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Near-infrared (NIR) luminescence of two Tm(III)-based dicarboxylate coordination polymers 两种Tm(III)基二羧酸盐配位聚合物的近红外发光研究
IF 3.2 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2026-04-01 Epub Date: 2025-12-27 DOI: 10.1016/j.ica.2025.123044
Liying Zhang , Yan Li , Wenzhe Zhou , Lu Gao , Yong Fan , Li Wang
Two novel Tm(III)-based coordination polymers formulated as [Tm(2,5-dtc)(NO3)(H2O)]n (1) (2,5-H₂dtc = thiophene-2,5-dicarboxylic acid) and {[Tm2(OH-bdc)2(H2O)10]·OH-bdc·H2O}n (2) (OH-H₂bdc = 5-hydroxyisophthalic acid) were synthesized hydrothermally. Compound 1 features a three dimensional (3D) pillared layer network containing [Tm2(NO3)2]4+ units and 2,5-dtc2− ligands. Compound 2 exhibits a 2D layer structure which is accomplished by connecting the 1D chain [Tm2(bdc)2(H2O)10]2+ to uncoordinated OH-bdc2− ligands via π···π stacking interactions. The striking feature of compounds 1 and 2 is near-infrared (NIR) luminescence of Tm(III) ions with microseconds luminescence lifetimes, after being excitated at the maximum absorption of ligands. This may be attributed to the efficient energy transfer from the ligands (2,5-H₂dtc and OH-H₂bdc) to central Tm(III) ions via an antenna effect. In addition, compounds 1 and 2 display antiferromagnetic coupling in the solid state at room temperature.
采用水热法合成了两种新型Tm(III)基配位聚合物[Tm(2,5-dtc)(NO3)(H2O)]n (1) (2,5- h₂dtc =噻吩-2,5-二羧酸)和{[Tm2(OH-bdc)2(H2O)10]·OH-bdc·H2O}n (2) (OH-H₂bdc = 5-羟基间苯二甲酸)。化合物1具有三维(3D)柱状层网络,包含[Tm2(NO3)2]4+单元和2,5-dtc2−配体。化合物2是通过π···π堆叠作用将一维链[Tm2(bdc)2(H2O)10]2+与不配位的OH-bdc2−配体连接而成的二维层状结构。化合物1和2的显著特征是在配体最大吸收处激发后,Tm(III)离子的近红外发光(NIR)寿命为微秒。这可能是由于配体(2,5- h₂dtc和OH-H₂bdc)通过天线效应有效地将能量转移到中心的Tm(III)离子上。此外,化合物1和2在室温下表现出固态的反铁磁耦合。
{"title":"Near-infrared (NIR) luminescence of two Tm(III)-based dicarboxylate coordination polymers","authors":"Liying Zhang ,&nbsp;Yan Li ,&nbsp;Wenzhe Zhou ,&nbsp;Lu Gao ,&nbsp;Yong Fan ,&nbsp;Li Wang","doi":"10.1016/j.ica.2025.123044","DOIUrl":"10.1016/j.ica.2025.123044","url":null,"abstract":"<div><div>Two novel Tm(III)-based coordination polymers formulated as [Tm(2,5-dtc)(NO<sub>3</sub>)(H<sub>2</sub>O)]<sub><em>n</em></sub> (<strong>1</strong>) (2,5-H₂dtc = thiophene-2,5-dicarboxylic acid) and {[Tm<sub>2</sub>(OH-bdc)<sub>2</sub>(H<sub>2</sub>O)<sub>10</sub>]·OH-bdc·H<sub>2</sub>O}<sub><em>n</em></sub> (<strong>2</strong>) (OH-H₂bdc = 5-hydroxyisophthalic acid) were synthesized hydrothermally. Compound <strong>1</strong> features a three dimensional (3D) pillared layer network containing [Tm<sub>2</sub>(NO<sub>3</sub>)<sub>2</sub>]<sup>4+</sup> units and 2,5-dtc<sup>2−</sup> ligands. Compound <strong>2</strong> exhibits a 2D layer structure which is accomplished by connecting the 1D chain [Tm<sub>2</sub>(bdc)<sub>2</sub>(H<sub>2</sub>O)<sub>10</sub>]<sup>2+</sup> to uncoordinated OH-bdc<sup>2−</sup> ligands via <em>π···π</em> stacking interactions. The striking feature of compounds <strong>1</strong> and <strong>2</strong> is near-infrared (NIR) luminescence of Tm(III) ions with microseconds luminescence lifetimes, after being excitated at the maximum absorption of ligands. This may be attributed to the efficient energy transfer from the ligands (2,5-H₂dtc and OH-H₂bdc) to central Tm(III) ions via an antenna effect. In addition, compounds <strong>1</strong> and <strong>2</strong> display antiferromagnetic coupling in the solid state at room temperature.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"593 ","pages":"Article 123044"},"PeriodicalIF":3.2,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145939886","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Nature of bonding between B2H4/B2H2 with Homo-/hetero- Di/tri-nuclear-metal-carbonyls B2H4/B2H2与Homo-/hetero- Di/三核金属羰基成键的性质
IF 3.2 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2026-04-01 Epub Date: 2025-12-30 DOI: 10.1016/j.ica.2025.123058
Harsha S. Karnamkkott, Sonam Suthar, Kartik Chandra Mondal
The diborane(4) (B2H4) and diborene(2) (B2H2) are the captivating chemical species which have been already stabilized by donor base ligands [L = carbene; (L)BH=BH(L)] and also by metal-carbonyls. Although the BB bonding in (L)BH=BH(L) has been examined using EDA-NOCV, the stabilizing influence of metal-carbonyl fragments on the related B2H4 and B2H2 species remains unexplored. Thus the bonding interactions between B2H4/B2H2 and homo/hetero- di-/tri-nuclear metal-carbonyl in [{CpMo(CO)2}2{B2H4}] (1) and three isostructural transition-metal-carbonyl compounds of diborene(2) [{CpMo(CO)2}2B2H2W(CO)4] (2), [{CpW(CO)2}2B2H2Mo(CO)4] (3) and [{CpW(CO)2}2B2H2W(CO)4] (4) were investigated using the EDA-NOCV analyses. The calculations provide key insights into the bonding features that account for their remarkable stability. The bonding interactions in 1–4 are primarily governed by electrostatic forces (ΔEelec) with notable covalent contributions (ΔEorb). Although 2–4 is isostructural diborene(2) compounds, EDA–NOCV reveals that the metal–carbonyl fragment dictates the preferred bonding mode. Compounds 2-3 show the interaction of fragments with charged doublet states (D+E) while the nature of bonds in 4 [M = M′ = W] shifts predominantly to dative interaction (D), similar to homo-dinuclear compound 1. The B2H2 metal-carbonyl bonding interaction is much stronger in 23 (∼80–90 kcal/mol higher) compared to 4. Orbital analysis indicates predominant σ-donation from B2H4/B2H2, and in 4, additional π-backdonation from the metal centers strengthens the BB bond.
二硼烷(4)(B2H4)和二硼烯(2)(B2H2)是已经被供体碱配体稳定的具有吸引力的化学物质[L =卡宾;(L)BH=BH(L)]以及金属羰基。虽然(L)BH=BH(L)中的BB键已经用EDA-NOCV进行了研究,但金属羰基片段对相关B2H4和B2H2的稳定作用仍未被探索。利用EDA-NOCV分析研究了[{CpMo(CO)2}2{B2H4}](1)中B2H4/B2H2与同源/杂二核/三核金属-羰基之间的成键作用,以及二硼烯(2)[{CpMo(CO)2}2B2H2W(CO)4](2)、[{CpW(CO)2}2B2H2Mo(CO)4](3)和[{CpW(CO)2}2B2H2W(CO)4](4)等结构过渡金属-羰基化合物[{CpW(CO)2}2B2H2W(CO)4](4)之间的成键作用。这些计算提供了对键合特征的关键见解,这些特征解释了它们非凡的稳定性。1-4中的键相互作用主要由静电力(ΔEelec)和显著的共价作用(ΔEorb)控制。虽然2 - 4是同结构二硼烯(2)化合物,但EDA-NOCV显示金属-羰基片段决定了首选键模式。化合物2-3表现出带电荷重态的碎片相互作用(D+E),而4 [M = M ' = W]中的键的性质主要转变为共轭相互作用(D),类似于同型双核化合物1。B2H2金属-羰基键相互作用在2-3 (~ 80-90 kcal/mol高)比4强得多。轨道分析表明,B2H4/B2H2的σ-给能占主导地位,在4中,金属中心的π-反给能增强了BB键。
{"title":"Nature of bonding between B2H4/B2H2 with Homo-/hetero- Di/tri-nuclear-metal-carbonyls","authors":"Harsha S. Karnamkkott,&nbsp;Sonam Suthar,&nbsp;Kartik Chandra Mondal","doi":"10.1016/j.ica.2025.123058","DOIUrl":"10.1016/j.ica.2025.123058","url":null,"abstract":"<div><div>The diborane(4) (B<sub>2</sub>H<sub>4</sub>) and diborene(2) (B<sub>2</sub>H<sub>2</sub>) are the captivating chemical species which have been already stabilized by donor base ligands [L = carbene; (L)BH=BH(L)] and also by metal-carbonyls. Although the B<img>B bonding in (L)BH=BH(L) has been examined using EDA-NOCV, the stabilizing influence of metal-carbonyl fragments on the related B<sub>2</sub>H<sub>4</sub> and B<sub>2</sub>H<sub>2</sub> species remains unexplored. Thus the bonding interactions between B<sub>2</sub>H<sub>4</sub>/B<sub>2</sub>H<sub>2</sub> and homo/hetero- di-/tri-nuclear metal-carbonyl in [{CpMo(CO)<sub>2</sub>}<sub>2</sub>{B<sub>2</sub>H<sub>4</sub>}] (<strong>1</strong>) and three isostructural transition-metal-carbonyl compounds of diborene(2) [{CpMo(CO)<sub>2</sub>}<sub>2</sub>B<sub>2</sub>H<sub>2</sub>W(CO)<sub>4</sub>] (<strong>2</strong>), [{CpW(CO)<sub>2</sub>}<sub>2</sub>B<sub>2</sub>H<sub>2</sub>Mo(CO)<sub>4</sub>] (<strong>3</strong>) and [{CpW(CO)<sub>2</sub>}<sub>2</sub>B<sub>2</sub>H<sub>2</sub>W(CO)<sub>4</sub>] (<strong>4</strong>) were investigated using the EDA-NOCV analyses. The calculations provide key insights into the bonding features that account for their remarkable stability. The bonding interactions in <strong>1–4</strong> are primarily governed by electrostatic forces (Δ<em>E</em><sub>elec</sub>) with notable covalent contributions (Δ<em>E</em><sub>orb</sub>). Although <strong>2–4</strong> is isostructural diborene(2) compounds, EDA–NOCV reveals that the metal–carbonyl fragment dictates the preferred bonding mode. Compounds <strong>2-3</strong> show the interaction of fragments with charged doublet states (D+E) while the nature of bonds in <strong>4</strong> [M = M′ = W] shifts predominantly to dative interaction (D), similar to homo-dinuclear compound <strong>1</strong>. The B<sub>2</sub>H<sub>2</sub> metal-carbonyl bonding interaction is much stronger in <strong>2</strong>–<strong>3</strong> (∼80–90 kcal/mol higher) compared to <strong>4</strong>. Orbital analysis indicates predominant σ-donation from B<sub>2</sub>H<sub>4</sub>/B<sub>2</sub>H<sub>2</sub>, and in <strong>4</strong>, additional π-backdonation from the metal centers strengthens the B<img>B bond.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"593 ","pages":"Article 123058"},"PeriodicalIF":3.2,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145939884","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Synthesis, structure and photooxidative dehydrogenation of chiral Ir(III) valine complexes based on precursor [Λ-Ir(dfppy)2(MeCN)2](PF6) 基于前驱体[Λ-Ir(dfppy)2(MeCN)2](PF6)的手性Ir(III) valine配合物的合成、结构和光氧化脱氢
IF 3.2 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2026-04-01 Epub Date: 2025-12-16 DOI: 10.1016/j.ica.2025.123041
Manli Cao , Suyang Yao , Lulu Ren, Zhiyu Zhao, Shaojun Mao, Shengqiang Jiang
Octahedral chiral-at-Ir(III) complexes exhibit high structural stability and stereoselectivity in asymmetric synthesis. These properties enable them to serve as efficient chiral templates, inducing asymmetry in coordinated ligands. In our previous work, we have proved such chiral-at-Ir(III) complexes could coordinate to commercial amino acids and further oxidative dehydrogenation to imines. To further investigate this oxidative dehydrogenation process in complexes with different cyclometalating ligands, here we employed a fluoro-substituted 2-(2,4-difluorophenyl)pyridine (dfppy) as a cyclometalating ligand to synthesize the chiral Ir(III) precursor Λ-[Ir(dfppy)₂(MeCN)₂]PF₆. This complex was coordinated with D- and L-valine to yield two diastereomeric complexes, Λ-[Ir(dfppy)₂(D-val)] and Λ-[Ir(dfppy)₂(L-val)] (Val is Valine). The structure and oxidative dehydrogenation ability of these obtained diastereomers were investigated. Under visible-light irradiation, both complexes underwent dehydrogenative oxidation of the valine moiety and Λ-[Ir(dfppy)₂(D-val)] exhibited faster photooxidation kinetics than its L-valine counterpart. Their component, structural and photophysical properties were characterized by 1H NMR, mass spectrometry, single-crystal X-ray diffraction, UV–vis spectra and emission spectra.
八面体手性ir (III)配合物在不对称合成中具有较高的结构稳定性和立体选择性。这些性质使它们能够作为有效的手性模板,在配位体中诱导不对称。在我们之前的工作中,我们已经证明了这种手性at- ir (III)配合物可以与商业氨基酸配合,并进一步氧化脱氢生成亚胺。为了进一步研究不同环金属化配体配合物的氧化脱氢过程,本文采用含氟取代的2-(2,4-二氟苯基)吡啶(dppy)作为环金属化配体合成了手性Ir(III)前体Λ-[Ir(dppy)₂(MeCN)₂]PF₆。该配合物与D-和l -缬氨酸配位得到两个非对映异构体配合物Λ-[Ir(dppy) 2 (D- Val)]和Λ-[Ir(dppy) 2 (L-val)] (Val为缬氨酸)。研究了这些非对映体的结构和氧化脱氢能力。在可见光照射下,这两种配合物都发生了缬氨酸部分的脱氢氧化,并且Λ-[Ir(dppy) 2 (D-val)]表现出比l -缬氨酸更快的光氧化动力学。采用1H NMR、质谱、单晶x射线衍射、紫外-可见光谱和发射光谱对其组成、结构和光物理性质进行了表征。
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引用次数: 0
Concurrent detection and removal of Hg2+ from potable water using ZnAl2O4 modified end off Schiff base ligand: Experimental and theoretical investigation ZnAl2O4修饰末端希夫碱配体同时检测和去除饮用水中的Hg2+:实验和理论研究
IF 3.2 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2026-04-01 Epub Date: 2025-12-24 DOI: 10.1016/j.ica.2025.123045
Sneha Biswas , Jaydeep Adhikary , Rama Rathi , Sreejeeb Ganguly , Ennio Zangrando , Abhijit Kumar Das
A Schiff base ligand, [4-Methyl-2,6-bis((E)-((2-(pyridin-2-yl)ethyl)imino)methyl)phenol], shortly Diformyl Amino Pyridine (DAP), has been developed as a homogeneous probe and characterized by different spectroscopic technique. Its fluorescence is quenched by Hg2+ binding, a process governed by multiple non-radiative pathways, including photoinduced electron transfer (PET) and heavy-atom effects, with a Stern-Volmer constant of 8.83 × 108 M−1 and a detection limit of 1.35 μM. To address limitations like reusability and sample matrix separation, the homogeneous probe DAP was converted into a heterogeneous solid-state material, ZnAl2O4 (ZA) conjugated DAP (ZDAP), by anchoring the imine ligand onto a ZA spinel. Surprisingly, this modification fundamentally altered the sensing mechanism. In contrast to DAP's quenching, ZDAP exhibits a “turn-on” response via Aggregation-Induced Emission (AIE), where Hg2+ binding restricts intramolecular motion and enhances fluorescence. This results in a superior detection limit of 1.01 nM. ICP-MS analysis confirmed that treatment with the sensor resulted in nearly complete mercury removal, achieving up to 98.46 % elimination of mercury. The sensing mechanisms for both systems have been confirmed through DFT calculations and experimental techniques like Stern-Volmer analysis and time-resolved fluorescence spectroscopy. Theoretical calculations show excellent agreement with experimental HOMO-LUMO transitions, where the energy gap decreases from 2.28 eV (ZA) to 2.15 eV (ZDAP), causing a bathochromic shift in emission. The observed fluorescence quenching of DAP upon anchoring to ZA arises from strong ligand-metal interactions, charge transfer–induced non-radiative decay, structural rigidification, and surface defect trapping, consistent with the experimental (2.93 eV) band gap. Crucially, ZDAP demonstrated outstanding reusability, maintaining its sensing efficiency and structural integrity for at least five cycles after regeneration with a chelating agent. This work demonstrates how a single Schiff base platform can be engineered to deliver two complementary sensing modes, offering a sensitive, selective, and sustainable solution for mercury detection and removal.
希夫碱配体[4-甲基-2,6-双((E)-((2-(吡啶-2-基)乙基)亚氨基)甲基)苯酚],简称二甲酰氨基吡啶(DAP),是一种均相探针,并通过不同的光谱技术进行了表征。它的荧光被Hg2+结合猝灭,这一过程受多种非辐射途径的控制,包括光诱导电子转移(PET)和重原子效应,Stern-Volmer常数为8.83 × 108 M−1,检测限为1.35 μM。为了解决可重复使用性和样品基质分离等限制,通过将亚胺配体锚定在ZA尖晶石上,将均相探针DAP转化为非均相固态材料ZnAl2O4 (ZA)共轭DAP (ZDAP)。令人惊讶的是,这种改变从根本上改变了感知机制。与DAP的猝灭相反,ZDAP通过聚集诱导发射(AIE)表现出“开启”反应,其中Hg2+结合限制了分子内运动并增强了荧光。该方法的检出限为1.01 nM。ICP-MS分析证实,使用该传感器处理后,汞几乎完全去除,汞去除率高达98.46%。这两个系统的传感机制已经通过DFT计算和实验技术,如斯特恩-沃尔默分析和时间分辨荧光光谱得到证实。理论计算结果与实验结果非常吻合,能隙从2.28 eV (ZA)减小到2.15 eV (ZDAP),引起发射的深色偏移。所观察到的DAP锚定在ZA上的荧光猝灭是由强配-金属相互作用、电荷转移诱导的非辐射衰变、结构硬化和表面缺陷捕获引起的,与实验(2.93 eV)带隙一致。至关重要的是,ZDAP具有出色的可重复使用性,在螯合剂再生后至少可以保持其传感效率和结构完整性5个循环。这项工作展示了单个希夫基平台如何设计为提供两种互补的传感模式,为汞检测和去除提供敏感,选择性和可持续的解决方案。
{"title":"Concurrent detection and removal of Hg2+ from potable water using ZnAl2O4 modified end off Schiff base ligand: Experimental and theoretical investigation","authors":"Sneha Biswas ,&nbsp;Jaydeep Adhikary ,&nbsp;Rama Rathi ,&nbsp;Sreejeeb Ganguly ,&nbsp;Ennio Zangrando ,&nbsp;Abhijit Kumar Das","doi":"10.1016/j.ica.2025.123045","DOIUrl":"10.1016/j.ica.2025.123045","url":null,"abstract":"<div><div>A Schiff base ligand, <em>[4-Methyl-2,6-bis((E)-((2-(pyridin-2-yl)ethyl)imino)methyl)phenol]</em>, shortly Diformyl Amino Pyridine (<strong>DAP</strong>), has been developed as a homogeneous probe and characterized by different spectroscopic technique. Its fluorescence is quenched by Hg<sup>2+</sup> binding, a process governed by multiple non-radiative pathways, including photoinduced electron transfer (PET) and heavy-atom effects, with a Stern-Volmer constant of 8.83 × 10<sup>8</sup> M<sup>−1</sup> and a detection limit of 1.35 μM. To address limitations like reusability and sample matrix separation, the homogeneous probe <strong>DAP</strong> was converted into a heterogeneous solid-state material, ZnAl<sub>2</sub>O<sub>4</sub> (<strong>ZA</strong>) conjugated <strong>DAP</strong> (<strong>ZDAP</strong>), by anchoring the imine ligand onto a ZA spinel. Surprisingly, this modification fundamentally altered the sensing mechanism. In contrast to <strong>DAP</strong>'s quenching, <strong>ZDAP</strong> exhibits a “turn-on” response via Aggregation-Induced Emission (AIE), where Hg<sup>2+</sup> binding restricts intramolecular motion and enhances fluorescence. This results in a superior detection limit of 1.01 nM. ICP-MS analysis confirmed that treatment with the sensor resulted in nearly complete mercury removal, achieving up to 98.46 % elimination of mercury. The sensing mechanisms for both systems have been confirmed through DFT calculations and experimental techniques like Stern-Volmer analysis and time-resolved fluorescence spectroscopy. Theoretical calculations show excellent agreement with experimental HOMO-LUMO transitions, where the energy gap decreases from 2.28 eV (ZA) to 2.15 eV (<strong>ZDAP</strong>), causing a bathochromic shift in emission. The observed fluorescence quenching of <strong>DAP</strong> upon anchoring to ZA arises from strong ligand-metal interactions, charge transfer–induced non-radiative decay, structural rigidification, and surface defect trapping, consistent with the experimental (2.93 eV) band gap. Crucially, <strong>ZDAP</strong> demonstrated outstanding reusability, maintaining its sensing efficiency and structural integrity for at least five cycles after regeneration with a chelating agent. This work demonstrates how a single Schiff base platform can be engineered to deliver two complementary sensing modes, offering a sensitive, selective, and sustainable solution for mercury detection and removal.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"593 ","pages":"Article 123045"},"PeriodicalIF":3.2,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145839361","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Dehydroacetic acid benzoyl hydrazone complexes of Ni(II) and Pd(II): Synthesis, characterization, computational studies, biomolecular interaction, and dual anticancer–antimicrobial activities Ni(II)和Pd(II)的脱氢乙酸苯甲酰腙配合物:合成、表征、计算研究、生物分子相互作用和双重抗癌-抗菌活性
IF 3.2 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2026-04-01 Epub Date: 2025-12-28 DOI: 10.1016/j.ica.2025.123047
Islam M. Elnabky , Mohamed M. Aboelnga , Hoda M. El-Gharabawy , Shadia A. Elsayed , Ahmed M. El-Hendawy
Four new Nickel(II) and Palladium(II) complexes of a dehydroacetic acid benzoyl hydrazone Schiff base ligand (H2L) with composition [M(L)(X)] (M = Ni or Pd; X = H2O for Ni1, Pd1, or imidazole for Ni2, Pd2) were synthesized. Elemental analyses (CHN), spectroscopic tools (FTIR, 1H NMR, HRMS, and UV–Vis spectroscopy), thermal analysis, and magnetic measurements were used to elucidate their molecular structures. The data obtained confirmed the bi-negative tridentate coordination nature of the ligand via deprotonated hydroxyl group/amide oxygen, and azomethine nitrogen as (ONO-donor). The complex Ni1) displayed a tetrahedral geometry, while the complexes (Ni2 and Pd1,2) displayed square planar geometry, which was also confirmed by DFT calculations. Their binding affinity towards DNA and BSA was investigated by UV–Vis and fluorescence spectroscopy revealed strong binding affinities (1.2–4.3 × 104 M−1). Molecular docking further confirmed stable interactions with both biomolecules. The in vitro cytotoxic of all complexes was evaluated using MTT assay against human breast cancer (MCF7 and MDA-MB-231), and hepatocellular (HepG2) cell line, as well as a normal human lung fibroblast cell line (WI-38), and cisplatin was used as a standard reference drug. Among these complexes, the Pd2 complex exhibited the most potent activity, especially against MDA-MB-231 (IC50 = 5.53 ± 0.4 μM; selectivity index = 12.07). Antimicrobial activity was assessed against Gram-positive/negative bacteria, yeasts, and filamentous fungi. The Ni1 and Ni2 complexes showed superior antimicrobial effects compared to Pd complexes and the free ligand. These findings highlight the promising biological potential of these metal complexes, particularly Pd2, as anticancer and antimicrobial agents, warranting further exploration for biomedical applications.
合成了四种新的脱氢乙酸苯甲酰腙希夫碱配体(H2L)的镍(II)和钯(II)配合物,其组成为[M(L)(X)] (M = Ni或Pd; Ni1、Pd1为X = H2O, Ni2、Pd2为咪唑)。元素分析(CHN)、光谱分析工具(FTIR、1H NMR、HRMS和UV-Vis光谱)、热分析和磁测量来阐明它们的分子结构。得到的数据证实了该配体通过去质子化羟基/酰胺氧和亚甲基氮作为(ono)供体的双负三叉配位性质。配合物Ni1)呈现四面体几何形状,而配合物Ni2和pd1,2呈现平面方形几何形状,DFT计算也证实了这一点。通过紫外可见光谱和荧光光谱研究了它们对DNA和牛血清白蛋白的结合亲和力,结果表明它们具有很强的结合亲和力(1.2-4.3 × 104 M−1)。分子对接进一步证实了与这两种生物分子的稳定相互作用。采用MTT法评估所有复合物对人乳腺癌(MCF7和MDA-MB-231)、肝细胞(HepG2)细胞系以及正常人肺成纤维细胞系(WI-38)的体外细胞毒性,并以顺铂作为标准参比药物。其中,Pd2配合物对MDA-MB-231的抑制作用最强(IC50 = 5.53±0.4 μM,选择性指数= 12.07)。对革兰氏阳性/阴性细菌、酵母和丝状真菌的抗菌活性进行了评估。与Pd配合物和游离配体相比,Ni1和Ni2配合物具有更好的抗菌效果。这些发现突出了这些金属配合物,特别是Pd2作为抗癌和抗菌药物的良好生物学潜力,值得进一步探索其在生物医学上的应用。
{"title":"Dehydroacetic acid benzoyl hydrazone complexes of Ni(II) and Pd(II): Synthesis, characterization, computational studies, biomolecular interaction, and dual anticancer–antimicrobial activities","authors":"Islam M. Elnabky ,&nbsp;Mohamed M. Aboelnga ,&nbsp;Hoda M. El-Gharabawy ,&nbsp;Shadia A. Elsayed ,&nbsp;Ahmed M. El-Hendawy","doi":"10.1016/j.ica.2025.123047","DOIUrl":"10.1016/j.ica.2025.123047","url":null,"abstract":"<div><div>Four new Nickel(II) and Palladium(II) complexes of a dehydroacetic acid benzoyl hydrazone Schiff base ligand (H<sub>2</sub>L) with composition [M(L)(X)] (M = Ni or Pd; X = H<sub>2</sub>O for <strong>Ni1</strong>, <strong>Pd1,</strong> or imidazole for <strong>Ni2</strong>, <strong>Pd2</strong>) were synthesized. Elemental analyses (CHN), spectroscopic tools (FTIR, <sup>1</sup>H NMR, HRMS, and UV–Vis spectroscopy), thermal analysis, and magnetic measurements were used to elucidate their molecular structures. The data obtained confirmed the bi-negative tridentate coordination nature of the ligand <em>via</em> deprotonated hydroxyl group/amide oxygen, and azomethine nitrogen as (ONO-donor). The complex Ni1) displayed a tetrahedral geometry, while the complexes (<strong>Ni2</strong> and <strong>Pd1,2</strong>) displayed square planar geometry, which was also confirmed by DFT calculations. Their binding affinity towards DNA and BSA was investigated by UV–Vis and fluorescence spectroscopy revealed strong binding affinities (1.2–4.3 × 10<sup>4</sup> M<sup>−1</sup>). Molecular docking further confirmed stable interactions with both biomolecules. The <em>in vitro</em> cytotoxic of all complexes was evaluated using MTT assay against human breast cancer (MCF7 and MDA-MB-231), and hepatocellular (HepG2) cell line, as well as a normal human lung fibroblast cell line (WI-38), and cisplatin was used as a standard reference drug. Among these complexes, the <strong>Pd2</strong> complex exhibited the most potent activity, especially against MDA-MB-231 (IC<sub>50</sub> = 5.53 ± 0.4 μM; selectivity index = 12.07). Antimicrobial activity was assessed against Gram-positive/negative bacteria, yeasts, and filamentous fungi. The <strong>Ni1</strong> and <strong>Ni2</strong> complexes showed superior antimicrobial effects compared to Pd complexes and the free ligand. These findings highlight the promising biological potential of these metal complexes, particularly <strong>Pd2</strong>, as anticancer and antimicrobial agents, warranting further exploration for biomedical applications.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"593 ","pages":"Article 123047"},"PeriodicalIF":3.2,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145882484","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Low-spin Fe(III)/Co(II) mixed-ligand benzimidazole/Schiff-base complexes: structural, electronic reactivity, and correlated antimicrobial and anti-inflammatory bioactivity against FabH-CoA and COX-2 低自旋Fe(III)/Co(II)混合配体苯并咪唑/希夫碱配合物:结构、电子反应性以及对FabH-CoA和COX-2的相关抗菌和抗炎生物活性
IF 3.2 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2026-04-01 Epub Date: 2026-01-03 DOI: 10.1016/j.ica.2026.123061
Saeed S. Samman , Aly Abdou , Abdulrahman A. Alsimaree , Munirah M. Al-Rooqi , Abdulaziz M. Almohyawi , Rabab.S. Jassas , Ziad Moussa , Sultan I. Alkubaysi , A. Timoumi , Saleh A. Ahmed
Two new low-spin iron(III) and cobalt(II) mixed-ligand complexes, FeSBMB [Fe(MB)(SB)(Cl)₂] and CoSBMB [Co(MB)(SB)(Cl)(H2O)], were synthesized from 1-isopropyl-1H-benzimidazole-2-carbaldehyde (MB) and 1-([(4-methylphenyl)imino]methyl)naphthalen-2-ol (SB). The structures and octahedral geometries were established by CHN analysis, FT-IR, UV–Vis, mass spectrometry, magnetic susceptibility, conductivity, TG/DTG, and Job's method. Conductivity values of 10.15 S cm2 mol−1 (FeSBMB) and 9.86 S cm2 mol−1 (CoSBMB) confirmed their non-electrolytic nature. Magnetic moments of 1.79 B.M. (FeSBMB) and 1.83 B.M. (CoSBMB) were consistent with low-spin octahedral configurations. Spectroscopic data indicated coordination through the imine nitrogen and phenolic oxygen atoms of SB, together with the imidazole ring nitrogen and carbonyl oxygen of MB. FeSBMB exhibited the strongest antibacterial performance, producing its largest inhibition zone against K. pneumoniae (25.0 ± 0.09 mm), while showing the highest activity index against E. coli (97.51 %), as derived from comparative analysis with the reference drug, 19.6 ± 0.11 mm against E. coli, 23.6 ± 0.11 mm against C. albicans, and 13.8 ± 0.20 mm against A. flavus. CoSBMB showed slightly lower but comparable activity, with zones of 22.5 ± 0.08 mm (K. pneumoniae), 17.2 ± 0.12 mm (E. coli), 21.8 ± 0.09 mm (C. albicans), and 12.9 ± 0.14 mm (A. flavus). Anti-inflammatory IC50 values were 21.26 μg mL−1 (FeSBMB) and 25.08 μg mL−1 (CoSBMB), both outperforming the uncoordinated ligands SB (54.50 μg mL−1) and MB (55.28 μg mL−1). DFT calculations confirmed the octahedral geometries and showed that FeSBMB had the smallest HOMO–LUMO gap (1.47 eV), the lowest hardness (0.74 eV), and the highest softness (0.68 eV−1), indicating greater reactivity compared with CoSBMB (ΔE = 1.64 eV, η = 0.82 eV, σ = 0.61 eV−1). TD-DFT spectra reproduced the experimental UV–Vis transitions. Docking studies demonstrated strong binding of FeSBMB and CoSBMB to FabH-CoA (−8.50 and −8.10 kcal/mol, respectively) and COX-2 (−9.90 and −9.50 kcal/mol), consistent with their antimicrobial and anti-inflammatory activity.
以1-异丙基- 1h -苯并咪唑-2-乙醛(MB)和1-([(4-甲基苯基)亚胺]甲基萘-2-醇(SB)为原料合成了两种新型低自旋铁(III)和钴(II)混合配体配合物FeSBMB [Fe(MB)(SB)(Cl) 2]和CoSBMB [Co(MB)(SB)(Cl)(H2O)]。通过CHN分析、FT-IR、UV-Vis、质谱、磁化率、电导率、TG/DTG和Job’s法确定了其结构和八面体几何形状。电导率为10.15 S cm2 mol−1 (FeSBMB)和9.86 S cm2 mol−1 (CoSBMB),证实了它们的非电解性质。磁矩为1.79 B.M. (FeSBMB)和1.83 B.M. (CoSBMB)符合低自旋八面体构型。FeSBMB的抑菌活性最强,对肺炎克雷伯菌的抑制区最大(25.0±0.09 mm),对大肠杆菌的抑菌活性指数最高(97.51%),与参比药的抑菌活性指数为19.6±0.11 mm,对大肠杆菌的抑菌活性指数最高。对白色念珠菌为23.6±0.11 mm,对黄芽孢杆菌为13.8±0.20 mm。CoSBMB活性较低,分别为肺炎克雷伯菌(22.5±0.08 mm)、大肠杆菌(17.2±0.12 mm)、白色念珠菌(21.8±0.09 mm)和黄芽胞杆菌(12.9±0.14 mm)。抗炎IC50值分别为21.26 μg mL−1 (FeSBMB)和25.08 μg mL−1 (CoSBMB),均优于非配位体SB (54.50 μg mL−1)和MB (55.28 μg mL−1)。DFT计算证实了八面体结构,结果表明FeSBMB具有最小的HOMO-LUMO间隙(1.47 eV),最低的硬度(0.74 eV)和最高的柔软度(0.68 eV−1),与CoSBMB (ΔE = 1.64 eV, η = 0.82 eV, σ = 0.61 eV−1)相比具有更强的反应性。TD-DFT光谱再现了实验紫外-可见跃迁。对接研究表明,FeSBMB和CoSBMB与FabH-CoA(分别为- 8.50和- 8.10 kcal/mol)和COX-2(分别为- 9.90和- 9.50 kcal/mol)有很强的结合,这与它们的抗菌和抗炎活性一致。
{"title":"Low-spin Fe(III)/Co(II) mixed-ligand benzimidazole/Schiff-base complexes: structural, electronic reactivity, and correlated antimicrobial and anti-inflammatory bioactivity against FabH-CoA and COX-2","authors":"Saeed S. Samman ,&nbsp;Aly Abdou ,&nbsp;Abdulrahman A. Alsimaree ,&nbsp;Munirah M. Al-Rooqi ,&nbsp;Abdulaziz M. Almohyawi ,&nbsp;Rabab.S. Jassas ,&nbsp;Ziad Moussa ,&nbsp;Sultan I. Alkubaysi ,&nbsp;A. Timoumi ,&nbsp;Saleh A. Ahmed","doi":"10.1016/j.ica.2026.123061","DOIUrl":"10.1016/j.ica.2026.123061","url":null,"abstract":"<div><div>Two new low-spin iron(III) and cobalt(II) mixed-ligand complexes, FeSBMB [Fe(MB)(SB)(Cl)₂] and CoSBMB [Co(MB)(SB)(Cl)(H<sub>2</sub>O)], were synthesized from 1-isopropyl-1H-benzimidazole-2-carbaldehyde (MB) and 1-([(4-methylphenyl)imino]methyl)naphthalen-2-ol (SB). The structures and octahedral geometries were established by CHN analysis, FT-IR, UV–Vis, mass spectrometry, magnetic susceptibility, conductivity, TG/DTG, and Job's method. Conductivity values of 10.15 S cm<sup>2</sup> mol<sup>−1</sup> (FeSBMB) and 9.86 S cm<sup>2</sup> mol<sup>−1</sup> (CoSBMB) confirmed their non-electrolytic nature. Magnetic moments of 1.79 B.M. (FeSBMB) and 1.83 B.M. (CoSBMB) were consistent with low-spin octahedral configurations. Spectroscopic data indicated coordination through the imine nitrogen and phenolic oxygen atoms of SB, together with the imidazole ring nitrogen and carbonyl oxygen of MB. FeSBMB exhibited the strongest antibacterial performance, producing its largest inhibition zone against <em>K. pneumoniae</em> (25.0 ± 0.09 mm), while showing the highest activity index against <em>E. coli</em> (97.51 %), as derived from comparative analysis with the reference drug, 19.6 ± 0.11 mm against <em>E. coli</em>, 23.6 ± 0.11 mm against <em>C. albicans</em>, and 13.8 ± 0.20 mm against <em>A. flavus</em>. CoSBMB showed slightly lower but comparable activity, with zones of 22.5 ± 0.08 mm (<em>K. pneumoniae</em>), 17.2 ± 0.12 mm (<em>E. coli</em>), 21.8 ± 0.09 mm (<em>C. albicans</em>), and 12.9 ± 0.14 mm (<em>A. flavus</em>). Anti-inflammatory IC<sub>50</sub> values were 21.26 μg mL<sup>−1</sup> (FeSBMB) and 25.08 μg mL<sup>−1</sup> (CoSBMB), both outperforming the uncoordinated ligands SB (54.50 μg mL<sup>−1</sup>) and MB (55.28 μg mL<sup>−1</sup>). DFT calculations confirmed the octahedral geometries and showed that FeSBMB had the smallest HOMO–LUMO gap (1.47 eV), the lowest hardness (0.74 eV), and the highest softness (0.68 eV<sup>−1</sup>), indicating greater reactivity compared with CoSBMB (ΔE = 1.64 eV, η = 0.82 eV, σ = 0.61 eV<sup>−1</sup>). TD-DFT spectra reproduced the experimental UV–Vis transitions. Docking studies demonstrated strong binding of FeSBMB and CoSBMB to FabH-CoA (−8.50 and −8.10 kcal/mol, respectively) and COX-2 (−9.90 and −9.50 kcal/mol), consistent with their antimicrobial and anti-inflammatory activity.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"593 ","pages":"Article 123061"},"PeriodicalIF":3.2,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145939817","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
New morpholine or triphenylphosphine-liganded palladium(II) N-heterocyclic carbene complexes: Synthesis, characterization, crystal structure, and anticancer activity 新的啉或三苯基膦配体钯(II) n杂环卡宾配合物:合成、表征、晶体结构和抗癌活性
IF 3.2 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2026-04-01 Epub Date: 2026-01-02 DOI: 10.1016/j.ica.2026.123062
Yetkin Gök , Gül Özkan , Ali Kuruçay , Burhan Ateş , Aydın Aktaş , Özlem Demirci , Muhittin Aygün
A series of morpholine(Morp.)-liganded palladium(II) complexes (1a–c) and triphenylphosphine(PPh3)-liganded palladium(II) complexes (2a–c) bearing 4-fluorobenzyl substituted N-heterocyclic carbene (NHC) were synthesized from NHC-Pd(II)-pyridine and Morp./PPh3 by ligand exchange method. The new complexes were fully characterized using 1H NMR, 13C NMR, 19F NMR, 31P NMR, FTIR spectroscopy and elemental analysis techniques. Furthermore, single crystal X-ray diffraction was used to elucidate the structures of complexes 1a and 2b. The anticancer activities of the new complexes against MCF-7 (Human Breast Cancer) cell line were investigated. With an IC50 value of 37.54 for complex 1a, it can be said that it is more cytotoxic to MCF-7 cells compared to other complexes, while the least cytotoxicity was observed in complex 1b.
一系列的morpholine(Morp.)以NHC- pd (II)-吡啶和Morp为原料合成了含4-氟苯取代n -杂环碳(NHC)的配体钯(II)配合物(1a-c)和三苯基膦(PPh3)配体钯(II)配合物(2a-c)。/PPh3通过配体交换法。利用1H NMR、13C NMR、19F NMR、31P NMR、FTIR光谱和元素分析技术对新化合物进行了表征。利用x射线单晶衍射分析了配合物1a和2b的结构。研究了新复合物对MCF-7(人乳腺癌)细胞株的抗癌活性。复合物1a的IC50值为37.54,可以说复合物1b对MCF-7细胞的细胞毒性高于其他复合物,而复合物1b的细胞毒性最小。
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引用次数: 0
The phase separation in K2O-PbO-CaO-P2O5-SiO2 glass doped by gold and Eu3+ ions 金和Eu3+离子掺杂K2O-PbO-CaO-P2O5-SiO2玻璃的相分离
IF 3.2 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2026-04-01 Epub Date: 2025-12-29 DOI: 10.1016/j.ica.2025.123048
Ilya Salakheev , Andrey Drozdov , Maksim Andreev , Claudio Pettinari
The addition of calcium phosphate to lead silicate glasses K2O-PbO-SiO2 results in phase separation. In this study, we synthesized glass samples doped with gold to investigate the mutual influence of phase separation on the formation and growth of gold nanoparticles. It was found that phase separation occurs prior to nanoparticle formation, with the nanoparticles forming within droplets of the phosphate-rich glass phase. Conversely, the presence of gold nanoparticles promotes the enlargement of calcium phosphate droplets dispersed within the silicate matrix. In the presence of europium ions in K2O-PbO-SiO2 glass the spherical form of gold nanoparticles converts to elliptical, but in the glass containing phosphate gold is distributed between the two phases. These processes provide a means to control the coloration of glasses induced by gold nanoparticles.
在K2O-PbO-SiO2中加入磷酸钙导致了相分离。在本研究中,我们合成了掺杂金的玻璃样品,以研究相分离对金纳米颗粒形成和生长的相互影响。研究发现,相分离发生在纳米颗粒形成之前,纳米颗粒在富磷酸盐玻璃相的液滴内形成。相反,金纳米颗粒的存在促进了分散在硅酸盐基质中的磷酸钙液滴的扩大。在含有铕离子的K2O-PbO-SiO2玻璃中,金纳米颗粒的球形转变为椭圆形,而在含有磷酸盐的玻璃中,金纳米颗粒分布在两相之间。这些方法提供了一种控制由金纳米颗粒诱导的玻璃着色的方法。
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引用次数: 0
Thiophene based chemosensors: a comprehensive review on synthesis and detection of cations and anions 噻吩基化学传感器:阳离子和阴离子的合成和检测综述
IF 3.2 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2026-04-01 Epub Date: 2025-12-20 DOI: 10.1016/j.ica.2025.123042
Zuverya Zareen , Aram Rahman , Anzar Jahan , Salahuddin Syed , Mohammad Arifuddin
Thiophene based chemosensors have emerged as versatile and efficient molecular tools for the selective detection of a wide range of analytes, including metal cations and anions. The unique electronic properties, structural flexibility, and strong π-conjugation of thiophene derivatives make them highly suitable scaffolds for designing colorimetric and fluorescent probes. Reported thiophene based sensors have demonstrated remarkable sensitivity towards cations such as Hg2+, Cu2+, Zn2+, Ag+, Al3+, Pb2+,Fe3+,Cd2+, Au3+, Pd2+, Ni2+, Cr3+, Ga3+, Zr4+ as well as anions including I, F and CN. Their sensing mechanisms involve diverse photophysical processes including excited-state intramolecular proton transfer (ESIPT), intramolecular charge transfer (ICT), fluorescence resonance energy transfer (FRET) and photoinduced electron transfer (PET). Several thiophene based chemosensors exhibit dual analyte recognition, enabling simultaneous detection of both cations and anions through reversible and selective interactions. Beyond fundamental sensing, applications extend to environmental monitoring and real sample analysis, underscoring their practical significance. The review concludes with detection mechanism of several thiophene based chemosensors as well as their practical applicability which may be useful for the synthesis of novel thiophene based chemosensor. Also highlights the sensing performances and comparison of them with some reported organic chemosensors.
基于噻吩的化学传感器已经成为一种多功能和高效的分子工具,用于选择性检测各种分析物,包括金属阳离子和阴离子。噻吩衍生物独特的电子性质、结构柔韧性和强π共轭性使其成为设计比色和荧光探针的非常合适的支架。已有的基于噻吩的传感器对阳离子(如Hg2+, Cu2+, Zn2+, Ag+, Al3+, Pb2+,Fe3+,Cd2+, Au3+, Pd2+, Ni2+, Cr3+, Ga3+, Zr4+)以及阴离子(包括I−,F−和CN−)具有显著的灵敏度。它们的传感机制涉及多种光物理过程,包括激发态分子内质子转移(ESIPT)、分子内电荷转移(ICT)、荧光共振能量转移(FRET)和光致电子转移(PET)。几种基于噻吩的化学传感器表现出双重分析物识别,能够通过可逆和选择性相互作用同时检测阳离子和阴离子。除了基础传感,应用扩展到环境监测和实际样品分析,强调其实际意义。综述了几种噻吩类化学传感器的检测机理及其实际应用情况,为新型噻吩类化学传感器的合成提供参考。重点介绍了它们的传感性能,并与一些已报道的有机化学传感器进行了比较。
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引用次数: 0
Sulfur and selenium compounds alter cellular oxidative stress by the NADH reduction of Fe3+ to Fe2+ 硫和硒化合物通过NADH将Fe3+还原为Fe2+来改变细胞氧化应激
IF 3.2 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2026-04-01 Epub Date: 2025-12-07 DOI: 10.1016/j.ica.2025.123031
Craig Goodman , Tyler Williams , Abigail G. McNamee , Julia L. Brumaghim
Oxidative DNA damage in cells causes a variety of pathologies including but not limited to cancers, cardiovascular diseases, and neurodegenerative disorders. Fe3+ reduction by NADH is the rate-limiting step in cellular hydroxyl radical generation and damage, but this aspect of the oxidative stress cycle is little explored. We established a rate law for the NADH-Fe system in vitro that indicates the Fe3+ reduction rate depends primarily on NADH concentration, indicating that NADH may be a critical participant in cellular oxidative stress. Kinetic experiments using ferene established that the overall stoichiometry of this reaction is 1:2 NADH:Fe, supporting an overall scheme in which two Fe3+ ions are separately reduced by NADH in a stepwise fashion. We also observed that sulfur- and selenium-containing antioxidants alter cellular oxidative stress by changing the rate by which NADH reduces Fe3+ into hydroxyl radical-generating Fe2+. Fe3+ reduction rates with and without antioxidants were quantified, demonstrating that the sulfur and selenium compounds that prevent greater Fe2+-mediated DNA damage also enhance the rate of Fe3+ reduction by NADH. Antioxidant rescues in wild-type E. coli and a mutant strain (Δndh) with elevated (∼3 fold higher) NADH levels corroborated this counterintuitive trend: compounds that increased the Fe3+ reduction rate rescued more cells from H2O2-mediated killing. By uncovering this balance involving NADH and iron, we have identified a previously overlooked antioxidant mechanism for these Fe-binding antioxidants, one by which they interact with and modify NADH-Fe redox cycling.
细胞中的DNA氧化损伤会引起多种病理,包括但不限于癌症、心血管疾病和神经退行性疾病。NADH还原Fe3+是细胞羟基自由基生成和损伤的限速步骤,但这方面的氧化应激循环很少被探索。我们在体外建立了NADH- fe系统的速率定律,表明Fe3+还原速率主要取决于NADH浓度,表明NADH可能是细胞氧化应激的关键参与者。利用ferene进行的动力学实验表明,该反应的总体化学计量为1:2 NADH:Fe,支持两个Fe3+离子分别被NADH逐步还原的总体方案。我们还观察到含硫和含硒的抗氧化剂通过改变NADH将Fe3+还原为生成羟基自由基的Fe2+的速率来改变细胞氧化应激。对有抗氧化剂和无抗氧化剂的Fe3+还原速率进行了定量分析,结果表明,硫和硒化合物可以防止更大的Fe2+介导的DNA损伤,也可以提高NADH对Fe3+的还原速率。野生型大肠杆菌和NADH水平升高的突变菌株(Δndh)中的抗氧化剂拯救证实了这一违反直觉的趋势:增加Fe3+还原率的化合物从h2o2介导的杀死中拯救了更多的细胞。通过揭示涉及NADH和铁的这种平衡,我们已经确定了这些铁结合抗氧化剂的一种先前被忽视的抗氧化机制,通过这种机制,它们与NADH-铁氧化还原循环相互作用并修改。
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Inorganica Chimica Acta
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