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Synthesis, structural elucidation, and DNA binding behavior of a ternary copper(II) complex featuring substituted bipyridyl and dicarboxylate ligands 具有取代联吡啶和二羧酸配体的三元铜(II)配合物的合成、结构阐明和 DNA 结合行为
IF 2.4 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-11-26 DOI: 10.1016/j.poly.2024.117318
Sk Khalid Rahaman , Taposi Chatterjee , Kalamoddin Shaikh , Samim Khan , Masoom Raza Siddiqui , Saikh M. Wabaidur , Md Maidul Islam , Seikh Mafiz Alam , Mohammad Hedayetullah Mir
The present research study is centered around the synthesis, characterization, and biological application of a ternary mixed-ligand based binuclear Cu(II) complex [Cu2(trans-1,4-chdc)(4,4′-Me2-2,2′-bpy)2(5,5′-Me2-2,2′-bpy)2]·2(cis-H21,4-chdc)·2(BF4¯) (1) by meticulous incorporation of 4,4′-dimethyl-2,2′-bipyridine (4,4′-Me2-2,2′-bpy), 5,5′-dimethyl-2,2′-bipyridine (5,5′-Me2-2,2′-bpy) and cis- and trans- mixture of 1,4-cyclohexanedicarboxylic acid (H21,4-chdc). Hirshfeld analysis is employed to validate non-bonded interactions, demonstrating the existence of widespread π···π stacking interactions between adjacent 4,4′-Me2-2,2′-bpy ligands at a distance of 3.757 Å, forming a one-dimensional (1D) supramolecular polymer chain. The biological activity of complex 1 is explored via docking study, driven by the inherent biological inclination of the Cu(II) complexes. Agreeably, the coordination complex 1 displays a favorable binding to DNA, specifically binds to the major groove of DNA and the aromatic pyridine ring of the ligand partially intercalates into the base pairs with a binding constant (Kb) of 1.98 × 105 M−1.
本研究围绕基于三元混合配体的双核 Cu(II) 复合物[Cu2(trans-1,4-chdc)(4,4′-Me2-2,2′-bpy)2(5,5′-Me2-2,2′-bpy)2]-2(cis-H21、4-chdc)-2(BF4¯)(1),通过将 4,4′-二甲基-2,2′-联吡啶(4,4′-Me2-2,2′-bpy)、5,5′-二甲基-2、2′-联吡啶(5,5′-Me2-2,2′-bpy)和 1,4-环己烷二羧酸(H21,4-chdc)的顺式和反式混合物。利用 Hirshfeld 分析验证了非键相互作用,证明相邻的 4,4′-Me2-2,2′-bpy 配体之间存在广泛的 π---π 堆叠相互作用,距离为 3.757 Å,形成了一维(1D)超分子聚合物链。根据 Cu(II)配合物固有的生物倾向,通过对接研究探讨了配合物 1 的生物活性。可以肯定的是,配位复合物 1 显示出与 DNA 的良好结合,特别是与 DNA 的主沟结合,配体的芳香吡啶环部分插入碱基对,结合常数(Kb)为 1.98 × 105 M-1。
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引用次数: 0
Highlighting non-covalent interactions to molecular structure, electronic and vibrational spectra in a new hybrid organic–inorganic cobalt complexes: Synthesis, characterization, experimental and computational studies 新型有机-无机杂化钴配合物的分子结构、电子和振动光谱中的非共价相互作用:合成、表征、实验和计算研究
IF 2.4 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-11-26 DOI: 10.1016/j.poly.2024.117320
Jawher Makhlouf , Youness El Bakri , Chin-Hung Lai , Arto Valkonen , Hatem A. Abuelizz , Rashad Al-Salahi , Wajda Smirani Sta
The cobalt (II) complexes have been synthesized from the reaction of the cationic entities (1-(2-methoxyphenyl) piperazine and the 1-(4-nitrophenyl) piperazine with metallic salt CoCl2·6H2O, then processing the evaporation crystal growth method at room temperature. The synthesized complexes have been fully characterized by single crystal X-ray diffraction, Hirshfeld surface analysis, as well as UV–visible, FTIR spectroscopy, Photoluminescence, and TGA/TDA analysis, and theoretical studies were also performed, in addition to the antioxidant DPPH+ radical and ABTS+ radical cation assays were performed. The crystal structural analysis reveals that both complexes crystallize in the orthorhombic system. The vibrational absorption bands were identified by infrared spectroscopy. The solid-state UV–visible absorption spectrum of the title compounds was obtained at room temperature to spotlight the optical properties. In the [300–700 K] range, the thermal behaviors were investigated and showed the decomposition of the two complexes with metal complexes residues. Hirshfeld surface analysis cum 2D fingerprint plots visualize the main intermolecular interactions with their contributions in the solid-state phase. The molecular geometries of both complexes obtained from the crystal structure were used for quantum chemical calculation. DPPH+ radical and ABTS+ radical cation assays were used to highlight the interesting antioxidant activity for both complexes, where the IC50 of compound (1) was greater than 45 mg.mL−1 and it was greater than 49 mg.mL−1 for compound (2). The anticancer activities of the complexes studied were also investigated in silico by molecular docking.
钴(II)配合物是由阳离子实体(1-(2-甲氧基苯基)哌嗪和 1-(4-硝基苯基)哌嗪)与金属盐 CoCl2-6H2O 反应,然后在室温下用蒸发晶体生长法合成的。合成的配合物通过单晶 X 射线衍射、Hirshfeld 表面分析、紫外可见光谱、傅立叶变换红外光谱、光致发光和 TGA/TDA 分析进行了全面表征,并进行了理论研究,此外还进行了抗氧化 DPPH+自由基和 ABTS+自由基阳离子检测。晶体结构分析表明,这两种复合物均为正方晶系结晶。红外光谱鉴定了振动吸收带。在室温下获得了标题化合物的固态紫外-可见吸收光谱,以观察其光学性质。在 [300-700 K] 范围内,对热行为进行了研究,结果表明这两种络合物与金属络合物残留物发生了分解。Hirshfeld 表面分析和二维指纹图显示了固态相中主要的分子间相互作用及其贡献。从晶体结构中获得的两种复合物的分子几何结构被用于量子化学计算。利用 DPPH+自由基和 ABTS+自由基阳离子检测法突出了这两种复合物的抗氧化活性,其中化合物(1)的 IC50 大于 45 毫克.毫升-1,化合物(2)的 IC50 大于 49 毫克.毫升-1。还通过分子对接对所研究复合物的抗癌活性进行了硅学研究。
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引用次数: 0
Triperiodic frameworks in the uranyl–2,5-thiophenedicarboxylate system: Effect of unidentate auxiliary ligands 2,5-噻吩二甲酸铀酰体系中的三周期框架:非识别辅助配体的影响
IF 2.4 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-11-20 DOI: 10.1016/j.poly.2024.117307
Pierre Thuéry , Youssef Atoini , Jack Harrowfield
2,5-Thiophenedicarboxylic acid (H2tdc) has been reacted with uranyl nitrate hexahydrate under solvo-hydrothermal conditions with N,N-dimethylacetamide (dma) as an organic cosolvent, giving the complex [UO2(tdc)(dma)] (1), isomorphous to the previously reported [UO2(tdc)(nmp)] (nmp = N-methyl-2-pyrrolidone). With tdc2− adopting the bis(μ21O1O’)-bridging coordination mode, complex 1 crystallizes as a triperiodic framework with the point symbol {42.84}. With acetonitrile as an organic cosolvent and in the presence of [Ni(PPh3)2Br2], triphenylphosphine oxide is formed in situ and it binds to uranyl to give [UO2(tdc)(OPPh3)] (2). Complex 2 is also a triperiodic framework, with the point symbol {4.102}2{42.104} and the dmd topological type with uranium as 3-coordinated (3-c) nodes and tdc2− as either a 4-c node in its bis(μ21O1O’)-bridging mode, or a simple edge in the bis(κ2O,O’)-chelating mode. In both 1 and 2, as in the previously described nmp complex, but not in [UO2(tdc)(dmf)] (dmf = N,N-dimethylformamide), coordination of a unidentate ligand disrupts the most common formation of diperiodic networks with tdc2− and tris-chelated uranyl, and promotes formation of frameworks in which channels accommodate the pendant, unidentate ligands. Complex 2 has a photoluminescence quantum yield of 3 % in the solid state, and its emission spectrum displays the typical vibronic progression with peak positions in the range usual for complexes with an O5 equatorial uranyl environment; the “hot band” observed at room temperature disappears at 77 K.
以 N,N-二甲基乙酰胺(dma)为有机共溶剂,在溶液-水热条件下,2,5-噻吩二甲酸(H2tdc)与六水合硝酸铀酰发生反应,得到[UO2(tdc)(dma)](1)复合物,它与之前报道的[UO2(tdc)(nmp)](nmp = N-甲基-2-吡咯烷酮)同构。tdc2-采用双(μ2-κ1O:κ1O')桥接配位模式时,配合物 1 结晶为三周期框架,点符号为 {42.84}。以乙腈为有机共溶剂,在[Ni(PPh3)2Br2]的存在下,三苯基膦氧化物在原位形成,并与铀酰结合得到[UO2(tdc)(OPPh3)](2)。复合物 2 也是一个三周期框架,其点符号为 {4.102}2{42.104},拓扑类型为 dmd,铀为 3 配位 (3-c) 节点,tdc2- 在其双(μ2-κ1O:κ1O')桥接模式中为 4-c 节点,或在双(κ2O,O')螯合模式中为单边。在 1 和 2 中,与之前描述的 nmp 复合物一样,但不包括 [UO2(tdc)(dmf)](dmf = N,N-二甲基甲酰胺),未识别配体的配位破坏了最常见的与tdc2-和三螯合铀酰形成的二周期网络,并促进了框架的形成,在框架中,通道容纳了悬挂的未识别配体。络合物 2 在固态下的光量子产率为 3%,其发射光谱显示出典型的振子级数,峰位在具有 O5 赤道铀酰环境的络合物的常见范围内;室温下观察到的 "热带 "在 77 K 时消失。
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引用次数: 0
Ruthenium-based macrocyclic and Schiff base complexes as prominent therapeutic agents: Their designing, synthesis and recent perspectives 钌基大环和希夫碱配合物作为重要的治疗药物:它们的设计、合成和最新前景
IF 2.4 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-11-17 DOI: 10.1016/j.poly.2024.117309
Urmila Phageria , Sushama Kumari , Krishna Atal , Swati Bugalia
The role of macrocyclic and Schiff base complexes in chemistry and life sciences offers vast opportunities to the researchers. Herein, this review focuses on the recent developments in ruthenium-based macrocyclic complexes and their utilities. Nowadays, ruthenium-based macrocyclic complexes are substantially exploited in copious applications, such as antioxidant, anticancer, antimicrobial, catalysis, sensors, pigments, dyes, etc. are a few of them. This study combines innovations in modelling and employment of these macrocyclic ligands and their complexes with ruthenium that serves as an interaction between the fields of chemistry, physics and biology. Probably Ru(II) and Ru(III) complexes achieve a wider holder of a three-dimensional scaffold through octahedral bonding, which opens up the possibility for a greater level of site diversity for attaching to their biological substrates. This study also expresses a broader overview of the topic and aims to highlight developments in ligand designing, synthetic methods, and potent applications especially as prominent therapeutic agents of these metal complexes in diverse areas. Additionally, some of the Schiff bases complexes with the same metal are also highlighted with their prominent applications.
大环和希夫碱配合物在化学和生命科学中的作用为研究人员提供了大量机会。在此,本综述将重点介绍钌基大环配合物的最新发展及其用途。如今,钌基大环配合物在抗氧化、抗癌、抗菌、催化、传感器、颜料、染料等众多领域都得到了广泛的应用。本研究结合了这些大环配体及其与钌配合物的建模和应用方面的创新,是化学、物理学和生物学领域的一次互动。可能是 Ru(II) 和 Ru(III) 复合物通过八面体键实现了更广泛的三维支架固定,这就为其生物底物的附着点多样性提供了更大的可能性。本研究还对这一主题进行了更广泛的概述,旨在强调配体设计、合成方法和有效应用方面的发展,特别是这些金属配合物在不同领域作为突出治疗药物的应用。此外,本研究还重点介绍了一些与同种金属的希夫碱配合物及其突出应用。
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引用次数: 0
Robust Y and Lu TrenSal catalysts for ring-opening polymerisation 用于开环聚合反应的强效 Y 和 Lu TrenSal 催化剂
IF 2.4 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-11-17 DOI: 10.1016/j.poly.2024.117308
Eszter Fazekas , Alvaro Etcheverry-Berrios , Gary S. Nichol , Stergios Piligkos , Euan K. Brechin , Jennifer A. Garden
Mono and bimetallic cage-like TrenSal complexes based on rare-earth metals Y and Lu were synthesised and fully characterised by single crystal and powder X-ray diffraction, multinuclear NMR and IR spectroscopy, and MALDI-ToF mass spectrometry. These robust and air-stable complexes are active catalysts for the ring-opening polymerisation of rac-lactide. While the polymerisation activity is low, the complexes remain active in air using unpurified monomers, and are highly unusual examples of metal–organic cages applied in polymerisation. MALDI-ToF mass spectrometry studies of the obtained polymers revealed H and OBn end-capped chains suggesting that an ‘activated monomer’ mechanism predominates when BnOH is used as an exogenous initiator.
通过单晶和粉末 X 射线衍射、多核核磁共振和红外光谱以及 MALDI-ToF 质谱法,合成了基于稀土金属 Y 和 Lu 的单金属笼状 TrenSal 复合物和双金属笼状 TrenSal 复合物,并对其进行了全面表征。这些坚固且在空气中稳定的复合物是 rac-lactide 开环聚合反应的活性催化剂。虽然聚合活性较低,但使用未净化的单体时,这些复合物在空气中仍能保持活性,是将金属有机笼应用于聚合反应的极不寻常的例子。对获得的聚合物进行的 MALDI-ToF 质谱研究显示,H 和 OBn 端封端链表明,当 BnOH 用作外源引发剂时,"活化单体 "机制占主导地位。
{"title":"Robust Y and Lu TrenSal catalysts for ring-opening polymerisation","authors":"Eszter Fazekas ,&nbsp;Alvaro Etcheverry-Berrios ,&nbsp;Gary S. Nichol ,&nbsp;Stergios Piligkos ,&nbsp;Euan K. Brechin ,&nbsp;Jennifer A. Garden","doi":"10.1016/j.poly.2024.117308","DOIUrl":"10.1016/j.poly.2024.117308","url":null,"abstract":"<div><div>Mono and bimetallic cage-like TrenSal complexes based on rare-earth metals Y and Lu were synthesised and fully characterised by single crystal and powder X-ray diffraction, multinuclear NMR and IR spectroscopy, and MALDI-ToF mass spectrometry. These robust and air-stable complexes are active catalysts for the ring-opening polymerisation of <em>rac</em>-lactide. While the polymerisation activity is low, the complexes remain active in air using unpurified monomers, and are highly unusual examples of metal–organic cages applied in polymerisation. MALDI-ToF mass spectrometry studies of the obtained polymers revealed H and OBn end-capped chains suggesting that an ‘activated monomer’ mechanism predominates when BnOH is used as an exogenous initiator.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"266 ","pages":"Article 117308"},"PeriodicalIF":2.4,"publicationDate":"2024-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142702195","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
Synthesis of series of transition metal-ligand (TM-L), μ2-O-TM, μ3-O-TM-L borates: Characterization and oxygen reduction reaction (ORR) activity property exploration 合成一系列过渡金属配体(TM-L)、μ2-O-TM、μ3-O-TM-L 硼酸盐:表征和氧还原反应 (ORR) 活性特性探索
IF 2.4 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-11-17 DOI: 10.1016/j.poly.2024.117304
Zhen-Ping Liao , Shu-Sheng Xin , Wei Li , Chun-Yang Pan
A series of borates 16, have been synthesized under mild conditions, single crystal X-ray diffraction indicates that they possess three types of metal complex configurations in borate crystalline, exemplified as TM-L for 3 and 4, μ2-O-TM for 2, μ3-O-TM for 1, 5 and 6. 5 and 6 exhibit both four-coordinated and six-coordinated metal ions in one single crystal lattice. 1 to 6 are further characterized by powder X-ray diffraction, elemental analysis, IR spectrum and UV–vis spectroscopy. In addition, the ORR activities of them are performed. Among them, cobalt borate-based catalyst exhibits the best catalytic performance, with a half-wave potential of 0.82 V. Furthermore, the relationship between the ORR properties of TM complex borates and their framework densities was explored.
在温和的条件下合成了一系列硼酸盐 1-6,单晶 X 射线衍射表明它们在硼酸盐晶体中具有三种金属复合物构型,例如 3 和 4 为 TM-L,2 为 μ2-O-TM,1、5 和 6 为 μ3-O-TM。5 和 6 在一个单晶晶格中同时显示出四配位和六配位金属离子。粉末 X 射线衍射、元素分析、红外光谱和紫外-可见光谱对 1 至 6 做了进一步表征。此外,还对它们进行了 ORR 活性测试。其中,硼酸钴基催化剂的催化性能最好,半波电位为 0.82 V。此外,还探讨了 TM 复合硼酸盐的 ORR 特性与其框架密度之间的关系。
{"title":"Synthesis of series of transition metal-ligand (TM-L), μ2-O-TM, μ3-O-TM-L borates: Characterization and oxygen reduction reaction (ORR) activity property exploration","authors":"Zhen-Ping Liao ,&nbsp;Shu-Sheng Xin ,&nbsp;Wei Li ,&nbsp;Chun-Yang Pan","doi":"10.1016/j.poly.2024.117304","DOIUrl":"10.1016/j.poly.2024.117304","url":null,"abstract":"<div><div>A series of borates <strong>1</strong>–<strong>6</strong>, have been synthesized under mild conditions, single crystal X-ray diffraction indicates that they possess three types of metal complex configurations in borate crystalline, exemplified as TM-L for <strong>3</strong> and <strong>4</strong>, <em>μ</em><sub>2</sub>-O-TM for <strong>2</strong>, <em>μ</em><sub>3</sub>-O-TM for <strong>1</strong>, <strong>5</strong> and <strong>6</strong>. <strong>5</strong> and <strong>6</strong> exhibit both four-coordinated and six-coordinated metal ions in one single crystal lattice. <strong>1</strong> to <strong>6</strong> are further characterized by powder X-ray diffraction, elemental analysis, IR spectrum and UV–vis spectroscopy. In addition, the ORR activities of them are performed. Among them, cobalt borate-based catalyst exhibits the best catalytic performance, with a half-wave potential of 0.82 V. Furthermore, the relationship between the ORR properties of TM complex borates and their framework densities was explored.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"266 ","pages":"Article 117304"},"PeriodicalIF":2.4,"publicationDate":"2024-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142702197","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
Polyoxometalates ionic liquids based magnetic nanocomposites as an efficient heterogeneous catalysts for oxidation of thiobenzoic acid and dibenzothiophene by employing RP-HPLC-UV 利用 RP-HPLC-UV 将基于聚氧化金属离子液体的磁性纳米复合材料作为氧化硫代苯甲酸和二苯并噻吩的高效异相催化剂
IF 2.4 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-11-16 DOI: 10.1016/j.poly.2024.117311
Roman Jaffar , Najla AlMasoud , Khurram Shahzad Munawar , Sana Rauf , Taghrid S. Alomar , Hafiz Muhammad Asif , Zeinhom M. El-Bahy , Hameed Ullah , Saifullah
Sulfur compounds need to be effectively rejected from fuel to maintain a clean environment. The removal of sulfur compounds from thiocompounds has received increased attention due to the negative environmental and industrial consequences of sulfur emissions. We examine the effectiveness of polyoxometalate (POM) ionic liquid-based nanocomposites as catalysts for the oxidative desulfurization of thiobenzoic acid and other sulfur-containing chemicals. Na-POMIL@NCP and Cr-POMIL@NCP were synthesized and thoroughly characterized using a variety of analytical techniques, including Fourier-transform infrared spectroscopy (FT-IR), UV–visible spectroscopy, powder X-ray diffraction (P-XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), fluorescence spectroscopy, and vibrating sample magnetometer (VSM). POMIL-based nanocomposites with Fe3O4@SiO2 exhibit both catalytic activity and adsorption capability. To evaluate sulfur removal efficiency and investigate the transformation paths of the thio compounds, high-performance liquid chromatography (HPLC) was performed at 33 °C using a C18 column with an acetonitrile–water mobile phase (1:1 ratio). The catalytic conversion of thiobenzoic acid and dibenzothiophene occurs at temperature, oxidant O/S ratio and catalyst concentration were investigated to determine the best catalyst for a given process. Under moderate conditions, this work proposes a cost-effective and ecologically acceptable approach for thiobenzoic acid (TB) and dibenzothiophene (DBT) production employing H2O2 as an oxidant and Na-POMIL@NCP and Cr-POMIL@NCP as heterogeneous catalysts. They are highly effective for oxidizing sulfur compounds included in diesel to lower the sulfur levels of fuel. This study provides to the development of innovative materials for ecologically friendly sulfur removal applications.
为了保持环境清洁,需要有效地去除燃料中的硫化合物。由于硫排放对环境和工业造成的负面影响,从硫代化合物中去除硫化合物的研究受到越来越多的关注。我们研究了聚氧化金属(POM)离子液体基纳米复合材料作为催化剂对硫代苯甲酸和其他含硫化学品进行氧化脱硫的有效性。研究人员合成了 Na-POMIL@NCP 和 Cr-POMIL@NCP,并使用多种分析技术对其进行了全面表征,包括傅立叶变换红外光谱(FT-IR)、紫外-可见光谱、粉末 X 射线衍射(P-XRD)、扫描电子显微镜(SEM)、粉末 X 射线衍射(P-XRD)和傅立叶变换红外光谱(FT-IR)、扫描电子显微镜 (SEM)、能量色散 X 射线光谱仪 (EDX)、热重分析 (TGA)、差示扫描量热仪 (DSC)、荧光光谱仪和振动样品磁力计 (VSM)。基于 POMIL 的 Fe3O4@SiO2 纳米复合材料同时具有催化活性和吸附能力。为了评估硫的去除效率并研究硫代化合物的转化路径,在 33 °C下使用C18色谱柱和乙腈-水流动相(1:1)进行了高效液相色谱分析。研究了硫代苯甲酸和二苯并噻吩的催化转化温度、氧化剂 O/S 比率和催化剂浓度,以确定特定工艺的最佳催化剂。在中等条件下,本研究提出了一种具有成本效益且生态上可接受的硫代苯甲酸(TB)和二苯并噻吩(DBT)生产方法,该方法采用 H2O2 作为氧化剂,Na-POMIL@NCP 和 Cr-POMIL@NCP 作为异相催化剂。它们对氧化柴油中的硫化合物以降低燃料中的硫含量非常有效。这项研究为开发生态友好型脱硫应用的创新材料提供了思路。
{"title":"Polyoxometalates ionic liquids based magnetic nanocomposites as an efficient heterogeneous catalysts for oxidation of thiobenzoic acid and dibenzothiophene by employing RP-HPLC-UV","authors":"Roman Jaffar ,&nbsp;Najla AlMasoud ,&nbsp;Khurram Shahzad Munawar ,&nbsp;Sana Rauf ,&nbsp;Taghrid S. Alomar ,&nbsp;Hafiz Muhammad Asif ,&nbsp;Zeinhom M. El-Bahy ,&nbsp;Hameed Ullah ,&nbsp;Saifullah","doi":"10.1016/j.poly.2024.117311","DOIUrl":"10.1016/j.poly.2024.117311","url":null,"abstract":"<div><div>Sulfur compounds need to be effectively rejected from fuel to maintain a clean environment. The removal of sulfur compounds from thiocompounds has received increased attention due to the negative environmental and industrial consequences of sulfur emissions. We examine the effectiveness of polyoxometalate (POM) ionic liquid-based nanocomposites as catalysts for the oxidative desulfurization of thiobenzoic acid and other sulfur-containing chemicals. Na-POMIL@NCP and Cr-POMIL@NCP were synthesized and thoroughly characterized using a variety of analytical techniques, including Fourier-transform infrared spectroscopy (FT-IR), UV–visible spectroscopy, powder X-ray diffraction (P-XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), fluorescence spectroscopy, and vibrating sample magnetometer (VSM). POMIL-based nanocomposites with Fe<sub>3</sub>O<sub>4</sub>@SiO<sub>2</sub> exhibit both catalytic activity and adsorption capability. To evaluate sulfur removal efficiency and investigate the transformation paths of the thio compounds, high-performance liquid chromatography (HPLC) was performed at 33 °C using a C18 column with an acetonitrile–water mobile phase (1:1 ratio). The catalytic conversion of thiobenzoic acid and dibenzothiophene occurs at temperature, oxidant O/S ratio and catalyst concentration were investigated to determine the best catalyst for a given process. Under moderate conditions, this work proposes a cost-effective and ecologically acceptable approach for thiobenzoic acid (TB) and dibenzothiophene (DBT) production employing H<sub>2</sub>O<sub>2</sub> as an oxidant and Na-POMIL@NCP and Cr-POMIL@NCP as heterogeneous catalysts. They are highly effective for oxidizing sulfur compounds included in diesel to lower the sulfur levels of fuel. This study provides to the development of innovative materials for ecologically friendly sulfur removal applications.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"266 ","pages":"Article 117311"},"PeriodicalIF":2.4,"publicationDate":"2024-11-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142702202","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
New complexes of [5,10,15,20-(tetraphenylporphyrin)] and dichloride (5,10,15,20-tetraphenylporphyrinato) antimony(V) hexachloridoantimonate(V) functionalized with polyethyleneimine: Synthesis, characterization, and application in Eriochrome Black T adsorption from water 聚乙烯亚胺官能化的[5,10,15,20-(四苯基卟啉)]和二氯化(5,10,15,20-四苯基卟啉)锑(V)六氯锑酸(V)新配合物:合成、表征及在 Eriochrome Black T 水吸附中的应用
IF 2.4 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-11-16 DOI: 10.1016/j.poly.2024.117305
Raoudha Soury , Mahjoub Jabli , Mabrouka El Oudi , Khalaf M. Alenezi , Ahmed Al Otaibi , Fahad Abdulaziz , Hind A. AlGhamdi , Amor Bchetnia
In the current work, new complexes namely [5,10,15,20 (tetraphenylporphyrin)] /Polyethyleneimine (H2TPP-PEI) and Dichlorido(5,10,15,20-tetraphenylporphyrinato)antimony(V) hexachloridoantimonate(V)/Polyethyleneimine ([Sb(TPP)Cl2][SbCl6]-PEI) were successfully prepared and characterized. The prepared compounds were thoroughly analysed using 1H NMR, UV, XRD, XRF, TGA-DTA, SEM, and EDAX. SEM analysis showed that the addition of polyethyleneimine to the porphyrin core clearly changed the morphological properties. The optical gap values were calculated using the tauc plot method and were equal to 1.877, 2.030, 1.862, and 2.017 eV for H2TPP, [Sb(TPP)Cl2] [SbCl6], H2TPP-PEI and ([Sb(TPP)Cl2][SbCl6]-PEI), respectively. The existence of sharp peaks at 2θ between 16° and 80° displayed the crystalline nature of the prepared porphyrinic compounds. The change in thermal decompositions for H2TPP, [Sb(TPP)Cl2][SbCl6], H2TPP-PEI and ([Sb(TPP)Cl2][SbCl6]-PEI) revealed that the addition of polyethyleneimine to porphyrin affected the thermal characteristics. The prepared complexes were, further, investigated for the adsorption of Eriochrome Black T (an anionic dye) from water. Highest adsorption capacities were accomplished using [Sb(TPP)(Cl2)]-PEI (164 mg/g) and H2TPP-PEI (82 mg/g) under the following experimental conditions (pH = 5, temperature = 19 °C, time = 60 min). However, the adsorption capacities remains poor for H2TPP and Sn(TPP)(Cl2). The adsorption data complied well with pseudo second order, Freundlich, and Temkin equations. Overall, the adsorption results had confirmed that polyethyleneimine functionalized porphyrins could be used as a proficient adsorbent of anionic dyes from water.
本研究成功制备了[5,10,15,20(四苯基卟啉)]/聚乙烯亚胺(H2TPP-PEI)和二氯(5,10,15,20-四苯基卟啉)锑(V)六氯锑酸(V)/聚乙烯亚胺([Sb(TPP)Cl2][SbCl6]-PEI)新配合物,并对其进行了表征。使用 1H NMR、UV、XRD、XRF、TGA-DTA、SEM 和 EDAX 对制备的化合物进行了全面分析。扫描电镜分析表明,在卟啉核心中添加聚乙烯亚胺明显改变了其形态特性。通过陶氏图法计算得出,H2TPP、[Sb(TPP)Cl2] [SbCl6]、H2TPP-PEI 和 ([Sb(TPP)Cl2][SbCl6]-PEI) 的光隙值分别为 1.877、2.030、1.862 和 2.017 eV。在 16° 和 80° 之间的 2θ 处存在尖锐的峰值,这表明所制备的卟啉化合物具有结晶性质。H2TPP、[Sb(TPP)Cl2][SbCl6]、H2TPP-PEI 和([Sb(TPP)Cl2][SbCl6]-PEI)的热分解变化表明,在卟啉中加入聚乙烯亚胺会影响热特性。研究人员还进一步研究了制备的复合物对水中 Eriochrome Black T(一种阴离子染料)的吸附能力。在以下实验条件下(pH = 5、温度 = 19 °C、时间 = 60 分钟),[Sb(TPP)(Cl2)]-PEI(164 毫克/克)和 H2TPP-PEI(82 毫克/克)的吸附容量最高。然而,H2TPP 和 Sn(TPP)(Cl2) 的吸附容量仍然很低。吸附数据完全符合伪二阶、Freundlich 和 Temkin 方程。总之,吸附结果证实了聚乙烯亚胺官能化卟啉可用作水中阴离子染料的有效吸附剂。
{"title":"New complexes of [5,10,15,20-(tetraphenylporphyrin)] and dichloride (5,10,15,20-tetraphenylporphyrinato) antimony(V) hexachloridoantimonate(V) functionalized with polyethyleneimine: Synthesis, characterization, and application in Eriochrome Black T adsorption from water","authors":"Raoudha Soury ,&nbsp;Mahjoub Jabli ,&nbsp;Mabrouka El Oudi ,&nbsp;Khalaf M. Alenezi ,&nbsp;Ahmed Al Otaibi ,&nbsp;Fahad Abdulaziz ,&nbsp;Hind A. AlGhamdi ,&nbsp;Amor Bchetnia","doi":"10.1016/j.poly.2024.117305","DOIUrl":"10.1016/j.poly.2024.117305","url":null,"abstract":"<div><div>In the current work, new complexes namely [5,10,15,20 (tetraphenylporphyrin)] /Polyethyleneimine (H<sub>2</sub>TPP-PEI) and Dichlorido(5,10,15,20-tetraphenylporphyrinato)antimony(V) hexachloridoantimonate(V)/Polyethyleneimine ([Sb(TPP)Cl<sub>2</sub>][SbCl<sub>6</sub>]-PEI) were successfully prepared and characterized. The prepared compounds were thoroughly analysed using <sup>1</sup>H NMR, UV, XRD, XRF, TGA-DTA, SEM, and EDAX. SEM analysis showed that the addition of polyethyleneimine to the porphyrin core clearly changed the morphological properties. The optical gap values were calculated using the tauc plot method and were equal to 1.877, 2.030, 1.862, and 2.017 eV for H<sub>2</sub>TPP, [Sb(TPP)Cl<sub>2</sub>] [SbCl<sub>6</sub>], H<sub>2</sub>TPP-PEI and ([Sb(TPP)Cl<sub>2</sub>][SbCl<sub>6</sub>]-PEI), respectively. The existence of sharp peaks at 2θ between 16° and 80° displayed the crystalline nature of the prepared porphyrinic compounds. The change in thermal decompositions for H<sub>2</sub>TPP, [Sb(TPP)Cl<sub>2</sub>][SbCl<sub>6</sub>], H<sub>2</sub>TPP-PEI and ([Sb(TPP)Cl<sub>2</sub>][SbCl<sub>6</sub>]-PEI) revealed that the addition of polyethyleneimine to porphyrin affected the thermal characteristics. The prepared complexes were, further, investigated for the adsorption of Eriochrome Black T (an anionic dye) from water. Highest adsorption capacities were accomplished using [Sb(TPP)(Cl<sub>2</sub>)]-PEI (164 mg/g) and H<sub>2</sub>TPP-PEI (82 mg/g) under the following experimental conditions (pH = 5, temperature = 19 °C, time = 60 min). However, the adsorption capacities remains poor for H<sub>2</sub>TPP and Sn(TPP)(Cl<sub>2</sub>). The adsorption data complied well with pseudo second order, Freundlich, and Temkin equations. Overall, the adsorption results had confirmed that polyethyleneimine functionalized porphyrins could be used as a proficient adsorbent of anionic dyes from water.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"266 ","pages":"Article 117305"},"PeriodicalIF":2.4,"publicationDate":"2024-11-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142702110","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 of tetraphenylphosphonium/polysulfide hybrids and their temperature-induced switchable WORM/flash electrical memory behavior 四苯基膦/多硫化物混合物的合成及其温度诱导的可切换 WORM/flash 电存储器行为
IF 2.4 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-11-15 DOI: 10.1016/j.poly.2024.117301
Zhaoxun Lian, Ning Zhao
The development of innovative non-volatile storage materials is essential for the progression of next-generation high-performance storage devices. In this study, a hybrid material (Ph4P)2S7 was synthesized, and single crystal structure analysis demonstrated that the organic tetraphenylphosphonium cation (Ph)4P+ adopts a regular tetrahedral conformation and forms one-dimensional chains through CH···π interactions. The (S7)2- anion, characterized by quasi-bicentric symmetry and a right-handed helical cluster, is confined within the one-dimensional quantum well established by the (Ph)4P+ cation chain in the organic matrix. A device composed of FTO/(Ph4P)2S7/Ag was fabricated through spin-coating, demonstrating remarkable temperature-induced switchable binary write-once-read-many-times (WORM)/Flash electrical memory behavior. At room temperature, the material demonstrated nonvolatile binary WORM-type resistance switching behavior with a switching ratio of 1.95 × 103 and an onset voltage of 1.01 V. Conversely, at 150 °C, it transits into binary Flash-type resistance switching behavior characterized by current ratio of 3.34 × 102 and onset/reset voltages of 1.05/−1.99 V. The mechanism underlying binary resistive switching is identified as spatial charge-limited charge capture. Furthermore, the observed reversible transition between WORM- and Flash- type electrical memory behavior at elevated temperatures can be attributed to lattice expansion of the (Ph)4P+ cations at high temperatures, resulting in denser packing of organic molecules and deeper trapping potential wells for electrons within the active layer. This study provides theoretical insights into developing novel high-performance information storage materials.
创新型非易失性存储材料的开发对于下一代高性能存储设备的发展至关重要。本研究合成了一种混合材料 (Ph4P)2S7,单晶结构分析表明有机四苯基鏻阳离子 (Ph)4P+ 采用规则的四面体构象,并通过 CH---π 相互作用形成一维链。(S7)2- 阴离子具有准双心对称性和右手螺旋簇的特点,被限制在有机基质中由 (Ph)4P+ 阳离子链建立的一维量子阱内。通过旋涂技术制造出了一种由 FTO/(Ph4P)2S7/Ag 组成的器件,该器件在温度诱导下具有显著的可切换二元写入-一次读取-多次写入(WORM)/闪存电记忆行为。在室温下,该材料表现出非易失性二进制 WORM 型电阻开关行为,开关比为 1.95 × 103,起始电压为 1.01 V。反之,在 150 ℃ 时,它过渡到二进制闪存型电阻开关行为,电流比为 3.34 × 102,起始/复位电压为 1.05/-1.99 V。此外,在高温下观察到的 WORM 型和闪存型电子存储器行为之间的可逆转换可归因于 (Ph)4P+ 阳离子在高温下的晶格膨胀,从而导致有机分子堆积更密集,活性层内的电子捕获势阱更深。这项研究为开发新型高性能信息存储材料提供了理论依据。
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引用次数: 0
Sensitivity of pure and Ni-decorated boron nitride B12N12 nanocages toward CH4, H2S, and N2 biogases: A DFT study 纯氮化硼和镍装饰的 B12N12 纳米笼对 CH4、H2S 和 N2 生物气体的敏感性:DFT 研究
IF 2.4 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-11-14 DOI: 10.1016/j.poly.2024.117302
Tamer H.A. Hasanin , Manar H.A. Hamad , Nayra A.M. Moussa , Asmaa M.M. Mahmoud , Mohamed Y. El-Sayed , Al-shimaa S.M. Rady , Mahmoud A.A. Ibrahim
The sensitivity of pure and Ni-decorated boron nitride (B12N12) nanocages toward CH4, H2S, and N2 biogases was adequately unveiled by employing versatile density functional theory (DFT) calculations. In this regard, the Gas∙∙∙B12N12 and ∙∙∙Ni@B12N12 complexes were studied within all possible configurations. Based on the energetic quantities, the Ni@B12N12 nanocage exhibited higher sensitivity than the pure one toward the investigated gases. Among all studied complexes, the H2S∙∙∙Ni@B12N12 complex exhibited the most favorable adsorption (Eads) and interaction (Eint) energies with values of –29.25 and –29.46 kcal/mol, respectively. According to the outlines of the quantum theory of atoms in molecules (QTAIM) and noncovalent interaction (NCI) index analyses, the closed-shell nature of the interactions within the investigated complexes was ensured. Substantial alterations in the molecular orbitals distribution patterns of pure and Ni-decorated B12N12 nanocages were observed, announcing the occurrence of the adsorption process within the investigated complexes. The obtained negative values of thermodynamic parameters ensured the spontaneous exothermic nature of the investigated Ni-decorated complexes. Upon density of states (DOS) analysis, the influence of adsorbed gases on the electronic characteristics of the pure and Ni-decorated B12N12 nanocages was highlighted. According to the emerging findings, the pure and Ni-decorated B12N12 nanocages are promising sensing materials for biogas components, especially CH4, H2S, and N2 gases.
通过采用多功能密度泛函理论(DFT)计算,充分揭示了纯氮化硼(B12N12)纳米笼和镍装饰氮化硼(B12N12)纳米笼对 CH4、H2S 和 N2 生物气体的敏感性。在这方面,研究了所有可能构型中的 Gas∙∙∙B12N12 和 ∙∙∙Ni@B12N12 复合物。根据能量量,Ni@B12N12 纳米笼对所研究气体的灵敏度高于纯纳米笼。在所有研究的复合物中,H2S∙∙∙Ni@B12N12 复合物的吸附能(Eads)和相互作用能(Eint)最高,分别为 -29.25 和 -29.46 kcal/mol。根据分子中原子的量子理论(QTAIM)和非共价相互作用(NCI)指数分析,所研究复合物内部的相互作用具有闭壳性质。观察到纯 B12N12 纳米络合物和镍装饰 B12N12 纳米络合物的分子轨道分布模式发生了重大变化,这表明在所研究的络合物中存在吸附过程。所获得的热力学参数负值确保了所研究的镍装饰复合物具有自发放热的性质。通过状态密度(DOS)分析,吸附气体对纯 B12N12 纳米笼和镍装饰纳米笼电子特性的影响得到了强调。根据新的研究结果,纯的和镍装饰的 B12N12 纳米笼是很有前途的生物气体成分(尤其是 CH4、H2S 和 N2 气体)传感材料。
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引用次数: 0
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Polyhedron
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