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Exploring Schiff bases derived from 4-(diethylamino)salicylaldehyde and their copper(II) complexes as antidiabetes and antioxidant agents: Structural elucidation, DFT computational and in vitro studies 探索源自 4-(二乙氨基)水杨醛的希夫碱及其铜(II)配合物作为抗糖尿病和抗氧化剂:结构阐释、DFT 计算和体外研究
IF 2.7 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-11-13 DOI: 10.1016/j.ica.2024.122447
Segun D. Oladipo , Robert C. Luckay , Kolawole A. Olofinsan , Abosede A. Badeji , Sithabile Mokoena
A series of three Schiff base ligands and their metal complexes with copper(II) have been prepared. The ligands are (E)-5-(diethylamino)-2-(((2,6-dimethylphenyl)imino)methyl)phenol (C1), (E)-5-(diethylamino)-2-(((2,6-diisopropylphenyl)imino)methyl)phenol (C2) and (E)-5-(diethylamino)-2-((mesitylimino)methyl)phenol (C3). They were reacted with copper(II) nitrate trihydrate (Cu(NO3)2·3H2O) to give [Cu(C1)2] (1), [Cu(C2)2] (2), and [Cu(C3)2] (3). All the synthesized compounds were elucidated by exploring mass, FT-IR, UV–Vis, and NMR (1H &13C) spectroscopic techniques while elemental analysis was carried out to affirm their purity. The paramagnetic nature of 1, 2 and 3 was established using EPR spectra. The molecular structure of C1 and C2 were further confirmed using single crystal X-ray crystallography. The bond lengths of C7N1, C7C8 and C8C9 obtained from structural analysis for C1 and C2 depicted their enol-tautomeric characteristic form. Quantum chemical calculations revealed that all the compounds have small energy band gaps (ΔE) with complex 2 having the lowest ΔE of 0.21 eV. The antidiabetes potential of the compounds were evaluated using α-amylase and α-glucosidase assays. Compound C1 with an IC50 value of 0.11 mM, displayed almost equal α-amylase inhibition capacity as the one for acarbose (reference drug) with IC50 value of 0.07 mM. Compounds C3 and 2 displayed good α-glucosidase inhibition activities with IC50 value of 0.05 mM and 0.19 mM respectively. The synthesized compounds displayed moderate to excellent antioxidant potential. Complex 1 and the ligands (C1C3) have lower IC50 value than quercetin (reference drug) for nitric oxide assay. Estimated physicochemical parameters revealed that C1 and C3 fell within the threshold of Lipinski’s rule of five (Ro5) while C2 as well as complex 13 deviates minimally.
我们制备了一系列三种希夫碱配体及其与铜(II)的金属配合物。这些配体分别是(E)-5-(二乙基氨基)-2-(((2,6-二甲基苯基)亚氨基)甲基)苯酚(C1)、(E)-5-(二乙基氨基)-2-(((2,6-二异丙基苯基)亚氨基)甲基)苯酚(C2)和(E)-5-(二乙基氨基)-2-((甲磺酰亚胺)甲基)苯酚(C3)。它们与三水硝酸铜(Cu(NO3)2-3H2O)反应生成[Cu(C1)2](1)、[Cu(C2)2](2)和[Cu(C3)2](3)。所有合成化合物都通过质量、傅立叶变换红外光谱、紫外可见光谱和核磁共振(1H &13C )光谱技术进行了阐释,同时还进行了元素分析以确定其纯度。利用 EPR 光谱确定了 1、2 和 3 的顺磁性。利用单晶 X 射线晶体学进一步确认了 C1 和 C2 的分子结构。从 C1 和 C2 的结构分析中得到的 C7N1、C7C8 和 C8C9 的键长描述了它们的烯醇-同分异构体特征形式。量子化学计算显示,所有化合物的能带隙(ΔE)都很小,其中复合物 2 的ΔE 最低,为 0.21 eV。利用α-淀粉酶和α-葡萄糖苷酶测定法评估了化合物的抗糖尿病潜力。化合物 C1 的 IC50 值为 0.11 mM,与 IC50 值为 0.07 mM 的阿卡波糖(参考药物)的α-淀粉酶抑制能力几乎相同。化合物 C3 和 2 显示出良好的 α-葡萄糖苷酶抑制活性,IC50 值分别为 0.05 mM 和 0.19 mM。合成的化合物显示出中等到卓越的抗氧化潜力。复合物 1 和配体(C1-C3)在一氧化氮检测中的 IC50 值低于槲皮素(参考药物)。估算的理化参数显示,C1 和 C3 在利宾斯基 5 规则(Ro5)的阈值范围内,而 C2 以及复合物 1-3 的偏差很小。
{"title":"Exploring Schiff bases derived from 4-(diethylamino)salicylaldehyde and their copper(II) complexes as antidiabetes and antioxidant agents: Structural elucidation, DFT computational and in vitro studies","authors":"Segun D. Oladipo ,&nbsp;Robert C. Luckay ,&nbsp;Kolawole A. Olofinsan ,&nbsp;Abosede A. Badeji ,&nbsp;Sithabile Mokoena","doi":"10.1016/j.ica.2024.122447","DOIUrl":"10.1016/j.ica.2024.122447","url":null,"abstract":"<div><div>A series of three Schiff base ligands and their metal complexes with copper(II) have been prepared. The ligands are (E)-5-(diethylamino)-2-(((2,6-dimethylphenyl)imino)methyl)phenol (<strong>C1</strong>), (E)-5-(diethylamino)-2-(((2,6-diisopropylphenyl)imino)methyl)phenol (<strong>C2</strong>) and (E)-5-(diethylamino)-2-((mesitylimino)methyl)phenol (<strong>C3</strong>). They were reacted with copper(II) nitrate trihydrate (Cu(NO<sub>3</sub>)<sub>2</sub>·3H<sub>2</sub>O) to give [Cu(<strong>C1</strong>)<sub>2</sub>] (<strong>1</strong>), [Cu(<strong>C2</strong>)<sub>2</sub>] (<strong>2</strong>), and [Cu(<strong>C3</strong>)<sub>2</sub>] (<strong>3</strong>). All the synthesized compounds were elucidated by exploring mass, FT-IR, UV–Vis, and NMR (<sup>1</sup>H &amp;<sup>13</sup>C) spectroscopic techniques while elemental analysis was carried out to affirm their purity. The paramagnetic nature of <strong>1</strong>, <strong>2</strong> and <strong>3</strong> was established using EPR spectra. The molecular structure of <strong>C1</strong> and <strong>C2</strong> were further confirmed using single crystal X-ray crystallography. The bond lengths of C7<img>N1, C7<img>C8 and C8<img>C9 obtained from structural analysis for <strong>C1</strong> and <strong>C2</strong> depicted their enol-tautomeric characteristic form. Quantum chemical calculations revealed that all the compounds have small energy band gaps (ΔE) with complex <strong>2</strong> having the lowest ΔE of 0.21 eV. The antidiabetes potential of the compounds were evaluated using α-amylase and α-glucosidase assays. Compound <strong>C1</strong> with an IC<sub>50</sub> value of 0.11 mM, displayed almost equal α-amylase inhibition capacity as the one for acarbose (reference drug) with IC<sub>50</sub> value of 0.07 mM. Compounds <strong>C3 a</strong>nd <strong>2</strong> displayed good α-glucosidase inhibition activities with IC<sub>50</sub> value of 0.05 mM and 0.19 mM respectively. The synthesized compounds displayed moderate to excellent antioxidant potential. Complex <strong>1</strong> and the ligands (<strong>C1</strong>–<strong>C3</strong>) have lower IC<sub>50</sub> value than quercetin (reference drug) for nitric oxide assay. Estimated physicochemical parameters revealed that <strong>C1</strong> and <strong>C3</strong> fell within the threshold of Lipinski’s rule of five (Ro5) while <strong>C2</strong> as well as complex <strong>1</strong>–<strong>3</strong> deviates minimally.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"575 ","pages":"Article 122447"},"PeriodicalIF":2.7,"publicationDate":"2024-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142652516","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Functionalized metal–organic precursors derived CeO2 for catalytic synthesis of dimethyl carbonate from CO2 and methanol 源自 CeO2 的功能化金属有机前体用于催化合成二氧化碳和甲醇制碳酸二甲酯
IF 2.7 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-11-10 DOI: 10.1016/j.ica.2024.122435
Dongdu Zhang , Lejing Shen , Wei Mao , Daoyun Zhu , Qiaoyu Zhang , Qing Zu , Ling Tan , Libin Liu , Xiayi Hu , Yangqiang Huang , Hao Chen , Xiao Luo
Dimethyl carbonate (DMC) was synthesized using CO2 and methanol by different CeO2 catalysts obtained from functionalized metal–organic precursors. CeO2 produced from 1,2,4-benzenetricarboxylic acid (BTC) exhibits the greatest catalytic activity. The results of catalyst characterization manifested that the content of oxygen vacancy and Ce3+ on the surface of the CeO2 catalysts is affected by different organic ligand. At the same time, the content of Ce3+ is positively correlated with Hammett’s values. The high catalytic activity of CeO2-BTC is due to the highest oxygen vacancy and Ce3+ content. The solvothermal time and calcination temperature had great influence on the catalytic properties of the CeO2 catalysts.
利用功能化金属有机前体获得的不同 CeO2 催化剂,使用二氧化碳和甲醇合成了碳酸二甲酯(DMC)。由 1,2,4-苯三羧酸(BTC)制备的 CeO2 表现出最大的催化活性。催化剂表征结果表明,CeO2 催化剂表面氧空位和 Ce3+ 的含量受不同有机配体的影响。同时,Ce3+ 的含量与 Hammett 值呈正相关。CeO2-BTC 的催化活性高是因为其氧空位和 Ce3+ 含量最高。溶热时间和煅烧温度对 CeO2 催化剂的催化性能有很大影响。
{"title":"Functionalized metal–organic precursors derived CeO2 for catalytic synthesis of dimethyl carbonate from CO2 and methanol","authors":"Dongdu Zhang ,&nbsp;Lejing Shen ,&nbsp;Wei Mao ,&nbsp;Daoyun Zhu ,&nbsp;Qiaoyu Zhang ,&nbsp;Qing Zu ,&nbsp;Ling Tan ,&nbsp;Libin Liu ,&nbsp;Xiayi Hu ,&nbsp;Yangqiang Huang ,&nbsp;Hao Chen ,&nbsp;Xiao Luo","doi":"10.1016/j.ica.2024.122435","DOIUrl":"10.1016/j.ica.2024.122435","url":null,"abstract":"<div><div>Dimethyl carbonate (DMC) was synthesized using CO<sub>2</sub> and methanol by different CeO<sub>2</sub> catalysts obtained from functionalized metal–organic precursors. CeO<sub>2</sub> produced from 1,2,4-benzenetricarboxylic acid (BTC) exhibits the greatest catalytic activity. The results of catalyst characterization manifested that the content of oxygen vacancy and Ce<sup>3+</sup> on the surface of the CeO<sub>2</sub> catalysts is affected by different organic ligand. At the same time, the content of Ce<sup>3+</sup> is positively correlated with Hammett’s values. The high catalytic activity of CeO<sub>2</sub>-BTC is due to the highest oxygen vacancy and Ce<sup>3+</sup> content. The solvothermal time and calcination temperature had great influence on the catalytic properties of the CeO<sub>2</sub> catalysts.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"575 ","pages":"Article 122435"},"PeriodicalIF":2.7,"publicationDate":"2024-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142652509","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
Characterization (XRD/TGA-DSC) and assessment of calf thymus DNA interaction with single-crystalline novel complexes from Schiff base ligands 小牛胸腺 DNA 与希夫碱配体单晶新型复合物相互作用的表征(XRD/TGA-DSC)和评估
IF 2.7 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-11-09 DOI: 10.1016/j.ica.2024.122443
Jeniffer Meyer Moreira , Raphael Rodrigues , Magno Aparecido Gonçalves Trindade , Karine Cáceres dos Santos , Monize Martins da Silva , Bárbara Tirloni , Cândida Alíssia Brandl , Guilherme Caneppele Paveglio , Daiane Roman , Cláudio Teodoro de Carvalho
The Schiff base complexes [Zn(H2L)2Cl2] 2/3(CH3OH) 2/3(H2O) (1) and [Cd(H2L)2(NO3)2(CH3OH)2] (2), where H2L is an N-Acylhydrazone ligand, have been investigated mainly using a combinatory approach of single-crystal X-ray diffractometry (XRD), thermogravimetric and differential thermal analysis (TGA-DSC). XRD analysis revealed that both complexes coordinate through the nitrogen atom of the ligand’s pyridine ring. In complex (1), the zinc(II) ion coordinates with two ligands and two chloride ions, forming a distorted tetrahedral geometry. In complex (2), the cadmium(II) ion coordinates with two ligands, two nitrate ions, and two methanol molecules, resulting in an octahedral geometry. The crystalline material’s high purity and precise stoichiometry were crucial for accurate thermoanalytical analysis. Additionally, characterizations were performed using infrared (IR), ultraviolet–visible (UV–vis), molar conductivity, elemental analysis (EA) and nuclear magnetic resonance (NMR) spectroscopy. Biological studies with calf thymus DNA (CT-DNA), using UV–vis spectroscopy, viscosity measurements and ethidium bromide displacement assays indicated intercalative binding of the complexes with DNA. The binding (Kb) and quenching (Ksv) constants (104 L/mol) suggest moderate interaction with CT-DNA. The positive partition coefficients (log P) values in water and 1-octanol suggest a significant preference for the lipid-like organic phase, implying that these complexes can efficiently penetrate biological membranes.
主要采用单晶 X 射线衍射仪 (XRD)、热重分析和差热分析 (TGA-DSC) 等综合方法研究了希夫碱配合物 [Zn(H2L)2Cl2] 2/3(CH3OH) 2/3(H2O) (1) 和 [Cd(H2L)2(NO3)2(CH3OH)2](2)(其中 H2L 为 N-Acylhydrazone 配体)。X 射线衍射分析表明,这两种络合物都通过配体吡啶环的氮原子配位。在络合物(1)中,锌(II)离子与两个配体和两个氯离子配位,形成一个扭曲的四面体几何结构。在络合物(2)中,镉(II)离子与两个配体、两个硝酸根离子和两个甲醇分子配位,形成八面体几何结构。晶体材料的高纯度和精确的化学计量对于准确的热分析至关重要。此外,还利用红外线(IR)、紫外可见光(UV-vis)、摩尔电导率、元素分析(EA)和核磁共振(NMR)光谱进行了表征。利用紫外可见光谱、粘度测量和溴化乙锭位移测定法对小牛胸腺 DNA(CT-DNA)进行的生物研究表明,复合物与 DNA 之间存在插层结合。结合常数(Kb)和淬灭常数(Ksv)(104 L/mol)表明,复合物与 CT-DNA 之间存在中等程度的相互作用。水和 1-辛醇中的分配系数值(log P)为正值,表明这些复合物明显偏爱类脂有机相,这意味着它们可以有效地穿透生物膜。
{"title":"Characterization (XRD/TGA-DSC) and assessment of calf thymus DNA interaction with single-crystalline novel complexes from Schiff base ligands","authors":"Jeniffer Meyer Moreira ,&nbsp;Raphael Rodrigues ,&nbsp;Magno Aparecido Gonçalves Trindade ,&nbsp;Karine Cáceres dos Santos ,&nbsp;Monize Martins da Silva ,&nbsp;Bárbara Tirloni ,&nbsp;Cândida Alíssia Brandl ,&nbsp;Guilherme Caneppele Paveglio ,&nbsp;Daiane Roman ,&nbsp;Cláudio Teodoro de Carvalho","doi":"10.1016/j.ica.2024.122443","DOIUrl":"10.1016/j.ica.2024.122443","url":null,"abstract":"<div><div>The Schiff base complexes [Zn(H<sub>2</sub>L)<sub>2</sub>Cl<sub>2</sub>] <sup>2</sup>/<sub>3</sub>(CH<sub>3</sub>OH) <sup>2</sup>/<sub>3</sub>(H<sub>2</sub>O) (<strong>1</strong>) and [Cd(H<sub>2</sub>L)<sub>2</sub>(NO<sub>3</sub>)<sub>2</sub>(CH<sub>3</sub>OH)<sub>2</sub>] (<strong>2</strong>), where H<sub>2</sub>L is an <em>N</em>-Acylhydrazone ligand, have been investigated mainly using a combinatory approach of single-crystal X-ray diffractometry (XRD), thermogravimetric and differential thermal analysis (TGA-DSC). XRD analysis revealed that both complexes coordinate through the nitrogen atom of the ligand’s pyridine ring. In complex (<strong>1</strong>), the zinc(II) ion coordinates with two ligands and two chloride ions, forming a distorted tetrahedral geometry. In complex (<strong>2</strong>), the cadmium(II) ion coordinates with two ligands, two nitrate ions, and two methanol molecules, resulting in an octahedral geometry. The crystalline material’s high purity and precise stoichiometry were crucial for accurate thermoanalytical analysis. Additionally, characterizations were performed using infrared (IR), ultraviolet–visible (UV–vis), molar conductivity, elemental analysis (EA) and nuclear magnetic resonance (NMR) spectroscopy. Biological studies with calf thymus DNA (CT-DNA), using UV–vis spectroscopy, viscosity measurements and ethidium bromide displacement assays indicated intercalative binding of the complexes with DNA. The binding (K<sub>b</sub>) and quenching (K<sub>sv</sub>) constants (10<sup>4</sup> L/mol) suggest moderate interaction with CT-DNA. The positive partition coefficients (log P) values in water and 1-octanol suggest a significant preference for the lipid-like organic phase, implying that these complexes can efficiently penetrate biological membranes.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"575 ","pages":"Article 122443"},"PeriodicalIF":2.7,"publicationDate":"2024-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142652512","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
Elaboration of a new 4-(4-nitrophenyl)piperazin-1-ium tetrakis(thiocyanato)-cobalt hydrate: Crystal structure, optical properties, quantum computational investigation, electrical and biological study 一种新的 4-(4-硝基苯基)哌嗪-1-鎓四(硫氰酸根)钴水合物的制备:晶体结构、光学特性、量子计算研究、电学和生物学研究
IF 2.7 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-11-07 DOI: 10.1016/j.ica.2024.122438
Khaoula Abidi , Atazaz Ahsin , Jawher Makhlouf , Youness El Bakri , Hatem A. Abuelizz , Rashad Al-Salahi , Arto Valkonen , Wajda Smirani Sta
The preparation, spectroscopic, biological, and electrical characterization, in addition to the X-ray crystal structure investigation of a novel three-dimensional compound (C10H14N3O2)2 [Co(NCS)4].H2O ((NPP)2[Co(NCS)4].H2O) is reported. The synthesized compound crystallizes in the Pna21 space group. The structure comprises layers of cobalt (II) bridged by terminally bound thiocyanate-N ligand achieving distorted MN4 tetrahedron surroundings around the metal center. The vibrational modes of the functional groups were investigated using FT-IR measurements. Hirshfeld surface (HS) analysis and electronic structures calculations reveal the excellent reactivity and intermolecular interactions in stabilizing complex. The change transfer and NLO parameters were also computed using the DFT method. The study of the optical behavior reveals a high optical property. Explorations of impedance spectroscopy on (NPP)2[Co(NCS)4].H2O reveals fascinating electrical behavior which reveals that the Co complex component can be used as an electronic chip under certain conditions. The thermal analysis was used to confirm the crystal’s thermal stability. The compound’s antimicrobial activity suggested that the Cobalt complex acts as an inhibitor Agent against different types of bacteria.
报告了一种新型三维化合物 (C10H14N3O2)2 [Co(NCS)4].H2O ((NPP)2[Co(NCS)4].H2O)的制备、光谱、生物和电学表征以及 X 射线晶体结构研究。合成的化合物在 Pna21 空间群中结晶。其结构包括由硫氰酸盐-N 配体桥接的钴 (II) 层,在金属中心周围形成扭曲的 MN4 四面体。我们利用傅立叶变换红外光谱测量法研究了官能团的振动模式。Hirshfeld 表面(HS)分析和电子结构计算揭示了稳定复合物的出色反应性和分子间相互作用。此外,还使用 DFT 方法计算了变化传递和 NLO 参数。对光学行为的研究表明,该复合物具有很高的光学特性。对 (NPP)2[Co(NCS)4].H2O进行的阻抗光谱研究发现了其迷人的电学行为,这表明在特定条件下,Co 复合物成分可用作电子芯片。热分析证实了晶体的热稳定性。该化合物的抗菌活性表明,钴复合物对不同类型的细菌具有抑制作用。
{"title":"Elaboration of a new 4-(4-nitrophenyl)piperazin-1-ium tetrakis(thiocyanato)-cobalt hydrate: Crystal structure, optical properties, quantum computational investigation, electrical and biological study","authors":"Khaoula Abidi ,&nbsp;Atazaz Ahsin ,&nbsp;Jawher Makhlouf ,&nbsp;Youness El Bakri ,&nbsp;Hatem A. Abuelizz ,&nbsp;Rashad Al-Salahi ,&nbsp;Arto Valkonen ,&nbsp;Wajda Smirani Sta","doi":"10.1016/j.ica.2024.122438","DOIUrl":"10.1016/j.ica.2024.122438","url":null,"abstract":"<div><div>The preparation, spectroscopic, biological, and electrical characterization, in addition to the X-ray crystal structure investigation of a novel three-dimensional compound (C<sub>10</sub>H<sub>14</sub>N<sub>3</sub>O<sub>2</sub>)<sub>2</sub> [Co(NCS)<sub>4</sub>].H<sub>2</sub>O ((NPP)<sub>2</sub>[Co(NCS)<sub>4</sub>].H<sub>2</sub>O) is reported. The synthesized compound crystallizes in the Pna2<sub>1</sub> space group. The structure comprises layers of cobalt (II) bridged by terminally bound thiocyanate-N ligand achieving distorted MN4 tetrahedron surroundings around the metal center. The vibrational modes of the functional groups were investigated using FT-IR measurements. Hirshfeld surface (HS) analysis and electronic structures calculations reveal the excellent reactivity and intermolecular interactions in stabilizing complex. The change transfer and NLO parameters were also computed using the DFT method. The study of the optical behavior reveals a high optical property. Explorations of impedance spectroscopy on (NPP)<sub>2</sub>[Co(NCS)<sub>4</sub>].H<sub>2</sub>O reveals fascinating electrical behavior which reveals that the Co complex component can be used as an electronic chip under certain conditions. The thermal analysis was used to confirm the crystal’s thermal stability. The compound’s antimicrobial activity suggested that the Cobalt complex acts as an inhibitor Agent against different types of bacteria.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"575 ","pages":"Article 122438"},"PeriodicalIF":2.7,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142652505","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
Selective diesterase-like activity of bioinspired FeIIINiII and FeIIIZnII complexes and their 3-aminopropyl silica composites: A homo- and heterogeneous catalytic study 生物启发的 FeIIINiII 和 FeIIIZnII 复合物及其 3-aminopropyl 硅复合材料的选择性类似二酯酶的活性:同质和异质催化研究
IF 2.7 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-11-07 DOI: 10.1016/j.ica.2024.122439
Clovis Piovezan , Jaqueline M.R. Silva , Daniele C. Durigon , Maiara I.N. dos Santos , Eduardo E. Castellano , Adailton J. Bortoluzzi , Ademir Neves , Fernando R. Xavier , Rosely A. Peralta
In this study, the preparation and characterization of two new mixed-valence heterodinuclear complexes [FeIIINiII(BPPAMFF)(μ-OAc)2(H2O)]ClO4 (1) and [FeIIIZnII(BPPAMFF)(μ-OAc)2(H2O)]ClO4 (2) with the bioinspired ligand 2-[(N-benzyl-N-2-pyridylmethylamine)]-4-methyl-6-[N-(2-pyridylmethyl)aminomethyl)])-4-methyl-6-formylphenol (H2BPPAMFF) are reported. These compounds were immobilized in 3-aminopropyl silica (APS) to afford composites APS-1 and APS-2 successfully. The aldehyde-containing ligand provided a reactive functional group, which could serve as a cross-linking group to bind the complexes to the directly amino-modified SiO2 surface. The complexes’ chemical integrity on the APS inorganic platform were probed by spectroscopical techniques, such as FTIR, UV–Vis and EPR. Potentiometric and spectrophotometric titrations allowed the chemical species present in solution to be rationalized, and identified which of them were potentially active in the hydrolytic cleavage of phosphodiester 2,4-BDNPP. Kinetic studies showed that FeIIINiII species (1 and APS-1) presented higher catalytic efficiency (E = kcat/KM) than FeIIIZnII species (2 and APS-2). Catalytic mechanisms were proposed based on a series of kinetic experiments, in which all the catalysts tested behaved as selective phosphodiesterases. In addition, it was also demonstrated that the hydrolase activity of the immobilized catalytic centers, APS-1 and APS-2, was better than the homogeneous processes, where second coordination sphere effects may be involved in directing and stabilizing the transition state.
在这项研究中、制备和表征了两种新的混价异核配合物[FeIIINiII(BPPAMFF)(μ-OAc)2(H2O)]ClO4 (1)和[FeIIIZnII(BPPAMFF)(μ- OAc)2(H2O)]ClO4 (2)。OAc)2(H2O)]ClO4(2)的生物启发配体 2-[(N-苄基-N-2-吡啶基甲基胺)]-4-甲基-6-[N-(2-吡啶基甲基)氨基甲基)])-4-甲基-6-甲酰基苯酚(H2BPPAMFF)。将这些化合物固定在 3-氨基丙基二氧化硅(APS)中,成功地得到了 APS-1 和 APS-2 复合物。含醛配体提供了一个活性官能团,可作为交联基团将复合物结合到直接氨基修饰的二氧化硅表面。傅立叶变换红外光谱、紫外可见光光谱和电子发射光谱等光谱技术对 APS 无机平台上的配合物的化学完整性进行了探测。电位滴定法和分光光度滴定法使溶液中存在的化学物质更加合理,并确定了其中哪些化学物质在磷酸二酯 2,4-BDNPP 的水解裂解过程中具有潜在活性。动力学研究表明,FeIIINiII 物种(1 和 APS-1)比 FeIIIZnII 物种(2 和 APS-2)具有更高的催化效率(E = kcat/KM)。根据一系列动力学实验提出了催化机制,在这些实验中,所有测试的催化剂都表现为选择性磷酸二酯酶。此外,实验还证明固定化催化中心 APS-1 和 APS-2 的水解酶活性优于均相过程,其中第二配位球效应可能参与了过渡态的引导和稳定。
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引用次数: 0
Phosphatase-like activity of a newly synthesized and structurally characterized Zn(II) complex [ZnII2(L)(NCS)2] [LH2 = a Schiff base] in water and DMSO-water solvent systems 一种新合成并具有结构特征的 Zn(II) 复合物 [ZnII2(L)(NCS)2] [LH2 = 席夫碱] 在水和二甲基亚砜-水溶剂体系中的类似磷酸酶的活性
IF 2.7 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-11-07 DOI: 10.1016/j.ica.2024.122436
Indrani Ray Chowdhury , Saikat Samanta , Sakshi , Angshuman Roy Choudhury , Rajarshi Ghosh
Synthesis and single crystal X-ray diffraction characterization of a Zn(II) compound [Zn2(L)(NCS)2] (1) [H2L = 6,6′-((propane-1,3-diylbis(azaneylylidene))bis(methaneyl-ylidene))bis(2-methoxyphenol)] has been reported. The two Zn(II) centres in 1 separately have distorted square pyramidal and distorted trigonal bipyramidal geometries. On employing 1 with the model substrate disodium salt of 4-nitrophenylphosphate (4-NPP), the title compound is found to show phosphatase-like activity in water and 95% (v/v) DMSO-water solvent systems. The reactions were monitored spectrophotometrically. Increase in absorption intensity separately at 405 nm (water) and 419 nm (DMSO-water) indicates the catalytic dissociation of NPP to 4-nitrophenol. Kinetic measurements revealed the Kcat (s−1) as 4.92 × 10−2 and 10.69 × 10−2, respectively in water and 95% (v/v) DMSO-water system. The proposed reaction mechanism of the phosphatase-like reaction was supported by Density Functional Theory (DFT) calculations. The reaction-intermediate of the catalytic reaction was trapped by High Resolution Mass Spectrometry (HRMS).
据报道,一种 Zn(II) 化合物 [Zn2(L)(NCS)2] (1) [H2L = 6,6′-((propane-1,3-diylbis(azaneylylidene))bis(methaneyl-ylidene))bis(2-methoxyphenol)] 的合成和单晶 X 射线衍射表征已经完成。1 中的两个 Zn(II) 中心分别具有畸变正方金字塔和畸变三叉双金字塔几何结构。将 1 与模型底物 4-硝基苯磷酸(4-NPP)二钠盐一起使用时,发现标题化合物在水和 95% (v/v) DMSO-水溶剂体系中显示出类似磷酸酶的活性。反应采用分光光度法进行监测。在 405 nm(水)和 419 nm(二甲基亚砜-水)波长处的吸收强度分别增加,表明催化 NPP 分解为 4-硝基苯酚。动力学测量显示,在水和 95% (v/v) 二甲基亚砜-水体系中的 Kcat (s-1) 分别为 4.92 × 10-2 和 10.69 × 10-2。密度泛函理论(DFT)计算支持了所提出的类似磷酸酶的反应机理。高分辨质谱法(HRMS)捕获了催化反应的反应中间体。
{"title":"Phosphatase-like activity of a newly synthesized and structurally characterized Zn(II) complex [ZnII2(L)(NCS)2] [LH2 = a Schiff base] in water and DMSO-water solvent systems","authors":"Indrani Ray Chowdhury ,&nbsp;Saikat Samanta ,&nbsp;Sakshi ,&nbsp;Angshuman Roy Choudhury ,&nbsp;Rajarshi Ghosh","doi":"10.1016/j.ica.2024.122436","DOIUrl":"10.1016/j.ica.2024.122436","url":null,"abstract":"<div><div>Synthesis and single crystal X-ray diffraction characterization of a Zn(II) compound [Zn<sub>2</sub>(L)(NCS)<sub>2</sub>] (<strong>1</strong>) [H<sub>2</sub>L = 6,6′-((propane-1,3-diylbis(azaneylylidene))bis(methaneyl-ylidene))bis(2-methoxyphenol)] has been reported. The two Zn(II) centres in <strong>1</strong> separately have distorted square pyramidal and distorted trigonal bipyramidal geometries. On employing <strong>1</strong> with the model substrate disodium salt of 4-nitrophenylphosphate (4-NPP), the title compound is found to show phosphatase-like activity in water and 95% (v/v) DMSO-water solvent systems. The reactions were monitored spectrophotometrically. Increase in absorption intensity separately at 405 nm (water) and 419 nm (DMSO-water) indicates the catalytic dissociation of NPP to 4-nitrophenol. Kinetic measurements revealed the K<sub>cat</sub> (s<sup>−1</sup>) as 4.92 × 10<sup>−2</sup> and 10.69 × 10<sup>−2</sup>, respectively in water and 95% (v/v) DMSO-water system. The proposed reaction mechanism of the phosphatase-like reaction was supported by Density Functional Theory (DFT) calculations. The reaction-intermediate of the catalytic reaction was trapped by High Resolution Mass Spectrometry (HRMS).</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"575 ","pages":"Article 122436"},"PeriodicalIF":2.7,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142652508","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
Characterization of molecular oxygen binding to [CoII(1,4,8,11-tetraazacyclotetradecane)] in aqueous solutions 分子氧与水溶液中[CoII(1,4,8,11-四氮杂环十四烷)]的结合特征
IF 2.7 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-11-07 DOI: 10.1016/j.ica.2024.122437
Lu Quan Hau, Laouénan André, L’Her Maurice
1, 4, 8,11-tetraazacyclotetradecane (cyclam), a cyclic tetramine, binds various metal cations among which Co2+ is of a particular importance as its complex can bind molecular oxygen and help separate it from nitrogen of air. The stability constants of the O2 complexes have been the subject of many works but, due to kinetic complications, none of these studies yielded satisfactory results. In the present work spectrophotometry has been used to investigate the acid-base properties of the various species as well as the kinetic and thermodynamic aspects of their formation. For kinetic reasons the superoxo complex is formed primarily which then evolves to the µ-peroxo derivative, the most stable species. This study reveals why the many previous experiments conducted to measure the stability constants of the oxygen complexes have failed.
1,4,8,11-四氮杂环十四烷(cyclam)是一种环状四胺,可与多种金属阳离子结合,其中 Co2+ 尤为重要,因为其络合物可与分子氧结合,并有助于将分子氧从空气中的氮气中分离出来。关于 O2 复合物的稳定性常数已经有很多研究,但由于动力学上的复杂性,这些研究都没有取得令人满意的结果。在本研究中,我们使用分光光度法来研究各种物质的酸碱特性以及它们形成的动力学和热力学方面。由于动力学原因,形成的主要是超氧复合物,然后演变为 µ-peroxo 衍生物,这是最稳定的物种。这项研究揭示了以往许多测量氧络合物稳定性常数的实验失败的原因。
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引用次数: 0
Novel quinoline-based chemosensor as specific fluorescence sensing of copper ions in cancer cells and for organelle-specific imaging application 基于喹啉的新型化学传感器,可对癌细胞中的铜离子进行特异性荧光传感,并可用于细胞器特异性成像应用
IF 2.7 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-11-06 DOI: 10.1016/j.ica.2024.122440
Seniappan Kaleeswaran , D.S. Prabakaran , Madhappan Santhamoorthy , S. Ansar , Mohammad Abul Farah , Ramar Rajamanikandan , Kailasam Saravana Mani
This work reports a simple synthesis of a quinoline-based organic molecule, (E)-N′-((6-methoxy-2-oxo-1,2-dihydroquinolin-3-yl)methylene) picolinohydrazide (PHMQ), and its ability to distinguish Cu2+ ion. Through the use of spectroscopic and photometric titration techniques, PHMQ’s selectivity toward various cations and anions was examined. In just two minutes, PHMQ showed fast detection of Cu2+ ions, and clear spectral fluctuations proposed persistent PHMQ-Cu2+ complex formation. The calculated emission quenching constant (1.46 × 105 L/mol) and binding constant (1.25 × 104 L/mol) values suggested that strong emission quenching occurs between the PHMQ and Cu2+ ions. A linear reduction in fluorescence response was noted for Cu2+ ions concentrations between 2–26 μM, with a detection limit of 43.4 nM. Job’s plot, ESI-mass, NMR titration experiments, and density functional theory (DFT) simulations established a 1:1 stoichiometry for the PHMQ-Cu2+ complex. Additionally, PHMQ was efficaciously utilized to quantify Cu2+ ions in drinking and tap water samples and HeLa cells, illustrating durable cellular penetrability and a fluorescence ’Turn-Off’ response to Cu2+ ions. This sensor also established usefulness in mitochondrial-targeted imaging. For the detection of Cu2+ ions in biological and environmental environments, PHMQ is a promising detector due to its high sensitivity, selectivity, and quick response.
本研究报告了一种喹啉基有机分子--(E)-N′-((6-甲氧基-2-氧代-1,2-二氢喹啉-3-基)亚甲基)吡啶酰肼(PHMQ)的简单合成及其分辨 Cu2+ 离子的能力。通过使用光谱和光度滴定技术,研究人员检验了 PHMQ 对各种阳离子和阴离子的选择性。在短短两分钟内,PHMQ 就显示出对 Cu2+ 离子的快速检测能力,清晰的光谱波动表明 PHMQ 与 Cu2+ 复合物的形成具有持久性。计算得出的发射淬灭常数(1.46 × 105 L/mol)和结合常数(1.25 × 104 L/mol)表明,PHMQ 和 Cu2+ 离子之间存在强烈的发射淬灭作用。当 Cu2+ 离子浓度在 2-26 μM 之间时,荧光响应呈线性降低,检测限为 43.4 nM。约伯图、ESI-质谱、核磁共振滴定实验和密度泛函理论(DFT)模拟确定了 PHMQ-Cu2+ 复合物的 1:1 配比。此外,PHMQ 被有效地用于定量检测饮用水、自来水样品和 HeLa 细胞中的 Cu2+ 离子,显示出持久的细胞渗透性和对 Cu2+ 离子的荧光 "关闭 "响应。该传感器还可用于线粒体靶向成像。对于检测生物和环境环境中的 Cu2+ 离子,PHMQ 具有灵敏度高、选择性强和反应迅速等优点,是一种很有前途的检测器。
{"title":"Novel quinoline-based chemosensor as specific fluorescence sensing of copper ions in cancer cells and for organelle-specific imaging application","authors":"Seniappan Kaleeswaran ,&nbsp;D.S. Prabakaran ,&nbsp;Madhappan Santhamoorthy ,&nbsp;S. Ansar ,&nbsp;Mohammad Abul Farah ,&nbsp;Ramar Rajamanikandan ,&nbsp;Kailasam Saravana Mani","doi":"10.1016/j.ica.2024.122440","DOIUrl":"10.1016/j.ica.2024.122440","url":null,"abstract":"<div><div>This work reports a simple synthesis of a quinoline-based organic molecule, (<em>E</em>)-N′-((6-methoxy-2-oxo-1,2-dihydroquinolin-3-yl)methylene) picolinohydrazide (<strong>PHMQ</strong>), and its ability to distinguish Cu<sup>2+</sup> ion. Through the use of spectroscopic and photometric titration techniques, <strong>PHMQ</strong>’s selectivity toward various cations and anions was examined. In just two minutes, <strong>PHMQ</strong> showed fast detection of Cu<sup>2+</sup> ions, and clear spectral fluctuations proposed persistent PHMQ-Cu<sup>2+</sup> complex formation. The calculated emission quenching constant (1.46 × 10<sup>5</sup> L/mol) and binding constant (1.25 × 10<sup>4</sup> L/mol) values suggested that strong emission quenching occurs between the <strong>PHMQ</strong> and Cu<sup>2+</sup> ions. A linear reduction in fluorescence response was noted for Cu<sup>2+</sup> ions concentrations between 2–26 μM, with a detection limit of 43.4 nM. Job’s plot, ESI-mass, NMR titration experiments, and density functional theory (DFT) simulations established a 1:1 stoichiometry for the PHMQ-Cu2<sup>+</sup> complex. Additionally, <strong>PHMQ</strong> was efficaciously utilized to quantify Cu<sup>2+</sup> ions in drinking and tap water samples and HeLa cells, illustrating durable cellular penetrability and a fluorescence ’Turn-Off’ response to Cu<sup>2+</sup> ions. This sensor also established usefulness in mitochondrial-targeted imaging. For the detection of Cu<sup>2+</sup> ions in biological and environmental environments, <strong>PHMQ</strong> is a promising detector due to its high sensitivity, selectivity, and quick response.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"575 ","pages":"Article 122440"},"PeriodicalIF":2.7,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142652507","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, characterization and magnetic properties of a hexanuclear copper (II) complex with hydroxido, alkoxido and phenoxido bridges 具有羟基、烷氧基和苯氧基桥的六核铜 (II) 复合物的合成、表征和磁性能
IF 2.7 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-11-06 DOI: 10.1016/j.ica.2024.122442
Priyanka Chakraborty , Abhishikta Chatterjee , Samia Benmansour , Carlos J. Gómez-García , Subrata K. Dey
A new CuII6 complex, formulated as [Cu6(L)33-OH)(H2O)(OH)(NO3)]·2H2O·7CH3OH (1) has been prepared using the symmetrical N2O3-donor Schiff-base ligand H3L = N,N′-(2-hydroxypropane-1,3-diyl)bis(2-hydroxyacetophenimine). Compound 1 has been structurally and spectroscopically characterized. Single crystal X-ray diffraction analysis reveals that 1 crystallizes in the triclinic space group P-1 and consists of a CuII6 complex where each deprotonated ligand chelates two CuII centres. Three of the six independent CuII centres are arranged in an almost equilateral triangle with double Cu-O-Cu bridges, formed by a μ3-hydroxido and phenoxido bridges. Each of the three CuII centres in the triangle is further connected to one CuII centre through a single alkoxido bridge. The magnetic properties indicate the presence of moderate and weak antiferromagnetic interactions through the double and single oxido bridges, respectively.
利用对称的 N2O3 供体希夫碱配体 H3L = N,N′-(2-羟基丙烷-1,3-二基)双(2-羟基乙酰苯胺),制备了一种新的 CuII6 复合物,命名为 [Cu6(L)3(μ3-OH)(H2O)(OH)(NO3)]-2H2O-7CH3OH(1)。化合物 1 的结构和光谱特征已经确定。单晶 X 射线衍射分析表明,化合物 1 结晶于三linic 空间群 P-1,由 CuII6 复合物组成,其中每个去质子化配体螯合两个 CuII 中心。在六个独立的 CuII 中心中,有三个几乎呈等边三角形排列,并带有由 μ3- 羟基和苯氧基桥形成的双 Cu-O-Cu 桥。三角形中的三个 CuII 中心分别通过一个烷氧基桥与一个 CuII 中心相连。磁性表明,通过双氧桥和单氧桥,分别存在中等和弱的反铁磁相互作用。
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引用次数: 0
Arsenic (III) and (V) complexes from solvent free condition and their kinetic factors leading to arsenic nanoparticles 无溶剂条件下的砷(III)和砷(V)络合物及其生成砷纳米粒子的动力学因素
IF 2.7 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-11-05 DOI: 10.1016/j.ica.2024.122434
Kapilas Das , Sanjoy Kumar Maji , Debasish Pal , Anjali Pal , Samaresh Jana , Sohini Sarkar , Tinku Dhankhar , Sinjan Choudhary , Nibedita Das , Tarasankar Pal
A clear melt from catechol and sodium salts of arsenic (III and V) were obtained individually from the grinding mixing protocol (GMP). The as-obtained molten mass from exothermic reaction between catechol and arsenic salts motivated isothermal titration calorimetry (ITC) advocating the propensity of complex catecholate formation. Individual ITC results substantiated structurally two different mono-anionic complexes, one for arsenic (III) and the other for arsenic (V) ions, of catechol in water at room temperature. Then, the compositions of both the mono-anionic complexes with stoichiometry 1:2 and 1:3 (w∕w) were confirmed for arsenic (III) and (V), respectively. It was shown here for the 1st time that both the complexes supplemented two neat precursors for useful arsenic nanoparticle (As NP) preparation from pH control redox reactions. Again, galvanic replacement reaction (GRR) between As NP and HAuCl4 evolved Au NPs of comparable size as that of As NPs. Thus, thermodynamic results, binding constant (Kb) values, redox kinetic studies and ion associate formation of the two catecholates clearly differentiated the stability (labile and inert character) of As(III) and As(V) catecholates. Conclusively, electrochemistry, galvanic replacement reaction, DLS, thermal analysis, and diverse spectrometric results provided 1st hand support for the complex catecholates of arsenic, a p-block metalloid as labile and inert characters respectively in two different (III) and (V) oxidation states.
儿茶酚和砷(III 和 V)钠盐的透明熔体是通过研磨混合程序(GMP)单独获得的。儿茶酚和砷盐之间的放热反应产生的熔融物激发了等温滴定量热法(ITC),从而证明了复合物儿茶酚酸盐的形成倾向。单独的等温滴定量热结果从结构上证实了室温下邻苯二酚在水中形成的两种不同的单阴离子络合物,一种为砷 (III) 离子,另一种为砷 (V) 离子。然后,确认了这两种单阴离子络合物的组成,其中砷 (III) 和砷 (V) 的化学计量比分别为 1:2 和 1:3 (w∕w)。研究首次表明,这两种络合物可以补充两种纯净的前体,通过 pH 值控制氧化还原反应制备有用的砷纳米粒子(As NP)。同样,砷纳米粒子和 HAuCl4 之间的电化学置换反应(GRR)也生成了与砷纳米粒子大小相当的金纳米粒子。因此,两种邻苯二酚的热力学结果、结合常数(Kb)值、氧化还原动力学研究和离子缔合物的形成清楚地区分了 As(III) 和 As(V) 邻苯二酚的稳定性(易变性和惰性)。最终,电化学、电化学置换反应、DLS、热分析和多种光谱分析结果为砷的复合物儿茶酚提供了第一手支持,砷是一种对嵌段类金属,在两种不同的(III)和(V)氧化态中分别具有易变性和惰性特征。
{"title":"Arsenic (III) and (V) complexes from solvent free condition and their kinetic factors leading to arsenic nanoparticles","authors":"Kapilas Das ,&nbsp;Sanjoy Kumar Maji ,&nbsp;Debasish Pal ,&nbsp;Anjali Pal ,&nbsp;Samaresh Jana ,&nbsp;Sohini Sarkar ,&nbsp;Tinku Dhankhar ,&nbsp;Sinjan Choudhary ,&nbsp;Nibedita Das ,&nbsp;Tarasankar Pal","doi":"10.1016/j.ica.2024.122434","DOIUrl":"10.1016/j.ica.2024.122434","url":null,"abstract":"<div><div>A clear melt from catechol and sodium salts of arsenic (III and V) were obtained individually from the grinding mixing protocol (GMP). The as-obtained molten mass from exothermic reaction between catechol and arsenic salts motivated isothermal titration calorimetry (ITC) advocating the propensity of complex catecholate formation. Individual ITC results substantiated structurally two different mono-anionic complexes, one for arsenic (III) and the other for arsenic (V) ions, of catechol in water at room temperature. Then, the compositions of both the mono-anionic complexes with stoichiometry 1:2 and 1:3 (w∕w) were confirmed for arsenic (III) and (V), respectively. It was shown here for the 1st time that both the complexes supplemented two neat precursors for useful arsenic nanoparticle (As NP) preparation from pH control redox reactions. Again, galvanic replacement reaction (GRR) between As NP and HAuCl<sub>4</sub> evolved Au NPs of comparable size as that of As NPs. Thus, thermodynamic results, binding constant (K<em><sub>b</sub></em>) values, redox kinetic studies and ion associate formation of the two catecholates clearly differentiated the stability (labile and inert character) of As(III) and As(V) catecholates. Conclusively, electrochemistry, galvanic replacement reaction, DLS, thermal analysis, and diverse spectrometric results provided 1st hand support for the complex catecholates of arsenic, a p-block metalloid as labile and inert characters respectively in two different (III) and (V) oxidation states.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"575 ","pages":"Article 122434"},"PeriodicalIF":2.7,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142652038","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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