Pub Date : 2024-09-22DOI: 10.1016/j.poly.2024.117231
P.B. Anagha, S. Shibu Prasad
A new metal-organic framework of Sr(II) with phenylmalonic acid, {[Sr(PMA)(H2O)].H2O}n (SPMA) has been prepared by gel diffusion technique. SXRD data show that the crystal belongs to the orthorhombic space group Pbca. In the crystal structure, the phenylmalonate ligand adopts monodentate, bis-monodentate and bidentate coordination modes with the Sr(II) ions. The Sr-phenylmalonate units extend three dimensionally forming a network structure. Intermolecular hydrogen bonding further stabilizes the crystal system. The compound exhibits strong luminescence emission at 290 nm upon excitation at 240 nm. Sensing property of the title compound towards Fe3+ ion is also investigated.
{"title":"Crystal growth, characterization and sensing studies of a new metal-organic framework of Sr(II) with phenylmalonic acid","authors":"P.B. Anagha, S. Shibu Prasad","doi":"10.1016/j.poly.2024.117231","DOIUrl":"10.1016/j.poly.2024.117231","url":null,"abstract":"<div><div>A new metal-organic framework of Sr(II) with phenylmalonic acid, {[Sr(PMA)(H<sub>2</sub>O)].H<sub>2</sub>O}<sub>n</sub> (SPMA) has been prepared by gel diffusion technique. SXRD data show that the crystal belongs to the orthorhombic space group <em>Pbca</em>. In the crystal structure, the phenylmalonate ligand adopts monodentate, bis-monodentate and bidentate coordination modes with the Sr(II) ions. The Sr-phenylmalonate units extend three dimensionally forming a network structure. Intermolecular hydrogen bonding further stabilizes the crystal system. The compound exhibits strong luminescence emission at 290 nm upon excitation at 240 nm. Sensing property of the title compound towards Fe<sup>3+</sup> ion is also investigated.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"264 ","pages":"Article 117231"},"PeriodicalIF":2.4,"publicationDate":"2024-09-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142326372","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}
Pub Date : 2024-09-22DOI: 10.1016/j.poly.2024.117236
Charalampos Triantis , Antonio Shegani , Aristeidis Chiotellis , Catherine Raptopoulou , Vassilis Psycharis , Maria Pelecanou , Ioannis Pirmettis , Minas Papadopoulos
The synthesis and characterization of neutral tricarbonyl fac-[Re/99mTc(quin)(X)(CO)3] and dicarbonyl cis–trans-[Re/99mTc(quin)(X)2(CO)2] mixed ligand complexes with quinaldic acid (quin) as the bidentate ligand and trimethoxyphosphine [P(OCH3)3], tris(hydroxymethyl)-phosphine [P(CH2OH)3], triphenylphosphine (PPh3), and triphenylarsine (AsPh3) as the monodentate ligands (X) is described. The synthesis of the [2 + 1] tricarbonyl complexes proceeds by displacement of the water molecule of the fac-[Re/99mTc(quin)(H2O)(CO)3] by the monodentate ligand. Interestingly, the synthesis of the [2 + 1 + 1] dicarbonyl complexes was achieved only for PPh3 after replacing the CO group trans to PPh3 with a second PPh3 molecule. The latter complex was also obtained by refluxing quinaldic acid with the trans-mer-[Re(PPh3)2(Cl)(CO)3] precursor in toluene. Rhenium complexes were prepared in satisfactory yields and fully characterized. At the technetium-99 m level, complexes were produced in high radiochemical yields and characterized by comparative chromatographic analysis using the analogous rhenium complexes. Complexes have shown varying stability against transchelation by cysteine and histidine in agreement with the decreasing σ-donating capacity of the monodentate ligand (P(OCH3)3 > P(CH2OH)3 > PPh3 > AsPh3. The stable complexes with PPh3 showed high lipophilicity (LogP 2.90 and 3.10, respectively) due to the lipophilic nature of the monodentate ligands. The σ-donor and π-acceptor capacity of the monodentate ligand strongly influences the formation and stability of the complexes, and these characteristics should be considered before choosing the appropriate ligand for radiopharmaceuticals design.
{"title":"Synthesis and characterization of rhenium and Technetium-99 m tricarbonyl and dicarbonyl complexes with quinaldic acid and Arsenic/Phosphorus derivatives","authors":"Charalampos Triantis , Antonio Shegani , Aristeidis Chiotellis , Catherine Raptopoulou , Vassilis Psycharis , Maria Pelecanou , Ioannis Pirmettis , Minas Papadopoulos","doi":"10.1016/j.poly.2024.117236","DOIUrl":"10.1016/j.poly.2024.117236","url":null,"abstract":"<div><div>The synthesis and characterization of neutral tricarbonyl <em>fac-</em>[Re/<sup>99m</sup>Tc(quin)(X)(CO)<sub>3</sub>] and dicarbonyl <em>cis</em>–<em>trans-</em>[Re/<sup>99m</sup>Tc(quin)(X)<sub>2</sub>(CO)<sub>2</sub>] mixed ligand complexes with quinaldic acid (quin) as the bidentate ligand and trimethoxyphosphine [P(OCH<sub>3</sub>)<sub>3</sub>], tris(hydroxymethyl)-phosphine [P(CH<sub>2</sub>OH)<sub>3</sub>]<sub>,</sub> triphenylphosphine (PPh<sub>3</sub>), and triphenylarsine (AsPh<sub>3</sub>) as the monodentate ligands (X) is described. The synthesis of the [2 + 1] tricarbonyl complexes proceeds by displacement of the water molecule of the <em>fac</em>-[Re/<sup>99m</sup>Tc(quin)(H<sub>2</sub>O)(CO)<sub>3</sub>] by the monodentate ligand. Interestingly, the synthesis of the [2 + 1 + 1] dicarbonyl complexes was achieved only for PPh<sub>3</sub> after replacing the CO group <em>trans</em> to PPh<sub>3</sub> with a second PPh<sub>3</sub> molecule. The latter complex was also obtained by refluxing quinaldic acid with the <em>trans</em>-<em>mer</em>-[Re(PPh<sub>3</sub>)<sub>2</sub>(Cl)(CO)<sub>3</sub>] precursor in toluene. Rhenium complexes were prepared in satisfactory yields and fully characterized. At the technetium-99 m level, complexes were produced in high radiochemical yields and characterized by comparative chromatographic analysis using the analogous rhenium complexes. Complexes have shown varying stability against transchelation by cysteine and histidine in agreement with the decreasing <em>σ</em>-donating capacity of the monodentate ligand (P(OCH<sub>3</sub>)<sub>3</sub> > P(CH<sub>2</sub>OH)<sub>3</sub> > PPh<sub>3</sub> > AsPh<sub>3</sub>. The stable complexes with PPh<sub>3</sub> showed high lipophilicity (LogP 2.90 and 3.10, respectively) due to the lipophilic nature of the monodentate ligands. The <em>σ</em>-donor and <em>π</em>-acceptor capacity of the monodentate ligand strongly influences the formation and stability of the complexes, and these characteristics should be considered before choosing the appropriate ligand for radiopharmaceuticals design.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"264 ","pages":"Article 117236"},"PeriodicalIF":2.4,"publicationDate":"2024-09-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142314525","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}
Pub Date : 2024-09-22DOI: 10.1016/j.poly.2024.117234
João G. de Oliveira Neto , Jailton R. Viana , Marinaldo V. Souza Júnior , Luis H.S. Queiroz , Aramys S. Reis , Mateus R. Lage , Eliana B. Souto , Francisco F. de Sousa , Adenilson O. dos Santos
A dichloro-bis(theophylline)-copper(II) complex, named [Cu(theo)2Cl2], was synthesized, with the aim to characterize its physicochemical and pharmacological properties. The complex was obtained by the slow evaporation method, and the experimental and theoretical physicochemical properties were studied using X-ray powder diffraction (XRPD), ultraviolet (UV–vis) spectroscopy, density functional theory (DFT), Hirshfeld surfaces, thermogravimetric (TG), differential thermal analysis (DTA), Fourier-transform infrared (FT-IR) and Raman spectroscopy. XRPD study confirmed that its crystallographic phase belongs to the monoclinic symmetry with C2/c () space group. Important theoretical properties such as structural parameters, spin density, molecular frontier orbitals, chemical reactivity descriptors, and electrostatic potential maps were also predicted using the implicit solvation method in ethanol and water as solvents, and vacuum condition. Hirshfeld surfaces and crystal void analyses were employed to evaluate the intermolecular interactions and unit cell-free spaces. All Raman and FT-IR vibration bands were assigned with the aid of DFT studies. Thermal analyses revealed that the complex has thermodynamic stability between 293 K and ∼ 465 K. In addition, solubility was determined to evaluate the complex dissolution profile. Computational pharmacokinetic analysis revealed the topological polar surface area of 111.78 Å2, highlighting the potential of the developed complex for intestinal absorption, with low risk of hepatotoxicity and limited capacity to permeate the blood–brain barrier (BBB). Biological assays were carried out for the [Cu(theo)2Cl2] complex, suggesting that it has antitumor activity against PC-3 (prostate), MDA-MB-231 (breast), and HCT-116 (colorectal) tumor cells, also indicating a half-maximum inhibitory concentration value near 4.93–5.11 mM. Finally, molecular docking studies were computed to evaluate the mechanism of interaction between the complex and deoxyribonucleic acid double-stranded.
本研究合成了一种名为[Cu(theo)2Cl2]的二氯-双(茶碱)-铜(II)配合物，旨在研究其理化和药理特性。该配合物采用缓慢蒸发法获得，并利用 X 射线粉末衍射（XRPD）、紫外（UV-vis）光谱、密度泛函理论（DFT）、Hirshfeld 表面、热重（TG）、差热分析（DTA）、傅立叶变换红外（FT-IR）和拉曼光谱等方法对其理化性质进行了实验和理论研究。XRPD 研究证实，其结晶相属于单斜对称，空间群为 C2/c (C2h6)。此外，还在乙醇和水作为溶剂以及真空条件下，使用隐含溶解法预测了结构参数、自旋密度、分子前沿轨道、化学反应描述符和静电位图等重要理论特性。此外，还采用 Hirshfeld 表面和晶体空隙分析来评估分子间的相互作用和无单胞空间。所有的拉曼和傅立叶变换红外振动带都是在 DFT 研究的帮助下分配的。热分析表明，该复合物在 293 K 至 465 K 之间具有热力学稳定性。计算药代动力学分析表明，该复合物的拓扑极性表面积为 111.78 Å2，凸显了所开发复合物的肠道吸收潜力，而且肝毒性风险低，通过血脑屏障（BBB）的能力有限。对[Cu(theo)2Cl2]复合物进行了生物检测，结果表明它对 PC-3（前列腺）、MDA-MB-231（乳腺）和 HCT-116（结直肠）肿瘤细胞具有抗肿瘤活性，半最大抑制浓度值接近 4.93-5.11 mM。最后，还进行了分子对接研究，以评估复合物与脱氧核糖核酸双链之间的相互作用机制。
{"title":"Dichloro-bis(theophylline)-copper(II) complex: Characterization of the physicochemical, computational pharmacokinetics, molecular docking, and cytotoxicity as potential antitumoral medicine","authors":"João G. de Oliveira Neto , Jailton R. Viana , Marinaldo V. Souza Júnior , Luis H.S. Queiroz , Aramys S. Reis , Mateus R. Lage , Eliana B. Souto , Francisco F. de Sousa , Adenilson O. dos Santos","doi":"10.1016/j.poly.2024.117234","DOIUrl":"10.1016/j.poly.2024.117234","url":null,"abstract":"<div><div>A dichloro-bis(theophylline)-copper(II) complex, named [Cu(theo)<sub>2</sub>Cl<sub>2</sub>], was synthesized, with the aim to characterize its physicochemical and pharmacological properties. The complex was obtained by the slow evaporation method, and the experimental and theoretical physicochemical properties were studied using X-ray powder diffraction (XRPD), ultraviolet (UV–vis) spectroscopy, density functional theory (DFT), Hirshfeld surfaces, thermogravimetric (TG), differential thermal analysis (DTA), Fourier-transform infrared (FT-IR) and Raman spectroscopy. XRPD study confirmed that its crystallographic phase belongs to the monoclinic symmetry with <em>C</em><sub>2</sub>/<em>c</em> (<span><math><msubsup><mi>C</mi><mrow><mn>2</mn><mi>h</mi></mrow><mn>6</mn></msubsup></math></span>) space group. Important theoretical properties such as structural parameters, spin density, molecular frontier orbitals, chemical reactivity descriptors, and electrostatic potential maps were also predicted using the implicit solvation method in ethanol and water as solvents, and vacuum condition. Hirshfeld surfaces and crystal void analyses were employed to evaluate the intermolecular interactions and unit cell-free spaces. All Raman and FT-IR vibration bands were assigned with the aid of DFT studies. Thermal analyses revealed that the complex has thermodynamic stability between 293 K and ∼ 465 K. In addition, solubility was determined to evaluate the complex dissolution profile. Computational pharmacokinetic analysis revealed the topological polar surface area of 111.78 Å<sup>2</sup>, highlighting the potential of the developed complex for intestinal absorption, with low risk of hepatotoxicity and limited capacity to permeate the blood–brain barrier (BBB). Biological assays were carried out for the [Cu(theo)<sub>2</sub>Cl<sub>2</sub>] complex, suggesting that it has antitumor activity against PC-3 (prostate), MDA-MB-231 (breast), and HCT-116 (colorectal) tumor cells, also indicating a half-maximum inhibitory concentration value near 4.93–5.11 mM. Finally, molecular docking studies were computed to evaluate the mechanism of interaction between the complex and deoxyribonucleic acid double-stranded.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"264 ","pages":"Article 117234"},"PeriodicalIF":2.4,"publicationDate":"2024-09-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142326371","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}
Pub Date : 2024-09-22DOI: 10.1016/j.poly.2024.117230
Vikas Sangwan , D.P. Singh
In order to reduce the chances of multiple drug resistance, there is an urgent requirement for the designing of new antimicrobial agents. In this current research, series of novel hexaazamacrocyclic trivalent transition metal complexes of ChromiumIII and IronIII have been prepared by adopting the pathway of metal ion mediated template condensation. The newly synthesized macrocyclic complexes were analyzed by Infra-Red Spectroscopy, Carbon-Hydrogen-Nitrogen analyzer, UltraViolet–visible, Powder X-Ray Diffraction, Electron Paramagnetic Resonance, Magnetic Susceptibilities, Molar conductance, Electron Spray Ionisation-Mass Spectrometry and Thermogravimetric analysis techniques. The electro-lytic behaviour of the complexes was suggested by conductance (molar) values. All the complexes (T7-T12) can be formulated or represented as [MLX] X2·yH2O, where M = FeIII, CrIII and L is the macrocyclic ring resulting from 1,8-diaminonaphthalene and succinimide and X = NO3−, Cl−, CH3COO− and y = 1 or 2. All the macrocyclic complexes have been anticipated to have a penta coordinated square pyramidal shape using several physico-analytical approaches. Monomeric nature of the complexes was confirmed by CHN analysis and mass spectral data. Powder X-Ray Diffraction studies were carried out for interpreting the crystallinity of the complexes. Density Functional Theory studies were performed for energy optimization and theoretical calculations of UV & IR. The DNA interaction studies showed intercalative mode of binding is present in the newly designed complexes with the DNA. In addition to these, all the metal complexes were screened for their antibacterial and antifungal activity against pathogenic strains of bacteria and fungi, Complex T7 has effective bactericidal action against B. cereus and E. coli. Molecular docking studies were also performed on SARS Cov-2 and Mycobacterium tuberculosis. The used proteins are NSP15 Endoribonuclease from SARS CoV-2 and DNA of Mycobacterium tuberculosis H37Rv. The results revealed that complex T10 is having good binding affinity against DNA of Mycobacterium tuberculosis H37Rv.
为了降低多重耐药性的发生几率，迫切需要设计新的抗菌剂。在本研究中，通过采用金属离子介导的模板缩合途径，制备了一系列新型六氮杂环三价过渡金属铬Ⅲ和铁Ⅲ配合物。新合成的大环配合物通过红外光谱、碳氢氮分析仪、紫外可见光、粉末 X 射线衍射、电子顺磁共振、磁感应强度、摩尔电导、电子喷雾电离质谱和热重分析技术进行了分析。电导（摩尔）值表明了复合物的电解行为。所有络合物（T7-T12）都可以用 [MLX] X2-yH2O 表示，其中 M = FeIII、CrIII，L 是由 1,8-二氨基萘和琥珀酰亚胺形成的大环，X = NO3-、Cl-、CH3COO-，y = 1 或 2。通过几种物理分析方法，所有大环复合物都被认为具有五配位方形金字塔形状。CHN 分析和质谱数据证实了这些复合物的单体性质。为了解释复合物的结晶度，还进行了粉末 X 射线衍射研究。还进行了密度泛函理论研究，以优化能量，并对紫外和红外光谱进行理论计算。DNA 相互作用研究表明，新设计的配合物与 DNA 之间存在插层结合模式。此外，还对所有金属复合物进行了抗菌和抗真菌活性筛选，结果表明，复合物 T7 对蜡样芽孢杆菌和大肠杆菌具有有效的杀菌作用。此外，还对 SARS Cov-2 和结核分枝杆菌进行了分子对接研究。使用的蛋白质是来自 SARS CoV-2 的 NSP15 内切酶和结核分枝杆菌 H37Rv 的 DNA。结果表明，复合物 T10 与结核分枝杆菌 H37Rv 的 DNA 具有良好的结合亲和力。
{"title":"Trivalent transition metal ion mediated template synthesis: In silico molecular docking, DNA binding, antimicrobial evaluation and DFT studies","authors":"Vikas Sangwan , D.P. Singh","doi":"10.1016/j.poly.2024.117230","DOIUrl":"10.1016/j.poly.2024.117230","url":null,"abstract":"<div><div>In order to reduce the chances of multiple drug resistance, there is an urgent requirement for the designing of new antimicrobial agents. In this current research, series of novel hexaazamacrocyclic trivalent transition metal complexes of Chromium<sup>III</sup> and Iron<sup>III</sup> have been prepared by adopting the pathway of metal ion mediated template condensation. The newly synthesized macrocyclic complexes were analyzed by Infra-Red Spectroscopy, Carbon-Hydrogen-Nitrogen analyzer, UltraViolet–visible, Powder X-Ray Diffraction, Electron Paramagnetic Resonance, Magnetic Susceptibilities, Molar conductance, Electron Spray Ionisation-Mass Spectrometry and Thermogravimetric analysis techniques. The electro-lytic behaviour of the complexes was suggested by conductance (molar) values. All the complexes (T7-T12) can be formulated or represented as [MLX] X<sub>2</sub>·yH<sub>2</sub>O, where M = Fe<sup>III</sup>, Cr<sup>III</sup> and L is the macrocyclic ring resulting from 1,8-diaminonaphthalene and succinimide and X = NO<sub>3</sub><sup>−</sup>, Cl<sup>−</sup>, CH<sub>3</sub>COO<sup>−</sup> and y = 1 or 2. All the macrocyclic complexes have been anticipated to have a penta coordinated square pyramidal shape using several physico-analytical approaches. Monomeric nature of the complexes was confirmed by CHN analysis and mass spectral data. Powder X-Ray Diffraction studies were carried out for interpreting the crystallinity of the complexes. Density Functional Theory studies were performed for energy optimization and theoretical calculations of UV & IR. The DNA interaction studies showed intercalative mode of binding is present in the newly designed complexes with the DNA. In addition to these, all the metal complexes were screened for their antibacterial and antifungal activity against pathogenic strains of bacteria and fungi, Complex T7 has effective bactericidal action against B. cereus and E. coli. Molecular docking studies were also performed on SARS Cov-2 and Mycobacterium tuberculosis. The used proteins are NSP15 Endoribonuclease from SARS CoV-2 and DNA of Mycobacterium tuberculosis H37Rv. The results revealed that complex T10 is having good binding affinity against DNA of Mycobacterium tuberculosis H37Rv.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"264 ","pages":"Article 117230"},"PeriodicalIF":2.4,"publicationDate":"2024-09-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142322156","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}
Semiconductor with structure phase change is a special multi-functional material, which plays an important role in the field of Solar Energy, information computing, sensor technology, artificial intelligence, etc. In this paper, the organic–inorganic lead-free semiconductor phase change material [1-Methylimidazole][SbBr4] (1) was successfully constructed. The IR, TGA, DSC, VT-PXRD, solid-state UV–vis spectroscopy and temperature dependence of dielectric constant were characterized and analysed. Single crystal X-ray diffraction shows that at 298 K, the space group is P21/c, the point group 2/m; an endothermic and exothermic peak appeared near 386 K and 367 K in the DSC heating–cooling cycles. Near the corresponding phase transition temperature point, compound 1 exhibits a significant reversible change in the dielectric platform. Interestingly, the band gap of compound 1 is about 2.53 eV. The existence of such interesting physical properties is closely related to the interaction between cations and anions in the molecule and the connection of internal hydrogen bonds. By constructing organic–inorganic hybrid semiconductor materials, we hope to obtain semiconductor materials with phase transition properties and actively explore and provide some ideas and support for the application of new high-tech materials.
具有结构相变的半导体是一种特殊的多功能材料，在太阳能、信息计算、传感技术、人工智能等领域发挥着重要作用。本文成功构建了有机-无机无铅半导体相变材料[1-甲基咪唑][SbBr4]（1）。对其进行了红外光谱、TGA、DSC、VT-PXRD、固态紫外-可见光谱以及介电常数随温度变化的表征和分析。单晶 X 射线衍射显示，在 298 K 时，空间群为 P21/c，点群为 2/m；在 DSC 加热-冷却循环中，分别在 386 K 和 367 K 附近出现了一个内热峰和一个放热峰。在相应的相变温度点附近，化合物 1 的介电平台发生了显著的可逆变化。有趣的是，化合物 1 的带隙约为 2.53 eV。这种有趣物理性质的存在与分子中阳离子和阴离子之间的相互作用以及内部氢键的连接密切相关。我们希望通过构建有机-无机杂化半导体材料，获得具有相变性质的半导体材料，并积极探索，为高科技新材料的应用提供一些思路和支持。
{"title":"Lead-free semiconductor materials with high phase transition temperature: [1-Methylimidazole][SbBr4]","authors":"Ji-Xing Gao, Zheng-Hui Hu, Jia-Le Song, Ping-Yuan Zhang, Xiang-Yu Shi, Shu-Sheng Wang, Su-Jing Zhang","doi":"10.1016/j.poly.2024.117233","DOIUrl":"10.1016/j.poly.2024.117233","url":null,"abstract":"<div><div>Semiconductor with structure phase change is a special multi-functional material, which plays an important role in the field of Solar Energy, information computing, sensor technology, artificial intelligence, etc. In this paper, the organic–inorganic lead-free semiconductor phase change material [1-Methylimidazole][SbBr<sub>4</sub>] (<strong>1</strong>) was successfully constructed. The IR, TGA, DSC, VT-PXRD, solid-state UV–vis spectroscopy and temperature dependence of dielectric constant were characterized and analysed. Single crystal X-ray diffraction shows that at 298 K, the space group is <em>P</em>2<sub>1</sub>/<em>c</em>, the point group 2/<em>m</em>; an endothermic and exothermic peak appeared near 386 K and 367 K in the DSC heating–cooling cycles. Near the corresponding phase transition temperature point, compound <strong>1</strong> exhibits a significant reversible change in the dielectric platform. Interestingly, the band gap of compound <strong>1</strong> is about 2.53 eV. The existence of such interesting physical properties is closely related to the interaction between cations and anions in the molecule and the connection of internal hydrogen bonds. By constructing organic–inorganic hybrid semiconductor materials, we hope to obtain semiconductor materials with phase transition properties and actively explore and provide some ideas and support for the application of new high-tech materials.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"264 ","pages":"Article 117233"},"PeriodicalIF":2.4,"publicationDate":"2024-09-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142326374","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}
Pub Date : 2024-09-20DOI: 10.1016/j.poly.2024.117232
H.R. Abd El-Mageed , Mahmoud K. Abdel-Latif , Nayra A.M. Moussa , Abdallah I.M. Rabee , Mohamed A. El-Tayeb , Mahmoud A.A. Ibrahim , Abdallah J. Abu Namous , H.M. Abd El-Salam
The adsorption behavior of zinc oxide (Zn12O12) nanocage toward delivering the temozolomide (TMZ), carmustine (CM), procarbazine (PR), and lomustine (LO) anticancer drugs was herein investigated utilizing the density functional theory (DFT) method. The emerging outcomes unveiled the potential efficiency of the Zn12O12 nanocage toward adsorbing the TMZ, CM, PR, and LO drugs and showed prominent negative values of binding energies (ΔEbind) up to −14.69 kcal.mol−1. Among the studied complexes, the Zn12O12-TMZ complex showed the most preferential ΔEbind values in the gas and water phases compared to other studied complexes with values up to −14.69 and −12.88 kcal.mol−1, respectively. The quantum theory of atoms in molecules announced the occurrence of the adsorption process between the Zn12O12 nanocage and anticancer drugs via polar covalent interactions and electrostatic interactions. Based on frontier molecular orbital theory affirmations, the electronic parameters of Zn12O12 nanocage changed preferentially upon adsorption of the studied drug within the most stable configurations. Moreover, the Zn12O12-drug complexes exhibited short recovery times for drug desorption from the nanocage. The results clearly confirmed that the Zn12O12 nanocage is an ideal candidate for the highly efficient development of anticancer TMZ, CM, PR, and LO drug carriers.
{"title":"Adsorption behavior of temozolomide, carmustine, procarbazine, and lomustine anticancer drugs on zinc oxide nanocage: A DFT study","authors":"H.R. Abd El-Mageed , Mahmoud K. Abdel-Latif , Nayra A.M. Moussa , Abdallah I.M. Rabee , Mohamed A. El-Tayeb , Mahmoud A.A. Ibrahim , Abdallah J. Abu Namous , H.M. Abd El-Salam","doi":"10.1016/j.poly.2024.117232","DOIUrl":"10.1016/j.poly.2024.117232","url":null,"abstract":"<div><div>The adsorption behavior of zinc oxide (Zn<sub>12</sub>O<sub>12</sub>) nanocage toward delivering the temozolomide (TMZ), carmustine (CM), procarbazine (PR), and lomustine (LO) anticancer drugs was herein investigated utilizing the density functional theory (DFT) method. The emerging outcomes unveiled the potential efficiency of the Zn<sub>12</sub>O<sub>12</sub> nanocage toward adsorbing the TMZ, CM, PR, and LO drugs and showed prominent negative values of binding energies (Δ<em>E</em><sub>bind</sub>) up to −14.69 kcal.mol<sup>−1</sup>. Among the studied complexes, the Zn<sub>12</sub>O<sub>12</sub>-TMZ complex showed the most preferential Δ<em>E</em><sub>bind</sub> values in the gas and water phases compared to other studied complexes with values up to −14.69 and −12.88 kcal.mol<sup>−1</sup>, respectively. The quantum theory of atoms in molecules announced the occurrence of the adsorption process between the Zn<sub>12</sub>O<sub>12</sub> nanocage and anticancer drugs via polar covalent interactions and electrostatic interactions. Based on frontier molecular orbital theory affirmations, the electronic parameters of Zn<sub>12</sub>O<sub>12</sub> nanocage changed preferentially upon adsorption of the studied drug within the most stable configurations. Moreover, the Zn<sub>12</sub>O<sub>12</sub>-drug complexes exhibited short recovery times for drug desorption from the nanocage. The results clearly confirmed that the Zn<sub>12</sub>O<sub>12</sub> nanocage is an ideal candidate for the highly efficient development of anticancer TMZ, CM, PR, and LO drug carriers.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"264 ","pages":"Article 117232"},"PeriodicalIF":2.4,"publicationDate":"2024-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142319833","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}
Pub Date : 2024-09-19DOI: 10.1016/j.poly.2024.117229
José Gaete , Yuvaraja Dibdalli , Héctor Pérez , Cristian Valdebenito , Héctor Reyes , Alejandro Lopez-Telgie , Gabriel Abarca , Cesar Morales-Verdejo
This work reports the synthesis, characterization, and application of promising nanocatalysts on the thermal decomposition of ammonium perchlorate (AP). Magnetite nanoparticles were functionalized with Ferrocene-derivative groups through chemical and physical methods to obtain these composite materials. The characterization was done using TEM, FTIR, VSM, and TGA techniques. The composite material MNP-Fc2I causes a decrease in the high-temperature decomposition (HTD) of AP to 357 °C. On the other hand, the MNP-Fc1 obtained the lowest activation energy (138 kJ·mol−1), indicating that the reaction may initiate at a relatively high temperature due to the need to overcome the activation energy barrier; once it begins, it proceeds with reduced energy requirements. Furthermore, performing ion exchange with energetic anions results in a decrease in the decomposition temperature of AP for the MNP-Fc1(N3) and MNP-Fc1(DCA) catalysts.
本研究报告了在高氯酸铵（AP）热分解过程中具有前景的纳米催化剂的合成、表征和应用。通过化学和物理方法，磁铁矿纳米颗粒被二茂铁衍生物基团功能化，从而获得了这些复合材料。表征采用了 TEM、FTIR、VSM 和 TGA 技术。复合材料 MNP-Fc2I 使 AP 的高温分解温度（HTD）降低到 357 ℃。另一方面，MNP-Fc1 获得了最低的活化能（138 kJ-mol-1），这表明由于需要克服活化能障碍，反应可能会在相对较高的温度下开始；一旦反应开始，就会以较低的能量需求进行。此外，与高能阴离子进行离子交换可降低 MNP-Fc1(N3)和 MNP-Fc1(DCA)催化剂的 AP 分解温度。
{"title":"Evaluation of the synergistic effect of magnetic nanoparticles and Ferrocene-Based 1,2,3-Triazolyl compounds as burning rate catalysts for solid rocket Motors","authors":"José Gaete , Yuvaraja Dibdalli , Héctor Pérez , Cristian Valdebenito , Héctor Reyes , Alejandro Lopez-Telgie , Gabriel Abarca , Cesar Morales-Verdejo","doi":"10.1016/j.poly.2024.117229","DOIUrl":"10.1016/j.poly.2024.117229","url":null,"abstract":"<div><div>This work reports the synthesis, characterization, and application of promising nanocatalysts on the thermal decomposition of ammonium perchlorate (AP). Magnetite nanoparticles were functionalized with Ferrocene-derivative groups through chemical and physical methods to obtain these composite materials. The characterization was done using TEM, FTIR, VSM, and TGA techniques. The composite material MNP-Fc2I causes a decrease in the high-temperature decomposition (HTD) of AP to 357 °C. On the other hand, the MNP-Fc1 obtained the lowest activation energy (138 kJ·mol<sup>−1</sup>), indicating that the reaction may initiate at a relatively high temperature due to the need to overcome the activation energy barrier; once it begins, it proceeds with reduced energy requirements. Furthermore, performing ion exchange with energetic anions results in a decrease in the decomposition temperature of AP for the MNP-Fc1(N<sub>3</sub>) and MNP-Fc1(DCA) catalysts.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"264 ","pages":"Article 117229"},"PeriodicalIF":2.4,"publicationDate":"2024-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142312432","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}
Pub Date : 2024-09-17DOI: 10.1016/j.poly.2024.117226
Andrea O’Reilly , Andrew M.S. Booth , Claire L. McMullin , J. Robin Fulton , Martyn P. Coles
Under forcing conditions, the aluminyls [AM{Al(NON)}]2 ([NON]2− = [O(SiMe2NDipp)2]2−, Dipp = 2,6-iPr2C6H3, AM = Na, K) react with benzene to give the 1,4-phenylene di(hydrido)aluminate complexes, AM2[1,4-{Al(NON)(H)}2(C6H4)]. Crystal structure analysis of the products shows that the ’Al(NON)(H)’ groups are in the plane of the para-substituted C6-ring, with the alkali metals above and below forming an inverse sandwich structure. Density functional theory calculations were performed to analyse the mechanism leading to the di-substituted product. Results identify a viable dimeric pathway and show that each alumination step is preceded by a Meisenheimer-type intermediate leading to the observed trans-dialuminated product.
{"title":"1,4-Dialumination of benzene by sodium and potassium aluminyls","authors":"Andrea O’Reilly , Andrew M.S. Booth , Claire L. McMullin , J. Robin Fulton , Martyn P. Coles","doi":"10.1016/j.poly.2024.117226","DOIUrl":"10.1016/j.poly.2024.117226","url":null,"abstract":"<div><div>Under forcing conditions, the aluminyls [AM{Al(NON)}]<sub>2</sub> ([NON]<sup>2−</sup> = [O(SiMe<sub>2</sub>NDipp)<sub>2</sub>]<sup>2−</sup>, Dipp = 2,6-<em>i</em>Pr<sub>2</sub>C<sub>6</sub>H<sub>3</sub>, AM = Na, K) react with benzene to give the 1,4-phenylene di(hydrido)aluminate complexes, AM<sub>2</sub>[1,4-{Al(NON)(H)}<sub>2</sub>(C<sub>6</sub>H<sub>4</sub>)]. Crystal structure analysis of the products shows that the ’Al(NON)(H)’ groups are in the plane of the <em>para</em>-substituted C<sub>6</sub>-ring, with the alkali metals above and below forming an inverse sandwich structure. Density functional theory calculations were performed to analyse the mechanism leading to the di-substituted product. Results identify a viable dimeric pathway and show that each alumination step is preceded by a Meisenheimer-type intermediate leading to the observed <em>trans</em>-dialuminated product.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"264 ","pages":"Article 117226"},"PeriodicalIF":2.4,"publicationDate":"2024-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S0277538724004029/pdfft?md5=b3edc196e3b31541b06399aa946daefc&pid=1-s2.0-S0277538724004029-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142312433","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}
Pub Date : 2024-09-16DOI: 10.1016/j.poly.2024.117228
Zhenzhong Mei , Hongyu Wang , Xiuqi Kang , Jinzhong Gu , Mohammad Azam
A derivative of pyridine-dicarboxylic acid, 5-(3-carboxyphenyl)picolinic acid (H2cpic), was used as a versatile building block to synthesize a series of five novel coordination compounds under hydrothermal conditions and formulated as {[Cu2(μ-cpic)2(phen)]·H2O}n (1), [Co(μ-cpic)(phen)(H2O)]n (2), [Cu2(μ-cpic)2(2,2′-bipy)(H2O)2]·2H2O (3), {[Cu3(μ-cpic)3(μ-4,4′-bipy)1.5(H2O)3]·2H2O}n (4), and {[Zn2(μ-cpic)2(μ-dpe)0.5(H2O)3]·H2O}n (5). The auxiliary ligands used in the synthesis were 1,10-phenanthroline (phen), 2,2′-bipyridine (2,2′-bipy), 4,4′-bipyridine (4,4′-bipy), and 1,2-di(4-pyridyl)ethylene (dpe). The structures of the compounds 1–5 vary significantly, ranging from a 0D tetramer (3) to 1D metal–organic chains (1, 2, 4, and 5). Furthermore, these compounds were evaluated as heterogeneous catalysts for the Henry reaction, achieving high product yields under optimized conditions. We further investigated various reaction parameters, and substrate scope, and assessed the feasibility of catalyst recycling. This thorough investigation highlights the versatility of H2cpic as a dicarboxylate building block in the formation of functional coordination polymers.
{"title":"Construction of Co(II), Cu(II), and Zn(II) coordination compounds driven by a pyridine-dicarboxylic acid: Hydrothermal assembly, structural and topological versatility, and catalytic properties","authors":"Zhenzhong Mei , Hongyu Wang , Xiuqi Kang , Jinzhong Gu , Mohammad Azam","doi":"10.1016/j.poly.2024.117228","DOIUrl":"10.1016/j.poly.2024.117228","url":null,"abstract":"<div><p>A derivative of pyridine-dicarboxylic acid, 5-(3-carboxyphenyl)picolinic acid (H<sub>2</sub>cpic), was used as a versatile building block to synthesize a series of five novel coordination compounds under hydrothermal conditions and formulated as {[Cu<sub>2</sub>(<em>μ-</em>cpic)<sub>2(</sub>phen)]·H<sub>2</sub>O}<em><sub>n</sub></em> (<strong>1</strong>), [Co(<em>μ-</em>cpic)(phen)(H<sub>2</sub>O)]<em><sub>n</sub></em> (<strong>2</strong>), [Cu<sub>2</sub>(<em>μ-</em>cpic)<sub>2</sub>(2,2′-bipy)(H<sub>2</sub>O)<sub>2</sub>]·2H<sub>2</sub>O (<strong>3</strong>), {[Cu<sub>3</sub>(<em>μ-</em>cpic)<sub>3</sub>(<em>μ-</em>4,4′-bipy)<sub>1.5</sub>(H<sub>2</sub>O)<sub>3</sub>]·2H<sub>2</sub>O}<em><sub>n</sub></em> (<strong>4</strong>), and {[Zn<sub>2</sub>(<em>μ-</em>cpic)<sub>2</sub>(<em>μ-</em>dpe)<sub>0.5</sub>(H<sub>2</sub>O)<sub>3</sub>]·H<sub>2</sub>O}<em><sub>n</sub></em> (<strong>5</strong>). The auxiliary ligands used in the synthesis were 1,10-phenanthroline (phen), 2,2′-bipyridine (2,2′-bipy), 4,4′-bipyridine (4,4′-bipy), and 1,2-di(4-pyridyl)ethylene (dpe). The structures of the compounds <strong>1</strong>–<strong>5</strong> vary significantly, ranging from a 0D tetramer (<strong>3</strong>) to 1D metal–organic chains (<strong>1</strong>, <strong>2</strong>, <strong>4</strong>, and <strong>5</strong>). Furthermore, these compounds were evaluated as heterogeneous catalysts for the Henry reaction, achieving high product yields under optimized conditions. We further investigated various reaction parameters, and substrate scope, and assessed the feasibility of catalyst recycling. This thorough investigation highlights the versatility of H<sub>2</sub>cpic as a dicarboxylate building block in the formation of functional coordination polymers.</p></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"264 ","pages":"Article 117228"},"PeriodicalIF":2.4,"publicationDate":"2024-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142271493","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}
Pub Date : 2024-09-13DOI: 10.1016/j.poly.2024.117225
Olesya V. Pokidova , Veronika O. Novikova , Alexander V. Kulikov , Natalia A. Sanina
Nitrosyl complexes of non-heme iron (NICs) are the depot of nitric monoxide (NO) in the body. They nitrosylate heme-containing proteins in the process of decomposition. In this work, we studied the interaction of the thiosulfate complex Na2[Fe2(S2O3)2(NO)4]·4H2O (complex 1), as a promising drug agent, with hemoglobin and cytochrome c. It was found that complex 1 and its decomposition products are adsorbed on the surface of oxyhemoglobin, leading to longer NO generation compared to an aqueous buffer solution. In the system with metHb, the accumulation of the product (nitrosyl hemoglobin) occurs only under anaerobic conditions.
The article also presents experimental data on the nitrosylation of ferro- and ferricytochrome c (cyt c2+ and cyt c3+, respectively) in the presence of complex 1. Cyt c2+ forms the product (NO)cyt c2+, which serves as the “depot” form of NO. This protein has a lesser stabilizing effect on complex 1 compared to hemoglobin. In the system with cyt c3+, nitrosylation of protein occurs during mixing, due to the presence of an oxidizing agent K3[Fe(CN)6].
{"title":"Features of the decomposition of thiosulfate nitrosyl iron complex in the presence of hemoglobin and cytochrome c","authors":"Olesya V. Pokidova , Veronika O. Novikova , Alexander V. Kulikov , Natalia A. Sanina","doi":"10.1016/j.poly.2024.117225","DOIUrl":"10.1016/j.poly.2024.117225","url":null,"abstract":"<div><p>Nitrosyl complexes of non-heme iron (NICs) are the depot of nitric monoxide (NO) in the body. They nitrosylate heme-containing proteins in the process of decomposition. In this work, we studied the interaction of the thiosulfate complex Na<sub>2</sub>[Fe<sub>2</sub>(S<sub>2</sub>O<sub>3</sub>)<sub>2</sub>(NO)<sub>4</sub>]·4H<sub>2</sub>O (complex 1), as a promising drug agent, with hemoglobin and cytochrome <em>c</em>. It was found that complex 1 and its decomposition products are adsorbed on the surface of oxyhemoglobin, leading to longer NO generation compared to an aqueous buffer solution. In the system with metHb, the accumulation of the product (nitrosyl hemoglobin) occurs only under anaerobic conditions.</p><p>The article also presents experimental data on the nitrosylation of ferro- and ferricytochrome c (cyt c<sup>2+</sup> and cyt c<sup>3+</sup>, respectively) in the presence of complex 1. Cyt c<sup>2+</sup> forms the product (NO)cyt c<sup>2+</sup>, which serves as the “depot” form of NO. This protein has a lesser stabilizing effect on complex 1 compared to hemoglobin. In the system with cyt c<sup>3+</sup>, nitrosylation of protein occurs during mixing, due to the presence of an oxidizing agent K<sub>3</sub>[Fe(CN)<sub>6</sub>].</p></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"264 ","pages":"Article 117225"},"PeriodicalIF":2.4,"publicationDate":"2024-09-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142271492","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}
扫码关注我们
求助内容：
应助结果提醒方式：
京公网安备 11010802042870号