Penglei Xu, Huiluan Qin, Chen Wang, Feiyang Zhang, Zhixin Yu, Ran Duan, Chuncheng Chen, QI Shen, Chunyan Sun
Polybrominated diphenyl ethers (PBDEs) have garnered growing concern due to their biotoxicity and persistence. Herein, the visible photodegradation of BDE209 is achieved on diethylenetriamine (DETA) intercalated wide band gap ZnS, mediated by a photosensitized complex formed via a N···Br halogen bond. By regulating the amount of DETA, ZnS(DETA)1/2n, referred to as ZD, exhibit tunable photocatalytic activity towards BDE209. The most rapid degradation is observed on ZD-4, with 98% removal achieved within 6 hours. DFT calculation reveals that the halogen bond is preferentially form between amino N and para-Br atom in BDE209 with a bond length of 2.7548 Å. A novel degradation pathway for BDE209 is proposed, in which the DETA···BDE209 complex functions as a visible light photosensitizer, providing photoelectrons to the conduction band of ZnS, thereby participating in the degradation of BDE209 adsorbed on the ZnS surface. This process is significantly more effective than the indirect photolysis of BDE209 by DETA solely. Notably, this degradation phenomenon is also observed in other organic amines coordinated ZnS, suggesting a universal mechanism for BDE209 degradation by photosensitized halogen bond-based complexes. This work provides a novel strategy to utilize the weak interfacial halogen bonding for visible-light photosensitized degradation of brominated persistent organic pollutants by wide band gap inorganic semiconductors.
{"title":"N···Br Halogen Bond Broadened Visible-light Degradation of Decabromodiphenyl Ether on Organic Amine Intercalated Zinc Sulfide","authors":"Penglei Xu, Huiluan Qin, Chen Wang, Feiyang Zhang, Zhixin Yu, Ran Duan, Chuncheng Chen, QI Shen, Chunyan Sun","doi":"10.1039/d5qi00006h","DOIUrl":"https://doi.org/10.1039/d5qi00006h","url":null,"abstract":"Polybrominated diphenyl ethers (PBDEs) have garnered growing concern due to their biotoxicity and persistence. Herein, the visible photodegradation of BDE209 is achieved on diethylenetriamine (DETA) intercalated wide band gap ZnS, mediated by a photosensitized complex formed via a N···Br halogen bond. By regulating the amount of DETA, ZnS(DETA)1/2n, referred to as ZD, exhibit tunable photocatalytic activity towards BDE209. The most rapid degradation is observed on ZD-4, with 98% removal achieved within 6 hours. DFT calculation reveals that the halogen bond is preferentially form between amino N and para-Br atom in BDE209 with a bond length of 2.7548 Å. A novel degradation pathway for BDE209 is proposed, in which the DETA···BDE209 complex functions as a visible light photosensitizer, providing photoelectrons to the conduction band of ZnS, thereby participating in the degradation of BDE209 adsorbed on the ZnS surface. This process is significantly more effective than the indirect photolysis of BDE209 by DETA solely. Notably, this degradation phenomenon is also observed in other organic amines coordinated ZnS, suggesting a universal mechanism for BDE209 degradation by photosensitized halogen bond-based complexes. This work provides a novel strategy to utilize the weak interfacial halogen bonding for visible-light photosensitized degradation of brominated persistent organic pollutants by wide band gap inorganic semiconductors.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"1 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143575207","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}
Far ultraviolet-C (far-UVC; 200–230 nm) luminescent materials have garnered significant interest in recent years, driven by the growing demands for applications such as disinfection and solar-blind imaging due to their distinct wavelength features. However, the research and development of far-UVC persistent phosphors are lacking. Here, we report the realization of far-UVC persistent luminescence in CaSO4:Pr3+ and CaSO4:Pb2+ phosphors, which show emissions peaking at 220 nm and 230 nm with a long persistence time of >24 h after ceasing X-ray excitation. This is by far the shortest UVC afterglow emission to the best of our knowledge. The far-UVC afterglow from the charged phosphors can be readily detected by a solar-blind UV camera in both indoor-lighting and outdoor environments owing to the absence of background noise from ambient light. The continuous photostimulation of indoor white LED light and outdoor sunlight has different impact on the far-UVC afterglow performance of CaSO4:Pr3+ and CaSO4:Pb2+ phosphors, which is elucidated by the decay time-dependent thermoluminescence (TL) curves in different light conditions. This study expands the field of persistent luminescence to the far-UVC spectral region and will inspire the discovery of more excellent far-UVC persistent phosphors.
{"title":"Long-lasting far-UVC persistent luminescence for solar-blind optical tagging","authors":"Xihui Shan, Yi Zhang, Xulong Lv, Yanjie Liang","doi":"10.1039/d5qi00184f","DOIUrl":"https://doi.org/10.1039/d5qi00184f","url":null,"abstract":"Far ultraviolet-C (far-UVC; 200–230 nm) luminescent materials have garnered significant interest in recent years, driven by the growing demands for applications such as disinfection and solar-blind imaging due to their distinct wavelength features. However, the research and development of far-UVC persistent phosphors are lacking. Here, we report the realization of far-UVC persistent luminescence in CaSO4:Pr3+ and CaSO4:Pb2+ phosphors, which show emissions peaking at 220 nm and 230 nm with a long persistence time of >24 h after ceasing X-ray excitation. This is by far the shortest UVC afterglow emission to the best of our knowledge. The far-UVC afterglow from the charged phosphors can be readily detected by a solar-blind UV camera in both indoor-lighting and outdoor environments owing to the absence of background noise from ambient light. The continuous photostimulation of indoor white LED light and outdoor sunlight has different impact on the far-UVC afterglow performance of CaSO4:Pr3+ and CaSO4:Pb2+ phosphors, which is elucidated by the decay time-dependent thermoluminescence (TL) curves in different light conditions. This study expands the field of persistent luminescence to the far-UVC spectral region and will inspire the discovery of more excellent far-UVC persistent phosphors.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"67 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143570168","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}
Linshuai Li, Gaoqing Chen, Fengluan You, Jingtao Zhao, Danyang Shen, Shisheng Lin, Lei Lei, Shiqing Xu, Su Zhou
Scintillators possessing remarkable capabilities for converting high-energy irradiation into visible emission can be utilized to achieve indirect X-ray detection. Defect levels of oxide phosphors can effectively capture electron–hole pairs induced by ionizing radiation for carrier storage. Here, we fabricated a series of Y3AlxGa(5−x)O12:Ce phosphors with a broad trap depth distribution using the molten salt method by introducing aliovalent Na+ and F− ions into lattices. We found that charge carriers excited by X-ray irradiation are distributed at shallower defect levels than those excited by 450 nm blue light. We propose the photophysical mechanisms of the two excitation modes: high-energy electrons induced by ionizing radiation are transferred to the shallow traps through the conduction band, while photogenerated electrons are transferred to the deep traps, which are close to the excited state of the luminescence center. Flexible thin films prepared by embedding Y3Al2Ga3O12:Ce powder into polydimethylsiloxane (PDMS) are utilized as a scintillator screen, and X-ray imaging in real-time, time-lapse and storage modes has been achieved. This work reveals the mechanisms of ionizing radiation-induced carrier charging and further develops the application of oxide phosphors in X-ray imaging and information storage.
{"title":"X-ray imaging and storage based on a NaF modified Y3Al2Ga3O12:Ce phosphor","authors":"Linshuai Li, Gaoqing Chen, Fengluan You, Jingtao Zhao, Danyang Shen, Shisheng Lin, Lei Lei, Shiqing Xu, Su Zhou","doi":"10.1039/d4qi03312d","DOIUrl":"https://doi.org/10.1039/d4qi03312d","url":null,"abstract":"Scintillators possessing remarkable capabilities for converting high-energy irradiation into visible emission can be utilized to achieve indirect X-ray detection. Defect levels of oxide phosphors can effectively capture electron–hole pairs induced by ionizing radiation for carrier storage. Here, we fabricated a series of Y<small><sub>3</sub></small>Al<small><sub><em>x</em></sub></small>Ga<small><sub>(5−<em>x</em>)</sub></small>O<small><sub>12</sub></small>:Ce phosphors with a broad trap depth distribution using the molten salt method by introducing aliovalent Na<small><sup>+</sup></small> and F<small><sup>−</sup></small> ions into lattices. We found that charge carriers excited by X-ray irradiation are distributed at shallower defect levels than those excited by 450 nm blue light. We propose the photophysical mechanisms of the two excitation modes: high-energy electrons induced by ionizing radiation are transferred to the shallow traps through the conduction band, while photogenerated electrons are transferred to the deep traps, which are close to the excited state of the luminescence center. Flexible thin films prepared by embedding Y<small><sub>3</sub></small>Al<small><sub>2</sub></small>Ga<small><sub>3</sub></small>O<small><sub>12</sub></small>:Ce powder into polydimethylsiloxane (PDMS) are utilized as a scintillator screen, and X-ray imaging in real-time, time-lapse and storage modes has been achieved. This work reveals the mechanisms of ionizing radiation-induced carrier charging and further develops the application of oxide phosphors in X-ray imaging and information storage.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"67 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143561300","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}
Hydrodeoxygenation of bio-lipids into renewable alkanes is a promising strategy to substitute fossil resources. Bifunctional metals/zeolites have demonstrated high performance in hydrodeoxygenation reactions but suffer from severe mass transfer limitation and low carbon atom economy. Here, we synthesize a hierarchically porous metal/zeolite catalyst consisting of ZSM-5 zeolite nanosheet-supported bimetallic Ni–Co alloy nanoparticles. The strategy utilizes self-pillared ZSM-5 nanosheets as supports to grow layered bimetallic Ni–Co silicates. Following a hydrogen reduction, bimetallic Ni–Co alloy nanoparticles are anchored on zeolites. Compared to conventional metals/zeolites, the nanosheet self-supported Ni–Co alloy/ZSM-5 composites feature a rich mesoporous structure, high specific surface area, and highly dispersed alloy nanoparticles with tailored loading and atomic ratios of each metal component. In the hydrodeoxygenation of stearic acid, the prepared Ni–Co alloy/ZSM-5 catalysts achieve complete conversion of stearic acid within 50 minutes, with a reaction rate of 25.5 g gcat−1 h−1, five times higher than that of commercial ZSM-5-supported bimetallic Ni–Co alloy catalysts. In addition, the selectivity for octadecane in the product reaches 88%, which is 13.4% higher than that of monometallic Ni/ZSM-5 catalysts. The remarkable enhanced hydrodeoxygenation performance of the bifunctional catalysts is attributed to the open mesoporous nanoarchitecture and the synergistic effects of uniformly dispersed Ni–Co alloy nanoparticles and abundant Brønsted acid sites exposed by the ZSM-5 nanosheets. This synthetic strategy paves a pathway toward the rational construction of hierarchically porous metal alloy/zeolite catalysts for diverse potential applications.
{"title":"Construction of Ni–Co alloy/zeolite nanosheet catalysts for the hydrodeoxygenation of fatty acids to alkanes","authors":"Ge Tian, Guangrui Chen, Risheng Bai, Guoju Yang, Zhenheng Diao, Buyuan Guan, Jihong Yu","doi":"10.1039/d4qi02989e","DOIUrl":"https://doi.org/10.1039/d4qi02989e","url":null,"abstract":"Hydrodeoxygenation of bio-lipids into renewable alkanes is a promising strategy to substitute fossil resources. Bifunctional metals/zeolites have demonstrated high performance in hydrodeoxygenation reactions but suffer from severe mass transfer limitation and low carbon atom economy. Here, we synthesize a hierarchically porous metal/zeolite catalyst consisting of ZSM-5 zeolite nanosheet-supported bimetallic Ni–Co alloy nanoparticles. The strategy utilizes self-pillared ZSM-5 nanosheets as supports to grow layered bimetallic Ni–Co silicates. Following a hydrogen reduction, bimetallic Ni–Co alloy nanoparticles are anchored on zeolites. Compared to conventional metals/zeolites, the nanosheet self-supported Ni–Co alloy/ZSM-5 composites feature a rich mesoporous structure, high specific surface area, and highly dispersed alloy nanoparticles with tailored loading and atomic ratios of each metal component. In the hydrodeoxygenation of stearic acid, the prepared Ni–Co alloy/ZSM-5 catalysts achieve complete conversion of stearic acid within 50 minutes, with a reaction rate of 25.5 g g<small><sub>cat</sub></small><small><sup>−1</sup></small> h<small><sup>−1</sup></small>, five times higher than that of commercial ZSM-5-supported bimetallic Ni–Co alloy catalysts. In addition, the selectivity for octadecane in the product reaches 88%, which is 13.4% higher than that of monometallic Ni/ZSM-5 catalysts. The remarkable enhanced hydrodeoxygenation performance of the bifunctional catalysts is attributed to the open mesoporous nanoarchitecture and the synergistic effects of uniformly dispersed Ni–Co alloy nanoparticles and abundant Brønsted acid sites exposed by the ZSM-5 nanosheets. This synthetic strategy paves a pathway toward the rational construction of hierarchically porous metal alloy/zeolite catalysts for diverse potential applications.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"53 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143561301","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}
Wenjun Gong, Yating Pang, Chenyu Wang, Wenming Wang, Hong-Fei Wang
The dinitrosyl iron complex (DNIC) is a ubiquitous functional brick often used as a vehicle for the NO radical and chelatable iron pool, with a key role in chemical and biomedical applications. In this work, four DNICs modified with different thiolate bridging ligands (–SL) were synthesized. These complexes were characterized by 1H-NMR, electrospray ionization mass spectrometry, and X-ray crystal diffraction. Photoinduced NO release from the complexes in solution was further explored by time-resolved infrared and time-resolved electron paramagnetic resonance (EPR) spectra. The cluster complexes showed relatively lower cytotoxicity against the normal human liver cell line HL-7702 and higher cytotoxicity against human cervical cancer cells, with a selectivity index of 2.4–4.8. The cluster complexes with different L groups had different rates of NO release and protein binding constants. Moreover, NO released upon photoirradiation entered living cells, which were successfully imaged using an NO-selective fluorescent probe. The ferritin complex adducts further enhanced the cytotoxicity and cellular fluorescent intensity of NO, and the crystal structure revealed the coordination of the Fe(SL)2 unit with Cys102 of ferritin. This study provides insight into the photodynamic mechanism of nitrosyl iron−sulfur clusters to understand their physiological activity.
{"title":"Photoinduced NO release of [Fe2(µ-SL)2(NO)4] complexes and their protein adducts: insights from structure, cytotoxicity, and photodynamic studies","authors":"Wenjun Gong, Yating Pang, Chenyu Wang, Wenming Wang, Hong-Fei Wang","doi":"10.1039/d5qi00255a","DOIUrl":"https://doi.org/10.1039/d5qi00255a","url":null,"abstract":"The dinitrosyl iron complex (DNIC) is a ubiquitous functional brick often used as a vehicle for the NO radical and chelatable iron pool, with a key role in chemical and biomedical applications. In this work, four DNICs modified with different thiolate bridging ligands (–SL) were synthesized. These complexes were characterized by 1H-NMR, electrospray ionization mass spectrometry, and X-ray crystal diffraction. Photoinduced NO release from the complexes in solution was further explored by time-resolved infrared and time-resolved electron paramagnetic resonance (EPR) spectra. The cluster complexes showed relatively lower cytotoxicity against the normal human liver cell line HL-7702 and higher cytotoxicity against human cervical cancer cells, with a selectivity index of 2.4–4.8. The cluster complexes with different L groups had different rates of NO release and protein binding constants. Moreover, NO released upon photoirradiation entered living cells, which were successfully imaged using an NO-selective fluorescent probe. The ferritin complex adducts further enhanced the cytotoxicity and cellular fluorescent intensity of NO, and the crystal structure revealed the coordination of the Fe(SL)2 unit with Cys102 of ferritin. This study provides insight into the photodynamic mechanism of nitrosyl iron−sulfur clusters to understand their physiological activity.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"7 4 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143561302","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}
The optimization of electronic structure and increase of exposed surface sites represent the promising direction for enhancing the activity of Ni-based catalysts for urea oxidation reaction (UOR)-assisted electrolysis. Here, we have reported the designed synthesis of 2D porous NiCo alloy thin sheets (NiCo/C) based on NaCl-induced transformation of the EDTA-NiCo complex for effective UOR-assisted hydrogen evolution reaction (HER). The porous and thin-sheet structure endows a large specific surface area of 141.59 m2/g, greatly enhancing the exposure of active sites. The electron transfer from Co to Ni can optimize the electronic properties of Ni sites, decreasing energy barrier and accelerating reaction kinetics for UOR. The catalyst shows low UOR potential of 1.30 V at a current density of 10 mA cm-2, much lower than the traditional oxygen evolution reaction (1.51 V). The in-situ impedance/infrared spectroscopy indicates the fast UOR process and a more environmentally sustainable "carbonate" pathway. The catalyst also shows low HER overpotential of 30 mV at a current density of 10 mA cm-2, being comparable to Pt/C. The urea-assisted H2 production cell based on NiCo/C only requires 1.38 V at a current density of 10 mA cm-2, superior to the 1.45 V of Pt/C‖RuO2 cell.
{"title":"Porous NiCo alloy thin sheets with synergistic Co/Ni sites for high-efficiency urea-assisted electrocatalytic hydrogen production","authors":"Chengxu Jin, Aiping Wu, Yuying Fan, Xianyun Yue, Dongxu Wang, Chungui Tian","doi":"10.1039/d5qi00165j","DOIUrl":"https://doi.org/10.1039/d5qi00165j","url":null,"abstract":"The optimization of electronic structure and increase of exposed surface sites represent the promising direction for enhancing the activity of Ni-based catalysts for urea oxidation reaction (UOR)-assisted electrolysis. Here, we have reported the designed synthesis of 2D porous NiCo alloy thin sheets (NiCo/C) based on NaCl-induced transformation of the EDTA-NiCo complex for effective UOR-assisted hydrogen evolution reaction (HER). The porous and thin-sheet structure endows a large specific surface area of 141.59 m2/g, greatly enhancing the exposure of active sites. The electron transfer from Co to Ni can optimize the electronic properties of Ni sites, decreasing energy barrier and accelerating reaction kinetics for UOR. The catalyst shows low UOR potential of 1.30 V at a current density of 10 mA cm-2, much lower than the traditional oxygen evolution reaction (1.51 V). The in-situ impedance/infrared spectroscopy indicates the fast UOR process and a more environmentally sustainable \"carbonate\" pathway. The catalyst also shows low HER overpotential of 30 mV at a current density of 10 mA cm-2, being comparable to Pt/C. The urea-assisted H2 production cell based on NiCo/C only requires 1.38 V at a current density of 10 mA cm-2, superior to the 1.45 V of Pt/C‖RuO2 cell.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"18 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143545904","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}
Jannis Fidelius, Kai Schwedtmann, Sebastian Schellhammer, Rongjuan Huang, Felix Hennersdorf, Moritz Fink, Jan Haberstroh, Antonio Bauza, Antonio Frontera, Sebastian Reineke, Jan J Weigand
The advent of 1,3-dipolar cycloadditions in organic chemistry has introduced a powerful tool for constructing novel ring systems. However, methods for synthesizing inorganic, phosphorus-containing rings via 1,3-dipolar cycloadditions have remained scarce and are largely limited to the functionalization of phosphaalkynes. In this contribution, we describe the synthesis of 1,3-dipolar triflatophosphanes, demonstrating their ability to engage in (3+2)-cycloadditions with a variety of dipolarophiles. In addition to nitriles, (thio)-cyanates, iso-(thio)-cyanates, and (thio)-ketones, phosphaalkenes also exhibit reactivity, yielding a wide range of heteroatom-functionalized di- and triazaphospholium compounds. Density Functional Theory (DFT) calculations provide insight into the likely stepwise mechanism. Furthermore, the reduction of synthesized diazaphospholium salts affords neutral diazaphospholes, offering a novel route to this class of compounds. Importantly, we explored the photophysical properties of selected diazaphospholes that exhibit strong fluorcesence with photoluminescence quantum yields up to 37 %, making them attractive candidates for applications in optoelectronics.
{"title":"1,3-Dipolar Cycloaddition Reactions of Triflatophosphanes to Functionalized Azaphospholium Salts and Azaphospholes","authors":"Jannis Fidelius, Kai Schwedtmann, Sebastian Schellhammer, Rongjuan Huang, Felix Hennersdorf, Moritz Fink, Jan Haberstroh, Antonio Bauza, Antonio Frontera, Sebastian Reineke, Jan J Weigand","doi":"10.1039/d5qi00427f","DOIUrl":"https://doi.org/10.1039/d5qi00427f","url":null,"abstract":"The advent of 1,3-dipolar cycloadditions in organic chemistry has introduced a powerful tool for constructing novel ring systems. However, methods for synthesizing inorganic, phosphorus-containing rings via 1,3-dipolar cycloadditions have remained scarce and are largely limited to the functionalization of phosphaalkynes. In this contribution, we describe the synthesis of 1,3-dipolar triflatophosphanes, demonstrating their ability to engage in (3+2)-cycloadditions with a variety of dipolarophiles. In addition to nitriles, (thio)-cyanates, iso-(thio)-cyanates, and (thio)-ketones, phosphaalkenes also exhibit reactivity, yielding a wide range of heteroatom-functionalized di- and triazaphospholium compounds. Density Functional Theory (DFT) calculations provide insight into the likely stepwise mechanism. Furthermore, the reduction of synthesized diazaphospholium salts affords neutral diazaphospholes, offering a novel route to this class of compounds. Importantly, we explored the photophysical properties of selected diazaphospholes that exhibit strong fluorcesence with photoluminescence quantum yields up to 37 %, making them attractive candidates for applications in optoelectronics.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"18 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143561303","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}
Balázs Sándor, Ágnes Grenács, Gergő Zoltán Sajtos, Giuseppina Sabatino, Giuseppe Di Natale, Giuseppe Pappalardo, Katalin Várnagy
Alpha tubulin proteins are recognised as a key component in the process of cell division, due to their role in dimerisation and polymerisation, which results the formation of microtubules in eukaryotes, however in the context of Alzheimer's disease (AD) and other neurodegenerative diseases (ND), it may also play an important role, as alterations in their structure and disintegration have been observed. The present paper investigates the 189-195 region of the human tubulin α 1A protein, in the presence of essential copper(II), zinc(II) and the toxic nickel(II) metal ions. The aforementioned natural protein fragment contains the –(S/T)XH– amino acid motif, which sequences were previously identified as the active sites of a metal-ion-induced, sequence-specific hydrolysis process. The solution equilibrium studies (pH-potentiometry, UV-Vis- and CD spectroscopy) demonstrated that the metal complexes formed under the physiological pH conditions exhibit enhanced thermodynamic stability. The RP-HPLC and MS studies confirmed the irreversible behaviour of the heptapeptide, due to the formation of the intermediate and final products of the hydrolytic reaction, which were induced by the nickel(II) and copper(II) metal ions. In the presence of nickel(II) ions under conditions of pH 8.2 and temperature 37 °C, the kinetic parameters of the reaction were determined. The half-life value for the formation of the intermediate product were found to be 3.70 hours, while for the formation of the final product was 73.75 hours.
{"title":"The hydrolytic stability of the human tubulin α 1A protein fragment – a potential reason for the role of metal ions in the development of neurodegenerative diseases","authors":"Balázs Sándor, Ágnes Grenács, Gergő Zoltán Sajtos, Giuseppina Sabatino, Giuseppe Di Natale, Giuseppe Pappalardo, Katalin Várnagy","doi":"10.1039/d4qi03271c","DOIUrl":"https://doi.org/10.1039/d4qi03271c","url":null,"abstract":"Alpha tubulin proteins are recognised as a key component in the process of cell division, due to their role in dimerisation and polymerisation, which results the formation of microtubules in eukaryotes, however in the context of Alzheimer's disease (AD) and other neurodegenerative diseases (ND), it may also play an important role, as alterations in their structure and disintegration have been observed. The present paper investigates the 189-195 region of the human tubulin α 1A protein, in the presence of essential copper(II), zinc(II) and the toxic nickel(II) metal ions. The aforementioned natural protein fragment contains the –(S/T)XH– amino acid motif, which sequences were previously identified as the active sites of a metal-ion-induced, sequence-specific hydrolysis process. The solution equilibrium studies (pH-potentiometry, UV-Vis- and CD spectroscopy) demonstrated that the metal complexes formed under the physiological pH conditions exhibit enhanced thermodynamic stability. The RP-HPLC and MS studies confirmed the irreversible behaviour of the heptapeptide, due to the formation of the intermediate and final products of the hydrolytic reaction, which were induced by the nickel(II) and copper(II) metal ions. In the presence of nickel(II) ions under conditions of pH 8.2 and temperature 37 °C, the kinetic parameters of the reaction were determined. The half-life value for the formation of the intermediate product were found to be 3.70 hours, while for the formation of the final product was 73.75 hours.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"2 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143545905","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}
To enhance the kinetics of the electrochemical hydrogen evolution reaction (HER) in alkaline electrolytes, metallic Ru (Ru0)-RuO2-ZnO heterointerfaces are constructed by pyrolyzing hollow Ru-ZIF-8 nanostructures with varying shapes. Systematic characterizations and theoretical simulations reveal that the exposed facets and oxygen vacancy (Ov) contents of the heterointerfaces depend on the shape and pyrolysis temperature of Ru-ZIF-8. Rhombic dodecahedral Ru-ZIF-8-derived nanocrystals by pyrolyzing at 900°C expose Ru0{1-20}-RuO2{-221}-ZnO{001} heterointerfaces with suitable Ov content, resulting in an alleviated work function and a downshifted d-band center (εd). These structural optimizations accelerate H2O adsorption-dissociation on the nanocrystal surface, weaken the excessively strong electronic interaction between the catalytic surface and the H* intermediate, balance the strengths of H* adsorption and H2 desorption, facilitate the rate-determining stage (RDS, H2 desorption), and ultimately lower the apparent activation energy for HER. As a result, an overpotential of 25.0 mV at 10 mA cm-2 and a turnover frequency of H2 generation of 0.23 s-1 at 100 mV are achieved, surpassing other heterostructure analogues. An excellent linearity between the HER overpotentials and the Gibbs free energy change of H* adsorption is substantiated, highlighting the advantage of d-orbital manipulation in expediting activity.
{"title":"Work function and d-band center dual-modulation in hollow Ru-ZIF-8-derived Ru0-RuO2-ZnO heterointerfaces for boosted electrochemical hydrogen evolution","authors":"Xiaoxin Xu, Ruidong Shi, Yuanting Li, Xue Wang, Gongbing Zhou","doi":"10.1039/d4qi03353a","DOIUrl":"https://doi.org/10.1039/d4qi03353a","url":null,"abstract":"To enhance the kinetics of the electrochemical hydrogen evolution reaction (HER) in alkaline electrolytes, metallic Ru (Ru<small><sup>0</sup></small>)-RuO<small><sub>2</sub></small>-ZnO heterointerfaces are constructed by pyrolyzing hollow Ru-ZIF-8 nanostructures with varying shapes. Systematic characterizations and theoretical simulations reveal that the exposed facets and oxygen vacancy (O<small><sub>v</sub></small>) contents of the heterointerfaces depend on the shape and pyrolysis temperature of Ru-ZIF-8. Rhombic dodecahedral Ru-ZIF-8-derived nanocrystals by pyrolyzing at 900°C expose Ru0{1-20}-RuO2{-221}-ZnO{001} heterointerfaces with suitable O<small><sub>v</sub></small> content, resulting in an alleviated work function and a downshifted <em>d</em>-band center (<em>ε</em><small><sub>d</sub></small>). These structural optimizations accelerate H<small><sub>2</sub></small>O adsorption-dissociation on the nanocrystal surface, weaken the excessively strong electronic interaction between the catalytic surface and the H<small><sup>*</sup></small> intermediate, balance the strengths of H<small><sup>*</sup></small> adsorption and H<small><sub>2</sub></small> desorption, facilitate the rate-determining stage (RDS, H<small><sub>2</sub></small> desorption), and ultimately lower the apparent activation energy for HER. As a result, an overpotential of 25.0 mV at 10 mA cm<small><sup>-2</sup></small> and a turnover frequency of H<small><sub>2</sub></small> generation of 0.23 s<small><sup>-1</sup></small> at 100 mV are achieved, surpassing other heterostructure analogues. An excellent linearity between the HER overpotentials and the Gibbs free energy change of H<small><sup>*</sup></small> adsorption is substantiated, highlighting the advantage of <em>d</em>-orbital manipulation in expediting activity.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"35 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143545906","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}
Xinxin Jin, Zhen Shao, Pengxiang Fu, Yifan Deng, Qi Sui, Yi-Han Wang, Jin Xiong, Bingwu Wang, Zheming Wang, Song Gao
The integration of photochromism and photomagnetism is of great significance for developing photo-responsive multifunctional materials. Herein, we successfully synthesized four cyanido-bridged bimetallic frameworks formulated as (MVII)0.5[MIIIMII(CN)6]·(H2O)n (i.e., FeMn, FeZn, CrMn, CrZn; MVII = 1,1'-dimethyl-4,4'-bipyridine dication; MIII = FeIII, CrIII; MII = MnII, ZnII), by incorporating diverse polycyanidometallates and viologen moieties into the donor-acceptor (D-A) hybrid molecular-based materials. FeZn and CrZn both exhibit visible photoinduced electron transfer (PET) processes upon Xe lamp irradiation at room temperature. However, while CrZn undergoes a reversible photochromism, FeZn displays irreversible photochromism, which originates not only from photoinduced radicals but also from Fe reduction. Interestingly, the change in absorption band of FeZn spans the UV-visible-near infrared (UV-Vis-NIR) region (ca. 200-2600 nm) after irradiation. Although FeMn and CrMn do not exhibit photoinduced colour changes, they behave as two-dimensional (2D) and three-dimensional (3D) ferrimagnets, respectively, with CrMn exhibiting long-range ordering below ca. 80 K. FeZn exhibits photomagnetic behaviors upon irradiation due to the magnetic interactions between photoinduced viologen radicals and low-spin (LS) FeIII ions. Additionally, we investigate the remarkable influence of metal ions on photochromism and (photo)magnetism through detailed crystal structure analysis. This work provides a novel approach to photo-responsive multifunctional materials using cyanidometallic viologen hybrid compounds.
{"title":"Tuning Photochromism and Photomagnetism via Diverse Bimetal-cyanido Viologen Hybrid Materials","authors":"Xinxin Jin, Zhen Shao, Pengxiang Fu, Yifan Deng, Qi Sui, Yi-Han Wang, Jin Xiong, Bingwu Wang, Zheming Wang, Song Gao","doi":"10.1039/d4qi03115f","DOIUrl":"https://doi.org/10.1039/d4qi03115f","url":null,"abstract":"The integration of photochromism and photomagnetism is of great significance for developing photo-responsive multifunctional materials. Herein, we successfully synthesized four cyanido-bridged bimetallic frameworks formulated as (MVII)0.5[MIIIMII(CN)6]·(H2O)n (i.e., FeMn, FeZn, CrMn, CrZn; MVII = 1,1'-dimethyl-4,4'-bipyridine dication; MIII = FeIII, CrIII; MII = MnII, ZnII), by incorporating diverse polycyanidometallates and viologen moieties into the donor-acceptor (D-A) hybrid molecular-based materials. FeZn and CrZn both exhibit visible photoinduced electron transfer (PET) processes upon Xe lamp irradiation at room temperature. However, while CrZn undergoes a reversible photochromism, FeZn displays irreversible photochromism, which originates not only from photoinduced radicals but also from Fe reduction. Interestingly, the change in absorption band of FeZn spans the UV-visible-near infrared (UV-Vis-NIR) region (ca. 200-2600 nm) after irradiation. Although FeMn and CrMn do not exhibit photoinduced colour changes, they behave as two-dimensional (2D) and three-dimensional (3D) ferrimagnets, respectively, with CrMn exhibiting long-range ordering below ca. 80 K. FeZn exhibits photomagnetic behaviors upon irradiation due to the magnetic interactions between photoinduced viologen radicals and low-spin (LS) FeIII ions. Additionally, we investigate the remarkable influence of metal ions on photochromism and (photo)magnetism through detailed crystal structure analysis. This work provides a novel approach to photo-responsive multifunctional materials using cyanidometallic viologen hybrid compounds.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"7 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143539074","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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