Yi-Rong Hsiang, Naorem Jemes Meitei, Gifta Evangeline Henry, Sodio C. N. Hsu, Ya-Fan Lin
In this study, we employed DFT calculations to elucidate the mechanism of NO generation from nitrite via PPh3-induced oxygen atom transfer (OAT) in the unsymmetrical ß-diketiminato copper(II), LCuIIONO. We discovered that the OAT process involves the cooperation of the two PPh3 and follows the mechanism distinct from that of the symmetrical ß-diketiminato analogue. The ΔG‡ value, calculated to be 34.8 kcal/mol, closely matches experimental data. The finding is further supported by analyzing the OAT product yields with varying equivalents of PPh3. The penta-coordinated species 5a, with PPh3 occupying the axial site, forms in the final stage of the OAT process. The isomerization of 5a and the decoordination of the hemilabile pyridyl arm synergistically reduce Cu(II) to Cu(I), facilitating NO-releasing from the Cu(I) centre. These computational results provide valuable insights for the ligand design of PPh3-induced OAT reactions to produce NO in Cu(II) nitrite systems.
{"title":"Mechanistic insights into nitric oxide generation from nitrite via O-atom transfer in the unsymmetrical ꞵ-diketiminato copper(II) nitrite complex","authors":"Yi-Rong Hsiang, Naorem Jemes Meitei, Gifta Evangeline Henry, Sodio C. N. Hsu, Ya-Fan Lin","doi":"10.1039/d4dt02359e","DOIUrl":"https://doi.org/10.1039/d4dt02359e","url":null,"abstract":"In this study, we employed DFT calculations to elucidate the mechanism of NO generation from nitrite via PPh<small><sub>3</sub></small>-induced oxygen atom transfer (OAT) in the unsymmetrical ß-diketiminato copper(II), LCu<small><sup>II</sup></small>ONO. We discovered that the OAT process involves the cooperation of the two PPh<small><sub>3</sub></small> and follows the mechanism distinct from that of the symmetrical ß-diketiminato analogue. The ΔG<small><sup>‡</sup></small> value, calculated to be 34.8 kcal/mol, closely matches experimental data. The finding is further supported by analyzing the OAT product yields with varying equivalents of PPh<small><sub>3</sub></small>. The penta-coordinated species <strong>5a</strong>, with PPh<small><sub>3</sub></small> occupying the axial site, forms in the final stage of the OAT process. The isomerization of <strong>5a</strong> and the decoordination of the hemilabile pyridyl arm synergistically reduce Cu(II) to Cu(I), facilitating NO-releasing from the Cu(I) centre. These computational results provide valuable insights for the ligand design of PPh<small><sub>3</sub></small>-induced OAT reactions to produce NO in Cu(II) nitrite systems.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142452516","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}
Solid-state nuclear magnetic resonance (NMR) spectroscopy serves as a powerful technique for probing local structures. However, the interpretation of NMR signals mainly based on empirical knowledge could lead to unprecise local structural determinations. To address this, density functional theory (DFT)-based theoretical NMR calculations, aided by the experimental three-dimensional continuous rotation electronic diffraction (3D cRED) technique, were performed for ZnxY1-xBO3-0.5x borate oxide ion conductors and provided a fine local structure identification for the experimental 11B NMR spectra of ZnxY1-xBO3-0.5x, acquiring rich information on the multiple experimental 11B NMR signals to the complex boron oxide anions associated with bridging oxygen vacancies and the coexistence of the monoclinic phase (C2/c), hexagonal (P63/m), and trigonal (R32) phases in ZnxY1-xBO3-0.5x. Thanks to the advantages of solid-state NMR in identifying close phases exceeding X-ray/neutron diffraction technique, and the advanced 3D cRED technique that allows for rapid phase identification and structure determination, we provide a fine local structure identification and a more inclusive insight into the coexistence of multiple phases in borate with the same composition, and more importantly, in turn provides guidance for phase and property modulation. The phase modulation in ZnxY1-xBO3-0.5x was carried out in thermodynamic and kinetic, respectively, and eventually realized the modulation of the local structures and the resultant oxide ion conductivity of ZnxY1-xBO3-0.5x. This work provides a theoretical and experimental platform to access the flexible structural assignment of boron oxide anions and therefore offer new guidance and insights into the defect structures and the phase-property modulation of inorganic solid functional materials not only in the borate oxide ion conductors.
{"title":"DFT-based 11B solid state NMR calculations for guiding fine local structure identification and phase-property modulation in ZnxY1-xBO3-0.5x borate oxide ion conductors","authors":"Yuan Gou, Xiaohui Li, Xiaoge Wang, Mengjia Zhang, Jinxiao Zhang, Qiang Li, Xianran Xing, Xiaojun Kuang","doi":"10.1039/d4dt02339k","DOIUrl":"https://doi.org/10.1039/d4dt02339k","url":null,"abstract":"Solid-state nuclear magnetic resonance (NMR) spectroscopy serves as a powerful technique for probing local structures. However, the interpretation of NMR signals mainly based on empirical knowledge could lead to unprecise local structural determinations. To address this, density functional theory (DFT)-based theoretical NMR calculations, aided by the experimental three-dimensional continuous rotation electronic diffraction (3D cRED) technique, were performed for ZnxY1-xBO3-0.5x borate oxide ion conductors and provided a fine local structure identification for the experimental 11B NMR spectra of ZnxY1-xBO3-0.5x, acquiring rich information on the multiple experimental 11B NMR signals to the complex boron oxide anions associated with bridging oxygen vacancies and the coexistence of the monoclinic phase (C2/c), hexagonal (P63/m), and trigonal (R32) phases in ZnxY1-xBO3-0.5x. Thanks to the advantages of solid-state NMR in identifying close phases exceeding X-ray/neutron diffraction technique, and the advanced 3D cRED technique that allows for rapid phase identification and structure determination, we provide a fine local structure identification and a more inclusive insight into the coexistence of multiple phases in borate with the same composition, and more importantly, in turn provides guidance for phase and property modulation. The phase modulation in ZnxY1-xBO3-0.5x was carried out in thermodynamic and kinetic, respectively, and eventually realized the modulation of the local structures and the resultant oxide ion conductivity of ZnxY1-xBO3-0.5x. This work provides a theoretical and experimental platform to access the flexible structural assignment of boron oxide anions and therefore offer new guidance and insights into the defect structures and the phase-property modulation of inorganic solid functional materials not only in the borate oxide ion conductors.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142452517","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}
Kai Uwe Clausen, Xiangzhi Meng, Katrin Reisig, Christian Nather, Thomas Strunskus, Richard Berndt, Felix Tuczek
Deposition of dome-shaped metal-organic complexes on metallic surfaces to produce well-defined single site catalysts is a novel approach combining aspects of homogeneous and heterogeneous catalysis. In order to investigate the bonding of small molecules to such systems, a molybdenum(0) tricarbonyl complex supported by a thiacalix[3]pyridine is synthesized and deposited on Au(111) and Ag(111) surfaces by vacuum evaporation. The resulting mono- and submonolayers are investigated with surface spectroscopy and STM. All of these methods indicate a parallel orientation of the molybdenum complex with respect to the surface. The vibrational properties and frequency shifts of the adsorbed complexes with respect to the bulk are evaluated with the help of conventional IR and IRRA spectroscopy, coupled to DFT calculations. Compared to a similar Mo(0) tricarbonyl complex supported by an azacalixpyridine ligand, the title complex exhibits a higher stability in the bulk and adsorbed to surfaces which goes along with a lower reactivity towards oxygen.
{"title":"Monolayers of a Thiacalix[3]pyridine-Supported Molybdenum(0) Tricarbonyl Complex on Au(111): Characterisation with Surface Spectroscopy and Scanning Tunneling Microscopy","authors":"Kai Uwe Clausen, Xiangzhi Meng, Katrin Reisig, Christian Nather, Thomas Strunskus, Richard Berndt, Felix Tuczek","doi":"10.1039/d4dt02521k","DOIUrl":"https://doi.org/10.1039/d4dt02521k","url":null,"abstract":"Deposition of dome-shaped metal-organic complexes on metallic surfaces to produce well-defined single site catalysts is a novel approach combining aspects of homogeneous and heterogeneous catalysis. In order to investigate the bonding of small molecules to such systems, a molybdenum(0) tricarbonyl complex supported by a thiacalix[3]pyridine is synthesized and deposited on Au(111) and Ag(111) surfaces by vacuum evaporation. The resulting mono- and submonolayers are investigated with surface spectroscopy and STM. All of these methods indicate a parallel orientation of the molybdenum complex with respect to the surface. The vibrational properties and frequency shifts of the adsorbed complexes with respect to the bulk are evaluated with the help of conventional IR and IRRA spectroscopy, coupled to DFT calculations. Compared to a similar Mo(0) tricarbonyl complex supported by an azacalixpyridine ligand, the title complex exhibits a higher stability in the bulk and adsorbed to surfaces which goes along with a lower reactivity towards oxygen.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142452513","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}
Yongsu An, Yongju Lee, Yujing Ji, Young Dok Kim, Hyun Ook Seo, Duk-Young Jung
Nanostructures are critical to improve contact area with an electrolyte and catalytic efficiency for the CO2 reduction reaction (CO2RR). However, their hydrophobicity conflicts with the intended increase in contact area and complicates determination of active contact area. Here, bismuth-nickel (BiNi) micro-nano hierarchical catalysts for CO2RR were studied to understand the effects of electrolyte-catalyst contact area variation with immersion duration in an aqueous electrolyte. The immersed BiNi samples showed about 13.4-fold higher formate production compared to the pristine BiNi sample. The 2-day pre-immersed BiNi sample exhibited Faradaic efficiencies (FE%) of ~80.1% for formate and ~10% for H2 with a current density of 10.2 mA cm-2 at -1.5 V vs. Ag/AgCl. In contrast, the pristine BiNi catalysts exhibited an FE% of ~12.9% for formate and ~76.3% for H2 with a current density of 5.38 mA cm-2. Our experimental results reveal that improved contact between the electrolyte and catalyst surface through pre-immersion can lead to enhanced CO2RR efficiency of formate production in hierarchical BiNi catalysts.
纳米结构对于提高与电解质的接触面积和二氧化碳还原反应（CO2RR）的催化效率至关重要。然而，纳米结构的疏水性与预期增加的接触面积相冲突，并使活性接触面积的确定变得复杂。在此，我们研究了用于 CO2RR 的铋-镍（BiNi）微纳米分层催化剂，以了解电解质-催化剂接触面积随水性电解质浸泡时间变化的影响。与原始 BiNi 样品相比，浸泡过的 BiNi 样品的甲酸盐产量高出约 13.4 倍。与 Ag/AgCl 相比，预浸 2 天的 BiNi 样品在 -1.5 V 电压下的电流密度为 10.2 mA cm-2 时，甲酸的法拉第效率（FE%）约为 80.1%，H2 的法拉第效率（FE%）约为 10%。相比之下，原始 BiNi 催化剂在电流密度为 5.38 mA cm-2 时，甲酸的 FE% 约为 12.9%，H2 的 FE% 约为 76.3%。我们的实验结果表明，通过预浸泡改善电解质与催化剂表面之间的接触可提高分层 BiNi 催化剂生产甲酸盐的 CO2RR 效率。
{"title":"Enhancing CO2 Reduction Efficiency through Electrolyte Immersion in Hierarchical Bismuth-Nickel Catalysts","authors":"Yongsu An, Yongju Lee, Yujing Ji, Young Dok Kim, Hyun Ook Seo, Duk-Young Jung","doi":"10.1039/d4dt02441a","DOIUrl":"https://doi.org/10.1039/d4dt02441a","url":null,"abstract":"Nanostructures are critical to improve contact area with an electrolyte and catalytic efficiency for the CO2 reduction reaction (CO2RR). However, their hydrophobicity conflicts with the intended increase in contact area and complicates determination of active contact area. Here, bismuth-nickel (BiNi) micro-nano hierarchical catalysts for CO2RR were studied to understand the effects of electrolyte-catalyst contact area variation with immersion duration in an aqueous electrolyte. The immersed BiNi samples showed about 13.4-fold higher formate production compared to the pristine BiNi sample. The 2-day pre-immersed BiNi sample exhibited Faradaic efficiencies (FE%) of ~80.1% for formate and ~10% for H2 with a current density of 10.2 mA cm-2 at -1.5 V vs. Ag/AgCl. In contrast, the pristine BiNi catalysts exhibited an FE% of ~12.9% for formate and ~76.3% for H2 with a current density of 5.38 mA cm-2. Our experimental results reveal that improved contact between the electrolyte and catalyst surface through pre-immersion can lead to enhanced CO2RR efficiency of formate production in hierarchical BiNi catalysts.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142452515","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}
Stamatis Passadis, Mark Gray, Tatjana Parac-Vogt, Anastasios Keramidas, Haralampos Miras, Themistoklis Antonios Kabanos
Group (IV) metal oxo clusters represent a unique family of molecular species that are increasingly being utilized in applications ranging from catalysis and materials chemistry to electronics, and sensors. These clusters exhibit distinctive structural features, chemical reactivity, and electronic structure. Nevertheless, their full potential has yet to be fully realized due to the lack of deeper understanding regarding their structure and formation mechanisms, inherent traits, and intricacies in their design, which could ultimately enable significant customization of their properties and overall behaviour. Considering the recently observed reignited interest in the chemistry of Group IV molecular species, the scope of this article is to bring onto the readers the main chemical characteristics of the family of titanium, zirconium, and hafnium-based clusters, their structural features and their potential in future applications.
{"title":"Revitalisation of Group IV metal-oxo clusters: Synthetic approaches, structural motifs and applications","authors":"Stamatis Passadis, Mark Gray, Tatjana Parac-Vogt, Anastasios Keramidas, Haralampos Miras, Themistoklis Antonios Kabanos","doi":"10.1039/d4dt02417f","DOIUrl":"https://doi.org/10.1039/d4dt02417f","url":null,"abstract":"Group (IV) metal oxo clusters represent a unique family of molecular species that are increasingly being utilized in applications ranging from catalysis and materials chemistry to electronics, and sensors. These clusters exhibit distinctive structural features, chemical reactivity, and electronic structure. Nevertheless, their full potential has yet to be fully realized due to the lack of deeper understanding regarding their structure and formation mechanisms, inherent traits, and intricacies in their design, which could ultimately enable significant customization of their properties and overall behaviour. Considering the recently observed reignited interest in the chemistry of Group IV molecular species, the scope of this article is to bring onto the readers the main chemical characteristics of the family of titanium, zirconium, and hafnium-based clusters, their structural features and their potential in future applications.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142486766","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}
Xiaolong Lu, Yan Zhou, Cancan Li, Qi Wang, Bijun Fang, Yi Shi, Ningyi Yuan, Jian Ning Ding
Two-dimension (2D) transition metal carbide Ti3C2TX (MXene) possesses good electrical conductivity, high specific surface areas and metal oxide-like surfaces, which make it ideal for application in supercapacitors with both high energy density and power density. However, similar to other 2D materials, the issue of self-stacking leads to narrower ion transport channels, along with a drastic reduction of active sites, severe limiting the performance of MXene-based electrodes. To address this problem, this work proposes to introduce one-dimension (1D) reduced graphene oxide (rGO) nanoribbons as spacers between MXene nanosheets to construct composite structure for inhibiting the self-stacking. As expected, thanks to the steric effect and high aspect ratio of rGO nanoribbons, the fabricated MXene/rGO hybrid electrode with addition of 5 wt% graphene oxide (GO) exhibits a greatly improved specific capacitance (397.4 F g−1 at 5 mV s−1) and an unparalleled rate capability (with a capacitance retention of 52.9% at 2000 mV s−1). This work significantly shed light to develop MXene-based materials for advanced energy storage devices.
{"title":"Introduce 1D rGO nanoribbons as spacers between 2D MXene for high performance electrode of supercapacitor","authors":"Xiaolong Lu, Yan Zhou, Cancan Li, Qi Wang, Bijun Fang, Yi Shi, Ningyi Yuan, Jian Ning Ding","doi":"10.1039/d4dt02127d","DOIUrl":"https://doi.org/10.1039/d4dt02127d","url":null,"abstract":"Two-dimension (2D) transition metal carbide Ti3C2TX (MXene) possesses good electrical conductivity, high specific surface areas and metal oxide-like surfaces, which make it ideal for application in supercapacitors with both high energy density and power density. However, similar to other 2D materials, the issue of self-stacking leads to narrower ion transport channels, along with a drastic reduction of active sites, severe limiting the performance of MXene-based electrodes. To address this problem, this work proposes to introduce one-dimension (1D) reduced graphene oxide (rGO) nanoribbons as spacers between MXene nanosheets to construct composite structure for inhibiting the self-stacking. As expected, thanks to the steric effect and high aspect ratio of rGO nanoribbons, the fabricated MXene/rGO hybrid electrode with addition of 5 wt% graphene oxide (GO) exhibits a greatly improved specific capacitance (397.4 F g−1 at 5 mV s−1) and an unparalleled rate capability (with a capacitance retention of 52.9% at 2000 mV s−1). This work significantly shed light to develop MXene-based materials for advanced energy storage devices.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142452514","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}
Guan-Lin Lu, Shih-Ting Chiu, Po-Heng Lin, Jérôme Long
We report the synthesis, structures, and magnetic properties of two novel linear tetranuclear complexes with the general formula [Dy₄(Hheb)2(heb)4X₂(MeOH)₄] (X⁻ = NO₃⁻, OAc⁻; H2heb = (E)-N'-(1-(2-hydroxyphenyl)ethylidene)benzohydraz, OAc− = acetate). The rigid ligands (Hheb−/heb2−) incorporates phenoxide groups and bridge the Dy³⁺ ions in an unusual tetranuclear linear assembly. Notably, we demonstrate through magnetic measurements and theoretical calculations how the coordinated anion (X) coordinated at the peripheral Dy³⁺ centers acts as a switch, significantly changing the magnetic anisotropy of the entire complex. This control over magnetic anisotropy through the selection of the coordinated anion offers a promising avenue for tailoring the functionality of Single-Molecule Magnets.
{"title":"Modulating Magnetic Anisotropy in Linear Tetranuclear Dysprosium(III) Complexes via Coordinated Anions","authors":"Guan-Lin Lu, Shih-Ting Chiu, Po-Heng Lin, Jérôme Long","doi":"10.1039/d4dt01949k","DOIUrl":"https://doi.org/10.1039/d4dt01949k","url":null,"abstract":"We report the synthesis, structures, and magnetic properties of two novel linear tetranuclear complexes with the general formula [Dy₄(Hheb)2(heb)4X₂(MeOH)₄] (X⁻ = NO₃⁻, OAc⁻; H2heb = (E)-N'-(1-(2-hydroxyphenyl)ethylidene)benzohydraz, OAc− = acetate). The rigid ligands (Hheb−/heb2−) incorporates phenoxide groups and bridge the Dy³⁺ ions in an unusual tetranuclear linear assembly. Notably, we demonstrate through magnetic measurements and theoretical calculations how the coordinated anion (X) coordinated at the peripheral Dy³⁺ centers acts as a switch, significantly changing the magnetic anisotropy of the entire complex. This control over magnetic anisotropy through the selection of the coordinated anion offers a promising avenue for tailoring the functionality of Single-Molecule Magnets.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142452653","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}
The Thai Nguyen, Huyen-Tran Thi Nguyen, Thu Anh Nguyen, Khuong Quoc Vo, Phuong Hoang Tran
Herein, gold nanoparticle-decorated amorphous carbon (Au/AC) was prepared by reducing chloroauric acid and layering it on amorphous carbon. The characteristics of Au/AC were examined using FT-IR, XRD, TGA, SEM, EDS, and XPS. To assess its catalytic activity, Au/AC was tested in a reaction involving anthranilamide and benzyl alcohol at 110 °C for 24 hours. This reaction yielded various 2-phenylquinazolin-4(3H)-one derivatives in moderate to good yields (44-80%). Furthermore, control experiments were conducted to demonstrate the oxidation and cyclization functions of Au/AC. Noteworthy aspects of this approach included the ease of isolating Au/AC (via recrystallization) and the ability to recycle it.
{"title":"Gold nanoparticle-decorated amorphous carbon for oxidative cyclization of anthranilamide and aryl alcohols.","authors":"The Thai Nguyen, Huyen-Tran Thi Nguyen, Thu Anh Nguyen, Khuong Quoc Vo, Phuong Hoang Tran","doi":"10.1039/d4dt02355b","DOIUrl":"https://doi.org/10.1039/d4dt02355b","url":null,"abstract":"<p><p>Herein, gold nanoparticle-decorated amorphous carbon (Au/AC) was prepared by reducing chloroauric acid and layering it on amorphous carbon. The characteristics of Au/AC were examined using FT-IR, XRD, TGA, SEM, EDS, and XPS. To assess its catalytic activity, Au/AC was tested in a reaction involving anthranilamide and benzyl alcohol at 110 °C for 24 hours. This reaction yielded various 2-phenylquinazolin-4(3<i>H</i>)-one derivatives in moderate to good yields (44-80%). Furthermore, control experiments were conducted to demonstrate the oxidation and cyclization functions of Au/AC. Noteworthy aspects of this approach included the ease of isolating Au/AC (<i>via</i> recrystallization) and the ability to recycle it.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":3.5,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142453610","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}
Photodynamic therapy (PDT), a powerful anticancer approach converting oxygen to ROS for tumor ablation, encounters hurdles like limited spatio-temporal selectivity, and the consequent unnecessary damage to normal tissues. Addressing these challenges, developing controllable Ir(III)-based photosensitizers (PSs) emerges as a promising solution, offering enhanced efficacy and precision in cancer therapy, while propelling the clinical progression of metal-based PSs. Herein, we proposed a series of light-controlled PSs, integrating Ir(III)-based moiety with a light-responsive module, enabling non-invasive "off-on" control of ROS production via efficient energy transfer. The open form (OF) in this dual-state system has better lipid solubility and cellular uptake compared to the closed form (CF), which facilitates targeted delivery of metal drugs. Comprehensive intracellular experiments demonstrated the OF complex's superior cytotoxicity under light irradiation, with the CF complex achieving comparable toxicity post-conversion. Notably, the PSs inhibited 3D tumor growth and modulated intracellular ROS production. These findings underscore the potential of Ir(III)-based dual-state photoswitchable complexes as a platform for non-invasive, reversible ROS control, offering broad prospects in tumor therapy and beyond.
{"title":"Light Switchable Ir(III)-Based Photosensitizers: A Dual-State System for Non-Invasive, Reversible ROS Control in Tumor Therapy","authors":"Zhi-Tong Chu, Na Xu, Yan Su, Hongbao Fang, Zhi Su","doi":"10.1039/d4dt02673j","DOIUrl":"https://doi.org/10.1039/d4dt02673j","url":null,"abstract":"Photodynamic therapy (PDT), a powerful anticancer approach converting oxygen to ROS for tumor ablation, encounters hurdles like limited spatio-temporal selectivity, and the consequent unnecessary damage to normal tissues. Addressing these challenges, developing controllable Ir(III)-based photosensitizers (PSs) emerges as a promising solution, offering enhanced efficacy and precision in cancer therapy, while propelling the clinical progression of metal-based PSs. Herein, we proposed a series of light-controlled PSs, integrating Ir(III)-based moiety with a light-responsive module, enabling non-invasive \"off-on\" control of ROS production via efficient energy transfer. The open form (OF) in this dual-state system has better lipid solubility and cellular uptake compared to the closed form (CF), which facilitates targeted delivery of metal drugs. Comprehensive intracellular experiments demonstrated the OF complex's superior cytotoxicity under light irradiation, with the CF complex achieving comparable toxicity post-conversion. Notably, the PSs inhibited 3D tumor growth and modulated intracellular ROS production. These findings underscore the potential of Ir(III)-based dual-state photoswitchable complexes as a platform for non-invasive, reversible ROS control, offering broad prospects in tumor therapy and beyond.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142452310","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}
Yunhan Huang, Wei Guo, Xinyu Wang, Jingrui Chang, Bo Lu
It is crucial to precisely strike the bacterially infected area and avoid damaging healthy tissue in bacterial infection treatment. Herein, we report an acidity-triggered aggregation antibacterial nanoplatform based on biodegradable mesoporous organic silica nanoparticles (MON NPs). The surface of MON NPs modified with polydopamine (PDA) encapsulated ciprofloxacin (CIP) and methylene blue (MB) and was then further grafted with glycol chitosan to obtain MB/CIP@MON-PDA-GCS NPs (MCMPG NPs). In the bacterial infection environment with acidic characteristics, glycol chitosan (GCS) becomes positively charged. Consequently, the positively charged acidity-triggered GCS enables MCMPG NPs to accumulate on the negatively charged bacterial surfaces in the infected area and not in healthy tissue. The targeted method allows for the precise release of CIP and MB, ensuring the spatial accuracy of photodynamic therapy (PDT) and photothermal therapy (PTT) for effective bacteria-specific treatment.
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