Ru(bpy)2dppz-BTDZ]2+: A噻二唑延伸钌（II）配合物的插层结合、光开关行为和理论分析

IF 3.2 2区化学 Q2 BIOCHEMISTRY & MOLECULAR BIOLOGY

Journal of Inorganic Biochemistry Pub Date : 2025-09-22 DOI:10.1016/j.jinorgbio.2025.113083

Mariana O.T. Nogueira , Pedro Henrique L. da Silva , Ana Carolina C. do Nascimento , Nathan B. Soares , Joyce S.F. Diz , Steven R. LaPlante , Luiz Sérgio R. Lamego , Tanos C.C. França , Fabio S. Miranda

{"title":"Ru(bpy)2dppz-BTDZ]2+: A噻二唑延伸钌（II）配合物的插层结合、光开关行为和理论分析","authors":"Mariana O.T. Nogueira , Pedro Henrique L. da Silva , Ana Carolina C. do Nascimento , Nathan B. Soares , Joyce S.F. Diz , Steven R. LaPlante , Luiz Sérgio R. Lamego , Tanos C.C. França , Fabio S. Miranda","doi":"10.1016/j.jinorgbio.2025.113083","DOIUrl":null,"url":null,"abstract":"<div><div>The new ruthenium(II) polypyridyl complex [Ru(bpy)₂dppz-BTDZ]2+, featuring a thiadiazole-substituted dppz ligand, was synthesized and characterized to investigate its DNA-binding and photophysical properties. Its interaction with calf thymus DNA (Ct-DNA) was studied through UV–visible and emission spectroscopy, competitive binding assays with ethidium bromide (EB), anionic quenching with K4[Fe(CN)6], viscosity and molecular modeling. The results indicate that the complex intercalates into DNA, with a binding constant (Kb) of 6.57 ± 0.9 × 106 M−1 and has a 7 % enhancement in the light-switch effect compared to [Ru(bpy)₂dppz]2+. DFT calculations characterized the excited states, which were compared to those of [Ru(bpy)₂dppz]2+. The presence of the thiadiazole group promotes mixing of MLCT states. Franck–Condon analysis of emission spectra in MeCN, water, and DNA allowed for the estimation of the excited-state free energy. In water, the emissive bright state lies approximately 1300 cm−1 higher than in DNA and approximately 1100 cm−1 higher than in MeCN. This energy trend is consistent with the light-switch behavior observed in this class of complexes. Moreover, the bright-state energies correlated very well with all the observed lifetimes. Docking and molecular dynamics simulations revealed stable intercalative binding in the DNA minor groove, with the Δ-isomer showing enhanced stability.</div></div>","PeriodicalId":364,"journal":{"name":"Journal of Inorganic Biochemistry","volume":"274 ","pages":"Article 113083"},"PeriodicalIF":3.2000,"publicationDate":"2025-09-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Intercalative binding, light-switch behavior, and theoretical analysis of Ru(bpy)2dppz-BTDZ]2+: A thiadiazole-extended ruthenium(II) complex\",\"authors\":\"Mariana O.T. Nogueira , Pedro Henrique L. da Silva , Ana Carolina C. do Nascimento , Nathan B. Soares , Joyce S.F. Diz , Steven R. LaPlante , Luiz Sérgio R. Lamego , Tanos C.C. França , Fabio S. Miranda\",\"doi\":\"10.1016/j.jinorgbio.2025.113083\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>The new ruthenium(II) polypyridyl complex [Ru(bpy)₂dppz-BTDZ]2+, featuring a thiadiazole-substituted dppz ligand, was synthesized and characterized to investigate its DNA-binding and photophysical properties. Its interaction with calf thymus DNA (Ct-DNA) was studied through UV–visible and emission spectroscopy, competitive binding assays with ethidium bromide (EB), anionic quenching with K4[Fe(CN)6], viscosity and molecular modeling. The results indicate that the complex intercalates into DNA, with a binding constant (Kb) of 6.57 ± 0.9 × 106 M−1 and has a 7 % enhancement in the light-switch effect compared to [Ru(bpy)₂dppz]2+. DFT calculations characterized the excited states, which were compared to those of [Ru(bpy)₂dppz]2+. The presence of the thiadiazole group promotes mixing of MLCT states. Franck–Condon analysis of emission spectra in MeCN, water, and DNA allowed for the estimation of the excited-state free energy. In water, the emissive bright state lies approximately 1300 cm−1 higher than in DNA and approximately 1100 cm−1 higher than in MeCN. This energy trend is consistent with the light-switch behavior observed in this class of complexes. Moreover, the bright-state energies correlated very well with all the observed lifetimes. Docking and molecular dynamics simulations revealed stable intercalative binding in the DNA minor groove, with the Δ-isomer showing enhanced stability.</div></div>\",\"PeriodicalId\":364,\"journal\":{\"name\":\"Journal of Inorganic Biochemistry\",\"volume\":\"274 \",\"pages\":\"Article 113083\"},\"PeriodicalIF\":3.2000,\"publicationDate\":\"2025-09-22\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Inorganic Biochemistry\",\"FirstCategoryId\":\"99\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0162013425002636\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"BIOCHEMISTRY & MOLECULAR BIOLOGY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Inorganic Biochemistry","FirstCategoryId":"99","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0162013425002636","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"BIOCHEMISTRY & MOLECULAR BIOLOGY","Score":null,"Total":0}

引用次数: 0

摘要

合成了以噻二唑取代dppz为配体的新型钌（II）多吡啶配合物[Ru(bpy) 2 dppz- btdz]2+，并对其dna结合和光物理性质进行了表征。通过紫外可见光谱和发射光谱，与溴化乙啶（EB）的竞争结合实验，与K4[Fe(CN)6]的阴离子猝灭，粘度和分子模型研究了其与小牛胸腺DNA （Ct-DNA）的相互作用。结果表明，该配合物插入DNA，结合常数（Kb）为6.57±0.9 × 106 M−1，与[Ru（bpy）₂dppz]2+相比，其光开关效应增强了7%。DFT计算表征了激发态，并与[Ru(bpy) 2 dppz]2+的激发态进行了比较。噻二唑基团的存在促进了MLCT状态的混合。通过对MeCN、水和DNA的发射光谱进行frank - condon分析，可以估计激发态的自由能。在水中，发光亮态比DNA高约1300 cm−1，比MeCN高约1100 cm−1。这种能量趋势与在这类配合物中观察到的光开关行为是一致的。此外，光态能量与所有观测到的寿命都有很好的相关性。对接和分子动力学模拟显示，在DNA小槽中有稳定的插入结合，Δ-isomer显示出增强的稳定性。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

Intercalative binding, light-switch behavior, and theoretical analysis of Ru(bpy)2dppz-BTDZ]2+: A thiadiazole-extended ruthenium(II) complex

查看原文本刊更多论文

Intercalative binding, light-switch behavior, and theoretical analysis of Ru(bpy)2dppz-BTDZ]2+: A thiadiazole-extended ruthenium(II) complex

The new ruthenium(II) polypyridyl complex [Ru(bpy)₂dppz-BTDZ]²⁺, featuring a thiadiazole-substituted dppz ligand, was synthesized and characterized to investigate its DNA-binding and photophysical properties. Its interaction with calf thymus DNA (Ct-DNA) was studied through UV–visible and emission spectroscopy, competitive binding assays with ethidium bromide (EB), anionic quenching with K₄[Fe(CN)₆], viscosity and molecular modeling. The results indicate that the complex intercalates into DNA, with a binding constant (K_b) of 6.57 ± 0.9 × 10⁶ M⁻¹ and has a 7 % enhancement in the light-switch effect compared to [Ru(bpy)₂dppz]²⁺. DFT calculations characterized the excited states, which were compared to those of [Ru(bpy)₂dppz]²⁺. The presence of the thiadiazole group promotes mixing of MLCT states. Franck–Condon analysis of emission spectra in MeCN, water, and DNA allowed for the estimation of the excited-state free energy. In water, the emissive bright state lies approximately 1300 cm⁻¹ higher than in DNA and approximately 1100 cm⁻¹ higher than in MeCN. This energy trend is consistent with the light-switch behavior observed in this class of complexes. Moreover, the bright-state energies correlated very well with all the observed lifetimes. Docking and molecular dynamics simulations revealed stable intercalative binding in the DNA minor groove, with the Δ-isomer showing enhanced stability.

求助全文

通过发布文献求助，成功后即可免费获取论文全文。去求助

来源期刊

Journal of Inorganic Biochemistry 生物-生化与分子生物学

CiteScore

7.00

自引率

10.30%

发文量

336

审稿时长

41 days

期刊介绍： The Journal of Inorganic Biochemistry is an established international forum for research in all aspects of Biological Inorganic Chemistry. Original papers of a high scientific level are published in the form of Articles (full length papers), Short Communications, Focused Reviews and Bioinorganic Methods. Topics include: the chemistry, structure and function of metalloenzymes; the interaction of inorganic ions and molecules with proteins and nucleic acids; the synthesis and properties of coordination complexes of biological interest including both structural and functional model systems; the function of metal- containing systems in the regulation of gene expression; the role of metals in medicine; the application of spectroscopic methods to determine the structure of metallobiomolecules; the preparation and characterization of metal-based biomaterials; and related systems. The emphasis of the Journal is on the structure and mechanism of action of metallobiomolecules.