We report first quantitative estimates for the pKa and hydride donor ability of a fifth-row E-H bond besides Sn-H bonds. A new D2d-symmetric cluster type for M8 species (M = pnictogen) is shown, along with the first amido-stibanide. Sterically determined deprotontion and redox outcomes are demonstrated.
{"title":"Acidity/hydridicity evaluation of Sb-H bonds and formation of a new Group 15 metal cluster topology","authors":"Mitchell MacEachern, Tanner George, Saurabh Chitnis","doi":"10.1039/d5qi02115d","DOIUrl":"https://doi.org/10.1039/d5qi02115d","url":null,"abstract":"We report first quantitative estimates for the pKa and hydride donor ability of a fifth-row E-H bond besides Sn-H bonds. A new D2d-symmetric cluster type for M8 species (M = pnictogen) is shown, along with the first amido-stibanide. Sterically determined deprotontion and redox outcomes are demonstrated.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"206 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-11-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145608844","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}
Jing Liu, Jinyang Feng, Ze Sun, Chang Xin, Hulin Tai
Developing ligands that improve the stability of G-quadruplex DNA (G4) is a promising anticancer strategy. We constructed a Peptide-Heme-NH3/G4 hybrid complex possessing a unique NH3 axial ligand between the heme and G-quartet planes. The interface between the heme and G-quartet planes is well adapted to accommodate a NH3 molecule, with a ligand substituent constant (Ks) from 98,733 ± 7141 to 18,357 ± 284 M-1 at 15-35 °C. Compared with free Peptide-Heme-H2O, complexation with G4 resulted in a 22-35-fold increase in Ks value. The binding constant (Ka) between Peptide-Heme-NH3 and G4 was determined to be between 37.6 ± 4.9 and 121.8 ± 3.0 μM−1 at 15-35 °C, 21-30-fold higher than the value observed for the Peptide-Heme-H2O/G4 hybrid complex. Thermodynamic analysis of experimental data showed that interactions between the heme and G-quartet planes are highly sensitive to Fe-bound NH3 and H2O ligands. The findings provide novel insights and mechanistic clues for designing anticancer metal complexes targeting G4.
{"title":"Controlling interactions between peptide-heme and G-quadruplex DNA using Fe-bound NH3 and H2O ligands","authors":"Jing Liu, Jinyang Feng, Ze Sun, Chang Xin, Hulin Tai","doi":"10.1039/d5qi02103k","DOIUrl":"https://doi.org/10.1039/d5qi02103k","url":null,"abstract":"Developing ligands that improve the stability of G-quadruplex DNA (G4) is a promising anticancer strategy. We constructed a Peptide-Heme-NH<small><sub>3</sub></small>/G4 hybrid complex possessing a unique NH<small><sub>3</sub></small> axial ligand between the heme and G-quartet planes. The interface between the heme and G-quartet planes is well adapted to accommodate a NH<small><sub>3</sub></small> molecule, with a ligand substituent constant (<em>K</em><small><sub>s</sub></small>) from 98,733 ± 7141 to 18,357 ± 284 M<small><sup>-1</sup></small> at 15-35 °C. Compared with free Peptide-Heme-H<small><sub>2</sub></small>O, complexation with G4 resulted in a 22-35-fold increase in <em>K</em><small><sub>s</sub></small> value. The binding constant (<em>K</em><small><sub>a</sub></small>) between Peptide-Heme-NH<small><sub>3</sub></small> and G4 was determined to be between 37.6 ± 4.9 and 121.8 ± 3.0 μM<small><sup>−1</sup></small> at 15-35 °C, 21-30-fold higher than the value observed for the Peptide-Heme-H<small><sub>2</sub></small>O/G4 hybrid complex. Thermodynamic analysis of experimental data showed that interactions between the heme and G-quartet planes are highly sensitive to Fe-bound NH<small><sub>3</sub></small> and H<small><sub>2</sub></small>O ligands. The findings provide novel insights and mechanistic clues for designing anticancer metal complexes targeting G4.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"94 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-11-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145612014","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}
Jie Tan, Mingliang Guo, Hai Li, Yongcheng Qi, Mingyu Wang, Xiaohong Wang, Hualan Li, Lei Ding
The practical conversion of seawater to hydrogen faces critical limitations from chloride attack and anodic competition, requiring electrocatalysts with superior robustness. Herein, we constructed an amorphous/crystalline heterointerface catalyst, NiO/CoFe Prussian blue analogues, via low-temperature atomic layer deposition (ALD) toward efficient seawater oxidation. Experimental investigations revealed that utilization of the conformal coating capability of ALD enabled precise integration of a structurally disordered NiO layer onto the crystalline CoFe-PBA framework. This integration resulted in the formation of a robust heterointerface, which synergized the amorphous phase's isotropic corrosion resistance and the crystalline matrix's high conductivity. The catalyst achieved overpotentials of η10 = 257 mV and η100 = 301 mV in alkaline seawater. Computational analysis demonstrated that the oxygen-bridged Fe/Co–O–Ni covalent interactions induced strong electronic coupling, modulating the 3d orbital configuration of Fe/Co/Ni sites. This, in turn, led to a downshifted d-band center, optimizing oxygen intermediate adsorption and enhancing the chloride tolerance via Co sites. Notably, 100 hour stability at 100 mA cm−2 was maintained. This work introduces an ALD-enabled interfacial engineering methodology for fabricating durable heterointerface catalysts tailored for seawater electrolysis hydrogen production.
海水制氢的实际转化面临着氯化物侵蚀和阳极竞争的关键限制，需要具有优异稳健性的电催化剂。在此，我们通过低温原子层沉积（ALD）构建了一种非晶/晶体异质界面催化剂NiO/CoFe普鲁士蓝类似物，用于高效的海水氧化。实验研究表明，利用ALD的保形涂层能力，可以将结构无序的NiO层精确集成到结晶的咖啡- pba框架上。这种整合形成了一个强大的异质界面，它协同了非晶相的各向同性耐腐蚀性和晶体基体的高导电性。催化剂在碱性海水中获得了η10 = 257 mV和η100 = 301 mV的过电位。计算分析表明，氧桥接的Fe/Co - o - Ni共价相互作用诱导了强电子耦合，调节了Fe/Co/Ni位的三维轨道构型。这反过来又导致d带中心下移，优化了氧中间体的吸附并通过Co位点增强了氯化物耐受性。值得注意的是，在100 mA cm−2下保持了100小时的稳定性。这项工作介绍了一种支持ald的界面工程方法，用于制造适合海水电解制氢的耐用异质界面催化剂。
{"title":"ALD-engineered amorphous NiO/crystalline CoFe-PBA heterointerface for high-performance seawater oxygen evolution","authors":"Jie Tan, Mingliang Guo, Hai Li, Yongcheng Qi, Mingyu Wang, Xiaohong Wang, Hualan Li, Lei Ding","doi":"10.1039/d5qi01744k","DOIUrl":"https://doi.org/10.1039/d5qi01744k","url":null,"abstract":"The practical conversion of seawater to hydrogen faces critical limitations from chloride attack and anodic competition, requiring electrocatalysts with superior robustness. Herein, we constructed an amorphous/crystalline heterointerface catalyst, NiO/CoFe Prussian blue analogues, <em>via</em> low-temperature atomic layer deposition (ALD) toward efficient seawater oxidation. Experimental investigations revealed that utilization of the conformal coating capability of ALD enabled precise integration of a structurally disordered NiO layer onto the crystalline CoFe-PBA framework. This integration resulted in the formation of a robust heterointerface, which synergized the amorphous phase's isotropic corrosion resistance and the crystalline matrix's high conductivity. The catalyst achieved overpotentials of <em>η</em><small><sub>10</sub></small> = 257 mV and <em>η</em><small><sub>100</sub></small> = 301 mV in alkaline seawater. Computational analysis demonstrated that the oxygen-bridged Fe/Co–O–Ni covalent interactions induced strong electronic coupling, modulating the 3d orbital configuration of Fe/Co/Ni sites. This, in turn, led to a downshifted d-band center, optimizing oxygen intermediate adsorption and enhancing the chloride tolerance <em>via</em> Co sites. Notably, 100 hour stability at 100 mA cm<small><sup>−2</sup></small> was maintained. This work introduces an ALD-enabled interfacial engineering methodology for fabricating durable heterointerface catalysts tailored for seawater electrolysis hydrogen production.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"16 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145599681","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}
Alkyne coupling, pivotal for C-C bond formation, is dominated by transition-metal catalysis, while actinide-mediated variants remain underdeveloped and exclusively reliant on low-valent uranium (U(II/III)) intermediates. Here we report an unprecedented alkyne homocoupling and cross-coupling enabled by actinide-transition metal cooperativity within a heterometallic U-Pd cluster. This transformation bypasses low-valent uranium intermediates, changing a decades-old mechanistic paradigm. Both stepwise and one-pot protocols efficiently afford selective coupling products from identical or distinct alkynyl Grignard reagents. Structural and computational studies reveal unusual electron delocalization within the resulting products.
{"title":"Alkyne Coupling Enabled by Actinide-Transition Metal Cooperativity","authors":"Tianze Zhang, Thayalan Rajeshkumar, Peiyu Li, Yue Zhao, Laurent Maron, Congqing Zhu","doi":"10.1039/d5qi02002f","DOIUrl":"https://doi.org/10.1039/d5qi02002f","url":null,"abstract":"Alkyne coupling, pivotal for C-C bond formation, is dominated by transition-metal catalysis, while actinide-mediated variants remain underdeveloped and exclusively reliant on low-valent uranium (U(II/III)) intermediates. Here we report an unprecedented alkyne homocoupling and cross-coupling enabled by actinide-transition metal cooperativity within a heterometallic U-Pd cluster. This transformation bypasses low-valent uranium intermediates, changing a decades-old mechanistic paradigm. Both stepwise and one-pot protocols efficiently afford selective coupling products from identical or distinct alkynyl Grignard reagents. Structural and computational studies reveal unusual electron delocalization within the resulting products.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"99 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145608845","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}
Mikel Bernabeu de Maria, Tshering Zangmo, Andrzej Gawor, Luigi Messori, Ewa Bulska, Joanna Szpunar, Ryszard Lobinski, Karinne Miqueu and Luisa Ronga
Mercury (Hg) is a toxic metal that poses a serious threat to global health. Methylmercury (MeHg), an organic compound of Hg, is among the most toxic forms of the metal. The molecular mechanisms by which methylmercury produces its toxic effects are not fully understood. However, previous studies have shown that certain selenoenzymes, which play a vital role in maintaining cellular and tissue homeostasis (e.g. thioredoxin reductase (TrxR) and glutathione peroxidase (GPx)), are strongly inhibited by methylmercury in both in vitro and in vivo studies, and are therefore probable targets of its toxicity. This study aims to gain a comprehensive mechanistic understanding of the role of selenoproteins in methylmercury toxicity by investigating their reactivity towards MeHg+ and analysing their metal-binding mode using a joint experimental and computational approach. In particular, liquid chromatography (LC) coupled to tandem electrospray mass spectrometry (ESI-MS) was employed to characterise the reactivity of methylmercury with the C-terminal dodecapeptide of TrxR1 and the full-length Gpx1. Remarkably, clear evidence of Se–Hg bond formation in GPx1 has been achieved for the first time in this study. Conversely, DFT calculations provided a rational explanation and detailed description of the underlying reaction mechanisms involving the preferential reactivity of MeHg+ towards SeCys, followed by the participation of neighboring Cys residues. These reactions lead to the formation of robust S–Hg–S(e) bridges within the investigated selenoproteins. We propose that these molecular mechanisms also operate in vivo, determining the potent inhibition of selenoenzymes by MeHg and the associated severe toxicity.
{"title":"Molecular insights into the role of selenoenzymes in the toxicity of methylmercury","authors":"Mikel Bernabeu de Maria, Tshering Zangmo, Andrzej Gawor, Luigi Messori, Ewa Bulska, Joanna Szpunar, Ryszard Lobinski, Karinne Miqueu and Luisa Ronga","doi":"10.1039/D5QI01958C","DOIUrl":"10.1039/D5QI01958C","url":null,"abstract":"<p >Mercury (Hg) is a toxic metal that poses a serious threat to global health. Methylmercury (MeHg), an organic compound of Hg, is among the most toxic forms of the metal. The molecular mechanisms by which methylmercury produces its toxic effects are not fully understood. However, previous studies have shown that certain selenoenzymes, which play a vital role in maintaining cellular and tissue homeostasis (<em>e.g.</em> thioredoxin reductase (TrxR) and glutathione peroxidase (GPx)), are strongly inhibited by methylmercury in both <em>in vitro</em> and <em>in vivo</em> studies, and are therefore probable targets of its toxicity. This study aims to gain a comprehensive mechanistic understanding of the role of selenoproteins in methylmercury toxicity by investigating their reactivity towards MeHg<small><sup>+</sup></small> and analysing their metal-binding mode using a joint experimental and computational approach. In particular, liquid chromatography (LC) coupled to tandem electrospray mass spectrometry (ESI-MS) was employed to characterise the reactivity of methylmercury with the C-terminal dodecapeptide of TrxR1 and the full-length Gpx1. Remarkably, clear evidence of Se–Hg bond formation in GPx1 has been achieved for the first time in this study. Conversely, DFT calculations provided a rational explanation and detailed description of the underlying reaction mechanisms involving the preferential reactivity of MeHg<small><sup>+</sup></small> towards SeCys, followed by the participation of neighboring Cys residues. These reactions lead to the formation of robust S–Hg–S(e) bridges within the investigated selenoproteins. We propose that these molecular mechanisms also operate <em>in vivo</em>, determining the potent inhibition of selenoenzymes by MeHg and the associated severe toxicity.</p>","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":" 1","pages":" 32-44"},"PeriodicalIF":6.4,"publicationDate":"2025-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145594198","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}
Chengzhen Wei, Shuo Shan, Sitong Li, Weimin Du, Cheng Cheng, Zhuohan Zhang, Kaige Du
Electrode materials of supercapacitors with desirable compositions and architectures are poised to promote the electrochemical performance. Hierarchical tubular architectures, with the beneficial characteristics of one-dimensional and hierarchical hollow architectures, are prospective to be realized for excellent performance supercapacitors. Here we present a simple self-templated approach for the preparation of Co 11 (HPO 3 ) 8 (OH) 6 /Co 9 S 8 hierarchical tubular architectures as electrode materials in supercapacitors. At first, a facile hydrothermal process is carried out to synthesized Co 11 (HPO 3 ) 8 (OH) 6 nanofibers template, which are subsequently transformed into Co 11 (HPO 3 ) 8 (OH) 6 /Co 9 S 8 hierarchical tubular architectures by a sulfidation reaction. Both the structural and compositional benefits are guaranteed to deliver boosted electrochemical performance. As expected, the prepared Co 11 (HPO 3 ) 8 (OH) 6 /Co 9 S 8 shows a large specific capacitance of 1218 F g -1 at 4.0 A g -1 , enhanced rate capability and extended cycling stability with 91% capacitance retention at 10 A g -1 for 10000 consecutive charge-discharge cycles.Furthermore, an asymmetrical supercapacitor based on Co 11 (HPO 3 ) 8 (OH) 6 /Co 9 S 8 cathode and activated carbon anode was constructed for practical application. The constructed device demonstrates a high energy density of 96.9 W h kg -1 at power density of 1550 W kg -1 and robust stability of 6000 cycles at 5.0 A g -1 with a mere 3.5% decline. This work not only establishes a facile path to synthesize hollow architectures but also provides a potential candidate for supercapacitors.
具有理想成分和结构的超级电容器电极材料有望提高其电化学性能。层叠管结构具有一维结构和层叠空心结构的优点，是高性能超级电容器的发展方向。在这里，我们提出了一种简单的自模板方法来制备co11 (hpo3) 8 (OH) 6 / co9s8分层管状结构作为超级电容器的电极材料。首先采用简单的水热法合成了Co 11 (HPO 3) 8 (OH) 6纳米纤维模板，然后通过硫化反应将模板转化为Co 11 (HPO 3) 8 (OH) 6 /Co 9 s8层叠管状结构。结构和成分的优势都保证提供提升的电化学性能。正如预期的那样，制备的Co 11 (HPO 3) 8 (OH) 6 /Co 9 s8在4.0 a g -1下具有1218 F g -1的大比电容，提高了倍率能力和延长了循环稳定性，在10 a g -1下连续充放电循环10000次，电容保持率为91%。在此基础上，构建了以co11 (hpo3) 8 (OH) 6 / co9s8为阴极和活性炭为阳极的非对称超级电容器。所构建的器件在功率密度为1550 W kg -1时具有96.9 W h kg -1的高能量密度，在5.0 a g -1下具有6000次的鲁棒稳定性，仅下降3.5%。这项工作不仅建立了一种简单的合成空心结构的途径，而且为超级电容器提供了潜在的候选材料。
{"title":"Ultrlong Co 11 (HPO 3 ) 8 (OH) 6 /Co 9 S 8 hierarchical tubular architectures with highly enhanced electrochemical performance for supercapacitors","authors":"Chengzhen Wei, Shuo Shan, Sitong Li, Weimin Du, Cheng Cheng, Zhuohan Zhang, Kaige Du","doi":"10.1039/d5qi01655j","DOIUrl":"https://doi.org/10.1039/d5qi01655j","url":null,"abstract":"Electrode materials of supercapacitors with desirable compositions and architectures are poised to promote the electrochemical performance. Hierarchical tubular architectures, with the beneficial characteristics of one-dimensional and hierarchical hollow architectures, are prospective to be realized for excellent performance supercapacitors. Here we present a simple self-templated approach for the preparation of Co 11 (HPO 3 ) 8 (OH) 6 /Co 9 S 8 hierarchical tubular architectures as electrode materials in supercapacitors. At first, a facile hydrothermal process is carried out to synthesized Co 11 (HPO 3 ) 8 (OH) 6 nanofibers template, which are subsequently transformed into Co 11 (HPO 3 ) 8 (OH) 6 /Co 9 S 8 hierarchical tubular architectures by a sulfidation reaction. Both the structural and compositional benefits are guaranteed to deliver boosted electrochemical performance. As expected, the prepared Co 11 (HPO 3 ) 8 (OH) 6 /Co 9 S 8 shows a large specific capacitance of 1218 F g -1 at 4.0 A g -1 , enhanced rate capability and extended cycling stability with 91% capacitance retention at 10 A g -1 for 10000 consecutive charge-discharge cycles.Furthermore, an asymmetrical supercapacitor based on Co 11 (HPO 3 ) 8 (OH) 6 /Co 9 S 8 cathode and activated carbon anode was constructed for practical application. The constructed device demonstrates a high energy density of 96.9 W h kg -1 at power density of 1550 W kg -1 and robust stability of 6000 cycles at 5.0 A g -1 with a mere 3.5% decline. This work not only establishes a facile path to synthesize hollow architectures but also provides a potential candidate for supercapacitors.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"18 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145594235","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}
Jie Tu, Siyuan Du, Hangren Li, Jing Xia, Longyuan Shi, Jianjun Tian, Linxing Zhang
Strain engineering has emerged as a powerful strategy for optimizing the material structure and enhancing performance across a wide range of applications. Herein, we report the deployment of substrate-imposed strain to govern the dissolution kinetics of an epitaxial sacrificial layer. The epitaxial LaCoO3 (LCO) has been employed as a sacrificial layer: a lattice-matched and environmentally benign perovskite for releasing freestanding oxide membranes. Intriguingly, the decomposition efficiency of LCO can be precisely controlled by the substrate strain, whether tensile or compressive, which can induce changes in chemical bonds and lattice distortion, thereby altering the reactivity of LCO with the decomposition solution. Under a tensile strain of 2.09% on SrTiO3 substrate, the decomposition efficiency of LCO was accelerated by 66.7% compared with that on LaAlO3 substrate with compressive strain. Synchrotron X-ray absorption spectroscopy, high-angle annular dark-field scanning transmission electron microscopy and semi-in situ optical absorption spectra reveal that tensile strain reduces La–O bond energy and enhances octahedral distortion, making the lattice more susceptible to collapse. Furthermore, freestanding PbZrO3 films were fabricated using the LCO sacrificial layer, showing a ferroelectric-to-antiferroelectric transition. These findings underscore the potential of strain engineering in controlling material properties and fabrication processes, offering new strategies for developing flexible electronic devices.
{"title":"Strain-controlled decomposition efficiency of LaCoO3 perovskite epitaxial thin films","authors":"Jie Tu, Siyuan Du, Hangren Li, Jing Xia, Longyuan Shi, Jianjun Tian, Linxing Zhang","doi":"10.1039/d5qi01871d","DOIUrl":"https://doi.org/10.1039/d5qi01871d","url":null,"abstract":"Strain engineering has emerged as a powerful strategy for optimizing the material structure and enhancing performance across a wide range of applications. Herein, we report the deployment of substrate-imposed strain to govern the dissolution kinetics of an epitaxial sacrificial layer. The epitaxial LaCoO<small><sub>3</sub></small> (LCO) has been employed as a sacrificial layer: a lattice-matched and environmentally benign perovskite for releasing freestanding oxide membranes. Intriguingly, the decomposition efficiency of LCO can be precisely controlled by the substrate strain, whether tensile or compressive, which can induce changes in chemical bonds and lattice distortion, thereby altering the reactivity of LCO with the decomposition solution. Under a tensile strain of 2.09% on SrTiO<small><sub>3</sub></small> substrate, the decomposition efficiency of LCO was accelerated by 66.7% compared with that on LaAlO<small><sub>3</sub></small> substrate with compressive strain. Synchrotron X-ray absorption spectroscopy, high-angle annular dark-field scanning transmission electron microscopy and semi-<em>in situ</em> optical absorption spectra reveal that tensile strain reduces La–O bond energy and enhances octahedral distortion, making the lattice more susceptible to collapse. Furthermore, freestanding PbZrO<small><sub>3</sub></small> films were fabricated using the LCO sacrificial layer, showing a ferroelectric-to-antiferroelectric transition. These findings underscore the potential of strain engineering in controlling material properties and fabrication processes, offering new strategies for developing flexible electronic devices.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"14 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145594197","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}
Jack M. Hemingway, Xiao Yang, Paul G Waddell, Joel Cornelio, Matthew E. Lowe, James Alexander Dawson, Peter R. Slater, Roly J. Armstrong, Erli Lu
Separation of lithium and sodium is a topic of substantial scientific and industrial importance. Regarding Li/Na perchlorates, which are not only environmental hazardous but also useful oxidants in chemical synthesis, an efficient Li-Na perchlorate separation method has not been reported due to lack of a ligand which can selectively coordinate with one of the two. Herein, we report an efficient Li-Na perchlorate separation by using our hexa-dentate ligand N,N’,N’’-tris-(2-N-diethylaminoethyl)-1,4,7-triaza-cyclononane (DETAN), which can selectively coordinate with LiClO4 at room temperature to form a monomer in excellent yield, but does not coordinate with NaClO4 even at elevated temperature. The structure of the monomeric complex, [LiClO4(DETAN)] (1), was characterised by single-crystal X-ray diffraction and NMR spectroscopy.
{"title":"Non-aqueous Separation of Lithium and Sodium Perchlorates by Selective Coordination with a Hexa-Dentate Semi-Flexible Amine Ligand","authors":"Jack M. Hemingway, Xiao Yang, Paul G Waddell, Joel Cornelio, Matthew E. Lowe, James Alexander Dawson, Peter R. Slater, Roly J. Armstrong, Erli Lu","doi":"10.1039/d5qi01799h","DOIUrl":"https://doi.org/10.1039/d5qi01799h","url":null,"abstract":"Separation of lithium and sodium is a topic of substantial scientific and industrial importance. Regarding Li/Na perchlorates, which are not only environmental hazardous but also useful oxidants in chemical synthesis, an efficient Li-Na perchlorate separation method has not been reported due to lack of a ligand which can selectively coordinate with one of the two. Herein, we report an efficient Li-Na perchlorate separation by using our hexa-dentate ligand N,N’,N’’-tris-(2-N-diethylaminoethyl)-1,4,7-triaza-cyclononane (DETAN), which can selectively coordinate with LiClO4 at room temperature to form a monomer in excellent yield, but does not coordinate with NaClO4 even at elevated temperature. The structure of the monomeric complex, [LiClO4(DETAN)] (1), was characterised by single-crystal X-ray diffraction and NMR spectroscopy.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"190 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145594234","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}
Accumulation of amyloid-β peptide (Aβ) is a key hallmark of Alzheimer's disease (AD). A retinamide–platinum complex (RP) consisting of an Aβ-binding group, [Pt(bipyridine)Cl]+, and a derivative of neurotrophic retinoic acid was designed to diminish the neurotoxicity associated with Aβ aggregates and to quell the Aβ-induced neuroinflammation. RP remarkably inhibited the self- and metal-induced Aβ aggregation, reduced the production of reactive oxygen species, lowered the neurotoxicity of Aβ aggregates, and protected the plasma membrane of neural cells. The RP–Aβ conjugates are readily phagocytosed and degraded by microglial cells, thus preventing them from polarizing into the inflammatory M1 phenotype and secreting proinflammatory cytokines. Moreover, RP alleviated the behavioral dysfunction and paralysis of Aβ-transgenic C. elegans. The results demonstrate that RP is a potential nontoxic anti-AD agent capable of inhibiting Aβ aggregation and protecting nerve cells simultaneously. The dual action of RP expands the application range of platinum complexes and the structural types of anti-Alzheimer's drugs.
淀粉样蛋白-β肽（a β）的积累是阿尔茨海默病（AD）的一个关键标志。由Aβ结合基团[Pt（联吡啶）Cl]+和神经营养性维甲酸衍生物组成的维甲酸-铂复合物（RP）被设计用于减少与Aβ聚集相关的神经毒性，并抑制Aβ诱导的神经炎症。RP能显著抑制自身和金属诱导的Aβ聚集，减少活性氧的产生，降低Aβ聚集物的神经毒性，保护神经细胞的质膜。rp - a - β缀合物很容易被小胶质细胞吞噬和降解，从而阻止它们极化成炎性M1表型并分泌促炎细胞因子。此外，RP还能减轻转a β的秀丽隐杆线虫的行为功能障碍和瘫痪。结果表明，RP是一种潜在的无毒抗ad药物，具有抑制a β聚集和保护神经细胞的作用。RP的双重作用扩大了铂配合物的应用范围和抗阿尔茨海默病药物的结构类型。
{"title":"Mitigation of Aβ neurotoxicity in Alzheimer's disease using a non-toxic platinum complex derived from retinamide","authors":"Chengyuan Qian, Yicun Shang, Linxiang Cai, Yunhua Zhang, Chengyan Chu, Zijian Guo, Xiaoyong Wang","doi":"10.1039/d5qi01746g","DOIUrl":"https://doi.org/10.1039/d5qi01746g","url":null,"abstract":"Accumulation of amyloid-β peptide (Aβ) is a key hallmark of Alzheimer's disease (AD). A retinamide–platinum complex (RP) consisting of an Aβ-binding group, [Pt(bipyridine)Cl]<small><sup>+</sup></small>, and a derivative of neurotrophic retinoic acid was designed to diminish the neurotoxicity associated with Aβ aggregates and to quell the Aβ-induced neuroinflammation. RP remarkably inhibited the self- and metal-induced Aβ aggregation, reduced the production of reactive oxygen species, lowered the neurotoxicity of Aβ aggregates, and protected the plasma membrane of neural cells. The RP–Aβ conjugates are readily phagocytosed and degraded by microglial cells, thus preventing them from polarizing into the inflammatory M1 phenotype and secreting proinflammatory cytokines. Moreover, RP alleviated the behavioral dysfunction and paralysis of Aβ-transgenic <em>C. elegans</em>. The results demonstrate that RP is a potential nontoxic anti-AD agent capable of inhibiting Aβ aggregation and protecting nerve cells simultaneously. The dual action of RP expands the application range of platinum complexes and the structural types of anti-Alzheimer's drugs.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"41 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145594233","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}
Current efforts in materials science focus on developing efficient solid-state proton conductors for energy production and on achieving light-induced control of material properties at the molecular level. The convergence of these two aspects opens the way to entirely new functionalities. In this context, we present the synthesis, crystal structures, proton conductivity, and photomagnetic effect in two new CN-bridged (H3O)4{[CuII(cyclam(COOH)2)]3[MIV(CN)8]2}Cl2∙10H2O coordination complexes (M = MoIV (1), WIV (2)) incorporating dicarboxy-functionalized cyclam (cyclam(COOH)2 = 6,13-dicarboxy-1,4,8,14-tetraazacyclotetradecane). 1 and 2 crystallize in the P-1 space group, are isostructural, and consist of linear pentanuclear {CuII3MIV2}2− molecules with CuII complexes linked by [MIV(CN)8]4− anions. Due to the presence of protic COOH groups, H3O+ cations, and an extensive network of hydrogen bonds, the compounds 1 and 2 exhibit proton conductivity of 3.88(7)∙10−5 S cm−1 and 1.02(1)∙10−5 S cm−1 (298 K, 95% RH), respectively. Activation energies of 0.49 eV (1) and 0.46 eV (2) suggest that proton relay occurs predominantly along the network of moderate-strength H-bonds according to the Grotthuss mechanism. Both compounds exhibit a photomagnetic response to irradiation with 450 nm light at 10 K, which is attributed to photoinduced transition from singlet (S = 0) to triplet (S = 1) spin-state of MIV centers. The magnetic characteristics of irradiated materials indicate almost complete photoconversion, which activates magnetic superexchange between CuII (S = 1/2) and the photoexcited MIV exhibiting significant zero-field splitting. The coexistence of electrical and switchable magnetic properties in compounds 1 and 2 positions CuII–MIV assemblies as promising platforms for photoswitchable spin-ionics.
{"title":"Proton conductivity and magnetization photoswitching in CN-bridged CuII3MIV2 molecules (M = Mo, W) based on carboxy-functionalized macrocyclic ligand","authors":"Mateusz Reczyński, Michał Magott, Maciej Pazera","doi":"10.1039/d5qi01915j","DOIUrl":"https://doi.org/10.1039/d5qi01915j","url":null,"abstract":"Current efforts in materials science focus on developing efficient solid-state proton conductors for energy production and on achieving light-induced control of material properties at the molecular level. The convergence of these two aspects opens the way to entirely new functionalities. In this context, we present the synthesis, crystal structures, proton conductivity, and photomagnetic effect in two new CN-bridged (H<small><sub>3</sub></small>O)<small><sub>4</sub></small>{[Cu<small><sup>II</sup></small>(cyclam(COOH)<small><sub>2</sub></small>)]<small><sub>3</sub></small>[M<small><sup>IV</sup></small>(CN)<small><sub>8</sub></small>]<small><sub>2</sub></small>}Cl<small><sub>2</sub></small>∙10H<small><sub>2</sub></small>O coordination complexes (M = Mo<small><sup>IV</sup></small> (<strong>1</strong>), W<small><sup>IV</sup></small> (<strong>2</strong>)) incorporating dicarboxy-functionalized cyclam (cyclam(COOH)<small><sub>2</sub></small> = 6,13-dicarboxy-1,4,8,14-tetraazacyclotetradecane). <strong>1</strong> and <strong>2</strong> crystallize in the <em>P</em>-1 space group, are isostructural, and consist of linear pentanuclear {Cu<small><sup>II</sup></small><small><sub>3</sub></small>M<small><sup>IV</sup></small><small><sub>2</sub></small>}<small><sup>2−</sup></small> molecules with Cu<small><sup>II</sup></small> complexes linked by [M<small><sup>IV</sup></small>(CN)<small><sub>8</sub></small>]<small><sup>4−</sup></small> anions. Due to the presence of protic COOH groups, H<small><sub>3</sub></small>O<small><sup>+</sup></small> cations, and an extensive network of hydrogen bonds, the compounds <strong>1</strong> and <strong>2</strong> exhibit proton conductivity of 3.88(7)∙10<small><sup>−5</sup></small> S cm<small><sup>−1</sup></small> and 1.02(1)∙10<small><sup>−5</sup></small> S cm<small><sup>−1</sup></small> (298 K, 95% RH), respectively. Activation energies of 0.49 eV (<strong>1</strong>) and 0.46 eV (<strong>2</strong>) suggest that proton relay occurs predominantly along the network of moderate-strength H-bonds according to the Grotthuss mechanism. Both compounds exhibit a photomagnetic response to irradiation with 450 nm light at 10 K, which is attributed to photoinduced transition from singlet (<em>S</em> = 0) to triplet (<em>S</em> = 1) spin-state of M<small><sup>IV</sup></small> centers. The magnetic characteristics of irradiated materials indicate almost complete photoconversion, which activates magnetic superexchange between Cu<small><sup>II</sup></small> (<em>S</em> = 1/2) and the photoexcited M<small><sup>IV</sup></small> exhibiting significant zero-field splitting. The coexistence of electrical and switchable magnetic properties in compounds <strong>1</strong> and <strong>2</strong> positions Cu<small><sup>II</sup></small>–M<small><sup>IV</sup></small> assemblies as promising platforms for photoswitchable spin-ionics.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"8 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-11-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145583679","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}
京公网安备 11010802042870号
京ICP备2023020795号-1
扫码关注我们
求助内容：
应助结果提醒方式：