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A few examples of cis trans isomerization in complexes involving the oxamide function 涉及草酰胺功能的络合物中顺反异构化的几个例子
IF 2.7 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-08-13 DOI: 10.1016/j.ica.2024.122319

Synthesis of heterodinuclear 3d transition metal complexes in which two metal ions are introduced in equivalent coordination sites of a ligand is quite uncommon. We have previously shown that the application of the cis–trans isomerization of the oxamido group was able to furnish such a possibility. In the present paper we demonstrate that this synthetic pathway, relying on the possibility of changing the conformation (cis vs trans) of the oxamido group, can be extended to other ligands. Although we have not been able to characterize these complexes by structural determinations, FAB-MS, EPR and magnetic data do confirm the efficiency of this reaction pathway. We also demonstrate that the cis–trans isomerization of the oxamido group is not due to a particular property of the ion involved in the reaction. In fact, isomerization is governed by the basicity of the reaction medium. According to the reaction condition, it is possible to favor or not this phenomenon, and to increase the accessibility to a larger number of novel genuine complexes. But the oxophilic character of the lanthanide ions limits the use of this synthetic pathway because it impedes this isomerization. Eventually, the very weak magnetic interactions observed in these Cu-Gd complexes can be explained thanks to spin polarization.

在配体的等效配位上引入两个金属离子的异核 3d 过渡金属配合物的合成并不常见。我们之前已经证明,应用草酰胺基团的顺反异构化可以提供这种可能性。在本文中,我们证明了这种依靠改变草酰胺基团构象(顺式与反式)的合成途径可以扩展到其他配体。虽然我们无法通过结构测定来确定这些复合物的特征,但 FAB-MS、EPR 和磁性数据确实证实了这种反应途径的效率。我们还证明,草酰胺基团的顺反异构并不是由于参与反应的离子的特定性质造成的。事实上,异构化受反应介质碱性的影响。根据反应条件的不同,这种现象有可能发生,也有可能不发生,从而产生更多新的真正络合物。但镧系元素离子的亲氧化特性会阻碍这种异构化,从而限制了这种合成途径的使用。最终,在这些铜钆配合物中观察到的非常微弱的磁相互作用可以用自旋极化来解释。
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引用次数: 0
Double pseudo-polymeric complexes of [Au(S2CNBu2)2][AgCl2] and [Au(S2CNHm)2]3[AgCl2][Ag0.59Au0.41Cl2]2: Preparation, supramolecular self-assembly, thermal behaviour and anti-mycobacterial activity Au(S2CNBu2)2][AgCl2]和[Au(S2CNHm)2]3[AgCl2][Ag0.59Au0.41Cl2]2的双假聚合物配合物:制备、超分子自组装、热行为和抗霉菌活性
IF 2.7 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-08-13 DOI: 10.1016/j.ica.2024.122318

Pseudo-polymeric double complexes of [Au{S2CN(C4H9)2}2][AgCl2] (1) and [Au{S2CN(CH2)6}2]3[AgCl2][Ag0.59Au0.41Cl2]2 have been obtained and chemically identified using solution (1H, 13C{1H}) NMR and FT-IR spectroscopy. According to XRD analysis, it was established that both of the above crystalline compounds form complicated supramolecular architectures. Self-assembly and structural stabilization of these supramolecular formations are achieved due to numerous secondary interactions: Ag⋯S, Cl⋯S (in 1, 2) and Au⋯Cl, Au⋯S (in 2), which arose between the ionic structural units of the complexes. The combined manifestation of these interionic secondary interactions leads to the construction of two types of pseudo-polymeric chains of (⋯[Au(S2CNBu2)2]⋯[AgCl2]⋯)n (1) and (⋯[Au2(S2CNHm)4]⋯ [AgCl2]⋯)n (2). To study the thermal behaviour of the prepared compounds, the simultaneous thermal analysis (STA) technique was used, which allowed us to determine the conditions for the quantitative recovery of bound metals. Moreover, a high in vitro biological activity for each of the prepared gold(III)-silver(I) compounds against the non-pathogenic strain Mycolicibacterium smegmatis was experimentally revealed.

利用溶液(1H、13C{1H})核磁共振和傅立叶变换红外光谱,获得了[Au{S2CN(C4H9)2}2][AgCl2] (1)和[Au{S2CN(CH2)6}2]3[AgCl2][Ag0.59Au0.41Cl2]2的伪聚合双复合物,并对其进行了化学鉴定。根据 XRD 分析,上述两种晶体化合物都形成了复杂的超分子结构。这些超分子结构的自组装和结构稳定是通过许多次级相互作用实现的:Ag⋯S、Cl⋯S(在 1、2 中)和 Au⋯Cl、Au⋯S(在 2 中),它们在复合物的离子结构单元之间产生。这些离子间二级相互作用的综合表现导致了 (⋯[Au(S2CNBu2)2]⋯[AgCl2]⋯)n (1) 和 (⋯[Au2(S2CNHm)4]⋯[AgCl2]⋯)n (2) 两种假聚合物链的形成。为了研究制备的化合物的热性能,我们使用了同步热分析(STA)技术,从而确定了定量回收结合金属的条件。此外,实验还揭示了所制备的金(III)-银(I)化合物对非致病性烟曲霉菌株具有很高的体外生物活性。
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引用次数: 0
Photocatalytic applications and synthetic strategies of Ti and Fe-based MOFs 钛基和铁基 MOF 的光催化应用和合成策略
IF 2.7 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-08-13 DOI: 10.1016/j.ica.2024.122297

Metal-organic frameworks (MOFs) have emerged as promising materials for photocatalytic applications due to their tunable structures and exceptional surface areas. Among various types of MOFs, those based on titanium (Ti) and iron (Fe) have garnered significant attention for their potential in environmental remediation, energy conversion, and organic synthesis. This review paper comprehensively examines the recent advancements in the photocatalytic applications and synthetic strategies of Ti and Fe-based MOFs. In the first part, we provide an in-depth analysis of the synthetic strategies employed for the preparation of Ti and Fe-based MOFs with tailored photocatalytic properties. The second part of the review highlights the diverse photocatalytic applications of Ti and Fe-based MOFs, including environmental remediation through the degradation of organic pollutants, hydrogen evolution reaction (HER) for renewable energy production, carbon dioxide reduction for greenhouse gas mitigation, and catalysis of organic transformations. Overall, this review paper offers valuable insights into the current state-of-the-art in the field of Ti and Fe-based MOFs for photocatalytic applications, providing researchers and practitioners with a comprehensive understanding of the potential and limitations of these materials. The synthesis strategies discussed herein serve as guidelines for the rational design and development of highly efficient photocatalysts for various environmental and energy-related applications.

金属有机框架(MOFs)因其可调整的结构和特殊的比表面积,已成为光催化应用中极具前景的材料。在各种类型的 MOFs 中,基于钛(Ti)和铁(Fe)的 MOFs 因其在环境修复、能源转换和有机合成方面的潜力而备受关注。本综述全面探讨了钛基和铁基 MOFs 在光催化应用和合成策略方面的最新进展。在第一部分中,我们深入分析了制备具有定制光催化特性的钛基和铁基 MOFs 所采用的合成策略。综述的第二部分重点介绍了钛基和铁基 MOFs 的各种光催化应用,包括通过降解有机污染物进行环境修复、用于可再生能源生产的氢进化反应 (HER)、用于减缓温室气体排放的二氧化碳减排以及有机转化催化。总之,这篇综述论文为了解当前钛基和铁基 MOFs 在光催化应用领域的最新进展提供了宝贵的见解,使研究人员和从业人员对这些材料的潜力和局限性有了全面的了解。本文讨论的合成策略可作为合理设计和开发用于各种环境和能源相关应用的高效光催化剂的指南。
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引用次数: 0
Novel biocompatible pH-fluorescence responsive MOF nanocarriers for lung cancer treatment 用于肺癌治疗的新型生物相容性 pH 荧光响应 MOF 纳米载体
IF 2.7 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-08-12 DOI: 10.1016/j.ica.2024.122317

In this study, we synthesized two novel metal–organic frameworks [Cd(C4H4N2)(C12H19P3O9)]n (1) and {Ca[Cd(H2O)3]2(C24H15N6O6)2}n (2) distinguished by exceptional fluorescence properties. Focusing on 1, we innovatively combined it with hydroxypropyl cellulose (HPC) to create a pH-responsive, fluorescence-guided nanocarrier system (HPC-1@DOX) for targeted delivery of doxorubicin (DOX) in cancer treatment. We thoroughly evaluated the loading and release efficiency of DOX under varied pH conditions, demonstrating sustained and controlled drug release characteristics in vitro, along with substantial drug-loading capacity. Notably, HPC-1@DOX exhibited pH-responsive behavior, releasing DOX preferentially at pH 6.8, indicative of targeted delivery to tumor and inflammatory sites while minimizing release at higher pH values. Moreover, we explored its biological impact, confirming HPC-1@DOX’s ability to up-regulate miR-493-3p expression in lung carcinoma cells, thereby inhibiting proliferation, reducing invasiveness, and inducing apoptosis. This multifunctional nanocarrier system represents a significant advancement towards targeted and effective cancer therapy.

在本研究中,我们合成了两种新型金属有机框架[Cd(C4H4N2)(C12H19P3O9)]n(1)和{Ca[Cd(H2O)3]2(C24H15N6O6)2}n(2),这两种框架具有优异的荧光特性。针对 1,我们创新性地将其与羟丙基纤维素(HPC)结合,创建了一种 pH 响应、荧光引导的纳米载体系统(HPC-1@DOX),用于在癌症治疗中靶向递送多柔比星(DOX)。我们对不同 pH 值条件下 DOX 的负载和释放效率进行了全面评估,结果表明该系统在体外具有持续、可控的药物释放特性,并具有很强的药物负载能力。值得注意的是,HPC-1@DOX 表现出了 pH 值响应行为,在 pH 值为 6.8 时优先释放 DOX,这表明它能定向地向肿瘤和炎症部位释放药物,同时在较高的 pH 值下释放量最小。此外,我们还探究了它的生物学影响,证实 HPC-1@DOX 能够上调肺癌细胞中 miR-493-3p 的表达,从而抑制增殖、降低侵袭性并诱导细胞凋亡。这种多功能纳米载体系统是癌症靶向有效治疗的一大进步。
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引用次数: 0
Development of pivalic acid conjugated Nafion modified glassy carbon electrode for sensitive detection of Cu(II) by electrochemical approach 利用电化学方法开发用于灵敏检测铜(II)的特戊酸共轭 Nafion 修饰玻璃碳电极
IF 2.7 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-08-11 DOI: 10.1016/j.ica.2024.122309

In this work, pivalic acid (pivH) molecule is employed for an electrochemical sensing of copper cations in an aqueous medium. For sensitive as well as selective potential sensor application, pivH was fabricated onto a glassy carbon electrode (GCE) facilitated by adhesive conducting binder, nafion, so as make it selective and effective electrochemical probe (pivH/Nafion/GCE) towards specific heavy metal cations. This newly fabricated pivH/Nafion/GCE reveals enhance electrochemical activity toward copper ions in the presence of other interfering heavy metal cations in phosphate buffer solution (PBS) of pH=7. The calibration plot was linear (r2 = 0.9879) across broad linear dynamic range (LDR) spanning Cu2+ concentration from 0.1 nM to 0.01 M. The sensitivity and detection limit was found to be 0.0212 × 10−2 µAµM−1cm−2 and 0.014 nM, respectively. So, this newly fabricated GCE as selective electrochemical probe offers a sensitive as well as selective detection of Cu2+ cations in real environmental samples using a novel electrochemical, current–potential (I-V), approach, for the first time. Further, we explored pivalic acid for the preparation of new di-nuclear copper complex, [Cu2(piv)4(pivH)2] (where piv = pivalate; pivH=pivalic acid) and characterized by Fourier transform infrared spectroscopy (FTIR) spectroscopy, elemental analysis and single crystal X-ray diffractometry. Density functional theory (DFT) calculations were carried out to confirm the interactions and these calculations well-support to experimental data. In case of deprotonated form of pivH, Molecular Electrostatic Potential (MEP) analysis exhibits electrostatic potential equals to −148.4 kcal/mol which suggest about the strong interaction of –COOH with copper centers. Similarly, interaction energies, the quantum theory of atoms in molecules (QTAIM) study and Natural Bond Orbital (NBO) analysis also favor to experimental work. Thus, this novel study demonstrates an excellent approach for highly selective and sensitive detection of Cu2+ cations in short response time with low detection limit and good reproducibility by using I-V method based on newly designed pivH/Nafion/GCE as selective Cu2+ cationic electrochemical sensor. The experimental data was compactable with theoretical calculations.

本研究利用特戊酸(pivH)分子对水介质中的铜阳离子进行电化学检测。为了实现灵敏且有选择性的电位传感器应用,在玻璃碳电极(GCE)上用导电粘合剂 nafion 制作了 pivH,使其成为对特定重金属阳离子有选择性的有效电化学探针(pivH/Nafion/GCE)。这种新制造的 pivH/Nafion/GCE 在 pH=7 的磷酸盐缓冲溶液(PBS)中,在有其他重金属阳离子干扰的情况下,对铜离子具有更强的电化学活性。在 Cu2+ 浓度从 0.1 nM 到 0.01 M 的宽线性动态范围 (LDR) 内,校准图呈线性(r2 = 0.9879);灵敏度和检测限分别为 0.0212 × 10-2 µAµM-1cm-2 和 0.014 nM。因此,这种新制作的 GCE 作为选择性电化学探针,首次利用新型电化学电流-电位(I-V)方法灵敏且选择性地检测了真实环境样品中的 Cu2+ 阳离子。此外,我们还利用特戊酸制备了新的双核铜配合物 [Cu2(piv)4(pivH)2](其中 piv = 特戊酸;pivH = 特戊酸),并通过傅立叶变换红外光谱(FTIR)、元素分析和单晶 X 射线衍射仪对其进行了表征。为了证实这些相互作用,我们进行了密度泛函理论(DFT)计算,这些计算结果与实验数据完全吻合。在 pivH 的去质子化形式中,分子静电位(MEP)分析显示静电位等于 -148.4 kcal/mol,这表明 -COOH 与铜中心有很强的相互作用。同样,相互作用能、分子中原子量子理论(QTAIM)研究和天然键轨道(NBO)分析也与实验结果一致。因此,这项新颖的研究展示了一种极佳的方法,即利用基于新设计的 pivH/Nafion/GCE 作为选择性 Cu2+ 阳离子电化学传感器的 I-V 方法,在短响应时间内对 Cu2+ 阳离子进行高选择性、高灵敏度的检测,且检测限低、重现性好。实验数据与理论计算结果吻合。
{"title":"Development of pivalic acid conjugated Nafion modified glassy carbon electrode for sensitive detection of Cu(II) by electrochemical approach","authors":"","doi":"10.1016/j.ica.2024.122309","DOIUrl":"10.1016/j.ica.2024.122309","url":null,"abstract":"<div><p>In this work, pivalic acid (pivH) molecule is employed for an electrochemical sensing of copper cations in an aqueous medium. For sensitive as well as selective potential sensor application, pivH was fabricated onto a glassy carbon electrode (GCE) facilitated by adhesive conducting binder, nafion, so as make it selective and effective electrochemical probe (pivH/Nafion/GCE) towards specific heavy metal cations. This newly fabricated pivH/Nafion/GCE reveals enhance electrochemical activity toward copper ions in the presence of other interfering heavy metal cations in phosphate buffer solution (PBS) of pH=7. The calibration plot was linear (r<sup>2</sup> = 0.9879) across broad linear dynamic range (LDR) spanning Cu<sup>2+</sup> concentration from 0.1 nM to 0.01 M. The sensitivity and detection limit was found to be 0.0212 × 10<sup>−2</sup> µAµM<sup>−1</sup>cm<sup>−2</sup> and 0.014 nM, respectively. So, this newly fabricated GCE as selective electrochemical probe offers a sensitive as well as selective detection of Cu<sup>2+</sup> cations in real environmental samples using a novel electrochemical, current–potential (I-V), approach, for the first time. Further, we explored pivalic acid for the preparation of new di-nuclear copper complex, [Cu<sub>2</sub>(piv)<sub>4</sub>(pivH)<sub>2</sub>] (where piv = pivalate; pivH=pivalic acid) and characterized by Fourier transform infrared spectroscopy (FTIR) spectroscopy, elemental analysis and single crystal X-ray diffractometry. Density functional theory (DFT) calculations were carried out to confirm the interactions and these calculations well-support to experimental data. In case of deprotonated form of pivH, Molecular Electrostatic Potential (MEP) analysis exhibits electrostatic potential equals to −148.4 kcal/mol which suggest about the strong interaction of –COOH with copper centers. Similarly, interaction energies, the quantum theory of atoms in molecules (QTAIM) study and Natural Bond Orbital (NBO) analysis also favor to experimental work. Thus, this novel study demonstrates an excellent approach for highly selective and sensitive detection of Cu<sup>2+</sup> cations in short response time with low detection limit and good reproducibility by using I-V method based on newly designed pivH/Nafion/GCE as selective Cu<sup>2+</sup> cationic electrochemical sensor. The experimental data was compactable with theoretical calculations.</p></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-08-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142001907","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
Superiority of imidazolium over triazole moiety in bis-heteroleptic ruthenium(II) complex toward selective sensing of phosphates 双杂环钌(II)复合物中咪唑分子对磷酸盐选择性传感的优越性优于三唑分子
IF 2.7 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-08-11 DOI: 10.1016/j.ica.2024.122311

A new phosphorescent ruthenium-based receptor, designated as Ru-1, functionalized with imidazolium as an anion-binding moiety was synthesized and characterized for selective recognition and sensing of H2PO4 and HP2O73−. The binding affinity of Ru-1 towards numerous anions was assessed using UV–visible and phosphorescent spectroscopic techniques in CH3CN solvents. Notably, phosphate and pyrophosphate exhibited superior binding constants compared to other anions, with measured binding constants (Ka) of 7.95 × 104 and 4.78 × 104 M−1 respectively. Moreover, discernible blue shifts of 25 nm and 28 nm respectively, corresponding to H2PO4 and HP2O73− and significant enhancements in photoluminescence intensities by ∼5-fold and ∼4-fold, respectively were observed with H2PO4 and HP2O73−. Despite the existence of excess other anions, Ru-1 demonstrated selectivity towards these ions, facilitating sensitive detection with a limit of detection (LOD) of 0.045 µM for H2PO4 and 0.017 µM for HP2O73−. In the presence of H2PO4, the lifetime of Ru-1 was amplified noticeably from 0.2329 μs to 0.7914 μs, whereas exposure to HP2O73− resulted in an observed increase of 0.7465 μs. Furthermore, comparative photophysical studies revealed that the imidazolium moiety-based Ru-1 receptor outperformed the triazole-based Ru-2 receptor in terms of excited state lifetime, binding constant, and detection limit of the anions.

研究人员合成了一种新的磷光钌基受体(命名为 Ru-1),并对其进行了表征,该受体以咪唑为阴离子结合基团,可选择性地识别和感知 H2PO4- 和 HP2O73-。在 CH3CN 溶剂中,使用紫外可见光和磷光光谱技术评估了 Ru-1 与多种阴离子的结合亲和力。值得注意的是,与其他阴离子相比,磷酸盐和焦磷酸盐表现出更高的结合常数,测得的结合常数(Ka)分别为 7.95 × 104 和 4.78 × 104 M-1。此外,还观察到 H2PO4- 和 HP2O73- 分别产生了 25 nm 和 28 nm 的明显蓝移,光致发光强度分别提高了 5 倍和 4 倍。尽管存在过量的其他阴离子,但 Ru-1 对这些离子具有选择性,从而促进了灵敏的检测,对 H2PO4- 和 HP2O73- 的检测限(LOD)分别为 0.045 µM 和 0.017 µM。在 H2PO4- 的存在下,Ru-1 的寿命明显延长,从 0.2329 μs 延长到 0.7914 μs,而在 HP2O73- 的存在下,Ru-1 的寿命延长了 0.7465 μs。此外,光物理比较研究表明,基于咪唑分子的 Ru-1 受体在激发态寿命、结合常数和阴离子检测限方面都优于基于三唑分子的 Ru-2 受体。
{"title":"Superiority of imidazolium over triazole moiety in bis-heteroleptic ruthenium(II) complex toward selective sensing of phosphates","authors":"","doi":"10.1016/j.ica.2024.122311","DOIUrl":"10.1016/j.ica.2024.122311","url":null,"abstract":"<div><p>A new phosphorescent ruthenium-based receptor, designated as <strong>Ru-1,</strong> functionalized with imidazolium as an anion-binding moiety was synthesized and characterized for selective recognition and sensing of H<sub>2</sub>PO<sub>4</sub><sup>−</sup> and HP<sub>2</sub>O<sub>7</sub><sup>3−</sup>. The binding affinity of <strong>Ru-1</strong> towards numerous anions was assessed using UV–visible and phosphorescent spectroscopic techniques in CH<sub>3</sub>CN solvents. Notably, phosphate and pyrophosphate exhibited superior binding constants compared to other anions, with measured binding constants (K<sub>a</sub>) of 7.95 × 10<sup>4</sup> and 4.78 × 10<sup>4</sup> M<sup>−1</sup> respectively. Moreover, discernible blue shifts of 25 nm and 28 nm respectively, corresponding to H<sub>2</sub>PO<sub>4</sub><sup>−</sup> and HP<sub>2</sub>O<sub>7</sub><sup>3−</sup> and significant enhancements in photoluminescence intensities by ∼5-fold and ∼4-fold, respectively were observed with H<sub>2</sub>PO<sub>4</sub><sup>−</sup> and HP<sub>2</sub>O<sub>7</sub><sup>3−</sup>. Despite the existence of excess other anions, <strong>Ru-1</strong> demonstrated selectivity towards these ions, facilitating sensitive detection with a limit of detection (LOD) of 0.045 µM for H<sub>2</sub>PO<sub>4</sub><sup>−</sup> and 0.017 µM for HP<sub>2</sub>O<sub>7</sub><sup>3−</sup>. In the presence of H<sub>2</sub>PO<sub>4</sub><sup>−</sup>, the lifetime of <strong>Ru-1</strong> was amplified noticeably from 0.2329 μs to 0.7914 μs, whereas exposure to HP<sub>2</sub>O<sub>7</sub><sup>3−</sup> resulted in an observed increase of 0.7465 μs. Furthermore, comparative photophysical studies revealed that the imidazolium moiety-based <strong>Ru-1</strong> receptor outperformed the triazole-based <strong>Ru-2</strong> receptor in terms of excited state lifetime, binding constant, and detection limit of the anions.</p></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-08-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141990355","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
Bright yellow fluorescent carbon dots as selective nanoprobe for detection of 2-nitrophenol and 4-nitrophenol in aqueous medium 亮黄色荧光碳点作为选择性纳米探针,用于检测水介质中的 2-硝基苯酚和 4-硝基苯酚
IF 2.7 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-08-10 DOI: 10.1016/j.ica.2024.122312

Different types of phenolic pollutants pose a major risk to the environment and the health of living things. It is therefore crucial for their selective recognition especially nitrophenols. In this work, yellow fluorescent carbon dots (C-dots) were used as selective nanoprobe to efficiently detect 2-nitrophenol (2-NP) and 4-nitrophenol (4-NP). One-pot synthetic method was adopted for making C-dots from o-phenylenediamine and oleic acid mixture. The synthesized C-dots showed an excitation wavelength of 420 nm with Stokes shift of up to 135 nm. These C-dots exhibited instantaneous selective detection of 2-NP and 4-NP in aqueous solution with a detection limit of 6.4 nM and 4.8 nM respectively. Upon incubated with 2-NP and 4-NP, the C-dots’ fluorescence underwent quenching with a maximum extent of respective 80 % and 83 %. By comparing with other analogs of analyte, it was discovered that the emission intensity of the C-dots remained unchanged. Static quenching was proposed behind the changes of fluorescence after the treatment with 2-NP and 4-NP. Such type of C-dots will demonstrate the selective sensing platform in real field application.

不同类型的酚类污染物对环境和生物健康构成重大威胁。因此,对它们进行选择性识别至关重要,尤其是硝基苯酚。在这项研究中,黄色荧光碳点(C-dots)被用作选择性纳米探针,可有效检测 2-硝基苯酚(2-NP)和 4-硝基苯酚(4-NP)。该研究采用邻苯二胺和油酸混合物的单锅合成法制备 C-点。合成的 C 点的激发波长为 420 nm,斯托克斯位移高达 135 nm。这些 C 点可瞬间选择性地检测水溶液中的 2-NP 和 4-NP,检测限分别为 6.4 nM 和 4.8 nM。在与 2-NP 和 4-NP 共孵育时,C-点的荧光会发生淬灭,最大淬灭程度分别为 80% 和 83%。通过与其他分析物类似物进行比较,发现 C 点的发射强度保持不变。2-NP 和 4-NP 处理后荧光发生变化的原因是静态淬灭。这种 C 点将在实际应用中展示选择性传感平台。
{"title":"Bright yellow fluorescent carbon dots as selective nanoprobe for detection of 2-nitrophenol and 4-nitrophenol in aqueous medium","authors":"","doi":"10.1016/j.ica.2024.122312","DOIUrl":"10.1016/j.ica.2024.122312","url":null,"abstract":"<div><p>Different types of phenolic pollutants pose a major risk to the environment and the health of living things. It is therefore crucial for their selective recognition especially nitrophenols. In this work, yellow fluorescent carbon dots (C-dots) were used as selective nanoprobe to efficiently detect 2-nitrophenol (2-NP) and 4-nitrophenol (4-NP). One-pot synthetic method was adopted for making C-dots from <em>o</em>-phenylenediamine and oleic acid mixture. The synthesized C-dots showed an excitation wavelength of 420 nm with Stokes shift of up to 135 nm. These C-dots exhibited instantaneous selective detection of 2-NP and 4-NP in aqueous solution with a detection limit of 6.4 nM and 4.8 nM respectively. Upon incubated with 2-NP and 4-NP, the C-dots’ fluorescence underwent quenching with a maximum extent of respective 80 % and 83 %. By comparing with other analogs of analyte, it was discovered that the emission intensity of the C-dots remained unchanged. Static quenching was proposed behind the changes of fluorescence after the treatment with 2-NP and 4-NP. Such type of C-dots will demonstrate the selective sensing platform in real field application.</p></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-08-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142021296","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
Syntheses and antimicrobial activities of two coordination polymers assembled with AgN and AgO bonds 用 AgN 和 AgO 键组装的两种配位聚合物的合成与抗菌活性
IF 2.7 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-08-10 DOI: 10.1016/j.ica.2024.122290

Two new coordination polymers ({[Ag(p-phda)2](BF4)} n (1) and {[Ag2(1,5-nds)(DMSO)2] DMSO}n (2) (p-phda: p-phenyldiacetonitrile, 1,5-nds: 1,5-naphthalene disulfonic acid, DMSO: dimethyl sulfoxide) were synthesized and characterized by IR, EA,TG and X-ray single crystal diffraction. 1 was revealed as a 2D “fishing net” assembled by AgN bonds with BF4 as equilibrium charge. IR and PXRD analysis showed the BF4 can be irreversibly exchanged by six anions varied in atomic numbers, sizes, configurations and coordination abilities. 2 is constructed by AgO bonds where DMSO function both as guest and bridging ligand. Further diffusion of NO into the solution of 1 and 2 generated two new compounds (1′ and 2′). All four compounds showed excellent broad-spectrum antimicrobial activities against gram-negative bacteria, gram-positive bacteria and yeast. The stronger antibacterial abilities of 1 against S. aureus and P. aeruginosa than those of 2 were evidenced by the smaller minimum inhibitory concentrations of silver ions (AgMICs) and the higher silver ion release rate in aqueous solution. It was concluded that the looser packing of 1 facilitate the silver ions releasing and play a more crucial role than binding mode and ligand-exchangeability. The enhanced P. aeruginosa inhibitions of 1′ and 2′ were elementarily ascribed to NO incorporation, supporting by their increased diameter of inhibition zones and decreased AgMICs.

合成了两种新型配位聚合物({[Ag(p-phda)2](BF4)} n (1)和 {[Ag2(1,5-nds)(DMSO)2] DMSO}n (2)(p-phda:对苯二乙腈;1,5-nds:1,5-萘二磺酸;DMSO:二甲亚砜):DMSO:二甲亚砜)的合成,并通过红外、EA、TG 和 X 射线单晶衍射对其进行了表征。结果表明,1 是由 AgN 键组装而成的二维 "渔网",BF4- 为平衡电荷。红外和 PXRD 分析表明,BF4- 可被六种不同原子数、大小、构型和配位能力的阴离子不可逆地交换。2 由 AgO 键构成,其中 DMSO 既是客体配体,也是桥接配体。NO 进一步扩散到 1 和 2 的溶液中生成了两种新化合物(1′ 和 2′)。这四种化合物对革兰氏阴性菌、革兰氏阳性菌和酵母菌都具有很好的广谱抗菌活性。银离子最小抑菌浓度(AgMICs)较小,银离子在水溶液中的释放率较高,这证明 1 对金黄色葡萄球菌和绿脓杆菌的抗菌能力强于 2。结论是 1 的松散填料有利于银离子的释放,其作用比结合模式和配体交换性更为重要。1′ 和 2′ 对铜绿假单胞菌抑制作用的增强主要归因于 NO 的掺入,抑制区直径的增加和 AgMICs 的减少也证明了这一点。
{"title":"Syntheses and antimicrobial activities of two coordination polymers assembled with AgN and AgO bonds","authors":"","doi":"10.1016/j.ica.2024.122290","DOIUrl":"10.1016/j.ica.2024.122290","url":null,"abstract":"<div><p>Two new coordination polymers ({[Ag(<em>p</em>-phda)<sub>2</sub>](BF<sub>4</sub>)} <sub>n</sub> (<strong>1</strong>) and {[Ag<sub>2</sub>(1,5-nds)(DMSO)<sub>2</sub>] DMSO}<sub>n</sub> (<strong>2</strong>) (<em>p</em>-phda: <em>p</em>-phenyldiacetonitrile, 1,5-nds: 1,5-naphthalene disulfonic acid, DMSO: dimethyl sulfoxide) were synthesized and characterized by IR, EA,TG and X-ray single crystal diffraction. <strong>1</strong> was revealed as a 2D “fishing net” assembled by Ag<img>N bonds with BF<sub>4</sub><sup>−</sup> as equilibrium charge. IR and PXRD analysis showed the BF<sub>4</sub><sup>−</sup> can be irreversibly exchanged by six anions varied in atomic numbers, sizes, configurations and coordination abilities. <strong>2</strong> is constructed by Ag<img>O bonds where DMSO function both as guest and bridging ligand. Further diffusion of NO into the solution of <strong>1</strong> and <strong>2</strong> generated two new compounds (<strong>1′</strong> and <strong>2′)</strong>. All four compounds showed excellent broad-spectrum antimicrobial activities against gram-negative bacteria, gram-positive bacteria and yeast. The stronger antibacterial abilities of <strong>1</strong> against <em>S. aureus</em> and <em>P. aeruginosa</em> than those of <strong>2</strong> were evidenced by the smaller minimum inhibitory concentrations of silver ions (AgMICs) and the higher silver ion release rate in aqueous solution. It was concluded that the looser packing of <strong>1</strong> facilitate the silver ions releasing and play a more crucial role than binding mode and ligand-exchangeability. The enhanced <em>P. aeruginosa</em> inhibitions of <strong>1′</strong> and <strong>2′</strong> were elementarily ascribed to NO incorporation, supporting by their increased diameter of inhibition zones and decreased AgMICs.</p></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-08-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141985330","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 and application of a novel turn-on fluorescent probe for the determination of sulfur ions in real samples 用于测定实际样品中硫离子的新型开启式荧光探针的合成与应用
IF 2.7 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-08-10 DOI: 10.1016/j.ica.2024.122308

A novel and highly selective reactive sulfur ions (S2-) probe, 4′-(benzo[d]thiazol-2-yl)-3′-((7-nitrobenzo[c][1,2,5] oxadiazol-4-yl) oxy)-N, N-diphenyl-[1,1′-biphenyl]-4-amine (DBA), has been synthesized through covalent bonding of a 4-chloro-7-nitro-1,2,3-benzoxadiazole (NBD-Cl) unit with 4-(benzo[d]thiazol-2-yl)-4′-(diphenylamino)-3-phenylphenol (BO-OH). The structure was meticulously characterized using a combination of IR, NMR, HRMS, and LC-MS techniques. Notably, upon the addition of S2-, the fluorescence of the probe DBA solution underwent a marked enhancement, transitioning from nearly colorless to brilliant yellow-green luminescence. The Ultraviolet–visible absorption spectrum and fluorescence emission were utilized to assess the probe DBA efficacy in detecting and identifying S2-. It exhibited a substantial fluorescence amplification, enabling quantitative detection within a concentration range of 0 to 17.1 μM, and possessed a low detection limit of 66.89 nM. Moreover, this method boasts a high recovery rate, excellent accuracy, and usefulness for analysis when tracking S2- in real samples.

通过 4-(苯并[d]噻唑-2-基)-3′-((7-硝基苯并[c][1,2,5] 恶二唑-4-基)氧基)-N, N-二苯基-[1,1′-联苯]-4-胺 (DBA) 与 4-氯-7-硝基-1,2,3-苯并噁二唑 (NBD-Cl) 单元的共价键合,合成了一种新型高选择性活性硫离子 (S2-) 探针、是通过 4-氯-7-硝基-1,2,3-苯并噁二唑(NBD-Cl)单元与 4-(苯并[d]噻唑-2-基)-4′-(二苯基氨基)-3-苯基苯酚(BO-OH)的共价键合成的。利用红外光谱、核磁共振、质谱和液相色谱-质谱技术对该结构进行了细致的表征。值得注意的是,加入 S2- 后,探针 DBA 溶液的荧光明显增强,从接近无色过渡到明亮的黄绿色荧光。我们利用紫外可见吸收光谱和荧光发射来评估探针 DBA 在检测和识别 S2- 方面的功效。结果表明,探针 DBA 在 0 至 17.1 μM 的浓度范围内具有显著的荧光放大效应,可进行定量检测,检测限低至 66.89 nM。此外,该方法的回收率高、准确性好,可用于实际样品中 S2- 的跟踪分析。
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引用次数: 0
Synthesis, crystal Structure, theoretical calculation and luminescence properties of Cu(Ⅱ), Co(Ⅱ), Ni(Ⅱ) and Zn(Ⅱ) quinolinyl benzimidazole complexes with multiple coordination number induced by proton 质子诱导的多配位数 Cu(Ⅱ)、Co(Ⅱ)、Ni(Ⅱ)和 Zn(Ⅱ)喹啉基苯并咪唑配合物的合成、晶体结构、理论计算和发光特性
IF 2.7 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-08-10 DOI: 10.1016/j.ica.2024.122315

The innovative ligand H2L, featuring a benzimidazole structure substituted with 8-hydroxyquinoline and equipped with N,O donor sites, underwent successful synthesis and meticulous characterization. Notably, this ligand was exclusively synthesized through catalysis under protonated conditions, accompanied by an in-depth exploration of the catalytic mechanism. Employing single-crystal X-ray diffraction, we acquired and authenticated four distinct asymmetric double-decker sandwich mononuclear transition metal complexes: [Cu(HL)2]·2H2O, [Co(HL)2]·CH3OH, [Ni(HL)2] and [Zn(HL)2]·CH2Cl2. Among these, complex 1 revealed an intriguing five-coordinate Cu(II) center adopting a distorted square pyramidal geometry, whereas the central metal ions in complexes 24 exhibited a six-coordinate configuration, characterized by a distorted octahedral geometry. Noteworthy is the observation that the dihedral angles within the crystal structures of complexes 24 approached approximately 90° to a significant extent. To delve deeper into the electronic properties and transitions, meticulous DFT and TD-DFT calculations were performed on both the ligand H2L and complexes 14. Furthermore, a comprehensive investigation into the luminescence properties of both H2L and its complexes was conducted, revealing a pronounced luminescence quenching effect in the complexes compared to the ligand. Through thorough analysis utilizing Hirshfeld surface examination and IRI analysis, various weak intermolecular interactions within the system were elucidated.

创新配体 H2L 具有被 8-羟基喹啉取代的苯并咪唑结构,并配备有 N、O 供体位点。值得注意的是,这种配体完全是在质子化条件下通过催化合成的,同时还对催化机理进行了深入探讨。通过单晶 X 射线衍射,我们获得并鉴定了四个不同的不对称双层夹心单核过渡金属配合物:[Cu(HL)2]-2H2O、[Co(HL)2]-CH3OH、[Ni(HL)2]和[Zn(HL)2]-CH2Cl2。其中,络合物 1 揭示了一个有趣的五配位 Cu(II) 中心,其几何形状为扭曲的正方金字塔形,而络合物 2-4 中的中心金属离子则呈现出六配位构型,其特征为扭曲的八面体几何形状。值得注意的是,在复合物 2-4 的晶体结构中,二面角在很大程度上接近 90°。为了深入研究其电子特性和转变,我们对配体 H2L 和复合物 1-4 进行了细致的 DFT 和 TD-DFT 计算。此外,还对 H2L 及其配合物的发光特性进行了全面研究,发现与配体相比,配合物具有明显的发光淬灭效应。通过利用 Hirshfeld 表面检查和 IRI 分析进行深入分析,阐明了体系内各种微弱的分子间相互作用。
{"title":"Synthesis, crystal Structure, theoretical calculation and luminescence properties of Cu(Ⅱ), Co(Ⅱ), Ni(Ⅱ) and Zn(Ⅱ) quinolinyl benzimidazole complexes with multiple coordination number induced by proton","authors":"","doi":"10.1016/j.ica.2024.122315","DOIUrl":"10.1016/j.ica.2024.122315","url":null,"abstract":"<div><p>The innovative ligand H<sub>2</sub>L, featuring a benzimidazole structure substituted with 8-hydroxyquinoline and equipped with N,O donor sites, underwent successful synthesis and meticulous characterization. Notably, this ligand was exclusively synthesized through catalysis under protonated conditions, accompanied by an in-depth exploration of the catalytic mechanism. Employing single-crystal X-ray diffraction, we acquired and authenticated four distinct asymmetric double-decker sandwich mononuclear transition metal complexes: [Cu(HL)<sub>2</sub>]·2H<sub>2</sub>O, [Co(HL)<sub>2</sub>]·CH<sub>3</sub>OH, [Ni(HL)<sub>2</sub>] and [Zn(HL)<sub>2</sub>]·CH<sub>2</sub>Cl<sub>2</sub>. Among these, complex <strong>1</strong> revealed an intriguing five-coordinate Cu(II) center adopting a distorted square pyramidal geometry, whereas the central metal ions in complexes <strong>2</strong>–<strong>4</strong> exhibited a six-coordinate configuration, characterized by a distorted octahedral geometry. Noteworthy is the observation that the dihedral angles within the crystal structures of complexes <strong>2</strong>–<strong>4</strong> approached approximately 90° to a significant extent. To delve deeper into the electronic properties and transitions, meticulous DFT and TD-DFT calculations were performed on both the ligand H<sub>2</sub>L and complexes <strong>1</strong>–<strong>4</strong>. Furthermore, a comprehensive investigation into the luminescence properties of both H<sub>2</sub>L and its complexes was conducted, revealing a pronounced luminescence quenching effect in the complexes compared to the ligand. Through thorough analysis utilizing Hirshfeld surface examination and IRI analysis, various weak intermolecular interactions within the system were elucidated.</p></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-08-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141990357","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
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Inorganica Chimica Acta
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