Xu Li, Hongwei Pan, Guijie Yin, Yang Xiang, Xitao Lin, Zhu Liu, Yinzhu Jiang, Qun Hui, Xuan Zhang, Maowen Xu
The simultaneous realization of high safety and high electrochemical performance of quasi-solid-state electrolytes (QSSEs) has been challenging to accomplish since decades. Herein, a flame retardant-encapsulated metal–organic framework (MOFs) was incorporated as a filler into a poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) QSSE, addressing its safety concerns and enhancing the electrochemical performance. Notably, the mechanical properties and electrochemical performance of PVDF-HFP QSSE were improved by the introduction of UiO-66 fillers. As the flame retardant was trapped in the channels of MOFs, this approach effectively prevented side reactions arising from it. Moreover, the introduction of the flame retardant hexachlorocyclotriphosphazene (HCCP) modulated the electronic distribution characteristics within the channels of UiO-66 and reduced the zeta potential of UiO-66, thereby further enhancing the performance of the QSSE. The resultant QSSEs (PHU-QSSE) remained intact at 180 °C and exhibited excellent self-quenching characteristics. The flame retardant-encapsulated UiO-66 filler boosted the ionic conductivity of the PVDF-HFP electrolyte from 3.1 × 10−4 S cm−1 to 6.9 × 10−4 S cm−1 and elevated the Li+ transfer number of the electrolyte from 0.27 to 0.59. At a current density of 0.5 mA cm−2, a lithium symmetric battery based on PHU-QSSE maintained a stable cycling for over 2500 hours, 15 times longer than those of PVDF-HFP electrolytes. When PHU-QSSE was paired with a LiFePO4 cathode, it showed a high capacity of 156 mA h g−1 at 1 C, exhibiting outstanding rate performance and maintaining 84.6% capacity after 500 cycles. This work not only provides a new pathway to solve the dilemma between safety and high electrochemical performance of QSSEs but also proves that the modification of MOF channels could provide more possibilities for future solid battery designs.
{"title":"Achieving multifunctional MOF/polymer-based quasi-solid electrolytes via functional molecule encapsulation in MOFs","authors":"Xu Li, Hongwei Pan, Guijie Yin, Yang Xiang, Xitao Lin, Zhu Liu, Yinzhu Jiang, Qun Hui, Xuan Zhang, Maowen Xu","doi":"10.1039/d5qi00052a","DOIUrl":"https://doi.org/10.1039/d5qi00052a","url":null,"abstract":"The simultaneous realization of high safety and high electrochemical performance of quasi-solid-state electrolytes (QSSEs) has been challenging to accomplish since decades. Herein, a flame retardant-encapsulated metal–organic framework (MOFs) was incorporated as a filler into a poly(vinylidene fluoride-<em>co</em>-hexafluoropropylene) (PVDF-HFP) QSSE, addressing its safety concerns and enhancing the electrochemical performance. Notably, the mechanical properties and electrochemical performance of PVDF-HFP QSSE were improved by the introduction of UiO-66 fillers. As the flame retardant was trapped in the channels of MOFs, this approach effectively prevented side reactions arising from it. Moreover, the introduction of the flame retardant hexachlorocyclotriphosphazene (HCCP) modulated the electronic distribution characteristics within the channels of UiO-66 and reduced the zeta potential of UiO-66, thereby further enhancing the performance of the QSSE. The resultant QSSEs (PHU-QSSE) remained intact at 180 °C and exhibited excellent self-quenching characteristics. The flame retardant-encapsulated UiO-66 filler boosted the ionic conductivity of the PVDF-HFP electrolyte from 3.1 × 10<small><sup>−4</sup></small> S cm<small><sup>−1</sup></small> to 6.9 × 10<small><sup>−4</sup></small> S cm<small><sup>−1</sup></small> and elevated the Li<small><sup>+</sup></small> transfer number of the electrolyte from 0.27 to 0.59. At a current density of 0.5 mA cm<small><sup>−2</sup></small>, a lithium symmetric battery based on PHU-QSSE maintained a stable cycling for over 2500 hours, 15 times longer than those of PVDF-HFP electrolytes. When PHU-QSSE was paired with a LiFePO<small><sub>4</sub></small> cathode, it showed a high capacity of 156 mA h g<small><sup>−1</sup></small> at 1 C, exhibiting outstanding rate performance and maintaining 84.6% capacity after 500 cycles. This work not only provides a new pathway to solve the dilemma between safety and high electrochemical performance of QSSEs but also proves that the modification of MOF channels could provide more possibilities for future solid battery designs.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"28 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143797724","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Since their introduction in the early 20th century, scintillators have become essential components in a wide range of applications, including high-energy physics, medical imaging, cryptography, and nuclear detection. As the demand for high-performance scintillating materials continues to rise in particle physics experiments and medical imaging technologies, the development of novel scintillator materials has become a critical area of research. In recent years, advancements in scintillators have flourished, presenting new opportunities for practical applications. This review presents a comprehensive overview of standard performance parameters for scintillators, aimed at enhancing understanding and evaluation of their advancements. We highlight the latest developments in scintillator materials, emphasizing research from the past three years and focusing on their intrinsic properties. Our analysis includes perovskite scintillators, nanoclusters scintillators as well as those doped with rare-earth ions, organic scintillators and the scintillators along with specialized structures. This classification offers a scientific perspective on the overall progress in the field of scintillators, and several forward-looking insights into the future development of scintillators were proposed, employing a problem-oriented approach. Eventually, we discuss the challenges encountered in scintillator development, explore future prospects, and provide valuable insights for improving their performances and expanding their applications.
{"title":"Materials Innovation in Scintillators for X-ray Detection","authors":"Kuilin Li, Wenqing Li, Qi Nie, Xiao Luo","doi":"10.1039/d5qi00671f","DOIUrl":"https://doi.org/10.1039/d5qi00671f","url":null,"abstract":"Since their introduction in the early 20th century, scintillators have become essential components in a wide range of applications, including high-energy physics, medical imaging, cryptography, and nuclear detection. As the demand for high-performance scintillating materials continues to rise in particle physics experiments and medical imaging technologies, the development of novel scintillator materials has become a critical area of research. In recent years, advancements in scintillators have flourished, presenting new opportunities for practical applications. This review presents a comprehensive overview of standard performance parameters for scintillators, aimed at enhancing understanding and evaluation of their advancements. We highlight the latest developments in scintillator materials, emphasizing research from the past three years and focusing on their intrinsic properties. Our analysis includes perovskite scintillators, nanoclusters scintillators as well as those doped with rare-earth ions, organic scintillators and the scintillators along with specialized structures. This classification offers a scientific perspective on the overall progress in the field of scintillators, and several forward-looking insights into the future development of scintillators were proposed, employing a problem-oriented approach. Eventually, we discuss the challenges encountered in scintillator development, explore future prospects, and provide valuable insights for improving their performances and expanding their applications.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"59 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143797852","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Han Wu, Lincong Shu, Sihan Yan, Shulin Sha, Qing-Hua Zhang, Zeng Liu, Shan Li, Weihua Tang, Yuehui Wang, Jiaying Shen, Zhenping Wu, Kun Lin, Qiang Li, Jun Miao, Xianran Xing
Wide bandgap semiconductors have emerged as a valuable class of deep-ultraviolet sensitive materials, showing great potential for next-generation integrated devices. Yet, to achieve a high performance of deep-ultraviolet detector without complicated designs at low supply voltage and weak light intensity has proven challenging. Herein, we design a new way to fabricate an ultrasensitive vertical-structured Ga2O3 photodetector with epitaxial oxygen-vacancy-rich In2O3 as the bottom conductive layer, realizing the detection to a rare weak deep UV light intensity (0.1 μW/cm²) at a voltage below 5 V, and demonstrating a surge in responsivity (36 A/W at -4.8 V and 2.2 A/W at 4.8 V) and detectivity (2 × 1013 Jones at -4.8 V and 4.4 × 1013 Jones at 4.8 V) with ultrafast response of 0.64 μs/47.68 μs (rise/decay). Ultrathin (15 nm) Ga2O3 layer and sophisticated band engineering, combined with suppressed dark current through the interfacial oxygen vacancies on In2O3 layer, enhance the detection performance of the detector at low supply voltage and extremely low light intensity. These results provide a path towards highly sensitive, low-power-consumption and highly-integrated deep-ultraviolet detection, beyond conventional ones.
{"title":"Interfacial defect engineering to boost deep-ultraviolet photodetection based on a wide bandgap semiconductor heterostructure","authors":"Han Wu, Lincong Shu, Sihan Yan, Shulin Sha, Qing-Hua Zhang, Zeng Liu, Shan Li, Weihua Tang, Yuehui Wang, Jiaying Shen, Zhenping Wu, Kun Lin, Qiang Li, Jun Miao, Xianran Xing","doi":"10.1039/d5qi00691k","DOIUrl":"https://doi.org/10.1039/d5qi00691k","url":null,"abstract":"Wide bandgap semiconductors have emerged as a valuable class of deep-ultraviolet sensitive materials, showing great potential for next-generation integrated devices. Yet, to achieve a high performance of deep-ultraviolet detector without complicated designs at low supply voltage and weak light intensity has proven challenging. Herein, we design a new way to fabricate an ultrasensitive vertical-structured Ga2O3 photodetector with epitaxial oxygen-vacancy-rich In2O3 as the bottom conductive layer, realizing the detection to a rare weak deep UV light intensity (0.1 μW/cm²) at a voltage below 5 V, and demonstrating a surge in responsivity (36 A/W at -4.8 V and 2.2 A/W at 4.8 V) and detectivity (2 × 1013 Jones at -4.8 V and 4.4 × 1013 Jones at 4.8 V) with ultrafast response of 0.64 μs/47.68 μs (rise/decay). Ultrathin (15 nm) Ga2O3 layer and sophisticated band engineering, combined with suppressed dark current through the interfacial oxygen vacancies on In2O3 layer, enhance the detection performance of the detector at low supply voltage and extremely low light intensity. These results provide a path towards highly sensitive, low-power-consumption and highly-integrated deep-ultraviolet detection, beyond conventional ones.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"87 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143797853","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Gang Liu, Jun Zheng, Xianqiang Huang, Shiqi Fu, Shiqi Xi, Yalin Zhang, Zhen Li, Fei Yu, Yifa Chen
One-pot direct conversion of cheap and abundant fructose to 2,5-diformylfuran (DFF) is highly sought to achieve hundreds-fold value-increase and high atomic economy yet is still challenging by the lack of suitable catalysts with cascade conversion ability. In this work, we have developed a kind of porous hybrid catalyst (i.e. PMo10V2@2Br-PIL) based on the assembly of polyoxometalates and porous polyionic liquids that can be applied in one-pot conversion of fructose to DFF. The integration of PMo10V2 with 2Br-PIL can impart both Brönsted acid sites and oxidation sites in the porous structure that enables the one-pot cascade conversion. As a result, PMo10V2@2Br-PIL demonstrates remarkable DFF yield (95% yield), satisfying stability, recyclability and scale-up production ability (≈12.3 g in a batch experiment), demonstrating great potential in the industrial production of DFF from fructose. Theoretical calculations reveal the synergistic effect of Brönsted acid sites and oxidation sites in PMo10V2@2Br-PIL that can promote the one-pot conversion of fructose to DFF. This study deepens the insight of biomass transformation over hybrid catalysts by acidic/oxidative synergetic catalysis and contributes to the effort of designing highly active, selective, and multifunctional catalysts for one-pot biomass conversion.
{"title":"One-pot Cascade Conversion of Fructose to 2,5-Diformylfuran Enabled by a Polyionic Liquids based Porous Catalyst","authors":"Gang Liu, Jun Zheng, Xianqiang Huang, Shiqi Fu, Shiqi Xi, Yalin Zhang, Zhen Li, Fei Yu, Yifa Chen","doi":"10.1039/d5qi00135h","DOIUrl":"https://doi.org/10.1039/d5qi00135h","url":null,"abstract":"One-pot direct conversion of cheap and abundant fructose to 2,5-diformylfuran (DFF) is highly sought to achieve hundreds-fold value-increase and high atomic economy yet is still challenging by the lack of suitable catalysts with cascade conversion ability. In this work, we have developed a kind of porous hybrid catalyst (i.e. PMo10V2@2Br-PIL) based on the assembly of polyoxometalates and porous polyionic liquids that can be applied in one-pot conversion of fructose to DFF. The integration of PMo10V2 with 2Br-PIL can impart both Brönsted acid sites and oxidation sites in the porous structure that enables the one-pot cascade conversion. As a result, PMo10V2@2Br-PIL demonstrates remarkable DFF yield (95% yield), satisfying stability, recyclability and scale-up production ability (≈12.3 g in a batch experiment), demonstrating great potential in the industrial production of DFF from fructose. Theoretical calculations reveal the synergistic effect of Brönsted acid sites and oxidation sites in PMo10V2@2Br-PIL that can promote the one-pot conversion of fructose to DFF. This study deepens the insight of biomass transformation over hybrid catalysts by acidic/oxidative synergetic catalysis and contributes to the effort of designing highly active, selective, and multifunctional catalysts for one-pot biomass conversion.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"23 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143797854","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Short-wave ultraviolet optical crystals are widely used in various fields. Exploring organic-inorganic hybrid compounds is an effective approach for discovering crystal materials simultaneously possessing large band gap and birefringence. In this work, two novel organic-inorganic hybrid fluorosilicates, (C2H7N4O)2SiF6 and (C2H4N4)4ZnSiF6·H2O were obtained. (C2H7N4O)2SiF6 has the largest band gap among organic-inorganic hybrid fluorosilicates and unique [(C2H7N4O)2SiF6]∞ layered structure. (C2H4N4)4ZnSiF6·H2O has the largest birefringence (0.282@0.546 μm) among reported organic-inorganic hybrid fluorosilicates. In addition, we systematically analyze the structural and optical properties transformation from (C2H7N4O)2SiF6 to (C2H4N4)4ZnSiF6·H2O.
{"title":"Greatly Enhancing Birefringence of Fluosilicate through the Synergy Effect of Functional Units","authors":"Liang Ma, Yi-Lei Lv, Bing-Wei Miao, Guo-Ren Zhu, Wen-Long Liu, Sheng-Ping Guo, Ru-Ling Tang","doi":"10.1039/d5qi00468c","DOIUrl":"https://doi.org/10.1039/d5qi00468c","url":null,"abstract":"Short-wave ultraviolet optical crystals are widely used in various fields. Exploring organic-inorganic hybrid compounds is an effective approach for discovering crystal materials simultaneously possessing large band gap and birefringence. In this work, two novel organic-inorganic hybrid fluorosilicates, (C2H7N4O)2SiF6 and (C2H4N4)4ZnSiF6·H2O were obtained. (C2H7N4O)2SiF6 has the largest band gap among organic-inorganic hybrid fluorosilicates and unique [(C2H7N4O)2SiF6]∞ layered structure. (C2H4N4)4ZnSiF6·H2O has the largest birefringence (0.282@0.546 μm) among reported organic-inorganic hybrid fluorosilicates. In addition, we systematically analyze the structural and optical properties transformation from (C2H7N4O)2SiF6 to (C2H4N4)4ZnSiF6·H2O.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"23 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143797850","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Jin Wang, Xin Wang, Xuesong Li, Xiangmei Li, Hong-Tao Lei, Juewen Liu
Lanthanides are extremely important for a variety of technological applications. In this work, DNA aptamers were selected using the library-immobilization method (capture-SELEX) with Tb3+ and Ce3+ as target metal ions. The Tb3+ selection yielded a new sequence named Tb-1 that has a Kd of 26.9 nM for La3+, 3.9 nM for Tb3+, and 2.3 nM for Lu3+ as determined by a DNA strand displacement assay. Binding to other metal ions cannot be detected using a fluorescence DNA strand displacement assay. Therefore, it is a general lanthanide binding aptamer. Another aptamer Tb-4 has some sequence similarity to a previously reported Gd-1 aptamer and it exhibited a Kd of 290 nM, while Gd-1 had a Kd of 1.5 µM, as determined by a thioflavin T fluorescence assay. They showed little selectivity for different lanthanides. Compared to a previously reported aptamer named Sc-1, Tb-1 is an outersphere binder and fast release of bound lanthanides upon the addition of EDTA. By comparing different aptamers, we have gained fundamental insights into aptamer binding to lanthanides. Finally, using the strand displacement reaction, a detection limit of 0.5 nM Tb3+ was achieved in Lake Ontario water.
{"title":"A DNA aptamer for trivalent lanthanide ions with low nanomolar affinity","authors":"Jin Wang, Xin Wang, Xuesong Li, Xiangmei Li, Hong-Tao Lei, Juewen Liu","doi":"10.1039/d5qi00391a","DOIUrl":"https://doi.org/10.1039/d5qi00391a","url":null,"abstract":"Lanthanides are extremely important for a variety of technological applications. In this work, DNA aptamers were selected using the library-immobilization method (capture-SELEX) with Tb3+ and Ce3+ as target metal ions. The Tb3+ selection yielded a new sequence named Tb-1 that has a Kd of 26.9 nM for La3+, 3.9 nM for Tb3+, and 2.3 nM for Lu3+ as determined by a DNA strand displacement assay. Binding to other metal ions cannot be detected using a fluorescence DNA strand displacement assay. Therefore, it is a general lanthanide binding aptamer. Another aptamer Tb-4 has some sequence similarity to a previously reported Gd-1 aptamer and it exhibited a Kd of 290 nM, while Gd-1 had a Kd of 1.5 µM, as determined by a thioflavin T fluorescence assay. They showed little selectivity for different lanthanides. Compared to a previously reported aptamer named Sc-1, Tb-1 is an outersphere binder and fast release of bound lanthanides upon the addition of EDTA. By comparing different aptamers, we have gained fundamental insights into aptamer binding to lanthanides. Finally, using the strand displacement reaction, a detection limit of 0.5 nM Tb3+ was achieved in Lake Ontario water.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"183 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-04-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143789982","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Atomically precise coinage metal nanoclusters have been widely explored as model catalysts to study the structure-performance relationship, yet single atom addition onto the metal core to tailor the catalytic properties still remains challenging. Herein, we report a pair of atomically precise Cu nanoclusters, namely [Cu14(Fur)3(PPh3)8H10]+ and [Cu13(Nap)3(PPh3)7H10]0 (hereafter referred to as Cu14 and Cu13, Fur: 2-methyl-3-furanthiolate, Nap: 1-naphthalene thiolate), which exhibit an astonishingly high degree of structural similarity, differing merely by the addition of a single Cu atom yet possessing drastically different catalytic performance toward oxygen evolution reaction (OER). Specifically, in 1 M KOH solution, Cu14 has a much lower overpotential than Cu13 (306 mV vs. 382 mV) to afford a current density of 10 mA cm-2, a smaller Tafel slope and a lower charge transfer resistance. Density functional theory calculations were employed to further identify the catalytic acitve site, confirming that the additonal Cu atom in Cu14 is the key catalytic site which can significantly lower the energy barrier of the rate determining step in OER. This study highlights the crucial role of single-atom addition in modulating the properties and functionalties of atomically precise metal nanoclusters, shedding light on future catalyst design.
{"title":"Atomically precise Cu14 and Cu13 nanoclusters for oxygen evolution reaction: One additional Cu atom matters","authors":"Ziyi Liu, Pan Zhu, Xianxing Zhou, Lubing Qin, Xunying Liu, Qing Tang, Zhenghua Tang","doi":"10.1039/d5qi00735f","DOIUrl":"https://doi.org/10.1039/d5qi00735f","url":null,"abstract":"Atomically precise coinage metal nanoclusters have been widely explored as model catalysts to study the structure-performance relationship, yet single atom addition onto the metal core to tailor the catalytic properties still remains challenging. Herein, we report a pair of atomically precise Cu nanoclusters, namely [Cu14(Fur)3(PPh3)8H10]+ and [Cu13(Nap)3(PPh3)7H10]0 (hereafter referred to as Cu14 and Cu13, Fur: 2-methyl-3-furanthiolate, Nap: 1-naphthalene thiolate), which exhibit an astonishingly high degree of structural similarity, differing merely by the addition of a single Cu atom yet possessing drastically different catalytic performance toward oxygen evolution reaction (OER). Specifically, in 1 M KOH solution, Cu14 has a much lower overpotential than Cu13 (306 mV vs. 382 mV) to afford a current density of 10 mA cm-2, a smaller Tafel slope and a lower charge transfer resistance. Density functional theory calculations were employed to further identify the catalytic acitve site, confirming that the additonal Cu atom in Cu14 is the key catalytic site which can significantly lower the energy barrier of the rate determining step in OER. This study highlights the crucial role of single-atom addition in modulating the properties and functionalties of atomically precise metal nanoclusters, shedding light on future catalyst design.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"183 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-04-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143797855","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Marcos V. Palmeira-Mello, Tamara Teixeira, Analu R Costa, Aline Maria Machado, Rone Aparecido De Grandis, Leticia P de Oliveira, Carlos André F Moraes, João Honorato, Victor Marcelo Deflon, Adriano Andricopulo, Javier Ellena, Heloisa Selistre-de-Araujo, Fillipe Vieira Rocha, Alzir A Batista
Three Ruthenium(II)-phosphine based complexes with the general formula [Ru(N–S)(dppm)2]PF6 (Ru1–Ru3) were prepared and studied as anticancer agents [N–S are 2-mercapto-2-thiazoline (Hmtz), mercapto-1-methylimidazole (Hmmi) and 4,6-diamino-2-mercapto-pyrimidine (Hdmp) and dppm is the 1,1`-bis(diphenylphosphino)methane]. The coefficient distribution of these compounds was assessed, and Log P values indicated their preference for the organic phase. After confirming their stability in solution, their in vitro cytotoxicity was investigated on different breast cell lines. Our findings revealed Ru2 as 50-fold more cytotoxic and almost 2-fold more selective than cisplatin control, considering the MCF-7 cells. Also, Ru2 induces morphological changes and inhibits the colony formation in this cell line. Considering the advantages of 3D cell culture models for screening of new anticancer drug candidates, the effect of Ru2, which was found to be the best candidate compound, was investigated on multicellular tumor spheroids. Live/dead assay revealed dead cell population in both 2D-and 3D MCF-7 cell models upon treatment at IC50 concentration. The Ruthenium-phosphine complex was able to affect the cell cycle distribution and the mitochondrial membrane potential, inducing apoptosis cell death. Ames and Micronucleus tests indicated the absence of mutagenicity for Ru2. To the best of our knowledge, this work demonstrated the effects of a ruthenium-phosphine complex on MCF-7 breast cancer cells using 2D and 3D cell based experiments, highlighting its potential as promising antitumor agent.
{"title":"Non-mutagenic Ru(II)-phosphine-based Complexes Induce Mitochondria-mediated Apoptosis in Breast Cancer Cells: From 2D to 3D Investigations","authors":"Marcos V. Palmeira-Mello, Tamara Teixeira, Analu R Costa, Aline Maria Machado, Rone Aparecido De Grandis, Leticia P de Oliveira, Carlos André F Moraes, João Honorato, Victor Marcelo Deflon, Adriano Andricopulo, Javier Ellena, Heloisa Selistre-de-Araujo, Fillipe Vieira Rocha, Alzir A Batista","doi":"10.1039/d5qi00546a","DOIUrl":"https://doi.org/10.1039/d5qi00546a","url":null,"abstract":"Three Ruthenium(II)-phosphine based complexes with the general formula [Ru(N–S)(dppm)2]PF6 (Ru1–Ru3) were prepared and studied as anticancer agents [N–S are 2-mercapto-2-thiazoline (Hmtz), mercapto-1-methylimidazole (Hmmi) and 4,6-diamino-2-mercapto-pyrimidine (Hdmp) and dppm is the 1,1`-bis(diphenylphosphino)methane]. The coefficient distribution of these compounds was assessed, and Log P values indicated their preference for the organic phase. After confirming their stability in solution, their in vitro cytotoxicity was investigated on different breast cell lines. Our findings revealed Ru2 as 50-fold more cytotoxic and almost 2-fold more selective than cisplatin control, considering the MCF-7 cells. Also, Ru2 induces morphological changes and inhibits the colony formation in this cell line. Considering the advantages of 3D cell culture models for screening of new anticancer drug candidates, the effect of Ru2, which was found to be the best candidate compound, was investigated on multicellular tumor spheroids. Live/dead assay revealed dead cell population in both 2D-and 3D MCF-7 cell models upon treatment at IC50 concentration. The Ruthenium-phosphine complex was able to affect the cell cycle distribution and the mitochondrial membrane potential, inducing apoptosis cell death. Ames and Micronucleus tests indicated the absence of mutagenicity for Ru2. To the best of our knowledge, this work demonstrated the effects of a ruthenium-phosphine complex on MCF-7 breast cancer cells using 2D and 3D cell based experiments, highlighting its potential as promising antitumor agent.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"26 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-04-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143797885","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
AlMe3 sticks, GaMe3 quits. A series of Lewis acid stabilized scandium methylidenes with commercially available cyclopentadienyl ligands CpR (CpR = C5Me5 (Cp*), C5Me4SiMe3 (Cp’)) were synthesized. The-salt metathesis reaction of new half-sandwich dichloride precursors CpRScCl2(µ−Cl)Li(thf)3 with LiAlMe4 and AlMe3 at ambient temperature yielded [CpRSc(AlMe4)Cl]2. [Cp’Sc(AlMe4)Cl]2 was further methylated at ambient temperature to yield Cp’Sc(AlMe4)Me. At 70 °C, the reaction of CpRScCl2(µ−Cl)Li(thf)3 with LiAlMe4 and AlMe3 led to the formation of Lewis acid stabilized Sc/Al2 methylidenes CpRSc(CH2)(AlMe3)2. The new mixed Sc/Al/Ga methylidene Cp’Sc(CH2)(AlMe3)(GaMe3) was obtained from the reaction of Cp’Sc(AlMe4)Me with GaMe3. When heated, complex Cp’Sc(CH2)(AlMe3)(GaMe3) converted into the Sc/Al methylidene [Cp’Sc(CH2)2AlMe]3via release of the comparatively weak Lewis acid GaMe3 and methane. The core of trimeric [Cp’Sc(CH2)2AlMe]3 can be described as a triscandacyclohexane {Sc(CH2)}3 stabilized by a trialacyclohexane {Al(CH2)}3via Pearson hard/hard matching. Complexes CpRSc(CH2)(AlMe3)2 and [Cp’Sc(CH2)2AlMe]3 differ in rigidity, thermal stability and reactivities toward ketones and Lewis bases. The isolated methylidenes were analyzed by 1H, 13C, 45Sc, and variable temperature 1H NMR spectroscopy, SC-XRD, IR spectroscopy, and elemental analysis. Complexes CpRSc(CH2)(AlMe3)2 feature pronounced Sc---HC α-agostic interactions. The reaction of CpRScCl2(µ−Cl)Li(thf)3 with LiAlMe4 and AlMe3 was investigated viain situ1H and 45Sc NMR spectroscopy.
{"title":"Half-Sandwich Scandium Methylidenes","authors":"Gernot Tilman Linus Zug, Sylvia Zeiner, Jonas Reuter, Hartmut Schubert, Caecilia Maichle-Moessmer, Reiner Anwander","doi":"10.1039/d5qi00152h","DOIUrl":"https://doi.org/10.1039/d5qi00152h","url":null,"abstract":"AlMe3 sticks, GaMe3 quits. A series of Lewis acid stabilized scandium methylidenes with commercially available cyclopentadienyl ligands CpR (CpR = C5Me5 (Cp*), C5Me4SiMe3 (Cp’)) were synthesized. The-salt metathesis reaction of new half-sandwich dichloride precursors CpRScCl2(µ−Cl)Li(thf)3 with LiAlMe4 and AlMe3 at ambient temperature yielded [CpRSc(AlMe4)Cl]2. [Cp’Sc(AlMe4)Cl]2 was further methylated at ambient temperature to yield Cp’Sc(AlMe4)Me. At 70 °C, the reaction of CpRScCl2(µ−Cl)Li(thf)3 with LiAlMe4 and AlMe3 led to the formation of Lewis acid stabilized Sc/Al2 methylidenes CpRSc(CH2)(AlMe3)2. The new mixed Sc/Al/Ga methylidene Cp’Sc(CH2)(AlMe3)(GaMe3) was obtained from the reaction of Cp’Sc(AlMe4)Me with GaMe3. When heated, complex Cp’Sc(CH2)(AlMe3)(GaMe3) converted into the Sc/Al methylidene [Cp’Sc(CH2)2AlMe]3via release of the comparatively weak Lewis acid GaMe3 and methane. The core of trimeric [Cp’Sc(CH2)2AlMe]3 can be described as a triscandacyclohexane {Sc(CH2)}3 stabilized by a trialacyclohexane {Al(CH2)}3via Pearson hard/hard matching. Complexes CpRSc(CH2)(AlMe3)2 and [Cp’Sc(CH2)2AlMe]3 differ in rigidity, thermal stability and reactivities toward ketones and Lewis bases. The isolated methylidenes were analyzed by 1H, 13C, 45Sc, and variable temperature 1H NMR spectroscopy, SC-XRD, IR spectroscopy, and elemental analysis. Complexes CpRSc(CH2)(AlMe3)2 feature pronounced Sc---HC α-agostic interactions. The reaction of CpRScCl2(µ−Cl)Li(thf)3 with LiAlMe4 and AlMe3 was investigated viain situ1H and 45Sc NMR spectroscopy.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"183 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143776128","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Chen-Xi Yu, Le Ye, Hao Zhuo, Yun-Fan Yan, Wei-Xiong Zhang
The traditional pyrotechnic compositions formed by mechanically mixing flammable and oxidative agents face problems in complex formulations, inaccurate chemical stoichiometry, and inefficient colour-producing reactions. The emerging molecular perovskite energetic materials embedding ternary ions have evolved into a new platform for developing explosives, propellants, ignitions, and energetic biocides, by taking advantages of easy preparation and high adjustability, nevertheless their potentials in pyrotechnic applications have not been investigated yet. Herein, by assembling barium(II) perchlorate with imidazolium (Him+) and quinuclidinium (Hqe+), respectively, we obtained two new energetic compounds, (Him)(Ba)(ClO4)3 (IBP) in cubic perovskite structure and (Hqe)2(Ba)(ClO4)4 (QBP) in layered perovskite structure. Both IBP and QBP have decomposition peak temperatures exceeding 290 °C and much higher moisture stabilities than barium perchlorate. With the layered structure, QBP has significantly reduced friction sensitivity (144 N) than IBP (5 N). Moreover, the tightly stacking of barium(II), oxidative perchlorate ions, and carbon-rich fuel components at molecular level endows QBP with a high-efficiency and stable combustion outputting a maximum combustion pressure up to 550 kPa, a maximum pressure pulse rate up to 10.48 MPa/s, and a bright green flame. These findings well demonstrated that molecular perovskite energetic compounds integrating luminescent component, oxidative anions, and organic cations are promising contenders for next-generation pyrotechnic materials.
{"title":"Barium(II)-based molecular perovskite energetic compounds for next-generation pyrotechnic materials","authors":"Chen-Xi Yu, Le Ye, Hao Zhuo, Yun-Fan Yan, Wei-Xiong Zhang","doi":"10.1039/d5qi00442j","DOIUrl":"https://doi.org/10.1039/d5qi00442j","url":null,"abstract":"The traditional pyrotechnic compositions formed by mechanically mixing flammable and oxidative agents face problems in complex formulations, inaccurate chemical stoichiometry, and inefficient colour-producing reactions. The emerging molecular perovskite energetic materials embedding ternary ions have evolved into a new platform for developing explosives, propellants, ignitions, and energetic biocides, by taking advantages of easy preparation and high adjustability, nevertheless their potentials in pyrotechnic applications have not been investigated yet. Herein, by assembling barium(II) perchlorate with imidazolium (Him+) and quinuclidinium (Hqe+), respectively, we obtained two new energetic compounds, (Him)(Ba)(ClO4)3 (IBP) in cubic perovskite structure and (Hqe)2(Ba)(ClO4)4 (QBP) in layered perovskite structure. Both IBP and QBP have decomposition peak temperatures exceeding 290 °C and much higher moisture stabilities than barium perchlorate. With the layered structure, QBP has significantly reduced friction sensitivity (144 N) than IBP (5 N). Moreover, the tightly stacking of barium(II), oxidative perchlorate ions, and carbon-rich fuel components at molecular level endows QBP with a high-efficiency and stable combustion outputting a maximum combustion pressure up to 550 kPa, a maximum pressure pulse rate up to 10.48 MPa/s, and a bright green flame. These findings well demonstrated that molecular perovskite energetic compounds integrating luminescent component, oxidative anions, and organic cations are promising contenders for next-generation pyrotechnic materials.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"23 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143776129","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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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