Inorganica Chimica Acta最新文献

A cadmium-based coordination polymer as multifunctional fluorescent sensor for simultaneous detection of heavy metal ions and antibiotics in water 一种镉基配位聚合物作为多功能荧光传感器，可同时检测水中的重金属离子和抗生素

IF 2.7 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganica Chimica Acta

Pub Date : 2025-04-24 DOI: 10.1016/j.ica.2025.122727

Yun Cao , Shuo Zhou , Bei-Bei Yin , Yan Wang

This work successfully constructed a new three-dimensional coordination polymer [Zn(HEA)(L1)]_n (1) based on o-phenylenediacetic acid (H₂HEA) and 1,1′-(2,4,6-trimethyl-1,3-phenylene) bis(methylene) bis(1H-imidazole) (L1), demonstrating exceptional thermal stability and solvent resistance. The unique two-dimensional architecture of complex 1 features a distinctive “W”-shaped topology, assembled through the interconnection of nitrogen-rich and oxygen-containing coordination chains. These 2D layers subsequently extend into a three-dimensional framework via π–π stacking interactions and interlayer hydrogen bonding, creating a stable and porous network structure. As a multifunctional fluorescent probe, complex 1 exhibits remarkable sensing capabilities towards aqueous CrO₄²⁻, Cr₂O₇²⁻, and Fe³⁺ ions, and antibiotics including Ornidazole (ODZ) and Nitrofurazone (NFZ), with detection limits below 0.058 μM. Mechanistic investigations combining UV–vis absorption spectroscopy and density functional theory (DFT) calculations revealed that the fluorescence quenching originates from competitive energy absorption for metal ions, while a synergistic effect of photoinduced electron transfer (PET) and energy absorption accounts for antibiotic detection. Practical applicability was validated through real water sample analysis, achieving recovery rates of 97.3 %–103.7 % with relative standard deviations below 4 %. This study provides a new strategy for the simultaneous detection of multiple pollutants and expands the design principles for multifunctional fluorescent probes.

本文成功构建了以邻苯二乙酸（H2HEA）和1,1′-（2,4,6-三甲基-1,3-苯基）双（亚甲基）双（1h -咪唑）（L1）为基础的新型三维配位聚合物[Zn(HEA)(L1)]n(1)，具有优异的热稳定性和耐溶剂性。复合物1独特的二维结构具有独特的“W”形拓扑结构，通过富氮和含氧配位链的互连组装而成。这些二维层随后通过π -π堆叠相互作用和层间氢键扩展成三维框架，形成稳定的多孔网络结构。作为一种多功能荧光探针，配合物1对水溶液中的CrO42−、Cr2O72−和Fe3+离子以及抗生素（包括奥硝唑（ODZ）和硝基呋喃酮（NFZ））具有出色的传感能力，检出限低于0.058 μM。结合紫外-可见吸收光谱和密度泛函理论（DFT）计算的机理研究表明，荧光猝灭源于金属离子的竞争性能量吸收，而光致电子转移（PET）和能量吸收的协同效应是抗生素检测的主要原因。通过实际水样分析验证了该方法的实用性，回收率为97.3% ~ 103.7%，相对标准偏差小于4%。本研究为多种污染物的同时检测提供了一种新的策略，扩展了多功能荧光探针的设计原则。

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引用次数: 0

Biological activity evaluation and molecular docking studies of newly synthesized β-ketoiminato-based palladium complexes 新合成的β-酮氨基钯配合物的生物活性评价及分子对接研究

IF 2.7 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganica Chimica Acta

Pub Date : 2025-04-22 DOI: 10.1016/j.ica.2025.122711

Deeb Taher , Naim.H. Al-Said , Mohammad Albanna , Matous Kloda , Morad Mustafa , Wissam Helal , Khaleel I. Assaf , Wafa Hourani , Wael-Rémy Kotob , Sundus Saleh , Ahmad Makahleh , Manar Mohammad Rabba'a

A series of palladium(II) β-ketoiminato complexes, [Pd(CH₃C(NAr)CHC(O)Ph)₂] (4a–j), were synthesized via the reaction of N-aryl-substituted β-ketoiminate precursors with [PdCl₂(CH₃CN)₂] in the presence of ^tBuOK. Single-crystal X-ray diffraction of 4a–h and 4j confirmed a square-planar Pd(II) coordination. Notably, 4b exhibited C–H···Pd anagostic interactions, contributing to lattice stability, which was further analyzed using Hirshfeld surface 2D fingerprint plots. Computational studies, including non-covalent interaction (NCI) plots and quantum theory of atoms in molecules (QTAIM), provided insights into these interactions. Complexes 4a–j show characteristic ILCT (π → π *) bands in their UV–Vis spectra, which were additionally confirmed by TD-DFT calculations. DFT analysis reveals that the HOMO is composed of contributions from both the Pd(II) center and β-ketoiminato ligand orbitals, while the LUMO is primarily derived from β-ketoiminate ligand orbitals. The anticancer potential of 4a–j was evaluated against MCF-7 and HT-29 cell lines. Complexes 4a–d and 4f exhibited significant cytotoxicity, effectively inhibiting HT-29 cell migration. Among them, 4c demonstrated the highest potency, with an IC50 of 1.73 μM, significantly reducing HT-29 cell viability. The ability of Pd(II) complexes to interact with three targeted proteins, namely, PIK3CA-E545K, ERBB4-Y1242C, and BRAF-V600E was evaluated through molecular docking studies, revealing moderate to high binding affinities. Notably, complex 4c demonstrated the strongest interactions across all targets.

在tBuOK存在下，n -芳基取代β-酮亚胺酸前体与[PdCl2(CH3CN)2]反应合成了一系列钯(II) β-酮亚胺酸配合物[Pd(CH3C(NAr)CHC(O)Ph)2] （4a-j）。单晶x射线衍射证实了4a-h和4j的方平面Pd（II）配位。值得注意的是，4b表现出C-H···Pd的解析相互作用，有助于晶格稳定性，进一步使用Hirshfeld表面二维指纹图进行分析。计算研究，包括非共价相互作用（NCI）图和分子中原子的量子理论（QTAIM），提供了对这些相互作用的见解。配合物4a-j在UV-Vis光谱中表现出典型的ILCT （π→π *）带，并通过TD-DFT计算得到证实。DFT分析表明，HOMO由Pd（II）中心和β-酮酰亚胺配体轨道共同贡献，而LUMO主要来源于β-酮酰亚胺配体轨道。研究了4a-j对MCF-7和HT-29细胞株的抗癌作用。复合物4a-d和4f表现出显著的细胞毒性，有效抑制HT-29细胞迁移。其中4c效价最高，IC50为1.73 μM，显著降低HT-29细胞活力。通过分子对接研究，对Pd（II）复合物与PIK3CA-E545K、ERBB4-Y1242C、BRAF-V600E三种靶向蛋白的相互作用能力进行了评价，结果显示Pd（II）复合物具有中高的结合亲和力。值得注意的是，复合物4c在所有靶标之间表现出最强的相互作用。

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引用次数: 0

Dinitrogen fixation by alkali and alkaline earth hydride composites under plasma 等离子体下碱与碱土氢化物复合材料固氮

IF 2.7 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganica Chimica Acta

Pub Date : 2025-04-21 DOI: 10.1016/j.ica.2025.122720

Kai Ma , Jianping Guo , Ping Chen

The development of alternative methods for sustainable dinitrogen (N₂) fixation to ammonia (NH₃) is a cutting-edge research area. The presence of external stimuli, such as non-thermal plasma, can boost the activation of the inert N₂ molecules under ambient temperatures and pressures, thereby generating value-added products such as NH₃ or other nitrogen-containing compounds. Binary alkali metal hydrides such as NaH and KH have recently shown intriguing properties in the plasma nitrogen fixation process. Herein we report the different chemical behaviors of a series of hydride composites consist of potassium hydride (KH) and alkaline earth metal hydride (MgH₂, CaH₂, SrH₂, and BaH₂) under nitrogen plasma conditions. A nitrogen-relayed mechanism has been proposed to understand the different nitrogen fixation behaviors on these hydride composites. Under this scenario, KH is responsible for plasma N₂ fixation to form surface NH₂ species, which subsequently migrate and react with MgH₂, CaH₂, and SrH₂ to form N and NH species, respectively. This work enriches the plasma chemistry of metal hydrides, and provides a strategy to enhance the amounts of fixed nitrogen of single hydride material under nitrogen plasma conditions.

开发可持续的二氮（N2）固定到氨（NH3）的替代方法是一个前沿研究领域。外部刺激的存在，如非热等离子体，可以促进惰性N2分子在环境温度和压力下的活化，从而产生增值产品，如NH3或其他含氮化合物。二元碱金属氢化物如NaH和KH最近在等离子体固氮过程中显示出有趣的特性。本文报道了由氢化钾（KH）和碱土金属氢化物（MgH2、CaH2、SrH2和BaH2）组成的一系列氢化物复合材料在氮等离子体条件下的不同化学行为。我们提出了一种氮传递机制来理解这些氢化物复合材料不同的固氮行为。在这种情况下，KH负责血浆N2固定形成表面NH2， NH2随后迁移并与MgH2， CaH2和SrH2分别反应形成N和NH。本工作丰富了金属氢化物的等离子体化学，为提高氮等离子体条件下单个氢化物材料的固定氮量提供了一种策略。

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引用次数: 0

SNS pincer type Pd(II), Ni(II), and Fe(II) complexes: Synthesis, structural characterization, cytotoxic activity studies, molecular docking and simulation studies SNS钳形Pd（II）、Ni（II）、Fe（II）配合物：合成、结构表征、细胞毒活性研究、分子对接与模拟研究

IF 2.7 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganica Chimica Acta

Pub Date : 2025-04-18 DOI: 10.1016/j.ica.2025.122728

Hatice Gamze Sogukomerogullari , Salih Sinan Solak , Senem Akkoc , Ayşegül Köse , Muhammed Tılahun Muhammed , Mehmet Sönmez

A novel SNS pincer-type ligand, 2,6-bis[[(2-chlorophenyl)thio]carbonyl]pyridine (L), along with its metal complexes (L-Ni, L-Pd, L-Fe), were synthesized and examined through a variety of analytical techniques, including X-ray crystallography (for the ligand), NMR spectroscopy, UV–Vis spectroscopy, FT-IR spectroscopy, molar conductivity, and elemental analysis methods. X-ray single crystal structure determination was employed to characterize the molecular structure of ligand (L). A four-coordinated square planar shape characterizes the Pd complex, in contrast to the five-coordinate distorted trigonal bipyramidal geometry seen in the molecular structures of Fe and Ni complexes around their metal centers. The L-Pd pincer complex is bidentate, while the L-Fe, and L-Ni pincer complexes are tridentate. Within the scope of this study, the synthesized ligand and its palladium, nickel, and iron complexes were tested against two different human cancer cell lines for 48 and 96 h. According to the results obtained, the nickel and iron complex together with the ligand has a cytotoxic effect against both cancer cell lines tested. Consequently, the nickel complex (L-Ni) was identified as the most effective compound on the lung cancer cell line in the experiments. The binding potential of the synthesized compounds to 3Dpol was explored through molecular modeling as some compounds with similar scaffolds were reported to be inhibitors of this target. The docking study disclosed that the compounds could bind to the 3Dpol structure. The molecular dynamics (MD) simulation study disclosed that compound L formed a stable complex with the target structure and could remain inside its binding site during the simulation time.

合成了一种新型SNS钳型配体2,6-二[[（2-氯苯基）硫]羰基]吡啶(L)及其金属配合物（L- ni, L- pd, L- fe），并通过各种分析技术，包括x射线晶体学（配体），核磁共振光谱，紫外-可见光谱，红外光谱，摩尔电导率和元素分析方法进行了研究。x射线单晶结构测定法表征了配体(L)的分子结构。Pd配合物的分子结构为四坐标方形平面形状，而Fe和Ni配合物的金属中心周围的分子结构为五坐标畸变三角双锥体形状。L-Pd钳形配合物为双齿，而L-Fe和L-Ni钳形配合物为三齿。在本研究范围内，合成的配体及其钯、镍、铁配合物分别对两种不同的人类癌细胞进行了48和96 h的细胞毒性测试。结果表明，镍、铁配合物与配体对两种癌细胞都具有细胞毒性作用。因此，镍配合物（L-Ni）在实验中被确定为对肺癌细胞系最有效的化合物。由于一些具有类似支架的化合物被报道为该靶点的抑制剂，因此通过分子模拟探索了合成化合物与3Dpol的结合潜力。对接研究表明，化合物可以与3Dpol结构结合。分子动力学（MD）模拟研究表明，化合物L与靶结构形成稳定的配合物，并在模拟时间内保持在其结合位点内。

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引用次数: 0

A chiral coordination polymer with both fluorescence enhancement and photo-chromism 一种具有荧光增强和光致变色的手性配位聚合物

IF 2.7 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganica Chimica Acta

Pub Date : 2025-04-17 DOI: 10.1016/j.ica.2025.122726

Ya Liu , La-Hong Gong , Yu-Ting Zhang , Pen-Ji Yan , Xiao-Qiang Yao

A luminescent coordination polymer, {[Zn(TIPA)(D-cam)]·H₂O}_n(1), where TIPA = tris(4-(1H-imidazol-1-yl)phenyl)amine and D-H₂cam = D (+)-camphorate dianion, was successfully synthesized. This polymer exhibits a two-fold polythreading architecture characterized by undulated grid structures with a (4, 4) net topology. Unlike previously reported luminescent coordination polymers based on TIPA, the emission intensity of compound 1 is significantly higher than that of TIPA, with a slight red shift. This enhancement can be attributed to the electron-donating properties and flexibility of D-H₂cam. The investigation of the photoluminescence mechanism revealed that the emission of 1 originates from the intraligand charge transfer transitions (π → π*). In addition, 1 exhibits a good ability to recognize Fe³⁺, Cr₂O₇²⁻, nitromethane, and nitrobenzene. Interestingly, compound 1 also demonstrates a rapid photochromic reaction to UV irradiation under environmental conditions. This can be attributed to electron transfer (ET) between the polyimidazole ligand TIPA and D-H_₂cam.

成功合成了一种发光配位聚合物{[Zn(TIPA)(D-cam)]-H2O}n(1)，其中 TIPA = 三(4-(1H-咪唑-1-基)苯基)胺，D-H2cam = D (+) -樟脑二元离子。这种聚合物具有两重多线程结构，其特点是具有 (4, 4) 网状拓扑结构的波状网格结构。与之前报道的基于 TIPA 的发光配位聚合物不同，化合物 1 的发射强度明显高于 TIPA，并有轻微的红移。这种增强可归因于 D-H2cam 的电子捐赠特性和柔韧性。对光致发光机理的研究表明，1 的发射源于配位体内部的电荷转移跃迁（π → π*）。此外，1 还能很好地识别 Fe3+、Cr₂O₇2-、硝基甲烷和硝基苯。有趣的是，在环境条件下，化合物 1 在紫外线照射下也会迅速发生光致变色反应。这可归因于聚咪唑配体 TIPA 和 D-H₂cam 之间的电子转移（ET）。

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引用次数: 0

Assessment of the antimicrobial activity of Dinuclear Pt/Pt, Pt/Zn and Pt/cu complexes: Insights from docking studies 双核Pt/Pt、Pt/Zn和Pt/cu配合物抗菌活性的评估：来自对接研究的见解

IF 2.7 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganica Chimica Acta

Pub Date : 2025-04-16 DOI: 10.1016/j.ica.2025.122723

Svetlana Jeremić , Violeta Jakovljević , Darko Anđelković , Emilija Pecev-Marinković , Enisa Selimović

This study reports the successful synthesis and characterization of four novel dinuclear complexes, D2a, D2b, D2c, and D2d. These complexes incorporate complex [Pt(DMEAIm^iPr)Cl₂] on one side and cisplatin, transplatin, [ZnCl₂(terpy)], or [CuCl₂(terpy)] on the other, connected by

4,4′-bipyridine as a bridging ligand. The antimicrobial activity of the complexes was systematically evaluated. The D2a complex demonstrated strong activity against S. aureus ATCC, P. aeruginosa ATCC, and E. faecalis ATCC, while the D2b complex exhibited the highest efficacy in inhibiting E. faecalis ATCC. The D2c complex displayed potent activity across all tested bacterial strains, and the D2d complex showed exceptional inhibitory effects against E. faecalis ATCC. The inhibitory activity of the considered complex compounds to inhibit the gyrases of the mentioned bacterial species, as well as E. coli, was investigated using the molecular docking method. In is shown that all tested compounds can inhibit S. aureus' gyrase even more successfully than the drug Doxycycline, while only complexes D2a and D2b show significant activity against gyrases of other bacterial species. The mechanism of antibacterial action of complex compounds examined in this way indicated agreement between theoretically obtained results and those obtained experimentally.

本研究报告成功合成了四种新型双核配合物 D2a、D2b、D2c 和 D2d，并对其进行了表征。这些配合物一边是[Pt(DMEAImiPr)Cl2]配合物，另一边是顺铂、反铂、[ZnCl2(terpy)]或[CuCl2(terpy)]配合物，并以 4,4′-联吡啶作为桥接配体。对这些配合物的抗菌活性进行了系统评估。D2a 复合物对金黄色葡萄球菌 ATCC、绿脓杆菌 ATCC 和粪大肠杆菌 ATCC 具有很强的活性，而 D2b 复合物对粪大肠杆菌 ATCC 的抑制效果最好。D2c 复合物对所有测试的细菌菌株都有很强的活性，而 D2d 复合物对粪肠球菌 ATCC 的抑制效果尤为明显。利用分子对接法研究了所考虑的复合物对上述细菌种类以及大肠杆菌的回旋酶的抑制活性。结果表明，所有测试化合物都能抑制金黄色葡萄球菌的回旋酶，甚至比多西环素更有效，而只有复合物 D2a 和 D2b 对其他细菌种类的回旋酶具有显著的活性。通过这种方法对复合物的抗菌作用机制进行的研究表明，理论上得出的结果与实验中得出的结果是一致的。

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引用次数: 0

Exploring ferrocenyl derivatives of sulfa-drugs as potential antimalarial and anti-Mycobacterium tuberculosis agents 探索磺胺类药物的二茂铁衍生物作为潜在的抗疟疾和抗结核分枝杆菌药物

IF 2.7 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganica Chimica Acta

Pub Date : 2025-04-16 DOI: 10.1016/j.ica.2025.122725

Katleho Setlaba , Vuyo Mavumengwana , Lucinda Baatjies , Malcolm T. Ndlovu , Catherine H. Kaschula , Prinessa Chellan

A series of new ferrocenyl sulfonamide derivatives (C1-C5) were synthesized from ferrocene carboxylic acid. The complexes were evaluated for their in vitro antimicrobial activities against Plasmodium falciparum and Mycobacterium tuberculosis H37Rv strains. They demonstrated moderate activities against the chloroquine-sensitive (NF54) strain of Plasmodium falciparum, with complex C2 being the most active, displaying an IC₅₀ value of 3.715 μM. Furthermore, the complexes were non-cytotoxic towards the human embryonic kidney and normal prostate cells, indicating their selectivity towards parasitic cells. The complexes also exhibited moderate activity against Mycobacterium smegmatis mc²155, with an increase in activity observed against the Mycobacterium tuberculosis H37Rv strain. Among the complexes, C3 was the most active, displaying a MIC range of 31.73–15.86 μM. Moreover, all the complexes showed 10-fold greater potency than Isoniazid.

以二茂铁羧酸为原料合成了一系列新的二茂铁基磺酰胺衍生物（C1-C5）。研究了该配合物对恶性疟原虫和结核分枝杆菌H37Rv的体外抑菌活性。对氯喹敏感型（NF54）恶性疟原虫具有中等抑菌活性，其中复合物C2活性最强，IC50值为3.715 μM。此外，该复合物对人胚胎肾和正常前列腺细胞无细胞毒性，表明其对寄生细胞有选择性。这些复合物对耻垢分枝杆菌mc2155也表现出中等的活性，对结核分枝杆菌H37Rv菌株的活性增加。其中C3活性最强，MIC范围为31.73 ~ 15.86 μM。此外，所有配合物的效价都比异烟肼高10倍。

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引用次数: 0

Plumbylenes based on redox-active ligands: Synthesis, optoelectronic properties and electrochemical behavior 基于氧化还原活性配体的铅烯：合成、光电性质和电化学行为

IF 2.7 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganica Chimica Acta

Pub Date : 2025-04-16 DOI: 10.1016/j.ica.2025.122724

Sofya A. Fedoseeva , Pavel G. Shangin , Victoriya A. Balycheva , Irina V. Krylova , Nina M. Ivanova , Dmitry A. Bunin , Mikhail A. Syroeshkin , Mikhail P. Egorov , Sergey S. Karlov

At present, the chemistry of low-valent derivatives of the 14th group elements continues to develop intensively, primarily tetrylenes, i.e. carbenes and their heavy analogues – silylenes, germylenes, stannylenes and plumbylenes. This is related, among other things, with their promising properties as catalysts, new materials, etc. In this range the greatest stability is demostrated by the derivatives of Pb⁺²; moreover, among those listed only for lead derivatives, the main oxidation state is +2, and not +4. Despite this, their physicochemical properties, including redox and optoelectronic features, are the least studied. In this work, we obtained four lead(II) derivatives with redox-active ligands based on Schiff bases. Both the data from electron absorption spectroscopy and the study of redox behavior by cyclic voltammetry show that the obtained products have a fairly small HOMO/LUMO gap of about 3 eV or less. Complexation with lead in all cases promotes quenching of fluorescence of ligands both in solid form and in solution. Solutions of the compounds in DMF are electrochemically reduced in the moderate (−1.5..-2.0 V vs Fc⁺/Fc) region. The product of electrochemical reduction of plumbylenes is metallic lead, which was additionally confirmed by controlled potential electrolysis and subsequent study of the deposit obtained on the cathode using scanning electron microscopy and energy-dispersive X-ray spectroscopy. The studied plumbylenes are oxidized in DMF in a very soft potential range – +0.1.. + 0.7 V vs Fc⁺/Fc, which demonstrates the high level and availability of their HOMO. Thus, the presence of a strong electron pair donor in the coordination sphere of Pb(II) can be effectively used in the design of the plumbylenes structure in order to increase the availability of their HOMO and impart valuable and useful properties, such as the ability to readily undergo oxidative addition reactions.

目前，第14族元素的低价衍生物的化学研究仍在继续密集发展，主要是四烯，即碳烯和它们的重类似物——硅烯、二甲苯、锡烯和铅烯。除其他外，这与它们作为催化剂、新材料等有前途的特性有关。在这个范围内，Pb+2的导数表现出最大的稳定性；此外，在仅列出的铅衍生物中，主要氧化态为+2，而不是+4。尽管如此，它们的物理化学性质，包括氧化还原和光电子特性，研究得最少。在这项工作中，我们获得了四种基于希夫碱的具有氧化还原活性配体的铅（II）衍生物。电子吸收光谱数据和循环伏安法氧化还原行为研究表明，所得产物具有相当小的HOMO/LUMO隙，约为3 eV或更小。在所有情况下，铅的络合作用都促进了固体和溶液中配体荧光的猝灭。化合物在DMF中的溶液在中等（- 1.5…-2.0 V vs Fc+/Fc）范围内被电化学还原。铅的电化学还原产物是金属铅，这一点通过控制电位电解和随后使用扫描电子显微镜和能量色散x射线能谱对阴极上获得的沉积物进行研究进一步证实。所研究的铅烯在DMF中在- +0.1的非常软电位范围内氧化。+ 0.7 V vs Fc+/Fc，这证明了它们的HOMO的高水平和可用性。因此，在Pb（II）的配位球中存在一个强电子对供体可以有效地用于铅烯结构的设计，以增加其HOMO的可用性并赋予有价值和有用的性质，例如易于进行氧化加成反应的能力。

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引用次数: 0

A new 2D Zn(II)-based coordination polymer as highly sensitive selective fluorescent probe for of glutathione 新型二维锌（II）基配位聚合物作为谷胱甘肽高灵敏度选择性荧光探针

IF 2.7 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganica Chimica Acta

Pub Date : 2025-04-15 DOI: 10.1016/j.ica.2025.122718

Shan-Qi Li , Mithun Kumar Ghosh , Yong-Qi Zhang , Jun-Cheng Jin , Mohammad Khalid Parvez , Mohammed S. Al-Dosari , Tanmay Kumar Ghorai , Feng Xu

Fluorescence-based sensing has emerged as an effective strategy for detecting biomolecules with high sensitivity and selectivity. In this study, a new Zn(II)-based coordination polymer (CP), {Zn(Cl-L)(DPP)]·1.5DMF}_n (1), was synthesized and explored as a fluorescence sensor for the detection of glutathione (GSH). The coordination polymer was synthesized via a solvothermal method, and its structural characterization was confirmed using X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), and X-ray photoelectron spectroscopy (XPS). CP 1 exhibited strong quenched upon interaction with GSH, indicating a strong binding affinity. Mechanistic investigations, including Inner Filter Effect (IFE) correction and XPS analysis, confirmed that the fluorescence quenching was primarily attributed to IFE and possible electron transfer interactions between 1 and GSH. The quenching constant (K_sv) was determined to be 0.993 × 10⁻³ M⁻¹, and the detection limit (LOD) was calculated as 2.38 × 10⁻⁵ M, highlighting the high sensitivity of the sensor. Additionally, fluorescence lifetime analysis showed a decrease from 41.2 μs to 33.1 μs upon GSH interaction, indicating significant changes in the excited-state molecular environment. The practical applicability of this sensing method was evaluated in real water samples, including deionized (DI) water, tap water, and river water, with excellent recovery rates ranging from 93.04 % to 100.98 % and relative standard deviations (RSD) below 2.2 %, confirming the reliability and accuracy of the method. This study establishes 1 as an effective, selective, and sensitive fluorescence probe for GSH detection, with potential applications in environmental monitoring, biomedical diagnostics, and clinical research.

荧光传感已成为一种检测生物分子的有效策略，具有高灵敏度和选择性。本研究合成了一种新的Zn（II）基配位聚合物（CP） {Zn(Cl-L)(DPP)]·1.5DMF}n(1)，并对其作为检测谷胱甘肽（GSH）的荧光传感器进行了探索。采用溶剂热法合成了配位聚合物，并用x射线衍射（XRD）、傅里叶变换红外光谱（FT-IR）和x射线光电子能谱（XPS）对其结构进行了表征。cp1在与GSH相互作用时表现出强烈的猝灭，表明具有较强的结合亲和力。机制研究，包括内部过滤效应（IFE）校正和XPS分析，证实了荧光猝灭主要归因于IFE和1与GSH之间可能的电子转移相互作用。猝灭常数（Ksv）为0.993 × 10−3 M−1，检出限（LOD）为2.38 × 10−5 M，灵敏度高。荧光寿命分析显示，GSH相互作用后，荧光寿命从41.2 μs降至33.1 μs，表明激发态分子环境发生了显著变化。在去离子水（DI）、自来水、河水等实际水样中评价了该方法的实用性，回收率为93.04% ~ 100.98%，相对标准偏差（RSD）小于2.2%，验证了该方法的可靠性和准确性。本研究确立了1作为一种高效、选择性强、灵敏度高的谷胱甘肽检测荧光探针，在环境监测、生物医学诊断和临床研究等方面具有潜在的应用前景。

{"title":"A new 2D Zn(II)-based coordination polymer as highly sensitive selective fluorescent probe for of glutathione","authors":"Shan-Qi Li , Mithun Kumar Ghosh , Yong-Qi Zhang , Jun-Cheng Jin , Mohammad Khalid Parvez , Mohammed S. Al-Dosari , Tanmay Kumar Ghorai , Feng Xu","doi":"10.1016/j.ica.2025.122718","DOIUrl":"10.1016/j.ica.2025.122718","url":null,"abstract":"<div><div>Fluorescence-based sensing has emerged as an effective strategy for detecting biomolecules with high sensitivity and selectivity. In this study, a new Zn(II)-based coordination polymer (CP), {Zn(Cl-L)(DPP)]·1.5DMF}n (1), was synthesized and explored as a fluorescence sensor for the detection of glutathione (GSH). The coordination polymer was synthesized via a solvothermal method, and its structural characterization was confirmed using X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), and X-ray photoelectron spectroscopy (XPS). CP 1 exhibited strong quenched upon interaction with GSH, indicating a strong binding affinity. Mechanistic investigations, including Inner Filter Effect (IFE) correction and XPS analysis, confirmed that the fluorescence quenching was primarily attributed to IFE and possible electron transfer interactions between 1 and GSH. The quenching constant (Ksv) was determined to be 0.993 × 10−3 M−1, and the detection limit (LOD) was calculated as 2.38 × 10−5 M, highlighting the high sensitivity of the sensor. Additionally, fluorescence lifetime analysis showed a decrease from 41.2 μs to 33.1 μs upon GSH interaction, indicating significant changes in the excited-state molecular environment. The practical applicability of this sensing method was evaluated in real water samples, including deionized (DI) water, tap water, and river water, with excellent recovery rates ranging from 93.04 % to 100.98 % and relative standard deviations (RSD) below 2.2 %, confirming the reliability and accuracy of the method. This study establishes 1 as an effective, selective, and sensitive fluorescence probe for GSH detection, with potential applications in environmental monitoring, biomedical diagnostics, and clinical research.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"583 ","pages":"Article 122718"},"PeriodicalIF":2.7,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143844989","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

A facile chemical modification of polystyrene copolymer to its amine functional derivative: Exploration of Pd separation from PUREX originated simulated raffinate under acidic conditions 聚苯乙烯共聚物对其胺功能衍生物的简单化学改性：在酸性条件下从PUREX源模拟萃余液中分离Pd的探索

IF 2.7 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganica Chimica Acta

Pub Date : 2025-04-15 DOI: 10.1016/j.ica.2025.122715

K. Ariramganapathi , A.S. Suneesh , V. Hemalatha , N. Ramanathan

Pd separation from a synthetic acidic formulation mimicking the high active radioactive waste composition that could originate from nuclear fission of U (or Pu) has been studied by using a styrene based polymer-chemically functionalized with amine moiety. For this purpose, a straightforward synthetic protocol was adopted to introduce an amine moiety into a polystyrene copolymer by reacting chloromethylated resin with the ‘amine donor’ precursor, diethyelenetriamine. The emergence of the NH signature in the adsorbent by the disappearing CCl functional group of the resin precursor, as observed by FTIR, and the signature of N 1 s of the adsorbent, observed based on XPS studies, revealed the formation of the adsorbent, in addition to the thermogravimetric studies that corroborate a characteristic thermal degradation pattern typical of a polystyrene network. To qualify the adsorbent for Pd removal from nuclear waste, preliminary Pd adsorption studies from an acidic medium were performed by batch mode and fixed-bed adsorption using an extraction chromatography column. The studies revealed that Pd uptake increases with acidity, reaching a maximum of 5 M. A faster separation of Pd with a maximum adsorption capacity of approximately 710 mg/g and a breakthrough adsorption capacity of approximately 42 mg/g were achievable. An ion-exchange interaction between Pd and the amine ligand was attributed based on the XPS study, and the variation of NH vibrational stretching frequency with the increase in Pd concentration further corroborates the interaction between Pd and the amine moiety of the adsorbent. Fitting of the experimental data with different reaction kinetics and adsorption isotherm models suggests a pseudo-second-order type interaction between Pd and the amine ligands in the polystyrene matrix, wherein the interaction is mostly governed by a mono layered interaction of the Langmuir type. The recovery of adsorbed Pd from the resin was investigated using thiourea as a complexing agent. The Pd uptake was examined from acidic solutions in presence of a large excess of metal ions present in radioactive waste that corresponded to the compositions of PUREX raffinate.

通过使用苯乙烯基聚合物与胺分子进行化学官能化，研究了从模拟铀（或钚）核裂变产生的高活性放射性废物成分的合成酸性配方中分离钯的方法。为此，我们采用了一种简单的合成方法，通过氯甲基化树脂与 "胺供体 "前体二乙烯三胺的反应，在聚苯乙烯共聚物中引入胺分子。傅立叶变换红外光谱（FTIR）观察到树脂前体的氯化官能团消失，吸附剂中出现了 NH 标志，XPS 研究观察到吸附剂中出现了 N 1 s 标志，这些都揭示了吸附剂的形成，此外，热重研究也证实了聚苯乙烯网络典型的热降解模式特征。为了验证该吸附剂从核废料中去除钯的能力，利用萃取色谱柱通过间歇模式和固定床吸附对酸性介质中的钯进行了初步吸附研究。研究结果表明，钯的吸附量随酸度的增加而增加，最高可达 5 M。根据 XPS 研究，Pd 与胺配体之间存在离子交换作用，而 NH 振动伸展频率随 Pd 浓度增加而变化，进一步证实了 Pd 与吸附剂胺分子之间的相互作用。用不同的反应动力学和吸附等温线模型对实验数据进行拟合，结果表明钯与聚苯乙烯基体中的胺配体之间存在伪二阶型相互作用，这种相互作用主要受朗缪尔型单层相互作用的支配。使用硫脲作为络合剂，研究了从树脂中回收吸附钯的情况。在放射性废料中存在大量过量金属离子（与 PUREX 废液的成分相符）的情况下，对酸性溶液中钯的吸收情况进行了研究。

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引用次数: 0