Exploring new large-size crystal available deep-ultraviolet (DUV) transparent nonlinear optical (NLO) crystals is of the current research hotpots. Herein, a novel melting congruently alkali-mixed metal borophosphate, LiNa4B2P3O13 (LNBPO) with the DUV transparency has been successfully designed and synthesized via a high-temperature flux method. The LNBPO crystallizes in the non-centrosymmetric (NCS) and polar orthorhombic space group Pca21. Its structure features an interesting (B2P3O13)∞ chains along c axes. The LNBPO has a moderate SHG response (~0.38 × KDP) and a wide transmission range covering 0.18 to 3.68 μm (which is measured by a [001]-oriented crystal wafer). More importantly, a high-quality single crystal with sizes up to 14×14×12 mm3 has also been grown through the top seeded solution growth method, and their refractive indices were also studied by the minimum deviation angle method. These results show that the shortest phase-matching wavelength of LNBPO is 483 nm. These results indicate LNBPO is potential as a new DUV NLO crystal.
{"title":"Li3Na7B4P6O26: A New Ultraviolet Transparent Congruently-Melting Non-linear Optical Crystal","authors":"Su-Juan Yu, Jiangtao fan, Zhanggui Hu, Yicheng Wu","doi":"10.1039/d4dt01428f","DOIUrl":"https://doi.org/10.1039/d4dt01428f","url":null,"abstract":"Exploring new large-size crystal available deep-ultraviolet (DUV) transparent nonlinear optical (NLO) crystals is of the current research hotpots. Herein, a novel melting congruently alkali-mixed metal borophosphate, LiNa4B2P3O13 (LNBPO) with the DUV transparency has been successfully designed and synthesized via a high-temperature flux method. The LNBPO crystallizes in the non-centrosymmetric (NCS) and polar orthorhombic space group Pca21. Its structure features an interesting (B2P3O13)∞ chains along c axes. The LNBPO has a moderate SHG response (~0.38 × KDP) and a wide transmission range covering 0.18 to 3.68 μm (which is measured by a [001]-oriented crystal wafer). More importantly, a high-quality single crystal with sizes up to 14×14×12 mm3 has also been grown through the top seeded solution growth method, and their refractive indices were also studied by the minimum deviation angle method. These results show that the shortest phase-matching wavelength of LNBPO is 483 nm. These results indicate LNBPO is potential as a new DUV NLO crystal.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-06-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141462906","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}
A novel sheet-like tin-based metal–organic framework exhibited a specific capacity for lithium storage as high as 1033.3 mAh g−1 at 200 mA g−1 with excellent cycling stability. This framework, due to its unique porous structure and multiple lithium storage sites, could better cope with challenges occurring during lithium insertion/extraction than could traditional tin materials.
一种新型片状锡基金属有机框架在 200 mA g-1 电流条件下的锂储存比容量高达 1033.3 mAh g-1，并具有出色的循环稳定性。与传统的锡材料相比，这种框架因其独特的多孔结构和多个储锂位点，能更好地应对锂插入/提取过程中出现的挑战。
{"title":"A sheet-like tin-based metal–organic framework with enhanced lithium storage","authors":"Zikang Ruan, Tingting Jiang, Xianhe Meng, Xiaoyu Hu, Qiaoling Kang, Lijing Yan, Nengjun Yu, Bingyu Liu, Meiqiang Fan, Tingli Ma","doi":"10.1039/d4dt01350f","DOIUrl":"https://doi.org/10.1039/d4dt01350f","url":null,"abstract":"A novel sheet-like tin-based metal–organic framework exhibited a specific capacity for lithium storage as high as 1033.3 mAh g<small><sup>−1</sup></small> at 200 mA g<small><sup>−1</sup></small> with excellent cycling stability. This framework, due to its unique porous structure and multiple lithium storage sites, could better cope with challenges occurring during lithium insertion/extraction than could traditional tin materials.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-06-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141463033","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}
Ovas Ahmad Dar, Athar Adil Hashmi, Abdullah Saad Al-Bogami, Aijaz Ahmad, Mohmmad Younus Wani
Heteroleptic metal complexes containing CuII, CoII, and ZnII, incorporating curcumin and a Schiff base ligand (L), were synthesized and characterized, and their antifungal activity was evaluated. Their antifungal activities were investigated individually and in combination with fluconazole. Utilizing various analytical techniques such as UV-Vis, FT-IR, NMR, ESI-MS, TGA-DTG, elemental analyses, conductance, and magnetic susceptibility measurements, complex C1 ([Cu(Cur)LCl(H2O)]) was assigned a distorted octahedral geometry, while complexes C2 ([Co(Cur)LCl(H2O)]) and C3 ([Zn(Cur)LCl(H2O)]) were assigned octahedral geometries. Among these complexes, C2 exhibited the highest inhibitory activity against both FLC-susceptible and resistant strains of Candida albicans. Furthermore, C2 demonstrated candidicidal activity and synergistic interactions with fluconazole, effectively inhibiting the growth and survival of both FLC-resistant and FLC-sensitive C. albicans strains. The complex displayed a dose-dependent inhibition of drug efflux pumps in FLC-resistant C. albicans strains, indicating its potential to disrupt the cell membrane of these strains. The significant role of membrane efflux transporters in the development of antifungal drug resistance within Candida species has been extensively documented and our findings indicate that complex C2 specifically targets this crucial factor, thereby playing a pivotal role in mitigating drug resistance in C. albicans.
{"title":"Heteroleptic cobalt complex augments antifungal activity with fluconazole and causes membrane disruption in <i>Candida albicans</i>.","authors":"Ovas Ahmad Dar, Athar Adil Hashmi, Abdullah Saad Al-Bogami, Aijaz Ahmad, Mohmmad Younus Wani","doi":"10.1039/d4dt01209g","DOIUrl":"https://doi.org/10.1039/d4dt01209g","url":null,"abstract":"<p><p>Heteroleptic metal complexes containing Cu<sup>II</sup>, Co<sup>II</sup>, and Zn<sup>II</sup>, incorporating curcumin and a Schiff base ligand (L), were synthesized and characterized, and their antifungal activity was evaluated. Their antifungal activities were investigated individually and in combination with fluconazole. Utilizing various analytical techniques such as UV-Vis, FT-IR, NMR, ESI-MS, TGA-DTG, elemental analyses, conductance, and magnetic susceptibility measurements, complex C1 ([Cu(Cur)LCl(H<sub>2</sub>O)]) was assigned a distorted octahedral geometry, while complexes C2 ([Co(Cur)LCl(H<sub>2</sub>O)]) and C3 ([Zn(Cur)LCl(H<sub>2</sub>O)]) were assigned octahedral geometries. Among these complexes, C2 exhibited the highest inhibitory activity against both FLC-susceptible and resistant strains of <i>Candida albicans</i>. Furthermore, C2 demonstrated candidicidal activity and synergistic interactions with fluconazole, effectively inhibiting the growth and survival of both FLC-resistant and FLC-sensitive <i>C. albicans</i> strains. The complex displayed a dose-dependent inhibition of drug efflux pumps in FLC-resistant <i>C. albicans</i> strains, indicating its potential to disrupt the cell membrane of these strains. The significant role of membrane efflux transporters in the development of antifungal drug resistance within <i>Candida</i> species has been extensively documented and our findings indicate that complex C2 specifically targets this crucial factor, thereby playing a pivotal role in mitigating drug resistance in <i>C. albicans</i>.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":3.5,"publicationDate":"2024-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141453770","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}
Yingying Kong, Hongshan Wang, Wang Zhao, Qi Sun, Junjie Li, Shilie Pan
Hg-based compounds show abundant structure diversity and distinguished properties. Herein, a new phase transition compound CsHg2I5 was reported. The high-temperature phase β-CsHg2I5 with rare [Hg2I5] dimers was synthesized by the flux method at 573 K, and it shows a reversible phase transition at a low temperature of ~ 100 K to form low-temperature phase α-CsHg2I5. The two phases crystallize in the same P21/c space group, with different crystal structures. β-CsHg2I5 is composed of rare [Hg2I5] dimers, [CsI11] polyhedral units, while [Hg4I11], [CsI10] units for α-CsHg2I5. The experimental band gap of β-CsHg2I5 was measured to 2.58 eV. Owing to the presence of [Hg2I5]∞ pseudo-layers, β-CsHg2I5 exhibits a large optical anisotropy with a calculated birefringence of 0.132@1064 nm. Meanwhile, β-CsHg2I5 is a congruent compound and the congruent point is ~ 481 K. Theoretical calculations indicate that the rare [Hg2I5] dimer is a nonlinear active unit, which can be used as a new fundamental building block for the design of advanced nonlinear optical materials. Moreover, a CsI-HgI2 pseudo-binary diagram was drawn. The results enrich the structural diversity of the Hg-based halides and give some insights into the development of new functional materials based on the rare [Hg2I5] dimers.
汞基化合物具有丰富的结构多样性和独特的性质。本文报告了一种新的相变化合物 CsHg2I5。在 573 K 温度下，通过通量法合成了具有稀有[Hg2I5]二聚体的高温相 β-CsHg2I5，并在约 100 K 的低温下发生可逆相变，形成低温相 α-CsHg2I5。这两种相在相同的 P21/c 空间群中结晶，具有不同的晶体结构。β-CsHg2I5由罕见的[Hg2I5]二聚体和[CsI11]多面体单元组成，而α-CsHg2I5则由[Hg4I11]、[CsI10]单元组成。据测量，β-CsHg2I5 的实验带隙为 2.58 eV。由于[Hg2I5]∞伪层的存在，β-CsHg2I5 表现出很大的光学各向异性，计算得出的双折射为 0.132@1064 nm。理论计算表明，稀有的[Hg2I5]二聚体是一种非线性活性单元，可作为设计先进非线性光学材料的新基础构件。此外，还绘制了 CsI-HgI2 伪二元图。这些结果丰富了汞基卤化物的结构多样性，并为基于稀有[Hg2I5]二聚体的新型功能材料的开发提供了一些启示。
{"title":"β-CsHg2I5, a compound with rare [Hg2I5] dimers and large optical anisotropy","authors":"Yingying Kong, Hongshan Wang, Wang Zhao, Qi Sun, Junjie Li, Shilie Pan","doi":"10.1039/d4dt01536c","DOIUrl":"https://doi.org/10.1039/d4dt01536c","url":null,"abstract":"Hg-based compounds show abundant structure diversity and distinguished properties. Herein, a new phase transition compound CsHg2I5 was reported. The high-temperature phase β-CsHg2I5 with rare [Hg2I5] dimers was synthesized by the flux method at 573 K, and it shows a reversible phase transition at a low temperature of ~ 100 K to form low-temperature phase α-CsHg2I5. The two phases crystallize in the same P21/c space group, with different crystal structures. β-CsHg2I5 is composed of rare [Hg2I5] dimers, [CsI11] polyhedral units, while [Hg4I11], [CsI10] units for α-CsHg2I5. The experimental band gap of β-CsHg2I5 was measured to 2.58 eV. Owing to the presence of [Hg2I5]∞ pseudo-layers, β-CsHg2I5 exhibits a large optical anisotropy with a calculated birefringence of 0.132@1064 nm. Meanwhile, β-CsHg2I5 is a congruent compound and the congruent point is ~ 481 K. Theoretical calculations indicate that the rare [Hg2I5] dimer is a nonlinear active unit, which can be used as a new fundamental building block for the design of advanced nonlinear optical materials. Moreover, a CsI-HgI2 pseudo-binary diagram was drawn. The results enrich the structural diversity of the Hg-based halides and give some insights into the development of new functional materials based on the rare [Hg2I5] dimers.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141461722","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}
Maintaining a good specific energy without losing cycle stability is the focus of the supercapacitor field. In this study, carbon nanofibers including europium oxide nanoparticles (CNF/Eu2O3) have been synthesized in the presence of thiourea via a simple approach and applied for the first time as the electrode for SCs. The CNF/Eu2O3-1 electrode with nitrogen and sulfur heteroatoms doped possessed a favorable specific capacitance of 183.2 F/g, a specific energy of 9.15 Wh/kg, and an excellent cycle ability of 94.8% even after 10 000 cycles at 1 A/g. Such excellent performance is ascribed to the surface functionalities, high surface area, and good interaction of Eu2O3 with CNF. This strategy will provide guidance for other rare element-based electrodes in the field of energy storage.
{"title":"In-situ synthesis of europium oxide (Eu2O3) nanoparticles in heteroatom doped carbon nanofibers for boosting the cycle stability of the supercapacitors","authors":"HAMİDE AYDIN, BURCU ÜSTÜN, Ümran Kurtan, Utkan Şahintürk, Selcan Karakuş","doi":"10.1039/d4dt01297f","DOIUrl":"https://doi.org/10.1039/d4dt01297f","url":null,"abstract":"Maintaining a good specific energy without losing cycle stability is the focus of the supercapacitor field. In this study, carbon nanofibers including europium oxide nanoparticles (CNF/Eu2O3) have been synthesized in the presence of thiourea via a simple approach and applied for the first time as the electrode for SCs. The CNF/Eu2O3-1 electrode with nitrogen and sulfur heteroatoms doped possessed a favorable specific capacitance of 183.2 F/g, a specific energy of 9.15 Wh/kg, and an excellent cycle ability of 94.8% even after 10 000 cycles at 1 A/g. Such excellent performance is ascribed to the surface functionalities, high surface area, and good interaction of Eu2O3 with CNF. This strategy will provide guidance for other rare element-based electrodes in the field of energy storage.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141461585","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}
Constantin Vitre, Yann Le Gal, Antoine Vacher, Thierry Roisnel, Dominique Lorcy, Sofia Santana, Miguel Prudêncio, Teresa Pinheiro, Fernanda M. Marques
Monoanionic gold bis(dithiolene) complexes were recently shown to display activity against ovarian cancer cells, Gram-positive bacteria, Candida strains and the rodent malaria parasite, P. berghei. To date, only monoanionic gold(III) bis(dithiolene) complexes with a thiazoline backbone substituted with small alkyl chains have been evaluated for biomedical applications. We now analyzed the influence of the length and the hydrophobicity vs. hydrophilicity of these complexes’ alkyl chain on their anticancer and antiplasmodial properties. Isomer analogues of these monoanionic gold(III) bis(dithiolene) complexes, this time with a thiazole backbone, were also investigated in order to assess the influence of the nature of the heterocyclic ligand on their overall chemical and biological properties. In this report we present the total synthesis of four novel monoanionic gold(III) bis(dithiolene) complexes with a long alkyl chain and a polyoxygenated (PEG) chain aiming to improve their solubility and biological properties. Our results showed that the complexes with PEG chain showed promising anticancer and antiplasmodial activities beside improved solubility a key parameter in drug discovery and development.
{"title":"Structure-activity relationship of anticancer and antiplasmodial gold bis(dithiolene) complexes","authors":"Constantin Vitre, Yann Le Gal, Antoine Vacher, Thierry Roisnel, Dominique Lorcy, Sofia Santana, Miguel Prudêncio, Teresa Pinheiro, Fernanda M. Marques","doi":"10.1039/d4dt01458h","DOIUrl":"https://doi.org/10.1039/d4dt01458h","url":null,"abstract":"Monoanionic gold bis(dithiolene) complexes were recently shown to display activity against ovarian cancer cells, Gram-positive bacteria, Candida strains and the rodent malaria parasite, P. berghei. To date, only monoanionic gold(III) bis(dithiolene) complexes with a thiazoline backbone substituted with small alkyl chains have been evaluated for biomedical applications. We now analyzed the influence of the length and the hydrophobicity vs. hydrophilicity of these complexes’ alkyl chain on their anticancer and antiplasmodial properties. Isomer analogues of these monoanionic gold(III) bis(dithiolene) complexes, this time with a thiazole backbone, were also investigated in order to assess the influence of the nature of the heterocyclic ligand on their overall chemical and biological properties. In this report we present the total synthesis of four novel monoanionic gold(III) bis(dithiolene) complexes with a long alkyl chain and a polyoxygenated (PEG) chain aiming to improve their solubility and biological properties. Our results showed that the complexes with PEG chain showed promising anticancer and antiplasmodial activities beside improved solubility a key parameter in drug discovery and development.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141452847","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}
Lanthanide metal-organic frameworks (Ln-MOFs) have unique advantages in sensing due to their excellent optical properties. In this study, we synthesized a dicarboxylic acid ligand with amide groups and successfully synthesized a novel two-dimensional (2D) MOF with the molecular formula C42H31EuN4O10 (Eu-MOF) by solvothermal method. Single-crystal X-ray diffraction showed that amide groups are exposed on the outside of the two-dimensional coordination layer, with the possibility of recognizing specific molecules through hydrogen bonding interactions. The ligand's "antenna effect" enables Eu-MOF to emit a strong luminescence characterized by the "f-f" transition. Further studies have revealed that Eu-MOF could be used as a bifunctional fluorescent probe for the selective detection of benzaldehyde and Fe3+. The sensing mechanism has been analyzed in detail through powder X-ray diffraction (PXRD) analysis, UV-vis spectroscopy, fluorescence lifetime measurement, and density functional (DFT) theory calculation. This design and research can provide a reference for subsequent related work.
镧系元素金属有机框架（Ln-MOFs）因其优异的光学特性而在传感领域具有独特的优势。在本研究中，我们合成了带有酰胺基团的二羧酸配体，并通过溶热法成功合成了分子式为 C42H31EuN4O10 的新型二维（2D）MOF（Eu-MOF）。单晶 X 射线衍射显示，酰胺基团暴露在二维配位层的外部，可通过氢键相互作用识别特定分子。配体的 "天线效应 "使 Eu-MOF 能够发出以 "f-f "转变为特征的强荧光。进一步的研究表明，Eu-MOF 可用作选择性检测苯甲醛和 Fe3+ 的双功能荧光探针。通过粉末 X 射线衍射（PXRD）分析、紫外-可见光谱分析、荧光寿命测量和密度泛函（DFT）理论计算，对其传感机制进行了详细分析。该设计和研究可为后续相关工作提供参考。
{"title":"A Novel 2D Eu-MOF as a Dual-Functional Fluorescence Sensor for Detection of Benzaldehyde and Fe3+","authors":"Wei-Sheng Liu, xiaole wang","doi":"10.1039/d4dt01512f","DOIUrl":"https://doi.org/10.1039/d4dt01512f","url":null,"abstract":"Lanthanide metal-organic frameworks (Ln-MOFs) have unique advantages in sensing due to their excellent optical properties. In this study, we synthesized a dicarboxylic acid ligand with amide groups and successfully synthesized a novel two-dimensional (2D) MOF with the molecular formula C42H31EuN4O10 (Eu-MOF) by solvothermal method. Single-crystal X-ray diffraction showed that amide groups are exposed on the outside of the two-dimensional coordination layer, with the possibility of recognizing specific molecules through hydrogen bonding interactions. The ligand's \"antenna effect\" enables Eu-MOF to emit a strong luminescence characterized by the \"f-f\" transition. Further studies have revealed that Eu-MOF could be used as a bifunctional fluorescent probe for the selective detection of benzaldehyde and Fe3+. The sensing mechanism has been analyzed in detail through powder X-ray diffraction (PXRD) analysis, UV-vis spectroscopy, fluorescence lifetime measurement, and density functional (DFT) theory calculation. This design and research can provide a reference for subsequent related work.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141452973","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}
Ana Maria Da Costa Ferreira, Eduardo Guimarães Vieira, Raphael EF de Paiva, Rodrigo Miguel, Felipe Franco de Melo Bagatellib Franco de Melo Bagatelli, Carla Columbano Oliveira, Floriana Tuna, Ana A Oliveira
In this work, a polyhedral silsesquioxane (POSS) was used as an engineered drug delivery system for two oxindolimine-copper(II) anticancer complexes, [Cu(isaepy)]+ and [Cu(isapn)]+. The interest in hybrid POSS comes from the necessity of developing materials that can act as adjuvant to improve the cytotoxicity of non-soluble metallodrugs. Functionalization of POSS with a triazole ligand (POSS-atzac) permitted the anchorage of such copper complexes, producing hybrid materials with efficient cytotoxic effects. Structural and morphological characterization of these copper-POSS systems were performed by using different techniques (IR, NMR, thermogravimetric analysis). A combination of continuous-wave (CW) and pulsed EPR (HYSCORE) spectroscopies conducted at X-band have enabled the complete characterization of the coordination environment of the copper ion in the POSS-atzac matrix. Additionally, the cytotoxic effects of the loaded materials, [Cu(isapn)]@POSS-atzac and [Cu(isaepy)]@POSS-atzac, were assessed toward melanomas (SK-MEL), in comparison to non-tumorigenic cells (Fibroblast P4). Evaluation of their nuclease activity or ability to cleavage DNA indicated concentrations as low as 0.6 µg/mL, while complete DNA fragmentation was observed at 25 µg/mL. By using adequate scavengers, investigations on active intermediates responsible for their cytotoxicity were performed, both in the absence and in the presence of ascorbate as a reducing agent. Based on the observed selective cytotoxicity of these materials toward melanomas, investigations on the reactivity of complexes and corresponding POSS-materials with melanin, a molecule that contributes to melanoma resistance to chemotherapy, was carried out. Results indicated a main role of binuclear copper species, formed at the surface of the silica matrix, in the observed reactivity and selectivity.
在这项研究中，一种多面体硅倍半氧烷（POSS）被用作两种氧化吲哚-铜（II）抗癌复合物 [Cu(isaepy)]+ 和 [Cu(isapn)]+的工程化给药系统。人们之所以对混合型 POSS 感兴趣，是因为有必要开发可作为佐剂的材料，以提高非溶性金属药物的细胞毒性。用三唑配体（POSS-atzac）对 POSS 进行功能化处理，可以锚定此类铜复合物，从而产生具有高效细胞毒性作用的混合材料。利用不同的技术（红外、核磁共振、热重分析）对这些铜-POSS 系统进行了结构和形态表征。在 X 波段结合使用连续波（CW）和脉冲 EPR（HYSCORE）光谱对 POSS-atzac 基质中铜离子的配位环境进行了完整的表征。此外，还评估了负载材料 [Cu(isapn)]@POSS-atzac 和 [Cu(isaepy)]@POSS-atzac 对黑色素瘤（SK-MEL）和非致瘤细胞（成纤维细胞 P4）的细胞毒性作用。对其核酸酶活性或裂解 DNA 能力的评估表明，其浓度低至 0.6 微克/毫升，而在 25 微克/毫升时可观察到完全的 DNA 断裂。通过使用适当的清除剂，在没有抗坏血酸作为还原剂和有抗坏血酸作为还原剂的情况下，对造成其细胞毒性的活性中间体进行了研究。根据观察到的这些材料对黑色素瘤的选择性细胞毒性，研究人员对复合物和相应的 POSS 材料与黑色素（一种导致黑色素瘤对化疗产生抗药性的分子）的反应性进行了调查。结果表明，在二氧化硅基质表面形成的双核铜物种在观察到的反应性和选择性中发挥了主要作用。
{"title":"An engineered POSS drug delivery system for copper(II) anticancer metallodrugs in selective application toward melanoma cells","authors":"Ana Maria Da Costa Ferreira, Eduardo Guimarães Vieira, Raphael EF de Paiva, Rodrigo Miguel, Felipe Franco de Melo Bagatellib Franco de Melo Bagatelli, Carla Columbano Oliveira, Floriana Tuna, Ana A Oliveira","doi":"10.1039/d4dt00535j","DOIUrl":"https://doi.org/10.1039/d4dt00535j","url":null,"abstract":"In this work, a polyhedral silsesquioxane (POSS) was used as an engineered drug delivery system for two oxindolimine-copper(II) anticancer complexes, [Cu(isaepy)]+ and [Cu(isapn)]+. The interest in hybrid POSS comes from the necessity of developing materials that can act as adjuvant to improve the cytotoxicity of non-soluble metallodrugs. Functionalization of POSS with a triazole ligand (POSS-atzac) permitted the anchorage of such copper complexes, producing hybrid materials with efficient cytotoxic effects. Structural and morphological characterization of these copper-POSS systems were performed by using different techniques (IR, NMR, thermogravimetric analysis). A combination of continuous-wave (CW) and pulsed EPR (HYSCORE) spectroscopies conducted at X-band have enabled the complete characterization of the coordination environment of the copper ion in the POSS-atzac matrix. Additionally, the cytotoxic effects of the loaded materials, [Cu(isapn)]@POSS-atzac and [Cu(isaepy)]@POSS-atzac, were assessed toward melanomas (SK-MEL), in comparison to non-tumorigenic cells (Fibroblast P4). Evaluation of their nuclease activity or ability to cleavage DNA indicated concentrations as low as 0.6 µg/mL, while complete DNA fragmentation was observed at 25 µg/mL. By using adequate scavengers, investigations on active intermediates responsible for their cytotoxicity were performed, both in the absence and in the presence of ascorbate as a reducing agent. Based on the observed selective cytotoxicity of these materials toward melanomas, investigations on the reactivity of complexes and corresponding POSS-materials with melanin, a molecule that contributes to melanoma resistance to chemotherapy, was carried out. Results indicated a main role of binuclear copper species, formed at the surface of the silica matrix, in the observed reactivity and selectivity.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141461668","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}
Yuqi Wan, Ke gao, Zhi-Quan Pan, Tianshuo Zhao, Qingrong Cheng
The residue of antibiotics and various pollutants has led to urgent issue in environmental pollution. In this study, we constructed an S-scheme P-TiO2@Zn-MOF heterojunction by self-assembling phosphonate-based MOFs on mesoporous phosphate-TiO2 beads. Compared to the monomers, P-TiO2@Zn-MOF2.0 heterojunction exhibits significantly higher photocatalytic activity for the photo-oxidative degradation of ciprofloxacin (97.2% in 60 min) and tetracyclic (TC) (94.5% in 100 min), and the photo-reduction of Cr(VI) (92.7% in 60 min) under simulated sunlight. Experimental results and calculations revealed the effective separation and transfer of photogenerated carriers at the P-TiO2@Zn-MOF2.0 S-scheme heterojunction interface, enabling formation of highly active superoxide and hydroxyl radicals. Furthermore, the hybrid maintained excellent Cr(VI) photoreduction performance after recycling tests in actual electroplating industry wastewater at a strongly acidic pH.
抗生素和各种污染物的残留已成为亟待解决的环境污染问题。在这项研究中，我们通过在介孔磷酸盐-二氧化钛珠上自组装膦酸盐基 MOFs，构建了一种 S 型 P-TiO2@Zn-MOF 异质结。与单体相比，P-TiO2@Zn-MOF2.0 异质结在模拟阳光下光氧化降解环丙沙星（60 分钟内 97.2%）和四环素（TC）（100 分钟内 94.5%）以及光还原六价铬（60 分钟内 92.7%）方面表现出明显更高的光催化活性。实验结果和计算显示，光生载流子在 P-TiO2@Zn-MOF2.0 S 型异质结界面上得到了有效分离和转移，从而形成了高活性的超氧化物和羟基自由基。此外，在pH值呈强酸性的实际电镀工业废水中进行循环测试后，这种混合体仍能保持出色的六（六）铬光还原性能。
{"title":"Constructing TiO2@MOF S-scheme heterojunctions for enhanced photocatalytic degradation of antibiotic and Cr(VI) photoreduction","authors":"Yuqi Wan, Ke gao, Zhi-Quan Pan, Tianshuo Zhao, Qingrong Cheng","doi":"10.1039/d4dt00831f","DOIUrl":"https://doi.org/10.1039/d4dt00831f","url":null,"abstract":"The residue of antibiotics and various pollutants has led to urgent issue in environmental pollution. In this study, we constructed an S-scheme P-TiO2@Zn-MOF heterojunction by self-assembling phosphonate-based MOFs on mesoporous phosphate-TiO2 beads. Compared to the monomers, P-TiO2@Zn-MOF2.0 heterojunction exhibits significantly higher photocatalytic activity for the photo-oxidative degradation of ciprofloxacin (97.2% in 60 min) and tetracyclic (TC) (94.5% in 100 min), and the photo-reduction of Cr(VI) (92.7% in 60 min) under simulated sunlight. Experimental results and calculations revealed the effective separation and transfer of photogenerated carriers at the P-TiO2@Zn-MOF2.0 S-scheme heterojunction interface, enabling formation of highly active superoxide and hydroxyl radicals. Furthermore, the hybrid maintained excellent Cr(VI) photoreduction performance after recycling tests in actual electroplating industry wastewater at a strongly acidic pH.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141452833","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}
Vera Khrizanforova, Robert R. Fayzullin, Vladimir Morozov, Yulia H Budnikova
Herein, we report the record-breaking six-electron reduction of di-iso-propylphenyl-bis-iminoacenaphthene (dpp-bian) involving protons under chemical and electrochemical reduction conditions. Using the dpp-bian-H2 compound as a starting reagent, its mono- and trisodium salts were obtained. A voltammetric study showed that the trinuclear sodium salt can accept an additional seventh electron upon electrochemical reduction.
{"title":"Proton-assisted seven-electron acceptor properties of di-iso-propylphenyl-bis-iminoacenaphthene","authors":"Vera Khrizanforova, Robert R. Fayzullin, Vladimir Morozov, Yulia H Budnikova","doi":"10.1039/d4dt01039f","DOIUrl":"https://doi.org/10.1039/d4dt01039f","url":null,"abstract":"Herein, we report the record-breaking six-electron reduction of di-iso-propylphenyl-bis-iminoacenaphthene (dpp-bian) involving protons under chemical and electrochemical reduction conditions. Using the dpp-bian-H2 compound as a starting reagent, its mono- and trisodium salts were obtained. A voltammetric study showed that the trinuclear sodium salt can accept an additional seventh electron upon electrochemical reduction.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141452977","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}
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