Only merury(II) and silver(I) ions specifically bind to natural and naturally modified base pairs in duplex DNA to form metal-mediated base pairs. We found novel specific binding of copper ion to naturally modified base pairs involving 5-fluorouracil(FdU) in duplex DNA to form C–Cu–FdU and FdU–Cu–C.
{"title":"Novel specific binding of copper ions to naturally modified base pairs involving 5-fluorouracil in duplex DNA","authors":"Hidetaka Torigoe, Kei Hirabayashi, Saki Adachi, Jiro Kondo","doi":"10.1039/d5dt00619h","DOIUrl":"https://doi.org/10.1039/d5dt00619h","url":null,"abstract":"Only merury(II) and silver(I) ions specifically bind to natural and naturally modified base pairs in duplex DNA to form metal-mediated base pairs. We found novel specific binding of copper ion to naturally modified base pairs involving 5-fluorouracil(FdU) in duplex DNA to form C–Cu–FdU and FdU–Cu–C.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"74 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143832301","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Roman A Khalaniya, Valeriy Verchenko, Andrey V. Mironov, Alexander N. Samarin, Alexey Bogach, Aleksandr Kulchu, Alexey O. Polevik, Wei Zheng, Evgeny V. Dikarev, Raivo Stern, Andrei V Shevelkov
Fe32+δGe35−xSix was synthesized using solid-state and chemical vapor transport reactions both in powder and single crystalline forms. Single crystal and high-resolution powder X-ray diffraction experiments revealed Fe32+δGe35−xSix to be a third member of the Fe32+δGe35−xEx (E = p-element) family of ternary compounds alongside Fe32+δGe33As2 and Fe32+δGe35−xPx. Fe32+δGe35−xSix features a two-dimensional intergrowth structure of two parent structure types: MgFe6Ge6 and Co2Al5. Similarly to the other members, the stabilisation of the intergrowth structure in Fe32+δGe35−xSix occurs as a result of the p-element substitution in the MgFe6Ge6-type block. The intergrowth breaks the kagome net of MgFe6Ge6 into individual hexagrams, while providing additional layers of geometrically frustrated atomic arrangements. Magnetic measurements showed antiferromagnetic ordering at TN ~ 150–160 K and spin reorientation below 80–90 K owing to the competition between magnetic interactions in the frustrated magnetic lattice of Fe32+δGe35−xSix.
{"title":"Spin reorientation and magnetic frustration in Fe32+δGe35−xSix with a kagome lattice broken by crystallographic intergrowth","authors":"Roman A Khalaniya, Valeriy Verchenko, Andrey V. Mironov, Alexander N. Samarin, Alexey Bogach, Aleksandr Kulchu, Alexey O. Polevik, Wei Zheng, Evgeny V. Dikarev, Raivo Stern, Andrei V Shevelkov","doi":"10.1039/d5dt00654f","DOIUrl":"https://doi.org/10.1039/d5dt00654f","url":null,"abstract":"Fe<small><sub>32+δ</sub></small>Ge<small><sub>35−x</sub></small>Si<small><sub>x</sub></small> was synthesized using solid-state and chemical vapor transport reactions both in powder and single crystalline forms. Single crystal and high-resolution powder X-ray diffraction experiments revealed Fe<small><sub>32+δ</sub></small>Ge<small><sub>35−x</sub></small>Si<small><sub>x</sub></small> to be a third member of the Fe<small><sub>32+δ</sub></small>Ge<small><sub>35−x</sub></small>E<small><sub>x</sub></small> (E = <em>p</em>-element) family of ternary compounds alongside Fe<small><sub>32+δ</sub></small>Ge<small><sub>33</sub></small>As<small><sub>2</sub></small> and Fe<small><sub>32+δ</sub></small>Ge<small><sub>35−x</sub></small>P<small><sub>x</sub></small>. Fe<small><sub>32+δ</sub></small>Ge<small><sub>35−x</sub></small>Si<small><sub>x</sub></small> features a two-dimensional intergrowth structure of two parent structure types: MgFe<small><sub>6</sub></small>Ge<small><sub>6</sub></small> and Co<small><sub>2</sub></small>Al<small><sub>5</sub></small>. Similarly to the other members, the stabilisation of the intergrowth structure in Fe<small><sub>32+δ</sub></small>Ge<small><sub>35−x</sub></small>Si<small><sub>x</sub></small> occurs as a result of the p-element substitution in the MgFe<small><sub>6</sub></small>Ge<small><sub>6</sub></small>-type block. The intergrowth breaks the kagome net of MgFe<small><sub>6</sub></small>Ge<small><sub>6</sub></small> into individual hexagrams, while providing additional layers of geometrically frustrated atomic arrangements. Magnetic measurements showed antiferromagnetic ordering at <em>T</em><small><sub>N</sub></small> ~ 150–160 K and spin reorientation below 80–90 K owing to the competition between magnetic interactions in the frustrated magnetic lattice of Fe<small><sub>32+δ</sub></small>Ge<small><sub>35−x</sub></small>Si<small><sub>x</sub></small>.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"41 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143832296","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yoel Garrosa-Miró, Laura Muñoz-Moreno, Gerardino D'Errico, Matilde Tancredi, M. Jose Carmena, M. Francesca Ottaviani, Paula Ortega, Javier de la Mata
Ruthenium or copper complexes have emerged as some of the most promising alternatives for the treatment of many types of cancer. They have enhanced activity, greater selectivity and reduced side effects compared to their predecessors, cisplatin and its analogues. On the other hand, polyamine metabolism is often deregulated in cancer, leading to increased intracellular concentrations of polyamines that promote cell proliferation, differentiation, and tumorigenesis. In the present work, we report the synthesis and characterization of a family of mono- and binuclear Ru(II) and Cu(II) complexes functionalized with polyamine ligands derived from norspermine. The computer-aided analysis of the electron paramagnetic resonance (EPR) spectra provided magnetic and dynamic parameters, which helped to identify prevalent Cu–N2 coordination in a partially distorted square planar geometry of the Cu(II) complexes and the flexibility of the complexes in solution, slowed down by both the complex size and the hydrophobic interactions between chains. In vitro studies focused on advanced prostate cancer have demonstrated that these new metal complexes present a high level of cytotoxicity against PC3 cells. Furthermore, these metallic compounds exhibit the ability to inhibit cell adhesion and migration while reducing intracellular reactive oxygen species levels, which are key factors of metastasis.
{"title":"Ruthenium(II) and copper(II) polyamine complexes as promising antitumor agents: synthesis, characterization, and biological evaluation","authors":"Yoel Garrosa-Miró, Laura Muñoz-Moreno, Gerardino D'Errico, Matilde Tancredi, M. Jose Carmena, M. Francesca Ottaviani, Paula Ortega, Javier de la Mata","doi":"10.1039/d4dt03377a","DOIUrl":"https://doi.org/10.1039/d4dt03377a","url":null,"abstract":"Ruthenium or copper complexes have emerged as some of the most promising alternatives for the treatment of many types of cancer. They have enhanced activity, greater selectivity and reduced side effects compared to their predecessors, cisplatin and its analogues. On the other hand, polyamine metabolism is often deregulated in cancer, leading to increased intracellular concentrations of polyamines that promote cell proliferation, differentiation, and tumorigenesis. In the present work, we report the synthesis and characterization of a family of mono- and binuclear Ru(<small>II</small>) and Cu(<small>II</small>) complexes functionalized with polyamine ligands derived from norspermine. The computer-aided analysis of the electron paramagnetic resonance (EPR) spectra provided magnetic and dynamic parameters, which helped to identify prevalent Cu–N2 coordination in a partially distorted square planar geometry of the Cu(<small>II</small>) complexes and the flexibility of the complexes in solution, slowed down by both the complex size and the hydrophobic interactions between chains. <em>In vitro</em> studies focused on advanced prostate cancer have demonstrated that these new metal complexes present a high level of cytotoxicity against PC3 cells. Furthermore, these metallic compounds exhibit the ability to inhibit cell adhesion and migration while reducing intracellular reactive oxygen species levels, which are key factors of metastasis.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"108 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143832242","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pd-based catalysts have emerged as one unique class of the promising catalysts capable of selectively producing formate near the equilibrium potential during CO2 electroreduction, but still suffering from CO-poisoning at high overpotentials. Achieving an excellent overall performance, including a high formate selectivity, a wide potential window, and a high anti-CO-poisoning ability, remains a significant challenge. Herein, we report the surfactant-templated synthesis of ultrathin, two-dimensional (2D) binary PdAg alloy mesoporous nanosheets enriched with nanogaps among interlinked branches with regulated atomic stoichiometry for highly efficient CO2 reduction to formate. These advanced structural features enable the catalysts to expose abundant active sites, whereas a proper Ag concentration within alloy effectively tailors the electronic structure of Pd through the electron transfer from Ag to Pd. The synergy effect resulting from the structural and electronic perspectives contributes to greatly promoting electrocatalytic CO2 reduction to formate. As a result, the optimized Pd4Ag1 nanosheets display a maximal formate faradic efficiency of 99.4% at −0.1 V versus reversible hydrogen electrode and exhibit a wide potential window of 400 mV for high formate selectivity (>90 %) toward CO2 reduction. Moreover, the detailed electrochemical analyses collectively evidence that Pd4Ag1 nanosheets exhibit attenuated CO binding and CO poisoning. This work highlights a feasible avenue for elaborate designing and constructing efficient formate-targeted catalysts.
{"title":"Ultrathin, 2D PdAg alloy mesoporous nanosheets enriched with nanogaps promote electrocatalytic CO2 reduction to formate","authors":"Shangqing Sun, Miaomiao Liu, Yalan Mao, Fang Liu, Xinyuan Xu, Yuan Li, Ximei Lv, Shulin Zhao, Xiaojing Liu, Yuping Wu, Yuhui Chen","doi":"10.1039/d5dt00436e","DOIUrl":"https://doi.org/10.1039/d5dt00436e","url":null,"abstract":"Pd-based catalysts have emerged as one unique class of the promising catalysts capable of selectively producing formate near the equilibrium potential during CO2 electroreduction, but still suffering from CO-poisoning at high overpotentials. Achieving an excellent overall performance, including a high formate selectivity, a wide potential window, and a high anti-CO-poisoning ability, remains a significant challenge. Herein, we report the surfactant-templated synthesis of ultrathin, two-dimensional (2D) binary PdAg alloy mesoporous nanosheets enriched with nanogaps among interlinked branches with regulated atomic stoichiometry for highly efficient CO2 reduction to formate. These advanced structural features enable the catalysts to expose abundant active sites, whereas a proper Ag concentration within alloy effectively tailors the electronic structure of Pd through the electron transfer from Ag to Pd. The synergy effect resulting from the structural and electronic perspectives contributes to greatly promoting electrocatalytic CO2 reduction to formate. As a result, the optimized Pd4Ag1 nanosheets display a maximal formate faradic efficiency of 99.4% at −0.1 V versus reversible hydrogen electrode and exhibit a wide potential window of 400 mV for high formate selectivity (>90 %) toward CO2 reduction. Moreover, the detailed electrochemical analyses collectively evidence that Pd4Ag1 nanosheets exhibit attenuated CO binding and CO poisoning. This work highlights a feasible avenue for elaborate designing and constructing efficient formate-targeted catalysts.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"26 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143832294","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Metal oxide nanoparticles are commonly used as electron transport layers (ETLs) in quantum dot light emitting diodes (QLEDs) because of their wide band gap, high electron mobility, and appropriate conduction and valence band positions. Currently, ZnO nanoparticles are the most successfully electron transportation material in high-performance QLEDs. However, the positive aging effect is widely observed for ZnO-based QLEDs since the amphiprotic ZnO nanoparticles are not stable under the acidic, basic, and moisture conditions, which limits their applications. In this study, highly dispersible and alcohol-soluble TiO₂ nanoparticles are synthesized by using a non-hydrolytic sol-gel method, followed by a dimethyl sulfoxide post-treatment. The use of colloidal TiO₂ nanoparticles as an ETL yields optimal QLED, with a maximum external quantum efficiency of 12.03%, a highest luminance of 103,420 cd/m², and a current efficiency of 18.06 cd/A. These results reveal that TiO₂ nanoparticles hold great potential as ETL in the future QLEDs.
{"title":"Synthesis of Highly DispersibleTiO2 Nanoparticles and Their Application in Quantum Dot Light Emitting Diodes","authors":"Botao Hu, Mengxin Liu, Xinan Shi, Daocheng Pan","doi":"10.1039/d5dt00410a","DOIUrl":"https://doi.org/10.1039/d5dt00410a","url":null,"abstract":"Metal oxide nanoparticles are commonly used as electron transport layers (ETLs) in quantum dot light emitting diodes (QLEDs) because of their wide band gap, high electron mobility, and appropriate conduction and valence band positions. Currently, ZnO nanoparticles are the most successfully electron transportation material in high-performance QLEDs. However, the positive aging effect is widely observed for ZnO-based QLEDs since the amphiprotic ZnO nanoparticles are not stable under the acidic, basic, and moisture conditions, which limits their applications. In this study, highly dispersible and alcohol-soluble TiO₂ nanoparticles are synthesized by using a non-hydrolytic sol-gel method, followed by a dimethyl sulfoxide post-treatment. The use of colloidal TiO₂ nanoparticles as an ETL yields optimal QLED, with a maximum external quantum efficiency of 12.03%, a highest luminance of 103,420 cd/m², and a current efficiency of 18.06 cd/A. These results reveal that TiO₂ nanoparticles hold great potential as ETL in the future QLEDs.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"17 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143832297","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A series of rare earth iodate sulfate UV compounds, Ln(IO3)(SO4)·3H2O (Ln = Y, Gd, Er, Ho, Dy, Eu), have been successfully synthesized by hydrothermal method at 200 °C. These isostructural compounds all crystallize in the noncentrosymmetric space group P212121 (No. 19) and feature a neutral three-dimensional Ln(IO3)(SO4) framework which is composed of 2D cationic Ln[SO4]+ layers bridged by anionic [IO3]- trigonal pyramids through sharing corner oxygen atoms. Under 1064 nm laser irradiation, Y(IO3)(SO4)·3H2O exhibits a second-harmonic generation (SHG) with efficiency of 0.7 × KDP@1064 nm. Furthermore, Y(IO3)(SO4)·3H2O has a moderate birefringence (0.118@532 nm) and large band gap (4.60 eV) and may be a potential UV nonlinear optical material. For Eu(IO3)(SO4)·3H2O, it emits intense photoluminescence peaks at 594 nm and 617 nm when excited under 393 nm near-ultraviolet light, showing promising applications as red phosphors of white-LED. The current study elucidates that the incorporation of highly anisotropic lone-paired (IO3)- units into highly isotropic (SO4)2- sulfate groups can achieve balanced SHG response, optical band gap and birefringence, facilitating the development of novel iodate sulfate crystals for UV nonlinear optical applications.
{"title":"Achieving balanced UV SHG response, optical band gap and birefringence in rare earth compounds Ln(IO3)(SO4)·3H2O (Ln = Y, Gd, Er, Ho, Dy, Eu)","authors":"Shihua Ma, Lei Geng, Baozhu Zhu, Chang Yu Meng","doi":"10.1039/d5dt00613a","DOIUrl":"https://doi.org/10.1039/d5dt00613a","url":null,"abstract":"A series of rare earth iodate sulfate UV compounds, Ln(IO3)(SO4)·3H2O (Ln = Y, Gd, Er, Ho, Dy, Eu), have been successfully synthesized by hydrothermal method at 200 °C. These isostructural compounds all crystallize in the noncentrosymmetric space group P212121 (No. 19) and feature a neutral three-dimensional Ln(IO3)(SO4) framework which is composed of 2D cationic Ln[SO4]+ layers bridged by anionic [IO3]- trigonal pyramids through sharing corner oxygen atoms. Under 1064 nm laser irradiation, Y(IO3)(SO4)·3H2O exhibits a second-harmonic generation (SHG) with efficiency of 0.7 × KDP@1064 nm. Furthermore, Y(IO3)(SO4)·3H2O has a moderate birefringence (0.118@532 nm) and large band gap (4.60 eV) and may be a potential UV nonlinear optical material. For Eu(IO3)(SO4)·3H2O, it emits intense photoluminescence peaks at 594 nm and 617 nm when excited under 393 nm near-ultraviolet light, showing promising applications as red phosphors of white-LED. The current study elucidates that the incorporation of highly anisotropic lone-paired (IO3)- units into highly isotropic (SO4)2- sulfate groups can achieve balanced SHG response, optical band gap and birefringence, facilitating the development of novel iodate sulfate crystals for UV nonlinear optical applications.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"60 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143832295","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
To address the ignition and combustion issues associated with boron (B), B@Mg@AP high-energy boron-based nanoflower composites were synthesized through etching and crystallization, utilizing magnesium boride as the raw material. The B@Mg@AP high-energy composite is coated with a nano-flower-like ammonium perchlorate (AP), with boron (B) and magnesium (Mg) arranged alternately in the core. The inclusion of magnesium (Mg) and ammonium perchlorate (AP) enhances the reactivity and combustion efficiency of boron (B). The ignition combustion tests indicate that, compared to the B/AP system, the heat release of the B@Mg@AP sample at the same ratio has increased by 452.1%, with the maximum flame temperature rising by approximately 37.4%. In comparison to boron (B), the maximum calorific value of the B@Mg@AP composite has risen by 99.3%, while the combustion efficiency has improved by 31.12%. The successful synthesis of B@Mg@AP composites is expected to facilitate the application and advancement of boron-based rocket ramjet engines.
{"title":"Rapid construction and energy release efficiency of high energy boron based nanoflower-like composites","authors":"Qian Huang, Zhiwen Lin, Kaige Guo, Chengchen Zhang, Yikai Wang, Chenguang Zhu, Debin Ni, Yuxin Jia, Mingxing Zhang","doi":"10.1039/d5dt00133a","DOIUrl":"https://doi.org/10.1039/d5dt00133a","url":null,"abstract":"To address the ignition and combustion issues associated with boron (B), B@Mg@AP high-energy boron-based nanoflower composites were synthesized through etching and crystallization, utilizing magnesium boride as the raw material. The B@Mg@AP high-energy composite is coated with a nano-flower-like ammonium perchlorate (AP), with boron (B) and magnesium (Mg) arranged alternately in the core. The inclusion of magnesium (Mg) and ammonium perchlorate (AP) enhances the reactivity and combustion efficiency of boron (B). The ignition combustion tests indicate that, compared to the B/AP system, the heat release of the B@Mg@AP sample at the same ratio has increased by 452.1%, with the maximum flame temperature rising by approximately 37.4%. In comparison to boron (B), the maximum calorific value of the B@Mg@AP composite has risen by 99.3%, while the combustion efficiency has improved by 31.12%. The successful synthesis of B@Mg@AP composites is expected to facilitate the application and advancement of boron-based rocket ramjet engines.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"205 1 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143832243","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Boris V. Kramar, Tatiana V. Plakhova, Anastasiia S. Kuzenkova, Alexander L. Trigub, Roman D. Svetogorov, Andrey A. Shiryaev, Iurii M. Nevolin, Alexey D. Yapryntsev, Alexander E. Baranchikov, Georgy S. Peters, Vasily O. Yapaskurt, Alexander V. Egorov, Ilya A. Kostyukov, Maria D. Shaulskaya, Dmitry M. Tsymbarenko, Anna Yu. Romanchuk, Stepan N. Kalmykov
This study investigated the behaviour of nanoscale thorium dioxide in a sodium phosphate buffer under hydrothermal conditions under conditions ranging from weakly acidic (pH ∼ 5) to weakly basic (pH ∼ 8). The hydrothermal syntheses yielded a nanosized hydrated double sodium–thorium phosphate phase. The acidity of the medium affected particle size and elemental composition of the product. The phase, identified in all cases as a hydrated variant of the known sodium–thorium phosphate NaTh2(PO4)3, possesses a framework structure and is able to accommodate water and sodium cations within the channels; notably, the sodium content varied based on the acidity of the synthesis medium. Calcination of the nanosized phase in air produced mixtures of two distinct crystalline sodium–thorium phosphates, NaTh2(PO4)3 and Na2Th(PO4)2, in different ratios. The final product composition was determined by the pH used during synthesis and the related phosphate content of the nanosized phase. Characterization of the materials before and after calcination was carried out with a range of complementary methods: X-ray diffraction, small-angle X-ray scattering, electron microscopy, X-ray absorption spectroscopy, total X-ray scattering with pair distribution function analysis, infrared spectroscopy and 31P MAS NMR.
{"title":"Formation of a new hydrated sodium–thorium phosphate from thorium dioxide and its subsequent phase evolution","authors":"Boris V. Kramar, Tatiana V. Plakhova, Anastasiia S. Kuzenkova, Alexander L. Trigub, Roman D. Svetogorov, Andrey A. Shiryaev, Iurii M. Nevolin, Alexey D. Yapryntsev, Alexander E. Baranchikov, Georgy S. Peters, Vasily O. Yapaskurt, Alexander V. Egorov, Ilya A. Kostyukov, Maria D. Shaulskaya, Dmitry M. Tsymbarenko, Anna Yu. Romanchuk, Stepan N. Kalmykov","doi":"10.1039/d5dt00276a","DOIUrl":"https://doi.org/10.1039/d5dt00276a","url":null,"abstract":"This study investigated the behaviour of nanoscale thorium dioxide in a sodium phosphate buffer under hydrothermal conditions under conditions ranging from weakly acidic (pH ∼ 5) to weakly basic (pH ∼ 8). The hydrothermal syntheses yielded a nanosized hydrated double sodium–thorium phosphate phase. The acidity of the medium affected particle size and elemental composition of the product. The phase, identified in all cases as a hydrated variant of the known sodium–thorium phosphate NaTh<small><sub>2</sub></small>(PO<small><sub>4</sub></small>)<small><sub>3</sub></small>, possesses a framework structure and is able to accommodate water and sodium cations within the channels; notably, the sodium content varied based on the acidity of the synthesis medium. Calcination of the nanosized phase in air produced mixtures of two distinct crystalline sodium–thorium phosphates, NaTh<small><sub>2</sub></small>(PO<small><sub>4</sub></small>)<small><sub>3</sub></small> and Na<small><sub>2</sub></small>Th(PO<small><sub>4</sub></small>)<small><sub>2</sub></small>, in different ratios. The final product composition was determined by the pH used during synthesis and the related phosphate content of the nanosized phase. Characterization of the materials before and after calcination was carried out with a range of complementary methods: X-ray diffraction, small-angle X-ray scattering, electron microscopy, X-ray absorption spectroscopy, total X-ray scattering with pair distribution function analysis, infrared spectroscopy and <small><sup>31</sup></small>P MAS NMR.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"25 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143827491","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
S. Mrabet, N. Ihzaz, M. N. Bessadok, C. Vázquez-Vázquez, M. Alshammari, O. M. Lemine, D. Ananias, L. El Mir
Single-phase (Ca,V) co-doped ZnO nanoparticles (Zn0.93Ca0.04V0.03O, called hereinafter ZCVO) were synthesized via a modified sol–gel method. The hexagonal wurtzite symmetry of the ZnO phase nanostructure, belonging to the P63mc space group, has been confirmed through X-ray diffraction examinations using Rietveld refinement. No segregated secondary phases or Ca or/and V-rich clusters were detected. The TEM images clearly show the presence of nanoparticles exhibiting a diverse range of spherical shapes. The effect of co-doping on the optical band gap and crystalline quality was also investigated via photoluminescence (PL), UV–vis, and Raman spectrometers. The M–T curve suggests a tenability of magnetic coupling which was discussed within the context of three competing magnetic phases using the 3D spin wave model and Curie–Weiss law. The lack of saturation of the M–H loop at 10 K suggests the presence of both paramagnetic (PM) and ferromagnetic (FM) phases in ZCVO NPs. The bound magnetic polaron (BMP) model provides a plausible explanation for the observed magnetic phase transition. Moreover, a Griffiths-like phase was observed for the first time, to our knowledge, in co-doped ZnO nanoparticles. This novelty may stem from the interplay between the antiferromagnetic (AFM) and FM interactions of the Ca and V ions, which are acquired by oxygen deficiency.
{"title":"Structural, optical, and magnetic behavior and the nucleation of a Griffiths-like phase in (Ca,V)-doped ZnO nanoparticles","authors":"S. Mrabet, N. Ihzaz, M. N. Bessadok, C. Vázquez-Vázquez, M. Alshammari, O. M. Lemine, D. Ananias, L. El Mir","doi":"10.1039/d5dt00096c","DOIUrl":"https://doi.org/10.1039/d5dt00096c","url":null,"abstract":"Single-phase (Ca,V) co-doped ZnO nanoparticles (Zn<small><sub>0.93</sub></small>Ca<small><sub>0.04</sub></small>V<small><sub>0.03</sub></small>O, called hereinafter ZCVO) were synthesized <em>via</em> a modified sol–gel method. The hexagonal wurtzite symmetry of the ZnO phase nanostructure, belonging to the <em>P</em>6<small><sub>3</sub></small><em>mc</em> space group, has been confirmed through X-ray diffraction examinations using Rietveld refinement. No segregated secondary phases or Ca or/and V-rich clusters were detected. The TEM images clearly show the presence of nanoparticles exhibiting a diverse range of spherical shapes. The effect of co-doping on the optical band gap and crystalline quality was also investigated <em>via</em> photoluminescence (PL), UV–vis, and Raman spectrometers. The <em>M</em>–<em>T</em> curve suggests a tenability of magnetic coupling which was discussed within the context of three competing magnetic phases using the 3D spin wave model and Curie–Weiss law. The lack of saturation of the <em>M</em>–<em>H</em> loop at 10 K suggests the presence of both paramagnetic (PM) and ferromagnetic (FM) phases in ZCVO NPs. The bound magnetic polaron (BMP) model provides a plausible explanation for the observed magnetic phase transition. Moreover, a Griffiths-like phase was observed for the first time, to our knowledge, in co-doped ZnO nanoparticles. This novelty may stem from the interplay between the antiferromagnetic (AFM) and FM interactions of the Ca and V ions, which are acquired by oxygen deficiency.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"6 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143827493","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Xinyue Yao, Qiangqiang Wang, Xuejing Liu, Xuan Kuang, Xu Sun, Xiang Ren, Dan Wu, Qin Wei
The oxygen evolution reaction (OER) is usually considered a major obstacle to electrochemical water splitting, primarily because of its sluggish kinetics. Developing an effective and durable catalyst for the OER is indispensable for overcoming this challenge. In this study, a three-dimensional nanomaterial with a unique heterostructure (Co2CrO4@Cr-NiFe LDH/CF) was obtained by the deposition of Cr-doped double hydroxide (Cr-NiFe LDH) on Co2CrO4 nanosheet arrays grown on copper foam (Co2CrO4/CF). In particular, the catalyst had a current density of 100 mA cm−2 at a low overpotential of just 257 mV, a high turnover frequency (TOF) of 10.21 s−1 at an overpotential of 300 mV and a Tafel slope of merely 72 mV dec−1. This indicated that Co2CrO4@Cr-NiFe LDH/CF exhibited outstanding catalytic efficiency. Moreover, the catalyst exhibited stability for a duration of 40 h at a current density of 100 mA cm−2. The study introduces an innovative approach for the superior design of an OER catalyst and offers a significant reference for investigation within the realm of renewable energy.
{"title":"Heterostructure and atomic doping engineering in 3D Co2CrO4@Cr-NiFe LDH/CF nanosheet arrays for efficient electrocatalytic oxygen evolution","authors":"Xinyue Yao, Qiangqiang Wang, Xuejing Liu, Xuan Kuang, Xu Sun, Xiang Ren, Dan Wu, Qin Wei","doi":"10.1039/d5dt00351b","DOIUrl":"https://doi.org/10.1039/d5dt00351b","url":null,"abstract":"The oxygen evolution reaction (OER) is usually considered a major obstacle to electrochemical water splitting, primarily because of its sluggish kinetics. Developing an effective and durable catalyst for the OER is indispensable for overcoming this challenge. In this study, a three-dimensional nanomaterial with a unique heterostructure (Co<small><sub>2</sub></small>CrO<small><sub>4</sub></small>@Cr-NiFe LDH/CF) was obtained by the deposition of Cr-doped double hydroxide (Cr-NiFe LDH) on Co<small><sub>2</sub></small>CrO<small><sub>4</sub></small> nanosheet arrays grown on copper foam (Co<small><sub>2</sub></small>CrO<small><sub>4</sub></small>/CF). In particular, the catalyst had a current density of 100 mA cm<small><sup>−2</sup></small> at a low overpotential of just 257 mV, a high turnover frequency (TOF) of 10.21 s<small><sup>−1</sup></small> at an overpotential of 300 mV and a Tafel slope of merely 72 mV dec<small><sup>−1</sup></small>. This indicated that Co<small><sub>2</sub></small>CrO<small><sub>4</sub></small>@Cr-NiFe LDH/CF exhibited outstanding catalytic efficiency. Moreover, the catalyst exhibited stability for a duration of 40 h at a current density of 100 mA cm<small><sup>−2</sup></small>. The study introduces an innovative approach for the superior design of an OER catalyst and offers a significant reference for investigation within the realm of renewable energy.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"11 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143827487","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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：