Journal of Molecular Structure最新文献

Structural, optical, and biological investigations of a new hybrid compound Bis(1,8-diazabicyclo[5.4.0]undec‑7-enium) tetrachloridozincate(II) 新型杂化化合物双（1,8-重氮双环[5.4.0]undec - 7-enium）四氯碘酸酯（II）的结构、光学和生物学研究

IF 4.7 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Structure

Pub Date : 2026-01-26 DOI: 10.1016/j.molstruc.2026.145360

Sarra Bougossa , Ahlem Guesmi , Feriel Swayah , Noureddine Mhadhbi , Ali Ben Ahmed , Jeanneau Erwann , Khaled Hamden , Naoufel Ben Hamadi , Lotfi Khezami , Antonio Sánchez-Coronilla , Houcine Naϊli

Crystals of a novel organic-inorganic hybrid compound with the structural formula (C₉H₁₇N₂)₂[ZnCl₄] named Bis(1,8-diazabicyclo[5.4.0]undec‑7-enium) tetrachloridozincate (II), were generated and carefully investigated. The compound was comprehensively characterized through X-ray diffraction analysis under ambient conditions, differential scanning calorimetry, thermogravimetric analysis, infrared spectroscopy, nuclear magnetic resonance (NMR) spectroscopy, and optical absorption spectroscopy to evaluate its structural, thermal, vibrational, and electronic properties. X-ray diffraction showed that the compound has a monoclinic crystal structure and belongs to the P2₁/n space group. An infrared spectra analysis was conducted to identify the key vibration modes and their assignments. Optical analysis showed a direct allowed band gap of 4.54 eV, confirming the semiconductor nature of this hybrid material. Density functional theory (DFT) calculations were performed, followed by an analysis of the molecular electrostatic potential surface and Mulliken charge distribution. The TGA and DSC analyses confirmed the thermal stability at 340 °C, then gradually decomposes until 541 °C, releasing different compounds. A phase transition was also seen at 85 °C in the DSC curve. This study shows that DBU-Zn has dose-dependent anti-inflammatory effects, with the best result at 40mg/kg, reducing inflammation by 39%. It also has strong pain-relieving effects, lowering writhing episodes by 25% in the early phase and 61% in the late phase.

合成了一种新型的有机-无机杂化化合物晶体，其分子式为（C9H17N2）2[ZnCl4]，命名为双（1,8-重氮杂环[5.4.0]undec - 7-enium）四氯肼酸酯（II）。通过环境条件下的x射线衍射分析、差示扫描量热法、热重分析、红外光谱、核磁共振（NMR）光谱和光学吸收光谱对化合物进行了全面表征，评价了其结构、热、振动和电子性能。x射线衍射表明，该化合物具有单斜晶结构，属于P21/n空间群。通过红外光谱分析，确定了关键振型及其归属。光学分析表明，直接允许带隙为4.54 eV，证实了该杂化材料的半导体性质。进行了密度泛函理论（DFT）计算，分析了分子静电势面和Mulliken电荷分布。TGA和DSC分析证实了该化合物在340℃时的热稳定性，然后逐渐分解至541℃，释放出不同的化合物。在85℃时，DSC曲线也出现了相变。本研究表明，DBU-Zn具有剂量依赖性的抗炎作用，40mg/kg时效果最佳，可减轻39%的炎症。它也有很强的镇痛作用，在早期阶段将扭动发作减少25%，在晚期减少61%。

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引用次数: 0

Steric hindrance-driven structure engineering of hybrid Cu(I) halides for modulated optical performance 用于调制光学性能的杂化Cu(I)卤化物的位阻驱动结构工程

IF 4.7 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Structure

Pub Date : 2026-01-22 DOI: 10.1016/j.molstruc.2026.145441

Qiuyue Cao , Binling Yao , Yue Wang , Miaomiao Pang , Hui Min , Yuquan Zhu , Dong Shao

Zero-dimensional Cu(I)-based organic-inorganic metal halides demonstrate exceptional structural tunability arising from their flexible 3d¹⁰ electronic configuration, enabling precise control of cluster nuclearity and topology through rational ligand design. In this work, we systematically functionalized triethylenediamine through stepwise N-alkylation to obtain three sterically demanding ligands (L₁ = C₆H₁₂N₂²⁺, L₂ = C₁₀H₂₂N₂²⁺, L₃ = C₁₁H₂₄N₂²⁺), which directed assembly of mononuclear (L₁)CuI₃ (1), trinuclear (L₂)₂Cu₃I₇ (2) and heptanuclear (L₃)₃Cu₇I₁₃ (3) clusters. Single-crystal X-ray diffraction and optical characterization revealed that increasing ligand steric bulk drives nuclearity expansion from mononuclear to heptanuclear clusters, with concomitant emission shifts spanning red, green, and yellow regions. Microsecond-scale luminescence lifetimes (0.25–2.7 μs), large Stokes shift (200–285 nm) and broad emission peaks (FWHM > 100 nm) collectively demonstrate self-trapped exciton emission (STE) in all complexes. Complex 2 shows unusual anti-thermal fluorescence behavior between 180-220 K, contributing to its exceptional exciton binding energy of 604.5 meV and high photoluminescence quantum yield (PLQY) of 70.6 %. This study proposes a design strategy for controlling both structure and luminescence in zero-dimensional copper-based complexes through ligand steric engineering.

零维Cu(I)基有机-无机金属卤化物由于其灵活的3d10电子构型而表现出优异的结构可调性，通过合理的配体设计可以精确控制簇核和拓扑结构。在这项工作中，我们通过逐步n -烷基化系统地功能化了三乙二胺，得到了三个立体要求的配体（L1 = C6H12N22+, L2 = C10H22N22+, L3 = C11H24N22+），这些配体指导了单核（L1）CuI3(1)，三核（L2）2Cu3I7(2)和七核（L3）3Cu7I13(3)簇的组装。单晶x射线衍射和光学表征表明，配体空间体积的增加驱动核从单核团簇向七核团簇扩展，并伴随红、绿、黄区域的发射位移。微秒级的发光寿命（0.25-2.7 μs）、大的Stokes位移（200-285 nm）和宽的发射峰（FWHM > 100 nm）共同证明了所有配合物的自捕获激子发射（STE）。配合物2在180-220 K之间表现出不同寻常的反热荧光行为，这是由于其激子结合能高达604.5 meV，光致发光量子产率高达70.6%。本研究提出了一种通过配体空间工程控制零维铜基配合物结构和发光的设计策略。

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引用次数: 0

Coordination modes-directed two different octamolybdate-based architectures with diverse aqueous electrochemical energy storage performances 配位模式指导了两种不同的八胺钼酸盐基结构，具有不同的水电化学储能性能

IF 4.7 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Structure

Pub Date : 2026-01-22 DOI: 10.1016/j.molstruc.2026.145453

Haining Jiang, Yuchu Lin, Yaling Zhu, Zhifei Zu, Zhihan Chang, Xiuli Wang, Wenjie Hua

Two new octamolybdate-based metal-organic complexes were synthesized under solvothermal conditions: H₂[Cu(3-Hdpap)(β-Mo₈O₂₆)]·H₂O (1) and [Cu₂Cl(3-dpap)(β-Mo₈O₂₆)_0.5(H₂O)] (2). (3-Hdpap = N³,N⁵-bis(pyridin-3-ylmethyl)-4H-pyrazole-3,5-dicarboxamide) and structurally characterized by single-crystal X-ray diffraction. The ligand 3-Hdpap exhibits diverse coordination modes, resulting in two different architectures: complex 1 is a one-dimensional (1D) supramolecular chain formed by the hydrogen bond interaction between the metal-organic windmill and [β-Mo₈O₂₆]^4- anions; complex 2 exhibits a 2D layer constructed from metal-organic chain and [β-Mo₈O₂₆]^4- anions, and further consolidated by the chloridion. The rich coordination site and enhanced flexibility of 3-Hdpap not only drives the structural differences, but also results in their different electrochemical energy storage performances. At a current density of 1 A·g^-1, the specific capacitance of complex 2-modified glassy carbon electrode (2-GCE) can reach 1556.5 F·g^-1, which is greatly higher than that of 1-GCE (603.7 F·g^-1). Additionally, the aqueous zinc-ion battery performance with complexes 1/2-modified carbon cloth-based electrode (1-2/CC) as cathode were also investigated. The specific capacitance of 2/CC is 231.99 mAh·g^-1, which is higher than that of 1/CC (153.57 mAh·g^-1). The 2D layer of 2 facilitated rapid charge transport and significantly enhances its electrochemical energy storage performance.

在溶剂热条件下合成了两种新型八胺酸盐基金属有机配合物H2[Cu(3-Hdpap)(β-Mo8O26)]·H2O(1)和[Cu2Cl(3-dpap)(β-Mo8O26)0.5(H2O)] (2). （3-Hdpap = N3， n5 -双（吡啶-3-甲基）- 4h -吡唑-3,5-二甲酰胺），并用单晶x射线衍射对其结构进行了表征。配体3-Hdpap表现出不同的配位模式，形成两种不同的结构：配合物1是由金属有机风车与[β-Mo8O26]4-阴离子之间的氢键相互作用形成的一维（1D）超分子链；配合物2呈现由金属有机链和[β-Mo8O26]4-阴离子构成的二维层，并被氯离子进一步巩固。3-Hdpap丰富的配位位点和增强的灵活性不仅驱动了结构上的差异，也导致了它们不同的电化学储能性能。在电流密度为1 a·g-1时，复合2修饰玻碳电极（2-GCE）的比电容可达1556.5 F·g-1，大大高于1- gce的603.7 F·g-1。此外，还研究了以配合物1/2改性碳布基电极（1-2/CC）为阴极的水溶液锌离子电池性能。2/CC比电容为231.99 mAh·g-1，高于1/CC比电容（153.57 mAh·g-1）。2的二维层促进了电荷的快速传输，显著提高了其电化学储能性能。

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引用次数: 0

Cocrystal engineering confers photoresistance, tabletability, and anaerobic bactericidal synergy to metronidazole via NIR monitoring 通过近红外监测，共晶工程赋予甲硝唑光敏性、耐药性和厌氧杀菌协同作用

IF 4.7 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Structure

Pub Date : 2026-01-22 DOI: 10.1016/j.molstruc.2026.145452

Da-zhong Ding , Ying Fan , Yan Zhang , Meng-meng Niu , Xing-tong Zhou , Zhong-hua Sun , Yang Li , Ping Gao , Lin Pei , Zhao Yang

Metronidazole (MNZ), a widely used clinical agent for anaerobic infections, requires light-protected handling during manufacturing, storage, and administration owing to its inherent photolability. Accordingly, co-crystallization offers a distinctive strategy to optimize pharmaceutical properties, while preserving the chemical integrity of pharmaceutical ingredients. To address these limitations, a novel cocrystal of MNZ with the food antioxidant butyl gallate (BG) was successfully synthesized using ultrasound-assisted solvent evaporation and liquid-assisted grinding (LAG). Fourier-transform near-infrared (FT-NIR) spectroscopy was employed for near-real-time and in-situ monitoring of the LAG synthesis process. Single-crystal X-ray diffraction confirmed a 2:1 MNZ:BG stoichiometry of the cocrystal, which was stabilized by hydrogen bonding and intermolecular interactions within the lattice. Comprehensive solid-state characterization, including powder X-ray diffraction, fourier transform infrared spectroscopy, FT-NIR, differential scanning calorimetry, thermogravimetric analysis, and scanning electron microscopy, revealed distinct spectral and thermal signatures relative to pure MNZ, BG, and their physical mixture, validating the new crystalline phase. The cocrystal demonstrated markedly improved critical attributes: a threefold increase in photostability (with an 81% reduction in photolytic impurities), excellent tabletability despite the poor compressibility of pure MNZ, and a 50% lower minimum inhibitory concentration against the clinically relevant anaerobic bacterium Clostridium sporogenes, compared to MNZ alone. In conclusion, this study demonstrated cocrystal engineering as an effective strategy for enhancing the key pharmaceutical properties of MNZ, with FT-NIR monitoring presenting a viable tool for process control.

甲硝唑（MNZ）是一种广泛用于临床治疗厌氧感染的药物，由于其固有的光性，在制造、储存和给药过程中需要避光处理。因此，共结晶提供了一种独特的策略来优化药物性能，同时保持药物成分的化学完整性。为了解决这些问题，利用超声辅助溶剂蒸发和液体辅助研磨（LAG）技术，成功合成了一种新型MNZ与食品抗氧化剂没食子酸丁酯（BG）共晶。采用傅里叶变换近红外（FT-NIR）光谱对LAG合成过程进行了近实时和现场监测。单晶x射线衍射证实了共晶的2:1 MNZ:BG化学计量，晶格内的氢键和分子间相互作用稳定了共晶。综合固态表征，包括粉末x射线衍射，傅里叶变换红外光谱，FT-NIR，差示扫描量热法，热重分析和扫描电镜，揭示了相对于纯MNZ， BG及其物理混合物的独特光谱和热特征，验证了新的晶体相。该共晶表现出了显著改善的关键属性：光稳定性提高了三倍（光解杂质减少了81%），尽管纯MNZ的可压缩性较差，但其极好的耐药性，与单独MNZ相比，对临床相关的厌氧细菌芽孢梭菌的最低抑制浓度降低了50%。总之，本研究表明，共晶工程是提高MNZ关键药物性能的有效策略，FT-NIR监测为过程控制提供了可行的工具。

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引用次数: 0

A phenothiazine-based fluorescent probe for ratiometric sensing of mercury(II) with high selectivity and sensitivity 基于吩噻嗪的高选择性、高灵敏度汞（II）比例传感荧光探针

IF 4.7 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Structure

Pub Date : 2026-01-21 DOI: 10.1016/j.molstruc.2026.145439

Dan Mao , Chong Wu , Wan-Wan Zhao , Yu-Yan Ran , Qiu-Rong Hu , Huan Hong , Xiao-Ling Zuo , Rui An , Juan Zou

Due to the severe toxicity of mercury ions (Hg²⁺) to human health and the ecological environment, the development of fluorescent probes with high selectivity and sensitivity for Hg²⁺ detection is of considerable significance. Herein, a novel reaction-based fluorescent probe (PTZ-DT) was rationally designed and synthesized for Hg²⁺ sensing, based on the “protection–deprotection” principle. The probe employs phenothiazine as the fluorophore scaffold, incorporating a dithioacetal group as the sensing unit. The molecular structure of PTZ-DT was fully characterized by NMR, HRMS, and X-ray crystallography. The sensing mechanism was confirmed to involve a Hg²⁺-triggered thioacetal deprotection reaction. Upon addition of Hg²⁺, the fluorescence intensity at 454 nm decreased, while an enhancement was observed at 559 nm, providing a ratiometric fluorescent response accompanied by a visible color change from blue to yellow. PTZ-DT demonstrates highly sensitive detection of Hg²⁺ with a low detection limit of 20.6 nM and a fast response of <5 min. Additionally, the probe demonstrates reliable detection capabilities in real water samples.

由于汞离子（Hg2+）对人体健康和生态环境的严重毒性，开发高选择性、高灵敏度的荧光探针检测Hg2+具有相当的意义。本文基于“保护-去保护”原理，合理设计合成了一种新型反应型荧光探针（PTZ-DT），用于Hg2+传感。该探针采用吩噻嗪作为荧光团支架，结合二硫缩醛作为传感单元。通过核磁共振、HRMS和x射线晶体学对PTZ-DT的分子结构进行了表征。该传感机制被证实涉及Hg2+触发的硫缩醛脱保护反应。加入Hg2+后，454nm处的荧光强度降低，559 nm处荧光强度增强，呈现比例荧光响应，并伴有可见的颜色由蓝色变为黄色。PTZ-DT对Hg2+的检测灵敏度高，检出限低至20.6 nM，响应速度快至5 min。此外，该探针在实际水样中显示出可靠的检测能力。

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引用次数: 0

Synthesis, photophysical properties, and two-photon absorption behavior of pyrimidinyl urea derivatives 嘧啶脲基衍生物的合成、光物理性质及双光子吸收行为

IF 4.7 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Structure

Pub Date : 2026-01-21 DOI: 10.1016/j.molstruc.2026.145438

Julián Rodríguez-López , Eleftherios Laleas , Elio G. Soultse , Mihalis Fakis , Sylvain Achelle

A new family of unsymmetrical N-pyrimidinyl-N′-aryl/sulfonyl ureas incorporating a 4,6-distyrylpyrimidine chromophore was synthesized via two microwave-assisted strategies that alternate the order of urea formation and styryl installation. All products were isolated as the all-E isomers. In CH₂Cl₂, most derivatives absorb near 390 nm, while strong donor substitution (R³ = NMe₂) induces a pronounced red shift. Protonation with trifluoracetic acid (TFA) generally enhances fluorescence (Φ_F up to 0.41) and induces bathochromic shifts of up to ∼100 nm or more, except in the most intense push–pull systems, which undergo emission quenching. In the solid-state, the emission extends into the deep red/near-infrared (NIR) region (up to 755 nm) for high-donor-strength derivatives. Time-resolved studies reveal lifetime elongation upon protonation for moderate donors, but shortening for stronger ones. Two-photon absorption cross sections exceed 1000 GM (maximum ≈ 1600 GM) for some protonated derivatives, whereas the NMe₂-substituted compound 2f remains highly active in its neutral form. These results demonstrate proton-switchable photophysical and NLO properties, offering a versatile platform for responsive optical materials.

以4,6-二苯基嘧啶为发色团，通过改变尿素生成顺序和苯乙烯基安装顺序的两种微波辅助策略合成了一个新的不对称n -嘧啶基- n′-芳基/磺酰基脲族。所有产物均为全e异构体。在CH₂Cl₂中，大多数衍生物在390 nm附近吸收，而强供体取代（R3 = NMe₂）引起明显的红移。三氟乙酸（TFA）的质子化通常增强荧光（ΦF高达0.41），并诱导高达~ 100 nm或更多的色移，除了在最强烈的推挽系统中，其经历发射猝灭。在固态中，对于高给体强度衍生物，发射延伸到深红色/近红外（NIR）区域（高达755 nm）。时间分辨的研究揭示了中等供体质子化后的寿命延长，而较强供体的寿命缩短。某些质子化衍生物的双光子吸收截面超过1000 GM（最大≈1600 GM），而nme2取代的化合物2f在其中性形式下保持高活性。这些结果证明了质子可切换的光物理和NLO特性，为响应光学材料提供了一个多功能平台。

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引用次数: 0

Synthesis, structural characterisation, DFT analysis and conductivity studies of protonated 4-(2-bromophenyl)thiosemicarbazide dopant with carboxymethyl cellulose (CMC) 羧甲基纤维素（CMC）质子化4-（2-溴苯基）硫代氨基脲掺杂剂的合成、结构表征、DFT分析及电导率研究

IF 4.7 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Structure

Pub Date : 2026-01-21 DOI: 10.1016/j.molstruc.2026.145447

Teo Lie Vian , Uwaisulqarni M. Osman , Suhana Arshad , Nur Maisarah Batrisyia Mohd Bahaudin , Nurul Faeqah Mazalan , Mohd Ikmar Nizam Mohamad Isa

A new thiosemicarbazide derivative dopant, 4-(2-bromophenyl)thiosemicarbazide, was synthesized and comprehensively characterized using FT-IR, ¹H NMR, ¹³C NMR, UV–Vis, TGA and single crystal X-ray crystallography. These techniques confirmed the structure of the 4-(2-bromophenyl)thiosemicarbazide dopant, which crystallizes in the monoclinic system with a C2/c space group and exhibits intermolecular hydrogen bonding through N-H^…S atoms. Its electronic properties were further investigated using density functional theory (DFT) to obtain theoretical orbital distributions, energy gaps and molecular electrostatic potential analysis. The theoretical HOMO-LUMO band gap energy (E_gap) obtained from experimental tauc plot was 4.16 eV and the theoretical band gap calculated in the DMSO solution phase are 4.7546 eV, both lie within the range for organic insulators. The highest conductivity of 1.54 × 10⁻⁸ S·cm⁻¹ at 80 °C was measured for a solid biopolymer electrolyte (SBE) film containing 1 g of carboxymethyl cellulose (CMC), 10 wt% polyethylene glycol (PEG), 15 wt% dopant and 15 wt% dipicolinic acid. Temperature-dependent conductivity studies revealed Arrhenius-type conduction, where elevated temperatures facilitate proton hopping in the polymer.

合成了一种新的硫代氨基脲衍生物掺杂剂4-（2-溴苯基）硫代氨基脲，并利用FT-IR、1H NMR、13C NMR、UV-Vis、TGA和单晶x射线晶体学对其进行了综合表征。这些技术证实了4-（2-溴苯基）硫代氨基脲掺杂剂的结构，该掺杂剂在单斜晶系中具有C2/c空间基团，并通过N-H…S原子形成分子间氢键。利用密度泛函理论（DFT）进一步研究了其电子性质，得到了理论轨道分布、能隙和分子静电势分析。实验得到的HOMO-LUMO理论带隙能量（Egap）为4.16 eV， DMSO溶液计算得到的理论带隙能量为4.7546 eV，均在有机绝缘子的范围内。用含1g羧甲基纤维素（CMC）、10wt %聚乙二醇（PEG）、15wt %掺杂剂和15wt %二吡啶酸的固体生物聚合物电解质（SBE）薄膜，在80°C时的最高电导率为1.54 × 10⁻⁸S·cm⁻¹。温度相关的电导率研究揭示了arrhenius类型的传导，其中升高的温度促进了聚合物中的质子跳跃。

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引用次数: 0

Carboxylato-Phenyl-Terpyridine Pb(II) complex: Ligand-driven charge separation unlocks dual fluorescence–phosphorescence 羧基-苯基-三联吡啶Pb（II）配合物：配体驱动的电荷分离解锁双荧光-磷光

IF 4.7 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Structure

Pub Date : 2026-01-20 DOI: 10.1016/j.molstruc.2026.145432

Rongfang Li , Yiren Wang , Jingwen Hao , Xueyang Zeng , Xun Feng

A novel 3D Pb-polymer crystal [Pb₃(Htcpt)₃]ₙ (1) was hydrothermally synthesized from 4-(2,4,6-tricarboxyphenyl)-2,2′:6′,2″-terpyridine (H₃tcpt) and Pb(NO₃)₂. Its structure was characterized by IR, PXRD and single-crystal X-ray diffraction, and thermal stability was examined by TGA. Photoluminescence studies reveal that coordination induces peak splitting and a red-shift in the solid-state emission, giving three bands at 403, 513 and 618 nm. The 513 nm band shows a fluorescence lifetime of 3.45 ns. Under 365 nm excitation the crystal exhibits phosphorescence at 559 nm with a lifetime of 1.35 ms. The luminescence mechanisms of fluorescence and phosphorescence of the compound are analyzed through DFT calculations.

以4-（2,4,6-三羧基苯基）-2,2′：6′，2″-三吡啶（H₃tcpt）和Pb（NO₃）₂为原料，水热合成了新型三维Pb聚合物晶体[Pb₃（Htcpt）₃](1)。用IR、PXRD和单晶x射线衍射对其结构进行了表征，并用TGA对其热稳定性进行了表征。光致发光研究表明，配位引起固体发射峰分裂和红移，在403、513和618 nm处形成三个波段。513 nm波段的荧光寿命为3.45 ns。在365 nm激发下，晶体在559 nm处表现出磷光，寿命为1.35 ms。通过DFT计算分析了该化合物的荧光和磷光发光机理。

引用次数: 0

Homochiral Cd-MOF with D-Camphorate derived dicarboxylate ligand for enantioselective sensing of D/L-Glutamate in serum 含D-樟脑酸衍生二羧酸配体的同手性Cd-MOF对血清中D/ l -谷氨酸进行对映选择性感应

IF 4.7 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Structure

Pub Date : 2026-01-20 DOI: 10.1016/j.molstruc.2026.145429

Yu Li, Xuze Pan, Kun Zhang, Jing Ru, Qingfu Zhang

A novel homochiral luminescent metal-organic framework (MOF), [Cd₂(D-L)₂(bibt)₂·3DMF]_n (1), was rationally designed and synthesized for the highly efficient enantioselective sensing of D/L-glutamate (D/L-Glu). Single-crystal X-ray diffraction analysis revealedthat 1 forms a double helix structure based on the bimetallic [Cd₂(CO₂)₄] unit and the D-L²⁻ ligand. The chiral homogeneity of the crystal sample was confirmed by circular dichroism (CD) spectroscopy. As a luminescent probe, 1 exhibited enantioselectivity toward D/L-Glu in aqueous media, achieving a remarkable quenching constant ratio K_SV(D)/K_SV(L) of 4.29. Furthermore, 1 demonstrated robust practical applicability, enabling the reusable and specific detection of D/L-Glu in complex serum samples with high recovery rates. Beyond sensing capabilities, 1 was successfully processed into a luminescent ink, exhibiting superior stability and potential for anti-counterfeiting applications. This study highlights the promise of such homochiral luminescent MOF materials as ideal candidates for both chiral analyte recognition and optical information encryption.

合理设计并合成了一种新型的同手性发光金属-有机骨架[Cd2(D- l)2(bibt)2·3DMF]n(1)，用于D/ l-谷氨酸（D/L-Glu）的高效对体选择性传感。单晶x射线衍射分析表明，1由双金属[Cd2(CO2)4]单元和D-L2−配体构成双螺旋结构。用圆二色性（CD）光谱证实了晶体样品的手性均匀性。作为发光探针，1在水介质中对D/L- glu具有对映选择性，猝灭常数比KSV(D)/KSV(L)为4.29。此外，1显示了强大的实用性，可以在复杂血清样品中重复使用和特异性检测D/L-Glu，回收率高。除了传感能力，1被成功地加工成发光油墨，表现出卓越的稳定性和防伪应用的潜力。这项研究强调了这种同手性发光MOF材料作为手性分析物识别和光信息加密的理想候选者的前景。

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引用次数: 0

Synthesis, characterization, electrochemistry and magnetic properties of hepta-cobalt substituted lanthanoid-containing silico-tungstate nanoclusters 含七钴取代类镧钨酸硅纳米团簇的合成、表征、电化学和磁性能

IF 4.7 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Structure

Pub Date : 2026-01-20 DOI: 10.1016/j.molstruc.2026.145425

Shivani , Vivek Das , Masahiro Sadakane , Daisuke Ishikawa , Jun Manabe , Sadafumi Nishihara , Israël-Martyr Mbomekallé , Pedro de Oliveira , Firasat Hussain

Cobalt-substituted lanthanoid-containing silico-tungstate polyoxometalates represent a fascinating class of self-assembled nano-clusters with promising applications in molecular magnetism, catalysis, and material sciences. A series of heterometallic mono-lanthanoid containing cobalt-substituted silico-tungstate is reported and prepared by the trilacunary Na₁₀[A-α-SiW₉O₃₄] ligand. The nano-cluster [LnCo₇Si₃W₂₉O₁₀₈(OH)₅(H₂O)₄]^18- [Ln^III = Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu] consists of a trimeric structure. The compounds have been studied for magnetic properties and electrochemistry. The χ_mT curve of all the samples shows a gradual decrease with a decrease in temperature (300 K to 2 K), attributed to the depopulation of the excited Kramers state of the Co²⁺ ions. The electrochemical responses from the W, Co and Eu centres are observed, which are stable within the timescale of the experiments.

钴取代类镧系硅钨酸盐多金属氧酸盐是一类引人入胜的自组装纳米簇，在分子磁学、催化和材料科学方面具有广阔的应用前景。采用三元Na10[A-α-SiW9O34]配体制备了一系列含钴取代硅钨酸盐的异金属单镧系化合物。纳米团簇[LnCo7Si3W29O108(OH)5(H2O)4]18- [LnIII = Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb， Lu]由三聚体结构组成。对这些化合物进行了磁性和电化学研究。所有样品的χmT曲线显示，随着温度的降低（300 K至2 K）， Co2+离子的激发态克莱默斯态的减少而逐渐减少。W、Co和Eu中心的电化学响应在实验时间尺度内是稳定的。

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引用次数: 0