Interest in the biotoxicology of uranium resulting from its inherent radioactive as well as chemical properties has been growing intensely in recent years. Indeed, uranium in its stable form as UO22+ species is ubiquitously found on earth, and this form is commonly known as the uranyl(VI) ion. The unusual electronic environment at the core of the uranyl(VI) complex plays an important role in its interaction with biomacromolecules. Based on the spectroscopic and computational studies, we have explored the interaction of the uranyl(VI) complex with BSA. The results showed that the fluorescence intensity of BSA was quenched upon interaction with the uranyl(VI) complex largely through dynamic mode, which was authenticated by Stern-Volmer calculations and fluorescence lifetime measurements at different temperatures. Fluorescence anisotropy and synchronous fluorescence spectroscopy were performed to understand the micro-environments of the fluorophores. Furthermore, the binding constant, standard free energy and number of binding sites were also calculated. Thermodynamic parameters such as ΔH° and ΔS° revealed that the non-covalent interactions played a principal role in the binding of the uranyl(VI) complex to BSA, and the value of ΔG° indicated the spontaneity of the interaction. Using the site marker fluorescent probes, the binding location of the uranyl(VI) complex at the BSA site was established. This was further supported by the molecular docking technique with a docking free energy of -38.91 kJ mol-1, indicating the non-covalent binding of the uranyl(VI) complex with BSA active sites. This piece of work may contribute mostly to understanding the pharmacokinetics of the uranyl(VI) complex and provide fundamental data on its safe usage.
{"title":"Unravelling molecular interaction of the uranyl(VI) complex with bovine serum albumin.","authors":"Tankadhar Behera, Sipun Sethi, Jyotiprabha Rout, Bhawani Prasad Bag, Nabakrushna Behera","doi":"10.1039/d4cp02529f","DOIUrl":"https://doi.org/10.1039/d4cp02529f","url":null,"abstract":"<p><p>Interest in the biotoxicology of uranium resulting from its inherent radioactive as well as chemical properties has been growing intensely in recent years. Indeed, uranium in its stable form as UO<sub>2</sub><sup>2+</sup> species is ubiquitously found on earth, and this form is commonly known as the uranyl(VI) ion. The unusual electronic environment at the core of the uranyl(VI) complex plays an important role in its interaction with biomacromolecules. Based on the spectroscopic and computational studies, we have explored the interaction of the uranyl(VI) complex with BSA. The results showed that the fluorescence intensity of BSA was quenched upon interaction with the uranyl(VI) complex largely through dynamic mode, which was authenticated by Stern-Volmer calculations and fluorescence lifetime measurements at different temperatures. Fluorescence anisotropy and synchronous fluorescence spectroscopy were performed to understand the micro-environments of the fluorophores. Furthermore, the binding constant, standard free energy and number of binding sites were also calculated. Thermodynamic parameters such as Δ<i>H</i>° and Δ<i>S</i>° revealed that the non-covalent interactions played a principal role in the binding of the uranyl(VI) complex to BSA, and the value of Δ<i>G</i>° indicated the spontaneity of the interaction. Using the site marker fluorescent probes, the binding location of the uranyl(VI) complex at the BSA site was established. This was further supported by the molecular docking technique with a docking free energy of -38.91 kJ mol<sup>-1</sup>, indicating the non-covalent binding of the uranyl(VI) complex with BSA active sites. This piece of work may contribute mostly to understanding the pharmacokinetics of the uranyl(VI) complex and provide fundamental data on its safe usage.</p>","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":null,"pages":null},"PeriodicalIF":2.9,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142398755","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}
Satadeep Bhattacharjee, Namitha Anna Koshi, Seung-Cheol Lee
Accurate band gap prediction in semiconductors is crucial for materials science and semiconductor technology advancements. This paper extends the Perdew-Burke-Ernzerhof (PBE) functional for a wide range of semiconductors, tackling the exchange and correlation enhancement factor complexities within density functional theory (DFT). Our customized functionals offer a clearer and more realistic alternative to DFT+U methods, which demand large negative U values for elements like sulfur (S), selenium (Se), and phosphorus (P). Moreover, these functionals are more cost-effective than GW or Heyd-Scuseria-Ernzerhof (HSE) hybrid functional methods, therefore, significantly facilitating the way for unified workflows in analyzing electronic structure, dielectric constants, effective masses, and further transport and elastic properties, allowing for seamless calculations across various properties. We point out that such development could be helpful in the creation of comprehensive databases of band gap and dielectric properties of the materials without expensive calculations. Furthermore, for the semiconductors studied, we show that these customized functionals and the strongly constrained and appropriately normed semilocal density functional (SCAN) perform similarly in terms of the band gap.
{"title":"Customizing PBE exchange-correlation functionals: a comprehensive approach for band gap prediction in diverse semiconductors.","authors":"Satadeep Bhattacharjee, Namitha Anna Koshi, Seung-Cheol Lee","doi":"10.1039/d4cp03260h","DOIUrl":"10.1039/d4cp03260h","url":null,"abstract":"<p><p>Accurate band gap prediction in semiconductors is crucial for materials science and semiconductor technology advancements. This paper extends the Perdew-Burke-Ernzerhof (PBE) functional for a wide range of semiconductors, tackling the exchange and correlation enhancement factor complexities within density functional theory (DFT). Our customized functionals offer a clearer and more realistic alternative to DFT+<i>U</i> methods, which demand large negative <i>U</i> values for elements like sulfur (S), selenium (Se), and phosphorus (P). Moreover, these functionals are more cost-effective than GW or Heyd-Scuseria-Ernzerhof (HSE) hybrid functional methods, therefore, significantly facilitating the way for unified workflows in analyzing electronic structure, dielectric constants, effective masses, and further transport and elastic properties, allowing for seamless calculations across various properties. We point out that such development could be helpful in the creation of comprehensive databases of band gap and dielectric properties of the materials without expensive calculations. Furthermore, for the semiconductors studied, we show that these customized functionals and the strongly constrained and appropriately normed semilocal density functional (SCAN) perform similarly in terms of the band gap.</p>","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":null,"pages":null},"PeriodicalIF":2.9,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142398754","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}
Thainá Araujo Oliveira, Paloma Vieira Silva, Fabrício Morais de Vasconcelos, Vincent Meunier, Eduardo Costa Girão
Advances in surface-assisted synthesis routes now allow for precise control in the preparation and modification of low-dimensional structures. The choice of molecular precursors plays a fundamental role in these processes since the structural details and properties of the resulting nanostructures directly depend on the molecular block used. From this perspective, units based on porphyrins have proven to be promising candidates for the construction of nanosystems with nontrivial geometry. In particular, efforts have been made to synthesize different arrangements of π-conjugated porphyrins. With this motivation, we use computational simulations to investigate the electronic and magnetic properties of nanoribbons constructed from the concatenation of π-extended porphyrins hosting transition metal atoms. We show that the binding energy of these systems and the specific way the electrons populate the d-shells are strongly influenced by the type of the transition metal. Furthermore, it was observed that most systems with chelated metals (except Ni and Zn) feature magnetic properties. The systems considered in this work have analogs in finite structures recently synthesized in the laboratory so the nanomaterials proposed here have a high potential to be produced in the near future.
目前，表面辅助合成路线的进步使得低维结构的制备和改性得到了精确控制。分子前体的选择在这些过程中起着根本性的作用，因为所产生的纳米结构的结构细节和特性直接取决于所使用的分子块。从这个角度来看，以卟啉为基础的单元已被证明是构建具有非复杂几何形状的纳米系统的理想候选单元。特别是，人们一直在努力合成不同排列的π-共轭卟啉。基于这一动机，我们利用计算模拟来研究由承载过渡金属原子的π-扩展卟啉连接而成的纳米带的电子和磁性能。我们发现，这些系统的结合能和电子填充 d 壳的特定方式受到过渡金属类型的强烈影响。此外，我们还观察到，大多数含有螯合金属（镍和锌除外）的体系都具有磁性。这项工作中考虑的系统与实验室最近合成的有限结构类似，因此这里提出的纳米材料在不久的将来有很大的生产潜力。
{"title":"Electronic and magnetic properties of porphyrin nanoribbons with chelated metals","authors":"Thainá Araujo Oliveira, Paloma Vieira Silva, Fabrício Morais de Vasconcelos, Vincent Meunier, Eduardo Costa Girão","doi":"10.1039/d4cp02822h","DOIUrl":"https://doi.org/10.1039/d4cp02822h","url":null,"abstract":"Advances in surface-assisted synthesis routes now allow for precise control in the preparation and modification of low-dimensional structures. The choice of molecular precursors plays a fundamental role in these processes since the structural details and properties of the resulting nanostructures directly depend on the molecular block used. From this perspective, units based on porphyrins have proven to be promising candidates for the construction of nanosystems with nontrivial geometry. In particular, efforts have been made to synthesize different arrangements of π-conjugated porphyrins. With this motivation, we use computational simulations to investigate the electronic and magnetic properties of nanoribbons constructed from the concatenation of π-extended porphyrins hosting transition metal atoms. We show that the binding energy of these systems and the specific way the electrons populate the d-shells are strongly influenced by the type of the transition metal. Furthermore, it was observed that most systems with chelated metals (except Ni and Zn) feature magnetic properties. The systems considered in this work have analogs in finite structures recently synthesized in the laboratory so the nanomaterials proposed here have a high potential to be produced in the near future.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":null,"pages":null},"PeriodicalIF":3.3,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142405500","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}
Alexey V. Bogdanov, Longfei Gao, Arina Dalaloyan, Wenkai Zhu, Manas Seal, Xun-Cheng Su, Veronica Frydman, Yangping Liu, Angela M. Gronenborn, Daniella Goldfarb
19F electron-nuclear double resonance (ENDOR) has emerged as an attractive method for determining distance distributions in biomolecules in the range of 0.7–2 nm, which is not easily accessible by pulse electron dipolar spectroscopy. The 19F ENDOR approach relies on spin labeling, and in this work, we compare various labels’ performance. Four protein variants of GB1 and ubiquitin bearing fluorinated residues were labeled at the same site with nitroxide and trityl radicals and a Gd(III) chelate. Additionally, a double-histidine variant of GB1 was labeled with a Cu(II) nitrilotriacetic acid chelate. ENDOR measurements were carried out at W-band (95 GHz) where 19F signals are well separated from 1H signals. Differences in sensitivity were observed, with Gd(III) chelates providing the highest signal-to-noise ratio. The new trityl label, OXMA, devoid of methyl groups, exhibited a sufficiently long phase memory time to produce acceptable sensitivity. However, the longer tether of this label effectively reduces the maximum accessible distance between the 19F and the C of the spin-labeling site. The nitroxide and Cu(II) labels provide valuable additional geometric insights via orientation selection. Prediction of electron-nuclear distances based on the known structure of the proteins were the closest to the experimental values for Gd(III) labels, and distances obtained for Cu(II) labeled GB1 are in good agreement with previously published NMR results. Overall, our results offer valuable guidance for selecting optimal spin labels for 19F ENDOR distance measurement in proteins.
{"title":"Spin Labels for 19F ENDOR Distance Determination: Resolution, Sensitivity and Distance Predictability","authors":"Alexey V. Bogdanov, Longfei Gao, Arina Dalaloyan, Wenkai Zhu, Manas Seal, Xun-Cheng Su, Veronica Frydman, Yangping Liu, Angela M. Gronenborn, Daniella Goldfarb","doi":"10.1039/d4cp02996h","DOIUrl":"https://doi.org/10.1039/d4cp02996h","url":null,"abstract":"19F electron-nuclear double resonance (ENDOR) has emerged as an attractive method for determining distance distributions in biomolecules in the range of 0.7–2 nm, which is not easily accessible by pulse electron dipolar spectroscopy. The 19F ENDOR approach relies on spin labeling, and in this work, we compare various labels’ performance. Four protein variants of GB1 and ubiquitin bearing fluorinated residues were labeled at the same site with nitroxide and trityl radicals and a Gd(III) chelate. Additionally, a double-histidine variant of GB1 was labeled with a Cu(II) nitrilotriacetic acid chelate. ENDOR measurements were carried out at W-band (95 GHz) where 19F signals are well separated from 1H signals. Differences in sensitivity were observed, with Gd(III) chelates providing the highest signal-to-noise ratio. The new trityl label, OXMA, devoid of methyl groups, exhibited a sufficiently long phase memory time to produce acceptable sensitivity. However, the longer tether of this label effectively reduces the maximum accessible distance between the 19F and the C of the spin-labeling site. The nitroxide and Cu(II) labels provide valuable additional geometric insights via orientation selection. Prediction of electron-nuclear distances based on the known structure of the proteins were the closest to the experimental values for Gd(III) labels, and distances obtained for Cu(II) labeled GB1 are in good agreement with previously published NMR results. Overall, our results offer valuable guidance for selecting optimal spin labels for 19F ENDOR distance measurement in proteins.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":null,"pages":null},"PeriodicalIF":3.3,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142405501","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}
Daria Tkachenko, Radik Larionov, Sufia Ziganshina, Khasan Khayarov, Alexander Klimovitskii, Olga Babaeva, Valery Gorbatchuk, Marat Ziganshin
Heating of the linear dipeptides above a critical temperature initiates their cyclization even in the solid state. This method of obtaining cyclic dipeptides meets the requirements of “green chemistry”, provides a high yield of the main product and releases only water as a by-product of the reaction, and does not require solvents. However, to date, the cyclization of only a small number of dipeptides in the solid state has been studied, and some correlations of the process were discovered. The influence of the structure of dipeptide molecules and their crystal packing on the kinetics of solid-state cyclization is still not fully understood. In this work, the cyclization of l-alanyl-l-valine in the solid state upon heating was studied. Using non-isothermal kinetic approaches the kinetic parameters of this reaction and the optimal kinetic model describing this process were determined. The effect of the features of the crystal packing of dipeptides and their heat capacity on the temperature of the cyclization in the solid state was analyzed. This study expands our knowledge about solid-state reactions involving dipeptides and the ability to control such reactions.
{"title":"Cyclization of alanyl-valine dipeptide in the solid state. The effects of molecular radiator and heat capacity","authors":"Daria Tkachenko, Radik Larionov, Sufia Ziganshina, Khasan Khayarov, Alexander Klimovitskii, Olga Babaeva, Valery Gorbatchuk, Marat Ziganshin","doi":"10.1039/d4cp02795g","DOIUrl":"https://doi.org/10.1039/d4cp02795g","url":null,"abstract":"Heating of the linear dipeptides above a critical temperature initiates their cyclization even in the solid state. This method of obtaining cyclic dipeptides meets the requirements of “green chemistry”, provides a high yield of the main product and releases only water as a by-product of the reaction, and does not require solvents. However, to date, the cyclization of only a small number of dipeptides in the solid state has been studied, and some correlations of the process were discovered. The influence of the structure of dipeptide molecules and their crystal packing on the kinetics of solid-state cyclization is still not fully understood. In this work, the cyclization of l-alanyl-l-valine in the solid state upon heating was studied. Using non-isothermal kinetic approaches the kinetic parameters of this reaction and the optimal kinetic model describing this process were determined. The effect of the features of the crystal packing of dipeptides and their heat capacity on the temperature of the cyclization in the solid state was analyzed. This study expands our knowledge about solid-state reactions involving dipeptides and the ability to control such reactions.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":null,"pages":null},"PeriodicalIF":3.3,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142405498","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}
Ruthenium (II) polypyridyl complexes are attractive binders to DNA. Modifying the hydrophobicity, shape, or size of the ancillary ligands around the central ruthenium atom can induce changes in the binding mode to the DNA double helix. In this paper, we investigate the binding modes of [Ru(2,2$^prime$-bipyridine)$_2$(5-{4-[(pyren-1-yl)methyl]-1H-1,2,3-triazol-4-yl}-1,10-phenanthroline)]$^{2+}$ (RuPy for short), a metal complex featuring a flexible pyrene moiety known for its intercalative properties. Classical molecular dynamics simulations are employed to gain insight into the non-covalent binding interactions of RuPy with two different 20 base pair DNA sequences, poly(dA)poly(dT) (AT) and poly(dC)poly(dG) (CG). In addition to examining the intercalation of the pyrene moiety from the major groove, the stability of RuPy--DNA adducts is investigated when the metal complex interacts externally with the DNA and with the major and minor groove pockets. The results indicate that external and major groove binding are not stable binding modes. Instead, RuPy preferably intercalates and binds in the minor groove. Unbiased MD simulations show that intercalation is enabled not only through the pyrene moiety but also via one of the bipyridine (bpy) ligands, though relative binding free energies predict intercalation of the pyrene moiety as the most stable binding mode.
多吡啶钌（II）配合物是 DNA 的诱人结合剂。改变中心钌原子周围辅助配体的疏水性、形状或大小，可以改变与 DNA 双螺旋的结合模式。本文研究了[Ru(2,2$^prime$-bipyridine)$_2$(5-{4-[(pyren-1-yl)methyl]-1H-1,2,3-triazol-4-yl}-1,10-phenanthroline)]$^{2+}$（简称 RuPy）的结合模式。经典分子动力学模拟用于深入了解 RuPy 与两种不同的 20 碱基对 DNA 序列（聚(dA)聚(dT) (AT) 和聚(dC)聚(dG) (CG)）的非共价结合相互作用。除了研究芘分子从主沟插入的情况外，还研究了金属复合物与 DNA 外部以及与主沟和小沟口袋相互作用时 RuPy-DNA 加合物的稳定性。结果表明，外部结合和主沟结合并不是稳定的结合模式。相反，RuPy 更倾向于在小沟中插层和结合。无偏差 MD 模拟显示，插层不仅可以通过芘分子实现，还可以通过双吡啶 (bpy) 配体之一实现，尽管相对结合自由能预测芘分子的插层是最稳定的结合模式。
{"title":"Binding Modes of a Flexible Ruthenium Polypyridyl Complex to DNA","authors":"Meritxel Malagarriga, Leticia González","doi":"10.1039/d4cp02782e","DOIUrl":"https://doi.org/10.1039/d4cp02782e","url":null,"abstract":"Ruthenium (II) polypyridyl complexes are attractive binders to DNA. Modifying the hydrophobicity, shape, or size of the ancillary ligands around the central ruthenium atom can induce changes in the binding mode to the DNA double helix. In this paper, we investigate the binding modes of [Ru(2,2$^prime$-bipyridine)$_2$(5-{4-[(pyren-1-yl)methyl]-1H-1,2,3-triazol-4-yl}-1,10-phenanthroline)]$^{2+}$ (RuPy for short), a metal complex featuring a flexible pyrene moiety known for its intercalative properties. Classical molecular dynamics simulations are employed to gain insight into the non-covalent binding interactions of RuPy with two different 20 base pair DNA sequences, poly(dA)poly(dT) (AT) and poly(dC)poly(dG) (CG). In addition to examining the intercalation of the pyrene moiety from the major groove, the stability of RuPy--DNA adducts is investigated when the metal complex interacts externally with the DNA and with the major and minor groove pockets. The results indicate that external and major groove binding are not stable binding modes. Instead, RuPy preferably intercalates and binds in the minor groove. Unbiased MD simulations show that intercalation is enabled not only through the pyrene moiety but also via one of the bipyridine (bpy) ligands, though relative binding free energies predict intercalation of the pyrene moiety as the most stable binding mode.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":null,"pages":null},"PeriodicalIF":3.3,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142405610","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}
Niamh O'Neill, Christoph Schran, Stephen James Cox, Angelos Michaelides
Dissolution of ionic salts in water is ubiquitous, particularly for NaCl. However, an atomistic scale understanding of the process remains elusive. Simulations lend themselves conveniently to studying dissolution since they provide the spatio-temporal resolution that can be difficult to obtain experimentally. Nevertheless, the complexity of various inter- and intra-molecular interactions require careful treatment and long time scale simulations, both of which are typically hindered by computational expense. Here, we use advances in machine learning potential methodology to resolve at an ab initio level of theory the dissolution mechanism of NaCl in water. The picture that emerges is that of a steady ion-wise unwrapping of the crystal preceding its rapid disintegration, reminiscent of crumbling. The onset of crumbling can be explained by a strong increase in the ratio of the surface to volume of the crystal. Overall, dissolution comprises a series of highly dynamical microscopic sub-processes, resulting in an inherently stochastic mechanism. These atomistic level insights contribute to the general understanding of dissolution mechanisms in other crystals, and the methodology is primed for more complex systems of recent interest such as water/salt interfaces under flow and salt crystals under confinement.
{"title":"Crumbling Crystals: On the Dissolution Mechanism of NaCl in Water","authors":"Niamh O'Neill, Christoph Schran, Stephen James Cox, Angelos Michaelides","doi":"10.1039/d4cp03115f","DOIUrl":"https://doi.org/10.1039/d4cp03115f","url":null,"abstract":"Dissolution of ionic salts in water is ubiquitous, particularly for NaCl. However, an atomistic scale understanding of the process remains elusive. Simulations lend themselves conveniently to studying dissolution since they provide the spatio-temporal resolution that can be difficult to obtain experimentally. Nevertheless, the complexity of various inter- and intra-molecular interactions require careful treatment and long time scale simulations, both of which are typically hindered by computational expense. Here, we use advances in machine learning potential methodology to resolve at an ab initio level of theory the dissolution mechanism of NaCl in water. The picture that emerges is that of a steady ion-wise unwrapping of the crystal preceding its rapid disintegration, reminiscent of crumbling. The onset of crumbling can be explained by a strong increase in the ratio of the surface to volume of the crystal. Overall, dissolution comprises a series of highly dynamical microscopic sub-processes, resulting in an inherently stochastic mechanism. These atomistic level insights contribute to the general understanding of dissolution mechanisms in other crystals, and the methodology is primed for more complex systems of recent interest such as water/salt interfaces under flow and salt crystals under confinement.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":null,"pages":null},"PeriodicalIF":3.3,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142405499","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}
XuanFei Kuang, Zongtao Liu, Yongjuan Chen, Yang Hong, Yao Xiao, Zongcun liang
The paper describes the preparation of NiOx films using Atomic Layer Deposition (ALD) and analyzes their hole transport properties. During the ALD process, NiOx films with varying properties were fabricated by adjusting the number of nickel pulses in the reaction. Various characterization techniques were employed to investigate the morphology, composition, optical, and electrical properties of the films prepared with different numbers of nickel pulses. The study reveals that as the number of Ni pulses increases, the content of Ni metal and Ni (OH)2 in the NiOx films changes, and post-annealing treatment can significantly enhance the performance of the NiOx films. Finally, NiOx was used as a hole transport layer to successfully fabricate silicon solar cells, resulting in an increase in power conversion efficiency (PCE) from 17.89% to 18.89% compared to untreated cells.
{"title":"Effects of Adjusting Nickel Pulse Count on NiOx Films Prepared by Atomic Layer Deposition","authors":"XuanFei Kuang, Zongtao Liu, Yongjuan Chen, Yang Hong, Yao Xiao, Zongcun liang","doi":"10.1039/d4cp03553d","DOIUrl":"https://doi.org/10.1039/d4cp03553d","url":null,"abstract":"The paper describes the preparation of NiOx films using Atomic Layer Deposition (ALD) and analyzes their hole transport properties. During the ALD process, NiOx films with varying properties were fabricated by adjusting the number of nickel pulses in the reaction. Various characterization techniques were employed to investigate the morphology, composition, optical, and electrical properties of the films prepared with different numbers of nickel pulses. The study reveals that as the number of Ni pulses increases, the content of Ni metal and Ni (OH)2 in the NiOx films changes, and post-annealing treatment can significantly enhance the performance of the NiOx films. Finally, NiOx was used as a hole transport layer to successfully fabricate silicon solar cells, resulting in an increase in power conversion efficiency (PCE) from 17.89% to 18.89% compared to untreated cells.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":null,"pages":null},"PeriodicalIF":3.3,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142405502","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}
Muhammad Isa Khan, Mahnaz Khurshid, Saleh S. Alarfaji, Abdul Majid
In our research, we utilize density functional theory (DFT) to explore the properties of Magnesium and Zinc atoms adsorbed on bismuthene. Our findings reveal that the most favorable adsorption site for Mg and Zn atoms on bismuthene is the hollow site. The results indicate that Mg and Zn adsorption on the Bi surface results in significantly high conductivity, with notable adsorption energies of -3.38 eV for Mg and -3.91 eV for Zn. The bismuthene structure can adsorb 9 Mg and 18 Zn atoms with negative average adsorption energy. These findings suggest excellent stability of bismuthene during the adsorption of Magnesium and Zinc. Notably, we propose theoretical storage capacities of 2308 mAh/g for Magnesium-ion batteries (MgIBs) and 4616 mAh/g for Zinc-ion batteries (ZnIBs), while maintaining structural stability during the adsorption of these metal ions. The observed average open-circuit voltages for bismuthene are 0.01 V for Mg and 0.03 V for Zn, with the material retaining its metallic properties throughout the adsorption process. Furthermore, the calculated diffusion barriers for Mg and Zn are 0.1 eV and 0.21 eV, respectively. Our findings in storage capacity, diffusion energies, and low OCV surpass those of most studied two-dimensional materials, positioning bismuthene as a promising anode material for metal-ion rechargeable batteries.
{"title":"Bismuthene for novel anode material of Magnesium/Zinc ion batteries with high capacity and stability: A DFT calculation","authors":"Muhammad Isa Khan, Mahnaz Khurshid, Saleh S. Alarfaji, Abdul Majid","doi":"10.1039/d4cp03154g","DOIUrl":"https://doi.org/10.1039/d4cp03154g","url":null,"abstract":"In our research, we utilize density functional theory (DFT) to explore the properties of Magnesium and Zinc atoms adsorbed on bismuthene. Our findings reveal that the most favorable adsorption site for Mg and Zn atoms on bismuthene is the hollow site. The results indicate that Mg and Zn adsorption on the Bi surface results in significantly high conductivity, with notable adsorption energies of -3.38 eV for Mg and -3.91 eV for Zn. The bismuthene structure can adsorb 9 Mg and 18 Zn atoms with negative average adsorption energy. These findings suggest excellent stability of bismuthene during the adsorption of Magnesium and Zinc. Notably, we propose theoretical storage capacities of 2308 mAh/g for Magnesium-ion batteries (MgIBs) and 4616 mAh/g for Zinc-ion batteries (ZnIBs), while maintaining structural stability during the adsorption of these metal ions. The observed average open-circuit voltages for bismuthene are 0.01 V for Mg and 0.03 V for Zn, with the material retaining its metallic properties throughout the adsorption process. Furthermore, the calculated diffusion barriers for Mg and Zn are 0.1 eV and 0.21 eV, respectively. Our findings in storage capacity, diffusion energies, and low OCV surpass those of most studied two-dimensional materials, positioning bismuthene as a promising anode material for metal-ion rechargeable batteries.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":null,"pages":null},"PeriodicalIF":3.3,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142405607","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}
Silver nanowires (AgNWs) have gained much attention owing to their optoelectronic and mechanical properties and are therefore potential candidates to tackle intrinsic drawbacks of currently applied transparent electrodes in various (opto)electronic devices. In order for AgNWs to be justifiably considered as viable, it is necessary to address their insufficient stability by coupling them with another constituent into a nanocomposite. For this purpose, ZnO was chosen because of its low cost, solution processability and barrier properties. In this paper, a fully solution processed AgNW/ZnO TE film was investigated in order to understand the effect of ZnO coating on the electrical stability of AgNWs, including the mechanism of degradation during their exposure to high electrical current densities. The nanocomposite transparent electrode was processed with ZnO coatings to determine their effect on its optoelectronic properties and electrical stability, where the ZnO triple coated AgNW demonstrated the best combination of optoelectronic properties and stability at the highest working voltage.
{"title":"Wired for stability: evaluating the electrical performance of a solution-processed zinc oxide-modified silver nanowire transparent electrode.","authors":"Jovan N Lukic, Vuk V Radmilovic","doi":"10.1039/d4cp03141e","DOIUrl":"10.1039/d4cp03141e","url":null,"abstract":"<p><p>Silver nanowires (AgNWs) have gained much attention owing to their optoelectronic and mechanical properties and are therefore potential candidates to tackle intrinsic drawbacks of currently applied transparent electrodes in various (opto)electronic devices. In order for AgNWs to be justifiably considered as viable, it is necessary to address their insufficient stability by coupling them with another constituent into a nanocomposite. For this purpose, ZnO was chosen because of its low cost, solution processability and barrier properties. In this paper, a fully solution processed AgNW/ZnO TE film was investigated in order to understand the effect of ZnO coating on the electrical stability of AgNWs, including the mechanism of degradation during their exposure to high electrical current densities. The nanocomposite transparent electrode was processed with ZnO coatings to determine their effect on its optoelectronic properties and electrical stability, where the ZnO triple coated AgNW demonstrated the best combination of optoelectronic properties and stability at the highest working voltage.</p>","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":null,"pages":null},"PeriodicalIF":2.9,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142398756","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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