Journal of Inorganic Biochemistry最新文献_第3页

Structure, properties, and decomposition in biological systems of a new nitrosyl iron complex with 2-methoxythiophenolyls, promising for the treatment of cardiovascular diseases 一种新型亚硝基铁复合物与 2-甲氧基噻吩酚的结构、性质及在生物系统中的分解，有望用于治疗心血管疾病。

IF 3.8 2区化学 Q2 BIOCHEMISTRY & MOLECULAR BIOLOGY

Journal of Inorganic Biochemistry

Pub Date : 2024-09-29 DOI: 10.1016/j.jinorgbio.2024.112747

Оlesya V. Pokidova , Veronika O. Novikova , Nina S. Emel’yanova , Ludmila M. Mazina , Alina S. Konyukhova , Alexander V. Kulikov , Gennadii V. Shilov , Nikolai S. Ovanesyan , Tatyana S. Stupina , Natalia A. Sanina

A new promising binuclear tetranitrosyl iron complex with 2-methoxythiophenolyl of the composition [Fe₂(C₇H₇OS)₂(NO)₄] (complex 1), which acts on the therapeutic targets of cardiovascular diseases, guanylate and adenylate cyclase, has been synthesized. X-ray diffraction data show the presence of two isoforms of complex 1; according to quantum chemical calculations, the structure of only the trans isomer is stable in solutions.

The processes of transformation of complex 1 in DMSO, in aqueous solutions, as well as in the presence of bovine serum albumin, reduced glutathione, and mucin were studied. DMSO promotes the decomposition of the original complex 1 into mononuclear products. In biological systems, the mechanisms of decomposition of the complex 1 differ from aqueous solutions. In albumin solution, a gradual formation of a high-molecular-weight dinitrosyl complex is observed, obtained by coordinating the [Fe(NO)₂]⁺ fragment with the amino acid groups of the protein. In the presence of mucin, an EPR signal from stable mononitrosyl products is observed. The introduction of glutathione into the system of the complex 1 leads to the replacement of one initial thioligand with glutathione. In the model systems under study, a more efficient and prolonged generation of NO groups is observed compared to a buffer solution.

The obtained data on the influence of the environment on the properties of the complex 1 in combination with a study of their effect on enzymes allow us to recommend it for further study as a potential drug with vasodilator, antianginal, and hypotensive properties.

我们合成了一种新的双核四亚硝基铁络合物，其成分为[Fe2(C7H7OS)2(NO)4]（络合物 1），具有 2-甲氧基噻吩基，可作用于心血管疾病的治疗靶标鸟苷酸环化酶和腺苷酸环化酶。X 射线衍射数据显示复合物 1 存在两种异构体；根据量子化学计算，只有反式异构体的结构在溶液中是稳定的。研究了复合物 1 在二甲基亚砜、水溶液以及牛血清白蛋白、还原型谷胱甘肽和粘蛋白存在下的转化过程。二甲基亚砜能促进原始复合物 1 分解成单核产物。在生物体系中，复合物 1 的分解机制与水溶液不同。在白蛋白溶液中，[Fe(NO)2]+ 片段与蛋白质的氨基酸基团配位，逐渐形成高分子量的二硝基复合物。在粘蛋白存在的情况下，可观察到稳定的单亚硝基产物产生的 EPR 信号。在复合物 1 的体系中引入谷胱甘肽会导致一个初始硫配体被谷胱甘肽取代。在所研究的模型系统中，与缓冲溶液相比，NO 基团的生成更有效、更持久。通过研究环境对复合物 1 性能的影响以及它们对酶的影响，我们建议将其作为一种具有血管扩张、抗心绞痛和降血压性能的潜在药物进行进一步研究。

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引用次数: 0

Uridine triphosphate hybrid catalyst for carbon‑carbon bond formation reactions with enhanced enantioselectivity by mercury(II) ions 三磷酸尿苷杂化催化剂在汞(II)离子作用下提高碳-碳键形成反应的对映选择性。

IF 3.8 2区化学 Q2 BIOCHEMISTRY & MOLECULAR BIOLOGY

Journal of Inorganic Biochemistry

Pub Date : 2024-09-28 DOI: 10.1016/j.jinorgbio.2024.112748

Li Liu, Xingchen Dong, Weijun Qin, Yashao Chen, Changhao Wang

DNA hybrid catalysts are constructed by embedding active metal species into the chiral scaffolds of DNA, which have been successfully applied to some important aqueous-phase enantioselective transformations. Owing to simple components and inherent chirality, nucleotide hybrid catalysts are emerging in response to soving the unclear locations of catalytic centers and the plausible catalytic mechanisms in DNA-based asymmetric catalysis. However, the tertiary structure of nucleotides lacks tunability, severely impeding further design of nucleotide hybrid catalysts for potential applications. To this end, a design strategy for tunable nucleotide hybrid catalysts is put forward by introducing metal-mediated base pairs. Herein, we found that the formation of uracil‑mercury(II)-uracil (U-Hg²⁺-U) base pairs could enhance the enantioselectivity in uracil-containing nucleotide-based asymmetric reactions. Compared with uracil triphosphate (UTP) complexing with Cu²⁺ ions (UTP∙Cu²⁺), the presence of Hg²⁺ ions gave rise to an increased enantiomeric excess (ee) of 38 % in Diels-Alder reactions and 22 % ee in Michael reactions. The Hg²⁺-tuning behaviors of UTP hybrid catalyst have been demonstrated to largely depend on nucleotides, Hg²⁺ concentrations, metal cofactors, additives and reaction types. Based on ultraviolet-visible, circular dichroism and nuclear magnetic resonance spectroscopic techniques, the chiral enhancement of Hg²⁺-containing UTP hybrid catalyst is proved to largely depend on the formation of U-Hg²⁺-U base pairs and the plausible cross-linked structure of UTP-Hg²⁺-UTP/Cu²⁺ assembly. This work provides a tunable strategy based on the concept of metal-mediated base pairs, allowing further design of potent oligonucleotide-based catalysts for other enantioselective reactions.

DNA 混合催化剂是通过将活性金属物种嵌入 DNA 的手性支架而构建的，已成功应用于一些重要的水相对映选择性转化。由于核苷酸杂化催化剂成分简单且具有固有的手性，它的出现解决了基于 DNA 的不对称催化中催化中心位置不明确和催化机制似是而非的问题。然而，核苷酸的三级结构缺乏可调性，严重阻碍了进一步设计核苷酸杂化催化剂的潜在应用。为此，我们通过引入金属介导的碱基对，提出了一种可调核苷酸杂化催化剂的设计策略。在这里，我们发现尿嘧啶-汞（II）-尿嘧啶（U-Hg2+-U）碱基对的形成可以提高含尿嘧啶核苷酸不对称反应的对映选择性。与三磷酸尿嘧啶（UTP）与 Cu2+ 离子（UTP∙Cu2+）络合相比，Hg2+ 离子的存在使 Diels-Alder 反应中的对映体过量（ee）增加了 38%，使 Michael 反应中的对映体过量（ee）增加了 22%。研究表明，UTP 混合催化剂的 Hg2+ 调节行为在很大程度上取决于核苷酸、Hg2+ 浓度、金属辅助因子、添加剂和反应类型。基于紫外可见光谱、圆二色光谱和核磁共振光谱技术，证明了含 Hg2+ UTP 混合催化剂的手性增强主要取决于 U-Hg2+-U 碱基对的形成和 UTP-Hg2+-UTP/Cu2+ 组装的合理交联结构。这项工作提供了一种基于金属介导的碱基对概念的可调策略，从而可以进一步设计用于其他对映体选择性反应的基于寡核苷酸的强效催化剂。

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引用次数: 0

Pd(II)/1,10-phenanthroline complexes bearing arene ligands: On the role of N- vs O-coordination to tune their cellular activity and binding ability towards DNA and RNA 带有炔配体的钯（II）/1,10-菲罗啉配合物：N-配位与 O-配位在调整其细胞活性以及与 DNA 和 RNA 结合能力方面的作用。

IF 3.8 2区化学 Q2 BIOCHEMISTRY & MOLECULAR BIOLOGY

Journal of Inorganic Biochemistry

Pub Date : 2024-09-28 DOI: 10.1016/j.jinorgbio.2024.112749

Francesca Binacchi , Damiano Cirri , Eleonora Bimbi , Natalia Busto , Alessandro Pratesi , Tarita Biver

Three Pd(II)-based complexes of 1,10-phenanthroline and N- or O-coordinating ligands have been synthesised and tested with different relevant biosubstrates like double-stranded DNA, double and triple helix of RNA, DNA G-quadruplexes of different conformations and bovine serum albumin. Here a correlation between N- vs O-coordinating elements and binding mechanism emerged, where the N-coordinating ligands proved to be the most promising. These outcomes were confirmed also in the cellular experiments. The Pd(II) complex with naphthalene-1,8-diamine is the one that is able to be carried by BSA, to strongly bind nucleic acids, to produce reactive oxygen species (ROS) and to show the best cellular performances (poorly toxic towards healthy cells and highly toxic against the cisplatin-resistant cancer cell line). On the opposite, the complex with benzene-1,2-diolate may be sequestered by BSA, weakly binds nucleic acids, does not produce ROS and shows poor cellular activity. The complex with benzene-1,2-diamine stays in between. Other mechanistic details are discussed which show that the biophysical behaviour is the sum of the contribution of aromaticity, charge and N- or O-coordination.

我们合成了三种基于 1,10-菲罗啉和 N 或 O 配位体的钯(II)配合物，并用不同的相关生物基质（如双链 DNA、RNA 的双螺旋和三螺旋、不同构象的 DNA G-四链体以及牛血清白蛋白）进行了测试。在这里，N-配位元素和 O-配位元素与结合机制之间出现了相关性，其中 N-配位配体被证明是最有前途的。这些结果在细胞实验中也得到了证实。钯（II）与萘-1,8-二胺的配合物能够被 BSA 携带，与核酸紧密结合，产生活性氧（ROS），并显示出最佳的细胞性能（对健康细胞毒性较弱，而对顺铂抗性癌细胞系毒性较强）。相反，与苯-1,2-二酸酯的复合物可能会被 BSA 封闭，与核酸的结合力较弱，不产生 ROS，细胞活性较差。而与苯-1,2-二胺的复合物则介于两者之间。讨论的其他机理细节表明，生物物理行为是芳香性、电荷和 N-或 O-配位作用的总和。

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引用次数: 0

Corrigendum to "New insights into the O₂-sensing mechanism of FixL and other gas sensing heme proteins" [Journal of Inorganic Biochemistry 259 (2024) 112642]. 对 "FixL 和其他气体传感血红素蛋白的氧气传感机制的新认识"[《无机生物化学杂志》259 (2024) 112642]的更正。

IF 3.8 2区化学 Q2 BIOCHEMISTRY & MOLECULAR BIOLOGY

Journal of Inorganic Biochemistry

Pub Date : 2024-09-28 DOI: 10.1016/j.jinorgbio.2024.112746

Mark F Reynolds

引用次数: 0

Generating globin-like reactivities in [human serum albumin-FeII(heme)] complex through N-donor ligand addition 通过添加 N-供体配体在[人血清白蛋白-FeII(血红素)]复合物中产生类似球蛋白的反应性

IF 3.8 2区化学 Q2 BIOCHEMISTRY & MOLECULAR BIOLOGY

Journal of Inorganic Biochemistry

Pub Date : 2024-09-26 DOI: 10.1016/j.jinorgbio.2024.112743

Mary Grace I. Galinato , Christopher Wyant , Ashley L. Lombardo , Ethan K. MacIsaac , Daniella A. Rios-Martinez , Christopher D. Kimrey , Alexandra Alfonso Castro

Human serum albumin (HSA) has a strong binding affinity for heme b, forming a complex in a 1:1 ratio with the co-factor ([HSA-Fe^IIIheme]). This system displays spectroscopic and functional properties comparable to globins when chemical derivatives mimicking them are incorporated into the protein matrix. The aim of this study is to generate globin-like systems using [HSA-Fe^IIIheme] as a protein template and binding N-donor ligands (imidazole, Im; and 1-methylimidazole, 1-MeIm) to construct artificial [HSA-Fe(heme)-(N-donor)] complexes. Their electronic structure and binding thermodynamics are investigated using UV–vis and (synchronous) fluorescence spectroscopies, while ligand-protein interactions are visualized using docking simulations. The imidazole derivatives have a strong affinity for [HSA-Fe^IIIheme] (K ∼ 10⁴–10⁶), where the spontaneous binding of Im and 1-MeIm are dominated by entropic and enthalpic effects, respectively. The reduced form of the [HSA-Fe(heme)-(N-donor)] complexes demonstrate nitrite reductase (NiR) activity similar to that observed in globins, but with significant differences in their rates. [HSA-Fe^IIheme-(1-MeIm)] reduces nitrite ∼4× faster than the Im analogue, and ∼ 30× faster than myoglobin (Mb). The enhanced NiR activity of [HSA-Fe^IIheme-(1-MeIm)] is a cumulative effect of several factors including a slightly expanded and more optimal heme binding pocket, nearby residues as possible proton sources, and a H-bonding interaction between 1-MeIm and residues Arg160 and Lys181 that may have a long-distance influence on the heme π electron density.

人血清白蛋白（HSA）与血红素 b 有很强的结合亲和力，能与辅助因子（[HSA-FeIIIheme]）以 1:1 的比例形成复合物。当模仿球蛋白的化学衍生物加入到蛋白质基质中时，该系统显示出与球蛋白相当的光谱和功能特性。本研究的目的是利用[HSA-FeIIIheme]作为蛋白质模板，并结合 N-供体配体（咪唑，Im；和 1-甲基咪唑，1-MeIm）来构建人工[HSA-Fe（heme）-（N-供体）]复合物，从而生成类似球蛋白的系统。利用紫外-可见光谱和（同步）荧光光谱研究了它们的电子结构和结合热力学，同时利用对接模拟将配体与蛋白质的相互作用可视化。咪唑衍生物与[HSA-FeIIIheme]具有很强的亲和力（K ∼ 104-106），其中 Im 和 1-MeIm 的自发结合分别受熵效应和焓效应的支配。还原形式的[HSA-Fe（血红素）-（N-供体）]复合物显示出与在球蛋白中观察到的类似的亚硝酸盐还原酶（NiR）活性，但它们的还原速率有显著差异。[HSA-FeIIheme-(1-MeIm)]还原亚硝酸盐的速度比 Im 类似物快 4 倍，比肌红蛋白（Mb）快 30 倍。HSA-FeIIheme-(1-MeIm)]的 NiR 活性增强是多种因素的累积效应，包括血红素结合口袋略有扩大且更为理想，附近的残基可能是质子源，以及 1-MeIm 与 Arg160 和 Lys181 残基之间的 H 键相互作用可能对血红素 π 电子密度产生长距离影响。

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引用次数: 0

The application of X-ray fluorescence microscopy and micro-XANES spectroscopy to study neuro-metallomics. 应用 X 射线荧光显微镜和显微 XANES 光谱研究神经金属组学。

IF 3.8 2区化学 Q2 BIOCHEMISTRY & MOLECULAR BIOLOGY

Journal of Inorganic Biochemistry

Pub Date : 2024-09-24 DOI: 10.1016/j.jinorgbio.2024.112744

Meg Willans, Ashley Hollings, Rhiannon E Boseley, Thomas Munyard, Gaewyn C Ellison, Mark J Hackett

This early career research highlight provides a review of my own research program over the last decade, a time frame that encompasses my transition from postdoctoral fellowships to independent researcher. As an analytical chemist and applied spectroscopist, the central theme of my research program over this time has been protocol development at synchrotron facilities, with the main objective to investigate brain metal homeostasis during both brain health and brain disease. I will begin my review with an overview of brain metal homeostasis, before introducing analytical challenges associated with its study. I will then provide a brief summary of the two main X-ray techniques I have used to study brain metal homeostasis, X-ray fluorescence microscopy (XFM) and X-ray absorption near edge structure spectroscopy (XANES). The review then finishes with a summary of my main research contributions using these two techniques, put in the context of the results from others in the field.

这篇早期职业生涯研究亮点回顾了我自己过去十年的研究计划，这十年是我从博士后研究员转变为独立研究员的十年。作为一名分析化学家和应用光谱学家，这段时间我研究计划的中心主题是同步加速器设施的协议开发，主要目标是研究大脑健康和大脑疾病期间的大脑金属稳态。首先，我将概述脑金属稳态，然后介绍与脑金属稳态研究相关的分析挑战。然后，我将简要介绍我用于研究脑金属稳态的两种主要 X 射线技术：X 射线荧光显微镜 (XFM) 和 X 射线吸收近边缘结构光谱 (XANES)。最后，结合该领域其他学者的研究成果，总结了我使用这两种技术的主要研究成果。

引用次数: 0

Expanding the scope of resonance Raman spectroscopy in hydrogenase research: New observable states and reporter vibrations 扩大共振拉曼光谱在氢化酶研究中的应用范围：新的可观测状态和报告振动

IF 3.8 2区化学 Q2 BIOCHEMISTRY & MOLECULAR BIOLOGY

Journal of Inorganic Biochemistry

Pub Date : 2024-09-19 DOI: 10.1016/j.jinorgbio.2024.112741

Cornelius C.M. Bernitzky , Giorgio Caserta , Stefan Frielingsdorf , Janna Schoknecht , Andrea Schmidt , Patrick Scheerer , Oliver Lenz , Peter Hildebrandt , Christian Lorent , Ingo Zebger , Marius Horch

Oxygen-tolerant [NiFe] hydrogenases are valuable blueprints for the activation and evolution of molecular hydrogen under application-relevant conditions. Vibrational spectroscopic techniques play a key role in the investigation of these metalloenzymes. For instance, resonance Raman spectroscopy has been introduced as a site-selective approach for probing metal-ligand coordinates of the [NiFe] active site and FeS clusters. Despite its success, this approach is still challenged by a limited number of detectable active-site states – due to missing resonance enhancement or intrinsic light sensitivity – and difficulties in their assignment. Utilizing two oxygen-tolerant [NiFe] hydrogenases as model systems, we illustrate how these challenges can be met by extending excitation and detection wavelength regimes in resonance Raman spectroscopic studies. Specifically, we observe that this technique does not only probe low-frequency metal-ligand vibrations but also high-frequency intra-ligand modes of the diatomic CO/CN⁻ ligands at the active site of [NiFe] hydrogenases. These reporter vibrations are routinely probed by infrared absorption spectroscopy, so that direct comparison of spectra from both techniques allows an unambiguous assignment of states detected by resonance Raman spectroscopy. Moreover, we find that a previously undetected state featuring a bridging hydroxo ligand between Ni and Fe can be probed using higher excitation wavelengths, as photoconversion occurring at lower wavelengths is avoided. In summary, this study expands the applicability of resonance Raman spectroscopy to hydrogenases and other complex metalloenzymes by introducing new strategies for probing and assigning redox-structural states of the active site.

耐氧的[NiFe]氢酶是在应用相关条件下活化和进化分子氢的宝贵蓝图。振动光谱技术在研究这些金属酶方面发挥着关键作用。例如，共振拉曼光谱已被引入作为一种位点选择性方法，用于探测[NiFe]活性位点和 FeS 簇的金属配体坐标。尽管这种方法取得了成功，但由于共振增强缺失或固有的光敏感性，可探测到的活性位点状态数量有限，而且难以确定这些状态。我们利用两种耐氧[NiFe]氢化酶作为模型系统，说明了如何通过扩展共振拉曼光谱研究中的激发和检测波长范围来应对这些挑战。具体来说，我们观察到这种技术不仅能探测金属配体的低频振动，还能探测[NiFe] 氢酶活性位点上二原子 CO/CN- 配体的高频配体内模式。红外吸收光谱可对这些报告振动进行常规探测，因此直接比较这两种技术的光谱可对共振拉曼光谱探测到的状态进行明确分配。此外，我们还发现，由于可以避免在较低波长下发生的光电转换，因此可以使用较高的激发波长探测以前未探测到的以 Ni 和 Fe 之间的羟基配体桥接为特征的状态。总之，本研究通过引入探测和分配活性位点氧化还原结构状态的新策略，扩展了共振拉曼光谱对氢酶和其他复杂金属酶的适用性。

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引用次数: 0

EcNikA, a versatile tool in the field of artificial metalloenzymes EcNikA，人工金属酶领域的多功能工具。

IF 3.8 2区化学 Q2 BIOCHEMISTRY & MOLECULAR BIOLOGY

Journal of Inorganic Biochemistry

Pub Date : 2024-09-19 DOI: 10.1016/j.jinorgbio.2024.112740

Caroline Marchi-Delapierre, Christine Cavazza, Stéphane Ménage

This review describes the multiple advantages of using of EcNikA, a nickel transport protein, in the design of artificial metalloenzymes as alternative catalysts for synthetic biology. The rationale behind the strategy of artificial enzyme design is discussed, with particular emphasis on de novo active site reconstitution. The impact of the protein scaffold on the artificial active site and thus the final catalytic properties is detailed, highlighting the considerable aptitude of hybrid systems to catalyze selective reactions, from alkene to thioether transformations (epoxidation, hydroxychlorination, sulfoxidation). The different catalytic approaches – from in vitro to in cristallo – are compared, revealing the considerable advantages of protein crystals in terms of stabilization and acceleration of reaction kinetics. The versatility of proteins, based on metal and ligand diversity and medium/physical conditions, are thus illustrated for oxidation catalysis.

本综述介绍了使用镍转运蛋白 EcNikA 设计人工金属酶作为合成生物学替代催化剂的多种优势。文章讨论了人工酶设计策略的基本原理，特别强调了活性位点的重新构建。详细介绍了蛋白质支架对人工活性位点的影响以及最终的催化特性，强调了混合系统在催化从烯到硫醚转化（环氧化、羟基氯化、硫氧化）等选择性反应方面的巨大能力。比较了从体外到晶体内的不同催化方法，揭示了蛋白质晶体在稳定和加速反应动力学方面的巨大优势。基于金属和配体的多样性以及介质/物理条件，蛋白质在氧化催化方面的多功能性由此可见一斑。

引用次数: 0

Synthesis, characterization and comparative biological activity of a novel set of Cu(II) complexes containing azole-based ligand frames 一组含有唑基配体框架的新型 Cu(II) 复合物的合成、表征和生物活性比较

IF 3.8 2区化学 Q2 BIOCHEMISTRY & MOLECULAR BIOLOGY

Journal of Inorganic Biochemistry

Pub Date : 2024-09-19 DOI: 10.1016/j.jinorgbio.2024.112736

Courtney E. Elwell , Emily Stein , Adam Lewis , Stefan Hamaway , Kennedy A. Alexis , Joseph M. Tanski , Timothy J. Barnum , Colleen M. Connelly , Laurie A. Tyler

The synthesis and spectroscopic characterization of three complexes containing a substituted 2-(2-pyridyl)benzothiazole (PyBTh) group in the ligand frame are reported along with the comparative biological activity. The ligands have been substituted at the 6-position with either a methoxy (Py(OMe)BTh) or a methyl group (Py(Me)BTh). Reaction of Py(OMe)BTh with either CuCl₂ or Cu(NO₃)₂·2.5 H₂O yielded the monomeric [Cu(Py(OMe)BTh))₂(NO₃)]NO₃·1.5 MeOH, (1·1.5 MeOH) complex or the dimeric [Cu(Py(OMe)BTh)Cl₂]₂ (2), respectively, with the nuclearity of the complex dependent on the starting Cu(II) salt. Reaction between the methyl substituted ligand and Cu(NO₃)₂·2.5 H₂O resulted in the isolation of Cu(Py(Me)BTh)(NO₃)₂·0.5 THF (3·0.5 THF). Complexes 1–3 were fully characterized. Cyclic voltammetry measurements were performed on all three complexes as well as on [Cu(PyBTh)₂(H₂O)](BF₄)₂ (4), a compound previously reported by us which contains the unsubstituted 2-(2-pyridyl)benzothiazole ligand. The biological activity was studied and included concentration dependent DNA binding and cleavage, antibacterial activity, and cancer cell toxicity. All complexes exhibited DNA cleavage activity, however 2 and 4 were found to be the most potent. Mechanistic studies revealed that the nuclease activity is dependent on an oxidative mechanism reliant principally on O₂⁻. Antibacterial studies revealed complex 4 was more potent compared to 1–3. Cancer cell toxicity studies were carried out on HeLa, PC-3, and MCF7 cells with 1–4, Cu(QBTh)(NO₃)₂(H₂O) and Cu(PyBIm)₃(BF₄)₂. The differences in the observed toxicities suggests the importance of the ligand and its substituents in modulating cell death.

本研究报告了配体框架中含有取代的 2-(2-吡啶基)苯并噻唑（PyBTh）基团的三种配合物的合成、光谱特征以及生物活性比较。配体的 6 位被甲氧基（Py(OMe)BTh）或甲基（Py(Me)BTh）取代。Py(OMe)BTh与 CuCl2 或 Cu(NO3)2-2.5 H2O 反应分别产生单体[Cu(Py(OMe)BTh))2(NO3)]NO3-1.5 MeOH、(1-1.5 MeOH) 复合物或二聚体[Cu(Py(OMe)BTh)Cl2]2 (2)，复合物的核性取决于起始的 Cu(II) 盐。甲基取代配体与 Cu(NO3)2-2.5 H2O 反应后，分离出了 Cu(Py(Me)BTh)(NO3)2-0.5 THF（3-0.5 THF）。对 1-3 号配合物进行了全面表征。对所有这三种配合物以及[Cu(PyBTh)2(H2O)](BF4)2 (4)进行了循环伏安测量。研究的生物活性包括浓度依赖性 DNA 结合和裂解、抗菌活性和癌细胞毒性。所有复合物都具有 DNA 切割活性，但发现 2 和 4 的效力最强。机理研究表明，核酸酶活性主要依赖于 O2- 的氧化机制。抗菌研究表明，复合物 4 比 1-3 更有效。用 1-4、Cu(QBTh)(NO3)2(H2O) 和 Cu(PyBIm)3(BF4)2 对 HeLa、PC-3 和 MCF7 细胞进行了癌细胞毒性研究。观察到的毒性差异表明配体及其取代基在调节细胞死亡中的重要性。

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引用次数: 0

Mononuclear high-spin iron(III) phthalocyanines 单核高自旋铁(III)酞菁

IF 3.8 2区化学 Q2 BIOCHEMISTRY & MOLECULAR BIOLOGY

Journal of Inorganic Biochemistry

Pub Date : 2024-09-19 DOI: 10.1016/j.jinorgbio.2024.112737

Yusuke Okada, Nagao Kobayashi

2,9(or 10),16(or 17), 23(or 24)-Tetradecyloxycarbonylphthalocyaninatoiron, FeTDPc, and 2,3,9,10,16,17,23,24-octadecyloxycarbonylphthalocyaninatoiron, FeODPc, were synthesized and characterized. These compounds seem to be in trivalent iron high-spin state in solvents such as chloroform, dichloromethane, benzene, and chlorobenzene, although their counter anion could not be detected by elemental analyses. They react with strong bases such as pyridine and imidazoles to form their mono- and subsequently their di-base complexes with formation constant of >10⁶ and < 200 dm³ mol⁻¹, respectively, in dichloromethane at 20 °C. The resultant mono-adducts appear to be trivalent iron low-spin while the di-base adducts are bivalent iron low-spin state complexes. The addition of ca. 10–30 equivalent of tetrabutylammonium-chloride or -bromide (electrolyte) to the solution containing FeTDPc or FeODPc, causes their spin-state change from iron(III) high to low-spin state. In a solid power state, however, both FeTDPc and FeODPc exist as a mixture of high-spin iron(III)- and intermediate-spin iron(II) species. Strangely, when these compounds are dissolved in polystyrene, i.e. each molecules are isolated from each other, the signals originated from the iron(II) component disappear.

合成并鉴定了 2,9(或 10),16(或 17),23(或 24)-十四烷氧基羰基酞菁铁（FeTDPc）和 2,3,9,10,16,17,23,24-十八烷氧基羰基酞菁铁（FeODPc）。这些化合物在氯仿、二氯甲烷、苯和氯苯等溶剂中似乎处于三价铁高自旋态，但其反阴离子无法通过元素分析检测到。在 20 °C 的二氯甲烷中，它们会与吡啶和咪唑等强碱发生反应，形成单碱和双碱络合物，形成常数分别为 106 和 200 dm3 mol-1。生成的单加合物似乎是三价低旋铁，而二碱加合物则是二价低旋铁态络合物。在含有 FeTDPc 或 FeODPc 的溶液中加入约 10-30 等量的四丁基氯化铵或溴化铵（电解质），会使它们的自旋态从铁（III）的高自旋态转变为低自旋态。然而，在固态电源状态下，FeTDPc 和 FeODPc 都是高自旋铁（III）和中等自旋铁（II）的混合物。奇怪的是，当这些化合物溶解在聚苯乙烯中时，即各分子相互隔离时，来自铁（II）成分的信号消失了。

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引用次数: 0