Photoelectrochemical (PEC) cathodic protection based on semiconductor photoanodes, by combining solar energy utilization and metal anticorrosion, provides a promising platform for developing an environmentally friendly metal protection technology. In this context, semiconductors (e.g., TiO2, ZnO, SrTiO3, BiVO4, and g-C3N4), with merits of suitable band structure, good chemical stability, and low cost, have attracted extensive attention among the investigated photoanode candidates. However, the poor optical absorption properties and the high photogenerated charge recombination rate severely limit their photocathodic protection performances. In order to break these limitations, different modification strategies for these photoanodes have been developed toward the significant enhancement in PEC cathodic protection properties. In this Review, the rational engineering of semiconductor-based photoanodes, including nanostructure design, elemental doping, defect engineering, and heterostructure construction, has been overviewed to introduce the recent advances for PEC cathodic protection. This Review aims to provide fundamental references and principles for the design and fabrication of highly efficient semiconductor photoanodes for PEC cathodic protection of metals.
{"title":"Rational engineering of semiconductor-based photoanodes for photoelectrochemical cathodic protection","authors":"Xiangyan Chen, Shaopeng Wang, Shaohua Shen","doi":"10.1063/5.0183558","DOIUrl":"https://doi.org/10.1063/5.0183558","url":null,"abstract":"Photoelectrochemical (PEC) cathodic protection based on semiconductor photoanodes, by combining solar energy utilization and metal anticorrosion, provides a promising platform for developing an environmentally friendly metal protection technology. In this context, semiconductors (e.g., TiO2, ZnO, SrTiO3, BiVO4, and g-C3N4), with merits of suitable band structure, good chemical stability, and low cost, have attracted extensive attention among the investigated photoanode candidates. However, the poor optical absorption properties and the high photogenerated charge recombination rate severely limit their photocathodic protection performances. In order to break these limitations, different modification strategies for these photoanodes have been developed toward the significant enhancement in PEC cathodic protection properties. In this Review, the rational engineering of semiconductor-based photoanodes, including nanostructure design, elemental doping, defect engineering, and heterostructure construction, has been overviewed to introduce the recent advances for PEC cathodic protection. This Review aims to provide fundamental references and principles for the design and fabrication of highly efficient semiconductor photoanodes for PEC cathodic protection of metals.","PeriodicalId":72559,"journal":{"name":"Chemical physics reviews","volume":"61 9","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139440851","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Heterogeneous junctions extensively exist in electronic and photovoltaic devices. Due to essential differences, the contacts of heterogeneous junctions are imperfect with structural discontinuity and chemical inconsistency, which have negative impacts on the mechanical, electrical, and thermal properties of devices. To improve the heterogeneous interactions, surface/interfacial modification approaches are developed in which molecular assembly engineering appears to be a promising strategy. Versatile functionalities can be accomplished by smart arrangement and design of the functional groups and geometry of the organic molecular layers. Specific functionality can also be maximized by well organization of the grafting orientation of molecules at the heterogeneous contacts. This article comprehensively reviews the approaches of molecular assembly engineering employed in the construction of the heterogeneous junctions to improve their mechanical, electrical, and thermal properties. Following the introduction of molecular assembly engineering at the target surface/interface, examples are introduced to show the efficacy of molecular assembly engineering on the interfacial adhesion, atomic interdiffusion, dielectric nature, charge injection and recombination, and thermoelectric property in electronic and photovoltaic devices.
{"title":"Effects of molecular assembly on heterogeneous interactions in electronic and photovoltaic devices","authors":"Manik Chandra Sil, Sonali Yadav, Ting-An Chen, Chandrasekaran Pitchai, Chih-Ming Chen","doi":"10.1063/5.0173972","DOIUrl":"https://doi.org/10.1063/5.0173972","url":null,"abstract":"Heterogeneous junctions extensively exist in electronic and photovoltaic devices. Due to essential differences, the contacts of heterogeneous junctions are imperfect with structural discontinuity and chemical inconsistency, which have negative impacts on the mechanical, electrical, and thermal properties of devices. To improve the heterogeneous interactions, surface/interfacial modification approaches are developed in which molecular assembly engineering appears to be a promising strategy. Versatile functionalities can be accomplished by smart arrangement and design of the functional groups and geometry of the organic molecular layers. Specific functionality can also be maximized by well organization of the grafting orientation of molecules at the heterogeneous contacts. This article comprehensively reviews the approaches of molecular assembly engineering employed in the construction of the heterogeneous junctions to improve their mechanical, electrical, and thermal properties. Following the introduction of molecular assembly engineering at the target surface/interface, examples are introduced to show the efficacy of molecular assembly engineering on the interfacial adhesion, atomic interdiffusion, dielectric nature, charge injection and recombination, and thermoelectric property in electronic and photovoltaic devices.","PeriodicalId":72559,"journal":{"name":"Chemical physics reviews","volume":"36 16","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139442752","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Jae Bin Kim, Dae Sik Kim, Jin Seok Kim, Jin Hyun Choe, Da Won Ahn, Eun Su Jung, Sung Gyu Pyo
According to Moore's law, the semiconductor industry is experiencing certain challenges in terms of adapting to highly sophisticated integrated technology. Therefore, controlling materials at the atomic scale is considered a mandatory requirement for further development. To this end, atomic layer deposition and etching skills are being increasingly researched as potential solutions. However, several considerations exist for adopting atomic technology with respect to surface analysis. This review primarily focuses on the use of Raman scattering for evaluating atomic-layered materials. Raman scattering analysis is expected to gradually expand as a semiconductor process and mass-production monitoring technology. As this can enhance the applications of this method, our review can form the basis for establishing Raman scattering analysis as a new trend for atomic-scale monitoring.
{"title":"Raman scattering monitoring of thin film materials for atomic layer etching/deposition in the nano-semiconductor process integration","authors":"Jae Bin Kim, Dae Sik Kim, Jin Seok Kim, Jin Hyun Choe, Da Won Ahn, Eun Su Jung, Sung Gyu Pyo","doi":"10.1063/5.0147685","DOIUrl":"https://doi.org/10.1063/5.0147685","url":null,"abstract":"According to Moore's law, the semiconductor industry is experiencing certain challenges in terms of adapting to highly sophisticated integrated technology. Therefore, controlling materials at the atomic scale is considered a mandatory requirement for further development. To this end, atomic layer deposition and etching skills are being increasingly researched as potential solutions. However, several considerations exist for adopting atomic technology with respect to surface analysis. This review primarily focuses on the use of Raman scattering for evaluating atomic-layered materials. Raman scattering analysis is expected to gradually expand as a semiconductor process and mass-production monitoring technology. As this can enhance the applications of this method, our review can form the basis for establishing Raman scattering analysis as a new trend for atomic-scale monitoring.","PeriodicalId":72559,"journal":{"name":"Chemical physics reviews","volume":"14 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2023-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139014920","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Mixed conductors have recently garnered attention in the chemical physicist community due to their distinctive conducting nature and numerous potential applications. These species transport charges via both ionic and electronic pathways, where the coupling between these pathways facilitates an alternative mode of charge transport. Among the various mixed conductors examined, stable open-shell organic compounds are emerging as a promising class of materials. They have the potential to supplant existing organic mixed conductors thanks to their superior conductivity, ease of processing, environmental stability, and functional adaptability. Notably, recent advancements in open-shell macromolecules have been remarkable, ranging from their unprecedented solid-state electrical conductivity to their versatile roles in electrochemistry. Similarly, recent strides in small molecular open-shell species deserve attention. The solid-state electronic properties of these small molecular radicals can be compared to those of macromolecular (non-)conjugated organics materials, and they also play a significant role in wet (electrolyte-based) chemistry. In this review article, we offer a comprehensive overview of open-shell organic compounds, encompassing both small and macromolecular radicals. We particularly emphasize their role as a mixed conductor in various applications, the unique context of each species, and the interconnections between them.
{"title":"Recent advances in open-shell mixed conductors—From molecular radicals to polymers","authors":"J. Ko, Quynh H. Nguyen, Quyen Vu Thi, Y. Joo","doi":"10.1063/5.0163747","DOIUrl":"https://doi.org/10.1063/5.0163747","url":null,"abstract":"Mixed conductors have recently garnered attention in the chemical physicist community due to their distinctive conducting nature and numerous potential applications. These species transport charges via both ionic and electronic pathways, where the coupling between these pathways facilitates an alternative mode of charge transport. Among the various mixed conductors examined, stable open-shell organic compounds are emerging as a promising class of materials. They have the potential to supplant existing organic mixed conductors thanks to their superior conductivity, ease of processing, environmental stability, and functional adaptability. Notably, recent advancements in open-shell macromolecules have been remarkable, ranging from their unprecedented solid-state electrical conductivity to their versatile roles in electrochemistry. Similarly, recent strides in small molecular open-shell species deserve attention. The solid-state electronic properties of these small molecular radicals can be compared to those of macromolecular (non-)conjugated organics materials, and they also play a significant role in wet (electrolyte-based) chemistry. In this review article, we offer a comprehensive overview of open-shell organic compounds, encompassing both small and macromolecular radicals. We particularly emphasize their role as a mixed conductor in various applications, the unique context of each species, and the interconnections between them.","PeriodicalId":72559,"journal":{"name":"Chemical physics reviews","volume":"262 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2023-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139022092","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yue Xu, Yingjian He, Shaofeng Wang, Zhaomeng Wu, Haolin Hu, Samuel Jeong, Xi Lin, Kailong Hu
Hydrogen produced via proton exchange membrane (PEM) water electrolysis has been considered as one of the most promising alternatives to store and convert energy derived from renewable sources. The acidic environment within the PEM electrolyzer poses challenges to the metal-based electrocatalysts employed in both cathode and anode, necessitating a high level of corrosion resistance. This review provides a comprehensive overview of the emerging graphene-encapsulated metals in catalyzing cathodic and anodic reactions of water electrolysis under acidic media. The two major behaviors occurring at the graphene/metal interface, i.e., the electron transfer and ionic penetration, are systematically discussed owing to the experimental results and computational simulations. The correlation between the graphene shell and underlying metal, as well as their impact on the electron and ion behaviors, is further revealed. The mechanisms governed by the electron and ion behaviors are proposed for graphene encapsulated metal catalysts, providing valuable insights toward the design of cutting-edge metal catalysts for the acidic water electrolysis.
{"title":"Electron and ion behaviors at the graphene/metal interface during the acidic water electrolysis","authors":"Yue Xu, Yingjian He, Shaofeng Wang, Zhaomeng Wu, Haolin Hu, Samuel Jeong, Xi Lin, Kailong Hu","doi":"10.1063/5.0175537","DOIUrl":"https://doi.org/10.1063/5.0175537","url":null,"abstract":"Hydrogen produced via proton exchange membrane (PEM) water electrolysis has been considered as one of the most promising alternatives to store and convert energy derived from renewable sources. The acidic environment within the PEM electrolyzer poses challenges to the metal-based electrocatalysts employed in both cathode and anode, necessitating a high level of corrosion resistance. This review provides a comprehensive overview of the emerging graphene-encapsulated metals in catalyzing cathodic and anodic reactions of water electrolysis under acidic media. The two major behaviors occurring at the graphene/metal interface, i.e., the electron transfer and ionic penetration, are systematically discussed owing to the experimental results and computational simulations. The correlation between the graphene shell and underlying metal, as well as their impact on the electron and ion behaviors, is further revealed. The mechanisms governed by the electron and ion behaviors are proposed for graphene encapsulated metal catalysts, providing valuable insights toward the design of cutting-edge metal catalysts for the acidic water electrolysis.","PeriodicalId":72559,"journal":{"name":"Chemical physics reviews","volume":"28 9","pages":""},"PeriodicalIF":0.0,"publicationDate":"2023-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139018125","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Claire C. Carlin, Alan X. Dai, Alexander Al-Zubeidi, Emma M. Simmerman, Hyuncheol Oh, Niklas Gross, Stephen A. Lee, Stephan Link, C. Landes, Felipe H. da Jornada, Jennifer A. Dionne
Plasmonic photocatalysis uses the light-induced resonant oscillation of free electrons in a metal nanoparticle to concentrate optical energy for driving chemical reactions. By altering the joint electronic structure of the catalyst and reactants, plasmonic catalysis enables reaction pathways with improved selectivity, activity, and catalyst stability. However, designing an optimal catalyst still requires a fundamental understanding of the underlying plasmonic mechanisms at the spatial scales of single particles, at the temporal scales of electron transfer, and in conditions analogous to those under which real reactions will operate. Thus, in this review, we provide an overview of several of the available and developing nanoscale and ultrafast experimental approaches, emphasizing those that can be performed in situ. Specifically, we discuss high spatial resolution optical, tip-based, and electron microscopy techniques; high temporal resolution optical and x-ray techniques; and emerging ultrafast optical, x-ray, tip-based, and electron microscopy techniques that simultaneously achieve high spatial and temporal resolution. Ab initio and classical continuum theoretical models play an essential role in guiding and interpreting experimental exploration, and thus, these are also reviewed and several notable theoretical insights are discussed.
{"title":"Nanoscale and ultrafast in situ techniques to probe plasmon photocatalysis","authors":"Claire C. Carlin, Alan X. Dai, Alexander Al-Zubeidi, Emma M. Simmerman, Hyuncheol Oh, Niklas Gross, Stephen A. Lee, Stephan Link, C. Landes, Felipe H. da Jornada, Jennifer A. Dionne","doi":"10.1063/5.0163354","DOIUrl":"https://doi.org/10.1063/5.0163354","url":null,"abstract":"Plasmonic photocatalysis uses the light-induced resonant oscillation of free electrons in a metal nanoparticle to concentrate optical energy for driving chemical reactions. By altering the joint electronic structure of the catalyst and reactants, plasmonic catalysis enables reaction pathways with improved selectivity, activity, and catalyst stability. However, designing an optimal catalyst still requires a fundamental understanding of the underlying plasmonic mechanisms at the spatial scales of single particles, at the temporal scales of electron transfer, and in conditions analogous to those under which real reactions will operate. Thus, in this review, we provide an overview of several of the available and developing nanoscale and ultrafast experimental approaches, emphasizing those that can be performed in situ. Specifically, we discuss high spatial resolution optical, tip-based, and electron microscopy techniques; high temporal resolution optical and x-ray techniques; and emerging ultrafast optical, x-ray, tip-based, and electron microscopy techniques that simultaneously achieve high spatial and temporal resolution. Ab initio and classical continuum theoretical models play an essential role in guiding and interpreting experimental exploration, and thus, these are also reviewed and several notable theoretical insights are discussed.","PeriodicalId":72559,"journal":{"name":"Chemical physics reviews","volume":" 5","pages":""},"PeriodicalIF":0.0,"publicationDate":"2023-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138612477","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Thomas Khazanov, Suman Gunasekaran, Aleesha George, Rana Lomlu, Soham Mukherjee, Andrew J. Musser
Organic polaritonics has emerged as a captivating interdisciplinary field that marries the complexities of organic photophysics with the fundamental principles of quantum optics. By harnessing strong light–matter coupling in organic materials, exciton–polaritons offer unique opportunities for advanced device performance, including enhanced energy transport and low-threshold lasing, as well as new functionalities like polariton chemistry. In this review, we delve into the foundational principles of exciton–polaritons from an experimental perspective, highlighting the key states, processes, and timescales that govern polariton phenomena. Our review centers on the spectroscopy of exciton–polaritons. We overview the primary spectroscopic approaches that reveal polariton phenomena, and we discuss the challenges in disentangling polaritonic signatures from spectral artifacts. We discuss how organic materials, due to their complex photophysics and disordered nature, not only present challenges to the conventional polariton models but also provide opportunities for new physics, like manipulating dark electronic states. As the research field continues to grow, with increasingly complex materials and devices, this review serves as a valuable introductory guide for researchers navigating the intricate landscape of organic polaritonics.
{"title":"Embrace the darkness: An experimental perspective on organic exciton–polaritons","authors":"Thomas Khazanov, Suman Gunasekaran, Aleesha George, Rana Lomlu, Soham Mukherjee, Andrew J. Musser","doi":"10.1063/5.0168948","DOIUrl":"https://doi.org/10.1063/5.0168948","url":null,"abstract":"Organic polaritonics has emerged as a captivating interdisciplinary field that marries the complexities of organic photophysics with the fundamental principles of quantum optics. By harnessing strong light–matter coupling in organic materials, exciton–polaritons offer unique opportunities for advanced device performance, including enhanced energy transport and low-threshold lasing, as well as new functionalities like polariton chemistry. In this review, we delve into the foundational principles of exciton–polaritons from an experimental perspective, highlighting the key states, processes, and timescales that govern polariton phenomena. Our review centers on the spectroscopy of exciton–polaritons. We overview the primary spectroscopic approaches that reveal polariton phenomena, and we discuss the challenges in disentangling polaritonic signatures from spectral artifacts. We discuss how organic materials, due to their complex photophysics and disordered nature, not only present challenges to the conventional polariton models but also provide opportunities for new physics, like manipulating dark electronic states. As the research field continues to grow, with increasingly complex materials and devices, this review serves as a valuable introductory guide for researchers navigating the intricate landscape of organic polaritonics.","PeriodicalId":72559,"journal":{"name":"Chemical physics reviews","volume":"42 4","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"2023-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"136347098","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Nowotny chimney ladder (NCL) phases are intermetallic binary compounds that typically crystallize in a tetragonal crystal structure and constitute of two separate subsystems. The rich solid-state chemistry of NCL phases inherits fascinating lattice dynamics with unique abilities for structural modifications. As an extensively studied energy material for the thermoelectric application, we overview the emerging aspects for structural interpretation in higher manganese silicides (MnSiγ), a prominently explored example of NCL phase. The progress in understanding the incommensurate composite crystals of MnSiγ is discussed to highlight its functional crystallography for proposing the effective strategies to attain favorable modification of transport properties of charge carriers (concentration, mobility, effective mass), and phonons (lattice thermal conductivity). The application potential and prospective strategies for enabling the rational optimization of the dimensionless thermoelectric figure of merit (zT) are examined, and the possibilities of chemical modification in MnSiγ and related NCL phases are presented.
{"title":"Higher manganese silicides: A Nowotny chimney ladder phase for thermoelectric applications","authors":"Nagendra S. Chauhan, Yuzuru Miyazaki","doi":"10.1063/5.0167220","DOIUrl":"https://doi.org/10.1063/5.0167220","url":null,"abstract":"Nowotny chimney ladder (NCL) phases are intermetallic binary compounds that typically crystallize in a tetragonal crystal structure and constitute of two separate subsystems. The rich solid-state chemistry of NCL phases inherits fascinating lattice dynamics with unique abilities for structural modifications. As an extensively studied energy material for the thermoelectric application, we overview the emerging aspects for structural interpretation in higher manganese silicides (MnSiγ), a prominently explored example of NCL phase. The progress in understanding the incommensurate composite crystals of MnSiγ is discussed to highlight its functional crystallography for proposing the effective strategies to attain favorable modification of transport properties of charge carriers (concentration, mobility, effective mass), and phonons (lattice thermal conductivity). The application potential and prospective strategies for enabling the rational optimization of the dimensionless thermoelectric figure of merit (zT) are examined, and the possibilities of chemical modification in MnSiγ and related NCL phases are presented.","PeriodicalId":72559,"journal":{"name":"Chemical physics reviews","volume":"31 4","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"2023-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135366280","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The performance of metal–organic and covalent organic framework materials in sought-after applications—capture, storage, and delivery of gases and molecules, and separation of their mixtures—heavily depends on the host–guest interactions established inside the pores of these materials. Computational modeling provides information about the structures of these host–guest complexes and the strength and nature of the interactions present at a level of detail and precision that is often unobtainable from experiment. In this Review, we summarize the key simulation techniques spanning from molecular dynamics and Monte Carlo methods to correlate ab initio approaches and energy, density, and wavefunction partitioning schemes. We provide illustrative literature examples of their uses in analyzing and designing organic framework hosts. We also describe modern approaches to the high-throughput screening of thousands of existing and hypothetical metal–organic frameworks (MOFs) and covalent organic frameworks (COFs) and emerging machine learning techniques for predicting their properties and performances. Finally, we discuss the key methodological challenges on the path toward computation-driven design and reliable prediction of high-performing MOF and COF adsorbents and catalysts and suggest possible solutions and future directions in this exciting field of computational materials science.
{"title":"Host–guest interactions in framework materials: Insight from modeling","authors":"Michelle Ernst, Jack D. Evans, Ganna Gryn'ova","doi":"10.1063/5.0144827","DOIUrl":"https://doi.org/10.1063/5.0144827","url":null,"abstract":"The performance of metal–organic and covalent organic framework materials in sought-after applications—capture, storage, and delivery of gases and molecules, and separation of their mixtures—heavily depends on the host–guest interactions established inside the pores of these materials. Computational modeling provides information about the structures of these host–guest complexes and the strength and nature of the interactions present at a level of detail and precision that is often unobtainable from experiment. In this Review, we summarize the key simulation techniques spanning from molecular dynamics and Monte Carlo methods to correlate ab initio approaches and energy, density, and wavefunction partitioning schemes. We provide illustrative literature examples of their uses in analyzing and designing organic framework hosts. We also describe modern approaches to the high-throughput screening of thousands of existing and hypothetical metal–organic frameworks (MOFs) and covalent organic frameworks (COFs) and emerging machine learning techniques for predicting their properties and performances. Finally, we discuss the key methodological challenges on the path toward computation-driven design and reliable prediction of high-performing MOF and COF adsorbents and catalysts and suggest possible solutions and future directions in this exciting field of computational materials science.","PeriodicalId":72559,"journal":{"name":"Chemical physics reviews","volume":"2 1","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"2023-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135616928","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Qiaobin Li, Zoe Armstrong, Austin MacRae, Mary Lenertz, Li Feng, Zhongyu Yang
Confining proteins in synthetic nanoscale spatial compartments has offered a cell-free avenue to understand enzyme structure–function relationships and complex cellular processes near the physiological conditions, an important branch of fundamental protein biophysics studies. Enzyme confinement has also provided advancement in biocatalysis by offering enhanced enzyme reusability, cost-efficiency, and substrate selectivity in certain cases for research and industrial applications. However, the primary research efforts in this area have been focused on the development of novel confinement materials and investigating protein adsorption/interaction with various surfaces, leaving a fundamental knowledge gap, namely, the lack of understanding of the confined enzymes (note that enzyme adsorption to or interactions with surfaces differs from enzyme confinement as the latter offers an enhanced extent of restriction to enzyme movement and/or conformational flexibility). In particular, there is limited understanding of enzymes' structure, dynamics, translocation (into biological pores), folding, and aggregation in extreme cases upon confinement, and how confinement properties such as the size, shape, and rigidity affect these details. The first barrier to bridge this gap is the difficulty in “penetrating” the “shielding” of the confinement walls experimentally; confinement could also lead to high heterogeneity and dynamics in the entrapped enzymes, challenging most protein-probing experimental techniques. The complexity is raised by the variety in the possible confinement environments that enzymes may encounter in nature or on lab benches, which can be categorized to rigid confinement with regular shapes, rigid restriction without regular shapes, and flexible/dynamic confinement which also introduces crowding effects. Thus, to bridge such a knowledge gap, it is critical to combine advanced materials and cutting-edge techniques to re-create the various confinement conditions and understand enzymes therein. We have spearheaded in this challenging area by creating various confinement conditions to restrict enzymes while exploring experimental techniques to understand enzyme behaviors upon confinement at the molecular/residue level. This review is to summarize our key findings on the molecular level details of enzymes confined in (i) rigid compartments with regular shapes based on pre-formed, mesoporous nanoparticles and Metal–Organic Frameworks/Covalent-Organic Frameworks (MOFs/COFs), (ii) rigid confinement with irregular crystal defects with shapes close to the outline of the confined enzymes via co-crystallization of enzymes with certain metal ions and ligands in the aqueous phase (biomineralization), and (iii) flexible, dynamic confinement created by protein-friendly polymeric materials and assemblies. Under each case, we will focus our discussion on (a) the way to load enzymes into the confined spaces, (b) the structural basis of the function and behavior
{"title":"On the interface of enzyme and spatial confinement: The impacts of confinement rigidity, shape, and surface properties on the interplay of enzyme structure, dynamics, and function","authors":"Qiaobin Li, Zoe Armstrong, Austin MacRae, Mary Lenertz, Li Feng, Zhongyu Yang","doi":"10.1063/5.0167117","DOIUrl":"https://doi.org/10.1063/5.0167117","url":null,"abstract":"Confining proteins in synthetic nanoscale spatial compartments has offered a cell-free avenue to understand enzyme structure–function relationships and complex cellular processes near the physiological conditions, an important branch of fundamental protein biophysics studies. Enzyme confinement has also provided advancement in biocatalysis by offering enhanced enzyme reusability, cost-efficiency, and substrate selectivity in certain cases for research and industrial applications. However, the primary research efforts in this area have been focused on the development of novel confinement materials and investigating protein adsorption/interaction with various surfaces, leaving a fundamental knowledge gap, namely, the lack of understanding of the confined enzymes (note that enzyme adsorption to or interactions with surfaces differs from enzyme confinement as the latter offers an enhanced extent of restriction to enzyme movement and/or conformational flexibility). In particular, there is limited understanding of enzymes' structure, dynamics, translocation (into biological pores), folding, and aggregation in extreme cases upon confinement, and how confinement properties such as the size, shape, and rigidity affect these details. The first barrier to bridge this gap is the difficulty in “penetrating” the “shielding” of the confinement walls experimentally; confinement could also lead to high heterogeneity and dynamics in the entrapped enzymes, challenging most protein-probing experimental techniques. The complexity is raised by the variety in the possible confinement environments that enzymes may encounter in nature or on lab benches, which can be categorized to rigid confinement with regular shapes, rigid restriction without regular shapes, and flexible/dynamic confinement which also introduces crowding effects. Thus, to bridge such a knowledge gap, it is critical to combine advanced materials and cutting-edge techniques to re-create the various confinement conditions and understand enzymes therein. We have spearheaded in this challenging area by creating various confinement conditions to restrict enzymes while exploring experimental techniques to understand enzyme behaviors upon confinement at the molecular/residue level. This review is to summarize our key findings on the molecular level details of enzymes confined in (i) rigid compartments with regular shapes based on pre-formed, mesoporous nanoparticles and Metal–Organic Frameworks/Covalent-Organic Frameworks (MOFs/COFs), (ii) rigid confinement with irregular crystal defects with shapes close to the outline of the confined enzymes via co-crystallization of enzymes with certain metal ions and ligands in the aqueous phase (biomineralization), and (iii) flexible, dynamic confinement created by protein-friendly polymeric materials and assemblies. Under each case, we will focus our discussion on (a) the way to load enzymes into the confined spaces, (b) the structural basis of the function and behavior ","PeriodicalId":72559,"journal":{"name":"Chemical physics reviews","volume":"141 1","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"2023-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135730310","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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