24]。将得到的[VDAT24]进行聚合，得到聚(2-乙烯基-4,6-N,N'-双(2,4-二羟基苄基)-1,3,5-三嗪)[PVDAT24]。随后，又衍生出了以 s-三嗪为中心的铁(III)同核配合物[VDAT24Fe]和多核配合物[PVDAT24Fe]。因此，通过元素分析、ICP-AES、TGA、傅立叶变换红外光谱、1H NMR 和 13C NMR 获得了配体。分离出的配体复合物、傅立叶变换红外光谱（FTIR）、热重分析仪（TGA）和磁感应强度都显示了其结构。由此产生的两种不同的聚合物配体和某些络合物的傅立叶变换红外光谱、热重分析和奥斯特瓦尔德粘度计阐明了磁感应强度的结构。

引用次数: 0

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