Vijayakriti Mishra, Mahesh Sundararajan, Arup K Pathak, Pramilla D Sawant, Tusar Bandyopadhyay
The present study focuses on designing mutant peptides derived from the Lanthanide Binding Tag (LBT) to enhance selectivity for trivalent actinide (An³⁺) ions over lanthanides (Ln³⁺) metal ions (M). LBT, a short peptide known for its high affinity towards Ln³⁺, was modified by substituting hard-donor ligands like asparagine (Asn or N) and aspartic acid (Asp or D) with softer ligand cysteine (Cys or C) to create four mutant peptides: M-LBT (wild-type), M-N103C, M-D105C, and M-N103C-D105C. Molecular dynamics (MD) simulations were employed to analyze the binding dynamics and affinities of these mutants with Eu³⁺ and Am³⁺ as representatives for Ln and An ions, respectively. The study utilized enhance sampling method, namely, well-tempered meta-dynamics (WT-MtD) to overcome sampling challenges and obtain converged free energy profiles for the metal-binding interactions. Our simulations studies indicate that both single and double mutations alter the coordination environment within the peptide's binding pocket, potentially increasing Am3+ selectivity over Eu3+ ion. These insights contribute to the developmentofmore effective and selective chelating agents for the preferential actinide binding.
{"title":"Tuning the Lanthanide Binding Tags for Preferential Actinide Chelation: an all atom Molecular Dynamics study","authors":"Vijayakriti Mishra, Mahesh Sundararajan, Arup K Pathak, Pramilla D Sawant, Tusar Bandyopadhyay","doi":"10.1039/d4cp04203d","DOIUrl":"https://doi.org/10.1039/d4cp04203d","url":null,"abstract":"The present study focuses on designing mutant peptides derived from the Lanthanide Binding Tag (LBT) to enhance selectivity for trivalent actinide (An³⁺) ions over lanthanides (Ln³⁺) metal ions (M). LBT, a short peptide known for its high affinity towards Ln³⁺, was modified by substituting hard-donor ligands like asparagine (Asn or N) and aspartic acid (Asp or D) with softer ligand cysteine (Cys or C) to create four mutant peptides: M-LBT (wild-type), M-N103C, M-D105C, and M-N103C-D105C. Molecular dynamics (MD) simulations were employed to analyze the binding dynamics and affinities of these mutants with Eu³⁺ and Am³⁺ as representatives for Ln and An ions, respectively. The study utilized enhance sampling method, namely, well-tempered meta-dynamics (WT-MtD) to overcome sampling challenges and obtain converged free energy profiles for the metal-binding interactions. Our simulations studies indicate that both single and double mutations alter the coordination environment within the peptide's binding pocket, potentially increasing Am3+ selectivity over Eu3+ ion. These insights contribute to the developmentofmore effective and selective chelating agents for the preferential actinide binding.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"68 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142987409","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}
Control of the formation of liquid crystalline Ia3d gyroid phases and their nanostructures is critical to advance the materials chemistry based on the structural feature of three-dimensional helical networks. Here, we present that introducing methyl side-group(s) and slight non-symmetry into aryloyl-hydrazine-based molecules is unexpectedly crucial for the formation and can be the new design strategy through tuning intermolecular interaction: The two chemical modifications in the core portion of the chain-core-chain type molecules effectively lower and extend the Ia3d phase temperature ranges with the increased twist angle between neighboring molecules along the network. The detailed analyses of the aggregation structure revealed the change in the core assembly mode from the double-layered core mode of the mother molecule (without methyl groups) to the single-layered core mode. Such changes are explained in terms of modified intermolecular interaction in those phases employing quantum chemical calculations.
{"title":"Methyl side-groups control the Ia3d phase in core-non-symmetric aryloyl-hydrazine-based molecules","authors":"Sota Takebe, Nachia Isobe, Taro Udagawa, Yasuhisa Yamamura, Kazuya Saito, Yohei Miwa, Kei Hashimoto, Shoichi Kutsumizu","doi":"10.1039/d4cp03919j","DOIUrl":"https://doi.org/10.1039/d4cp03919j","url":null,"abstract":"Control of the formation of liquid crystalline <em>Ia</em>3<em>d</em> gyroid phases and their nanostructures is critical to advance the materials chemistry based on the structural feature of three-dimensional helical networks. Here, we present that introducing methyl side-group(s) and slight non-symmetry into aryloyl-hydrazine-based molecules is unexpectedly crucial for the formation and can be the new design strategy through tuning intermolecular interaction: The two chemical modifications in the core portion of the chain-core-chain type molecules effectively lower and extend the <em>Ia</em>3<em>d</em> phase temperature ranges with the increased twist angle between neighboring molecules along the network. The detailed analyses of the aggregation structure revealed the change in the core assembly mode from the double-layered core mode of the mother molecule (without methyl groups) to the single-layered core mode. Such changes are explained in terms of modified intermolecular interaction in those phases employing quantum chemical calculations.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"24 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142987411","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}
Zehao Lin, Qingyang Fan, Qing Pang, Jin Zhong Zhang, Dangli Gao, Yuling Song
Silicon germanium alloy materials have promising potential applications in the optoelectronic and photovoltaic industries due to their good electronic properties. However, due to the inherent brittleness of semiconductor materials, they are prone to rupturing under harsh working environments, such as high stress or high temperature. Here, we conducted a systematic search for silicon germanium alloy structures using a random sampling strategy, in combination with group theory and graph theory (RG2), and 12 stable SiGe structures in 2–8 stacking orders were predicted. All 12 stable SiGe crystals exhibit a popular bandwidth of 1.06–1.19 eV, approaching the optimal Shockley Queisser limit (≈1.4 eV). Among these, 6 structures showed quasi-direct band gaps. Considering their potential photovoltaic applications, we systematically studied the changes in their enthalpy, stability, mechanical stability (elastic moduli), lattice parameters, band structures, and light absorption under a stress load of up to 20 GPa. These new SiGe crystals featured relatively low enthalpies (even as low as 0.009 eV per atom), and good stability and mechanical properties. In addition, the absorption spectra of these materials demonstrated a high absorption intensity for the solar spectrum that was approximately 3 times higher than that of conventional diamond silicon, even under a 20 GPa stress. The present study uses the predicted 2–8H SiGe to provide new insights into the photovoltaic applications of SiGe alloy structures.
{"title":"A dozen predicted SiGe alloys with low enthalpies and strong absorption of sunlight for photovoltaic applications","authors":"Zehao Lin, Qingyang Fan, Qing Pang, Jin Zhong Zhang, Dangli Gao, Yuling Song","doi":"10.1039/d4cp03927k","DOIUrl":"https://doi.org/10.1039/d4cp03927k","url":null,"abstract":"Silicon germanium alloy materials have promising potential applications in the optoelectronic and photovoltaic industries due to their good electronic properties. However, due to the inherent brittleness of semiconductor materials, they are prone to rupturing under harsh working environments, such as high stress or high temperature. Here, we conducted a systematic search for silicon germanium alloy structures using a random sampling strategy, in combination with group theory and graph theory (RG<small><sup>2</sup></small>), and 12 stable SiGe structures in 2–8 stacking orders were predicted. All 12 stable SiGe crystals exhibit a popular bandwidth of 1.06–1.19 eV, approaching the optimal Shockley Queisser limit (≈1.4 eV). Among these, 6 structures showed quasi-direct band gaps. Considering their potential photovoltaic applications, we systematically studied the changes in their enthalpy, stability, mechanical stability (elastic moduli), lattice parameters, band structures, and light absorption under a stress load of up to 20 GPa. These new SiGe crystals featured relatively low enthalpies (even as low as 0.009 eV per atom), and good stability and mechanical properties. In addition, the absorption spectra of these materials demonstrated a high absorption intensity for the solar spectrum that was approximately 3 times higher than that of conventional diamond silicon, even under a 20 GPa stress. The present study uses the predicted <strong>2–8H</strong> SiGe to provide new insights into the photovoltaic applications of SiGe alloy structures.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"27 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142987401","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}
Feng GAO, Xinyu Jiang, Junjun Qiu, Tong An, Manyao Zhang, Xiaokun Song, Nan Shi, Xiuhong Li, Tongxiang Fan, Qibin Zhao
Mechanoresponsive colloidal photonic crystals embedded in elastic solid matrices exhibit tunable optical properties under mechanical force, showing great potential for various applications. However, the response of colloidal crystals embedded in a liquid matrix remains largely unexplored. In this study, we investigate the structural and optical transitions of colloidal crystals composed of particles suspended in a liquid oligomer under pressing and shear forces. We observe that pressing induces a transition from an ordered to a disordered particle arrangement, while subsequent bending shear, such as simple hand-flipping, restores the ordered structure. This reversible transition produces press-induced optical traces that can be erased by subsequent shear, making this material a promising candidate for applications in reversible direct-writing photonic paper and anti-counterfeiting technologies. Our work provides new insights into the structural dynamics of liquid colloidal photonic crystals under mechanical force and highlights their potential in mechanoresponsive applications.
{"title":"Disappearing and reappearing of structure order in colloidal photonic crystals","authors":"Feng GAO, Xinyu Jiang, Junjun Qiu, Tong An, Manyao Zhang, Xiaokun Song, Nan Shi, Xiuhong Li, Tongxiang Fan, Qibin Zhao","doi":"10.1039/d4cp04395b","DOIUrl":"https://doi.org/10.1039/d4cp04395b","url":null,"abstract":"Mechanoresponsive colloidal photonic crystals embedded in elastic solid matrices exhibit tunable optical properties under mechanical force, showing great potential for various applications. However, the response of colloidal crystals embedded in a liquid matrix remains largely unexplored. In this study, we investigate the structural and optical transitions of colloidal crystals composed of particles suspended in a liquid oligomer under pressing and shear forces. We observe that pressing induces a transition from an ordered to a disordered particle arrangement, while subsequent bending shear, such as simple hand-flipping, restores the ordered structure. This reversible transition produces press-induced optical traces that can be erased by subsequent shear, making this material a promising candidate for applications in reversible direct-writing photonic paper and anti-counterfeiting technologies. Our work provides new insights into the structural dynamics of liquid colloidal photonic crystals under mechanical force and highlights their potential in mechanoresponsive applications.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"95 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142987408","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}
Ayush Shivhare, Bharti Dehariya, Shridhar R. Gadre, Milind M. Deshmukh
In a recent communication (Phys. Chem. Chem. Phys., 2024, 26, 21332), we proposed a method for calculating the energy of a hydrogen bond (HB), which is common to two or more cyclic networks of HBs in water (H2O)n clusters. For this purpose, the sum of the cooperativity contributions of these cyclic structures, estimated using the molecular tailoring approach (MTA)-based method, was added to the energy of this HB in the respective water dimer isolated from the cluster. The HB energies calculated in this fashion (EHBSynergetic) were in excellent agreement with their actual cluster counterparts (EHBcluster). In this work, we test the generality of this methodology. For this purpose, we employed the clusters of ammonia (NH3)n, hydrogen sulphide (H2S)n, mixed (H2S)m(H2O)n, (NH3)m(H2O)n, methanol-water (CH3OH)m(H2O)n, and hydrogen fluoride-water (HF)m(H2O)n exhibiting HBs of variable strength (1 to 19 kcal/mol). The HB energies in all these molecular clusters calculated using the present method were found to be accurate. The absolute difference between the EHBSynergetic and EHBcluster values in these clusters is found to be less than 0.5 kcal/mol. Importantly, the present method not only enables the accurate HB energy estimation in molecular clusters but also offers qualitative guidelines for this purpose. The latter are based on the nature of cyclic cooperativity, exhibiting either full cyclic (FCC), partial cyclic cooperativity (PCC) or anti-cooperativity (AC).
{"title":"Cyclic Cooperativity Contributions Determine the Hydrogen Bond Strengths in Molecular Clusters","authors":"Ayush Shivhare, Bharti Dehariya, Shridhar R. Gadre, Milind M. Deshmukh","doi":"10.1039/d4cp04741a","DOIUrl":"https://doi.org/10.1039/d4cp04741a","url":null,"abstract":"In a recent communication (<em>Phys. Chem. Chem. Phys</em>., 2024, <strong>26</strong>, 21332), we proposed a method for calculating the energy of a hydrogen bond (HB), which is common to two or more cyclic networks of HBs in water (H2O)<small><sub>n</sub></small> clusters. For this purpose, the sum of the cooperativity contributions of these cyclic structures, estimated using the molecular tailoring approach (MTA)-based method, was added to the energy of this HB in the respective water dimer isolated from the cluster. The HB energies calculated in this fashion (E<small><sub>HB</sub></small><small><sup>Synergetic</sup></small>) were in excellent agreement with their actual cluster counterparts (E<small><sub>HB</sub></small><small><sup>cluster</sup></small>). In this work, we test the generality of this methodology. For this purpose, we employed the clusters of ammonia (NH<small><sub>3</sub></small>)<small><sub>n</sub></small>, hydrogen sulphide (H<small><sub>2</sub></small>S)<small><sub>n</sub></small>, mixed (H<small><sub>2</sub></small>S)<small><sub>m</sub></small>(H<small><sub>2</sub></small>O)<small><sub>n</sub></small>, (NH<small><sub>3</sub></small>)<small><sub>m</sub></small>(H<small><sub>2</sub></small>O)<small><sub>n</sub></small>, methanol-water (CH<small><sub>3</sub></small>OH)<small><sub>m</sub></small>(H<small><sub>2</sub></small>O)<small><sub>n</sub></small>, and hydrogen fluoride-water (HF)<small><sub>m</sub></small>(H<small><sub>2</sub></small>O)<small><sub>n</sub></small> exhibiting HBs of variable strength (1 to 19 kcal/mol). The HB energies in all these molecular clusters calculated using the present method were found to be accurate. The absolute difference between the E<small><sub>HB</sub></small><small><sup>Synergetic</sup></small> and E<small><sub>HB</sub></small><small><sup>cluster</sup></small> values in these clusters is found to be less than 0.5 kcal/mol. Importantly, the present method not only enables the accurate HB energy estimation in molecular clusters but also offers qualitative guidelines for this purpose. The latter are based on the nature of cyclic cooperativity, exhibiting either full cyclic (FCC), partial cyclic cooperativity (PCC) or anti-cooperativity (AC).","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"55 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142987410","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The influence on the mobility of polypeptide chains caused by strain misfit due to molecular electric dipole distortions under applied electric fields up to 769 kV m−1, in cow cortical femur samples annealed at 373 K, 423 K, and 530 K, is determined. The behaviour of strain misfit as a function of the electric field strength is determined from a mean-field model based on the Eshelby theory. In addition, Friedel's model for describing the mobility of dislocations in continuum media has been modified to determine the interaction energy between electrically generated obstacles and the polypeptide chains. Depending on the denaturation states from the bones due to the annealing treatments, the different locations of the activated dipoles and their effects on the mobility of the polypeptide chains were determined. Furthermore, it was also determined that dahllite does not affect the degree of chain mobility under an applied electric field. Dynamic mechanical analysis measurements conducted under a high electric field, differential thermal analysis and thermogravimetry are used in the present work. To our knowledge, this is the first time dynamic mechanical analysis studies have been carried out on bones subjected to high electric fields.
{"title":"The mobility of polypeptide chains in cow femur bones controlled by an electric field","authors":"Fernando Daniel Lambri, Federico Guillermo Bonifacich, Melania Lucila Lambri, Mariel Antonella Lambri, Ricardo Raúl Mocellini, Griselda Irene Zelada, Osvaldo Agustín Lambri","doi":"10.1039/d4cp03754e","DOIUrl":"https://doi.org/10.1039/d4cp03754e","url":null,"abstract":"The influence on the mobility of polypeptide chains caused by strain misfit due to molecular electric dipole distortions under applied electric fields up to 769 kV m<small><sup>−1</sup></small>, in cow cortical femur samples annealed at 373 K, 423 K, and 530 K, is determined. The behaviour of strain misfit as a function of the electric field strength is determined from a mean-field model based on the Eshelby theory. In addition, Friedel's model for describing the mobility of dislocations in continuum media has been modified to determine the interaction energy between electrically generated obstacles and the polypeptide chains. Depending on the denaturation states from the bones due to the annealing treatments, the different locations of the activated dipoles and their effects on the mobility of the polypeptide chains were determined. Furthermore, it was also determined that dahllite does not affect the degree of chain mobility under an applied electric field. Dynamic mechanical analysis measurements conducted under a high electric field, differential thermal analysis and thermogravimetry are used in the present work. To our knowledge, this is the first time dynamic mechanical analysis studies have been carried out on bones subjected to high electric fields.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"37 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142987404","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}
2-(2-Hydroxyphenyl)benzothiazole (HBT) derivatives with donor–π–acceptor (D–π–A) structure have received extensive attention as a class of excited state intramolecular proton transfer (ESIPT) compounds in the fields of biochemistry and photochemistry. The effects of electron-donors (triphenylamine and anthracenyl), the position of substituents and solvent polarity on the fluorescence properties and ESIPT mechanisms of HBT derivatives were investigated through time-dependent density functional theory (TDDFT) calculations. Potential energy curves (PECs) and frontier molecular orbitals (FMOs) reveal that the introduction of the triphenylamine group on the benzene ring enhances intramolecular HB, thereby benefiting the ESIPT process. Analysis of their spectra reveals that P-TPA (para position for TPA) and M-TPA (meta position for TPA) are both excellent candidates for fluorescent dyes because of their large Stokes shifts. The PECs of four derivatives indicate that the ESIPT process of P-TPA in dimethyl sulfoxide (DMSO) solvent is the most likely to occur. The research revealed that both P-TPA and P-En (para positions for both TPA and En) can undergo a spontaneous transformation from the enol to the keto form in the S1 state. Furthermore, the ESIPT process was found to be enhanced with an increase in polarity. The energy barrier of P-TPA(N*) → P-TPA(K*) is 3.06 kcal mol−1 in the S1 state and its reversed energy barrier is 4.47 kcal mol−1. The para triphenylamine group could accelerate the ESIPT reactions, as it has a greater impact on the excited state intramolecular hydrogen bond (ESIHB) compared to meta-substitution of the triphenylamine group.
{"title":"Elaborating H-bonding effect and excited state intramolecular proton transfer of 2-(2-hydroxyphenyl)benzothiazole based D–π–A fluorescent dye","authors":"Xiu-Min Liu, Yin Yu, Shu-Ying Xu, Xue-Hai Ju","doi":"10.1039/d4cp04141k","DOIUrl":"https://doi.org/10.1039/d4cp04141k","url":null,"abstract":"2-(2-Hydroxyphenyl)benzothiazole (HBT) derivatives with donor–π–acceptor (D–π–A) structure have received extensive attention as a class of excited state intramolecular proton transfer (ESIPT) compounds in the fields of biochemistry and photochemistry. The effects of electron-donors (triphenylamine and anthracenyl), the position of substituents and solvent polarity on the fluorescence properties and ESIPT mechanisms of HBT derivatives were investigated through time-dependent density functional theory (TDDFT) calculations. Potential energy curves (PECs) and frontier molecular orbitals (FMOs) reveal that the introduction of the triphenylamine group on the benzene ring enhances intramolecular HB, thereby benefiting the ESIPT process. Analysis of their spectra reveals that <em>P</em>-TPA (<em>para</em> position for TPA) and <em>M</em>-TPA (<em>meta</em> position for TPA) are both excellent candidates for fluorescent dyes because of their large Stokes shifts. The PECs of four derivatives indicate that the ESIPT process of <em>P</em>-TPA in dimethyl sulfoxide (DMSO) solvent is the most likely to occur. The research revealed that both <em>P</em>-TPA and <em>P</em>-En (<em>para</em> positions for both TPA and En) can undergo a spontaneous transformation from the enol to the keto form in the S<small><sub>1</sub></small> state. Furthermore, the ESIPT process was found to be enhanced with an increase in polarity. The energy barrier of <em>P</em>-TPA(N*) → <em>P</em>-TPA(K*) is 3.06 kcal mol<small><sup>−1</sup></small> in the S<small><sub>1</sub></small> state and its reversed energy barrier is 4.47 kcal mol<small><sup>−1</sup></small>. The <em>para</em> triphenylamine group could accelerate the ESIPT reactions, as it has a greater impact on the excited state intramolecular hydrogen bond (ESIHB) compared to <em>meta</em>-substitution of the triphenylamine group.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"2 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142987405","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}
It is a major challenge to obtain broadband microwave absorption (MA) properties using low dielectric or magnetic nanoparticles decorated- carbon composites due to the limited single conductive loss or polarization loss of the carbon materials used as substrates. The novel pure cellulose-derived graphite carbon materials (CGC) can be used as an exceptional substrate option due to its special defective graphitic carbon structure with conduction and polarization loss. Herein, the CGC@ZnO composites were first synthesized by atomic layer deposition (ALD) for microwave absorbents. Thanks to the multiple interfaces composed of graphitic carbon, defective carbon, and polar ZnO molecules, the CGC@ZnO composites exhibit superior MA properties. Specifically, the CZ-3 achieves a minimum reflection loss (RLmin) of -50.5 dB (over 99.999% MA) at 6.16 GHz in 2.98 mm. Amazingly, the maximum effective absorption bandwidth (RL < 10 dB, EABmax) can be up to 6.48 GHz only at 1.59 mm. Besides, the frequency range of EAB even extends to 12.7 GHz when the thickness is varied in the range of 1.0-3.0 mm. The ultra-broadband absorption property is mainly attributed to its strong electromagnetic attenuation capability and excellent impedance matching, making it one of the most promising materials for MA applications.
{"title":"A novel cellulose-derived graphite carbon/ZnO composite by atomic layer deposition as over-wideband microwave absorbents","authors":"Guangguang Guan, Xiaoqiang Li, Jiebai Li, Meng Chen, Hongpeng Liu, Wenbo Zhang, Jingyuan Wei, Yangtao Zhou","doi":"10.1039/d4cp04707a","DOIUrl":"https://doi.org/10.1039/d4cp04707a","url":null,"abstract":"It is a major challenge to obtain broadband microwave absorption (MA) properties using low dielectric or magnetic nanoparticles decorated- carbon composites due to the limited single conductive loss or polarization loss of the carbon materials used as substrates. The novel pure cellulose-derived graphite carbon materials (CGC) can be used as an exceptional substrate option due to its special defective graphitic carbon structure with conduction and polarization loss. Herein, the CGC@ZnO composites were first synthesized by atomic layer deposition (ALD) for microwave absorbents. Thanks to the multiple interfaces composed of graphitic carbon, defective carbon, and polar ZnO molecules, the CGC@ZnO composites exhibit superior MA properties. Specifically, the CZ-3 achieves a minimum reflection loss (RLmin) of -50.5 dB (over 99.999% MA) at 6.16 GHz in 2.98 mm. Amazingly, the maximum effective absorption bandwidth (RL < 10 dB, EABmax) can be up to 6.48 GHz only at 1.59 mm. Besides, the frequency range of EAB even extends to 12.7 GHz when the thickness is varied in the range of 1.0-3.0 mm. The ultra-broadband absorption property is mainly attributed to its strong electromagnetic attenuation capability and excellent impedance matching, making it one of the most promising materials for MA applications.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"12 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142987402","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}
Xiao-Luan Xie, Yi-Fan Li, Cheng Wang, Dawei Gu, Lei Wang, Qiao Qiao, Yang Zou, Zhi-Yuan Yao, Lin-Jiang Shen, Xiaoming Ren
In this study, a novel tunnel structure vanadate NaVO (Na0.4V2O4.96) cathode for aqueous zinc ion batteries (AZIBs), is facilely fabricated by thermal decomposition of polyoxovanadate containing NH4+ ions. The NaVO cathode is characterized by abundant oxygen vacancies and nanometer dimensions. These attributes can offer extra reaction sites and suppress structural collapse during circulation. In the charge-discharge process, a unique phenomenon occurs where NaVO undergoes opposite expansion (positive vs. negative expansion) along its different crystal planes. This opposite expansion produces an “expansion counteraction effect”, which effectively buffers volume change of NaVO. Additionally, the irreversibly inserted Zn2+ ions as “pillars” are maintained in the framework after the first discharge, further improving the structural stability of NaVO. Thereby, the NaVO cathode exhibits superior cyclic stability. The capacity retention rate can reach 87.3% after 350 cycles at 0.1 A g−1. With a high current density of 2 A g−1, the specific capacity can be maintained at 206.3 mA h g−1 with a capacity retention of 95.5% after 2100 cycles. This study not only provides a novel approach for synthesizing nanoscale vanadate cathode with rich oxygen vacancies, but also proposes the “expansion counteraction effect” theory, offering innovative insights into the design of the high cycling stability cathode for AZIBs.
{"title":"Expansion counteraction effect assisted vanadate with rich oxygen vacancies as a high cycling stability cathode for aqueous zinc-ion batteries","authors":"Xiao-Luan Xie, Yi-Fan Li, Cheng Wang, Dawei Gu, Lei Wang, Qiao Qiao, Yang Zou, Zhi-Yuan Yao, Lin-Jiang Shen, Xiaoming Ren","doi":"10.1039/d4cp03410d","DOIUrl":"https://doi.org/10.1039/d4cp03410d","url":null,"abstract":"In this study, a novel tunnel structure vanadate <strong>NaVO</strong> (Na<small><sub>0.4</sub></small>V<small><sub>2</sub></small>O<small><sub>4.96</sub></small>) cathode for aqueous zinc ion batteries (AZIBs), is facilely fabricated by thermal decomposition of polyoxovanadate containing NH<small><sub>4</sub></small><small><sup>+</sup></small> ions. The <strong>NaVO</strong> cathode is characterized by abundant oxygen vacancies and nanometer dimensions. These attributes can offer extra reaction sites and suppress structural collapse during circulation. In the charge-discharge process, a unique phenomenon occurs where <strong>NaVO</strong> undergoes opposite expansion (positive vs. negative expansion) along its different crystal planes. This opposite expansion produces an “expansion counteraction effect”, which effectively buffers volume change of <strong>NaVO</strong>. Additionally, the irreversibly inserted Zn<small><sup>2+</sup></small> ions as “pillars” are maintained in the framework after the first discharge, further improving the structural stability of <strong>NaVO</strong>. Thereby, the <strong>NaVO</strong> cathode exhibits superior cyclic stability. The capacity retention rate can reach 87.3% after 350 cycles at 0.1 A g<small><sup>−1</sup></small>. With a high current density of 2 A g<small><sup>−1</sup></small>, the specific capacity can be maintained at 206.3 mA h g<small><sup>−1</sup></small> with a capacity retention of 95.5% after 2100 cycles. This study not only provides a novel approach for synthesizing nanoscale vanadate cathode with rich oxygen vacancies, but also proposes the “expansion counteraction effect” theory, offering innovative insights into the design of the high cycling stability cathode for AZIBs.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"50 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142987403","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}
Xiaoqing Yang, Pan Guo, Shunbo Hu, Zhibin Gao, Wenliang Yao, Jinrong Cheng, Samuel Poncé, Baigeng Wang, Wei Ren
Correction for ‘Ab initio study of temperature-dependent piezoelectric and electronic properties of thermally stable GaPO4’ by Xiaoqing Yang et al., Phys. Chem. Chem. Phys., 2024, 26, 21530–21537, https://doi.org/10.1039/D4CP02270J.
{"title":"Correction: Ab initio study of temperature-dependent piezoelectric and electronic properties of thermally stable GaPO4","authors":"Xiaoqing Yang, Pan Guo, Shunbo Hu, Zhibin Gao, Wenliang Yao, Jinrong Cheng, Samuel Poncé, Baigeng Wang, Wei Ren","doi":"10.1039/d5cp90008e","DOIUrl":"https://doi.org/10.1039/d5cp90008e","url":null,"abstract":"Correction for ‘<em>Ab initio</em> study of temperature-dependent piezoelectric and electronic properties of thermally stable GaPO<small><sub>4</sub></small>’ by Xiaoqing Yang <em>et al.</em>, <em>Phys. Chem. Chem. Phys.</em>, 2024, <strong>26</strong>, 21530–21537, https://doi.org/10.1039/D4CP02270J.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"33 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142987406","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}
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