Juwita N. Rahmat, Jiayi Liu, Taili Chen, ZhiHong Li and Yong Zhang
Biological nanoparticles, or bionanoparticles, are small molecules manufactured in living systems with complex production and assembly machinery. The products of the assembly systems can be further engineered to generate functionalities for specific purposes. These bionanoparticles have demonstrated advantages such as immune system evasion, minimal toxicity, biocompatibility, and biological clearance. Hence, bionanoparticles are considered the new paradigm in nanoscience research for fabricating safe and effective nanoformulations for therapeutic purposes. Harnessing the power of the immune system to recognize and eradicate malignancies is a viable strategy to achieve better therapeutic outcomes with long-term protection from disease recurrence. However, cancerous tissues have evolved to become invisible to immune recognition and to transform the tumor microenvironment into an immunosuppressive dwelling, thwarting the immune defense systems and creating a hospitable atmosphere for cancer growth and progression. Thus, it is pertinent that efforts in fabricating nanoformulations for immunomodulation are mindful of the tumor-induced immune aberrations that could render cancer nanotherapy inoperable. This review systematically categorizes the immunosuppression mechanisms, the regulatory immunosuppressive cellular players, and critical suppressive molecules currently targeted as breakthrough therapies in the clinic. Finally, this review will summarize the engineering strategies for affording immune moderating functions to bionanoparticles that tip the tumor microenvironment (TME) balance toward cancer elimination, a field still in the nascent stage.
{"title":"Engineered biological nanoparticles as nanotherapeutics for tumor immunomodulation","authors":"Juwita N. Rahmat, Jiayi Liu, Taili Chen, ZhiHong Li and Yong Zhang","doi":"10.1039/D3CS00602F","DOIUrl":"10.1039/D3CS00602F","url":null,"abstract":"<p >Biological nanoparticles, or bionanoparticles, are small molecules manufactured in living systems with complex production and assembly machinery. The products of the assembly systems can be further engineered to generate functionalities for specific purposes. These bionanoparticles have demonstrated advantages such as immune system evasion, minimal toxicity, biocompatibility, and biological clearance. Hence, bionanoparticles are considered the new paradigm in nanoscience research for fabricating safe and effective nanoformulations for therapeutic purposes. Harnessing the power of the immune system to recognize and eradicate malignancies is a viable strategy to achieve better therapeutic outcomes with long-term protection from disease recurrence. However, cancerous tissues have evolved to become invisible to immune recognition and to transform the tumor microenvironment into an immunosuppressive dwelling, thwarting the immune defense systems and creating a hospitable atmosphere for cancer growth and progression. Thus, it is pertinent that efforts in fabricating nanoformulations for immunomodulation are mindful of the tumor-induced immune aberrations that could render cancer nanotherapy inoperable. This review systematically categorizes the immunosuppression mechanisms, the regulatory immunosuppressive cellular players, and critical suppressive molecules currently targeted as breakthrough therapies in the clinic. Finally, this review will summarize the engineering strategies for affording immune moderating functions to bionanoparticles that tip the tumor microenvironment (TME) balance toward cancer elimination, a field still in the nascent stage.</p>","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":null,"pages":null},"PeriodicalIF":46.2,"publicationDate":"2024-05-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/cs/d3cs00602f?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140875299","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Thermally activated delayed fluorescence (TADF) emitters have become increasingly prominent due to their promising applications across various fields, prompting a continuous demand for developing reliable synthetic methods to access them. This review aims to highlight the progress made in the last decade in synthesizing organic TADF compounds through C−H bond activation and functionalization. The review begins with a brief introduction to the basic features and design principles of TADF emitters. It then provides an overview of the advantages and concise development of C−H bond transformations in constructing TADF emitters. Subsequently, it summarizes both transition-metal-catalyzed and non-transition-metal-promoted C−H bond transformations used for the synthesis of TADF emitters. Finally, the review gives an outlook on further challenges and potential directions in this field.
{"title":"Synthetic progress of organic thermally activated delayed fluorescence emitters via C–H activation and functionalization†","authors":"Fan Ni, Yipan Huang, Longzhen Qiu and Chuluo Yang","doi":"10.1039/D3CS00871A","DOIUrl":"10.1039/D3CS00871A","url":null,"abstract":"<p >Thermally activated delayed fluorescence (TADF) emitters have become increasingly prominent due to their promising applications across various fields, prompting a continuous demand for developing reliable synthetic methods to access them. This review aims to highlight the progress made in the last decade in synthesizing organic TADF compounds through C−H bond activation and functionalization. The review begins with a brief introduction to the basic features and design principles of TADF emitters. It then provides an overview of the advantages and concise development of C−H bond transformations in constructing TADF emitters. Subsequently, it summarizes both transition-metal-catalyzed and non-transition-metal-promoted C−H bond transformations used for the synthesis of TADF emitters. Finally, the review gives an outlook on further challenges and potential directions in this field.</p>","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":null,"pages":null},"PeriodicalIF":46.2,"publicationDate":"2024-05-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140875301","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The long-range periodic atomic arrangement or the lack thereof in solids typically dictates the magnitude and temperature dependence of their lattice thermal conductivity (κlat). Compared to crystalline materials, glasses exhibit a much-suppressed κlat across all temperatures as the phonon mean free path reaches parity with the interatomic distances therein. While the occurrence of such glass-like thermal transport in crystalline solids captivates the scientific community with its fundamental inquiry, it also holds the potential for profoundly impacting the field of thermoelectric energy conversion. Therefore, efficient manipulation of thermal transport and comprehension of the microscopic mechanisms dictating phonon scattering in crystalline solids are paramount. As quantized lattice vibrations (i.e., phonons) drive κlat, atomistic insights into the chemical bonding characteristics are crucial to have informed knowledge about their origins. Recently, it has been observed that within the highly symmetric ‘averaged’ crystal structures, often there are hidden locally asymmetric atomic motifs (within a few Å), which exert far-reaching influence on phonon transport. Phenomena such as local atomic off-centering, atomic rattling or tunneling, liquid-like atomic motion, site splitting, local ordering, etc., which arise within a few Å scales, are generally found to drastically disrupt the passage of heat carrying phonons. Despite their profound implication(s) for phonon dynamics, they are often overlooked by traditional crystallographic techniques. In this review, we provide a brief overview of the fundamental aspects of heat transport and explore the status quo of innately low thermally conductive crystalline solids, wherein the phonon dynamics is majorly governed by local structural phenomena. We also discuss advanced techniques capable of characterizing the crystal structure at the sub-atomic level. Subsequently, we delve into the emergent new ideas with examples linked to local crystal structure and lattice dynamics. While discussing the implications of the local structure for thermal conductivity, we provide the state-of-the-art examples of high-performance thermoelectric materials. Finally, we offer our viewpoint on the experimental and theoretical challenges, potential new paths, and the integration of novel strategies with material synthesis to achieve low κlat and realize high thermoelectric performance in crystalline solids via local structure designing.
{"title":"Hidden structures: a driving factor to achieve low thermal conductivity and high thermoelectric performance","authors":"Debattam Sarkar, Animesh Bhui, Ivy Maria, Moinak Dutta and Kanishka Biswas","doi":"10.1039/D4CS00038B","DOIUrl":"10.1039/D4CS00038B","url":null,"abstract":"<p >The long-range periodic atomic arrangement or the lack thereof in solids typically dictates the magnitude and temperature dependence of their lattice thermal conductivity (<em>κ</em><small><sub>lat</sub></small>). Compared to crystalline materials, glasses exhibit a much-suppressed <em>κ</em><small><sub>lat</sub></small> across all temperatures as the phonon mean free path reaches parity with the interatomic distances therein. While the occurrence of such glass-like thermal transport in crystalline solids captivates the scientific community with its fundamental inquiry, it also holds the potential for profoundly impacting the field of thermoelectric energy conversion. Therefore, efficient manipulation of thermal transport and comprehension of the microscopic mechanisms dictating phonon scattering in crystalline solids are paramount. As quantized lattice vibrations (<em>i.e.</em>, phonons) drive <em>κ</em><small><sub>lat</sub></small>, atomistic insights into the chemical bonding characteristics are crucial to have informed knowledge about their origins. Recently, it has been observed that within the highly symmetric ‘averaged’ crystal structures, often there are hidden locally asymmetric atomic motifs (within a few Å), which exert far-reaching influence on phonon transport. Phenomena such as local atomic off-centering, atomic rattling or tunneling, liquid-like atomic motion, site splitting, local ordering, <em>etc.</em>, which arise within a few Å scales, are generally found to drastically disrupt the passage of heat carrying phonons. Despite their profound implication(s) for phonon dynamics, they are often overlooked by traditional crystallographic techniques. In this review, we provide a brief overview of the fundamental aspects of heat transport and explore the status quo of innately low thermally conductive crystalline solids, wherein the phonon dynamics is majorly governed by local structural phenomena. We also discuss advanced techniques capable of characterizing the crystal structure at the sub-atomic level. Subsequently, we delve into the emergent new ideas with examples linked to local crystal structure and lattice dynamics. While discussing the implications of the local structure for thermal conductivity, we provide the state-of-the-art examples of high-performance thermoelectric materials. Finally, we offer our viewpoint on the experimental and theoretical challenges, potential new paths, and the integration of novel strategies with material synthesis to achieve low <em>κ</em><small><sub>lat</sub></small> and realize high thermoelectric performance in crystalline solids <em>via</em> local structure designing.</p>","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":null,"pages":null},"PeriodicalIF":46.2,"publicationDate":"2024-05-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140875300","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Sheng-Yi Yang, Yingying Chen, Ryan T. K. Kwok, Jacky W. Y. Lam and Ben Zhong Tang
Transition metal-containing materials with aggregation-induced emission (AIE) have brought new opportunities for the development of biological probes, optoelectronic materials, stimuli-responsive materials, sensors, and detectors. Coordination compounds containing the platinum metal have emerged as a promising option for constructing effective AIE platinum complexes. In this review, we classified AIE platinum complexes based on the number of ligands. We focused on the development and performance of AIE platinum complexes with different numbers of ligands and discussed the impact of platinum ion coordination and ligand structure variation on the optoelectronic properties. Furthermore, this review analyzes and summarizes the influence of molecular geometries, stacking models, and aggregation environments on the optoelectronic performance of these complexes. We provided a comprehensive overview of the AIE mechanisms exhibited by various AIE platinum complexes. Based on the unique properties of AIE platinum complexes with different numbers of ligands, we systematically summarized their applications in electronics, biological fields, etc. Finally, we illustrated the challenges and opportunities for future research on AIE platinum complexes, aiming at giving a comprehensive summary and outlook on the latest developments of functional AIE platinum complexes and also encouraging more researchers to contribute to this promising field.
{"title":"Platinum complexes with aggregation-induced emission†","authors":"Sheng-Yi Yang, Yingying Chen, Ryan T. K. Kwok, Jacky W. Y. Lam and Ben Zhong Tang","doi":"10.1039/D4CS00218K","DOIUrl":"10.1039/D4CS00218K","url":null,"abstract":"<p >Transition metal-containing materials with aggregation-induced emission (AIE) have brought new opportunities for the development of biological probes, optoelectronic materials, stimuli-responsive materials, sensors, and detectors. Coordination compounds containing the platinum metal have emerged as a promising option for constructing effective AIE platinum complexes. In this review, we classified AIE platinum complexes based on the number of ligands. We focused on the development and performance of AIE platinum complexes with different numbers of ligands and discussed the impact of platinum ion coordination and ligand structure variation on the optoelectronic properties. Furthermore, this review analyzes and summarizes the influence of molecular geometries, stacking models, and aggregation environments on the optoelectronic performance of these complexes. We provided a comprehensive overview of the AIE mechanisms exhibited by various AIE platinum complexes. Based on the unique properties of AIE platinum complexes with different numbers of ligands, we systematically summarized their applications in electronics, biological fields, <em>etc.</em> Finally, we illustrated the challenges and opportunities for future research on AIE platinum complexes, aiming at giving a comprehensive summary and outlook on the latest developments of functional AIE platinum complexes and also encouraging more researchers to contribute to this promising field.</p>","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":null,"pages":null},"PeriodicalIF":46.2,"publicationDate":"2024-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/cs/d4cs00218k?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140845608","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Qiang Pan, Zhu-Xiao Gu, Ru-Jie Zhou, Zi-Jie Feng, Yu-An Xiong, Tai-Ting Sha, Yu-Meng You and Ren-Gen Xiong
Ferroelectricity, which has diverse important applications such as memory elements, capacitors, and sensors, was first discovered in a molecular compound, Rochelle salt, in 1920 by Valasek. Owing to their superiorities of lightweight, biocompatibility, structural tunability, mechanical flexibility, etc., the past decade has witnessed the renaissance of molecular ferroelectrics as promising complementary materials to commercial inorganic ferroelectrics. Thus, on the 100th anniversary of ferroelectricity, it is an opportune time to look into the future, specifically into how to push the boundaries of material design in molecular ferroelectric systems and finally overcome the hurdles to their commercialization. Herein, we present a comprehensive and accessible review of the appealing development of molecular ferroelectrics over the past 10 years, with an emphasis on their structural diversity, chemical design, exceptional properties, and potential applications. We believe that it will inspire intense, combined research efforts to enrich the family of high-performance molecular ferroelectrics and attract widespread interest from physicists and chemists to better understand the structure–function relationships governing improved applied functional device engineering.
{"title":"The past 10 years of molecular ferroelectrics: structures, design, and properties","authors":"Qiang Pan, Zhu-Xiao Gu, Ru-Jie Zhou, Zi-Jie Feng, Yu-An Xiong, Tai-Ting Sha, Yu-Meng You and Ren-Gen Xiong","doi":"10.1039/D3CS00262D","DOIUrl":"10.1039/D3CS00262D","url":null,"abstract":"<p >Ferroelectricity, which has diverse important applications such as memory elements, capacitors, and sensors, was first discovered in a molecular compound, Rochelle salt, in 1920 by Valasek. Owing to their superiorities of lightweight, biocompatibility, structural tunability, mechanical flexibility, <em>etc.</em>, the past decade has witnessed the renaissance of molecular ferroelectrics as promising complementary materials to commercial inorganic ferroelectrics. Thus, on the 100th anniversary of ferroelectricity, it is an opportune time to look into the future, specifically into how to push the boundaries of material design in molecular ferroelectric systems and finally overcome the hurdles to their commercialization. Herein, we present a comprehensive and accessible review of the appealing development of molecular ferroelectrics over the past 10 years, with an emphasis on their structural diversity, chemical design, exceptional properties, and potential applications. We believe that it will inspire intense, combined research efforts to enrich the family of high-performance molecular ferroelectrics and attract widespread interest from physicists and chemists to better understand the structure–function relationships governing improved applied functional device engineering.</p>","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":null,"pages":null},"PeriodicalIF":46.2,"publicationDate":"2024-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140835962","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Joshua O. Olowoyo, Vahid Shahed Gharahshiran, Yimin Zeng, Yang Zhao and Ying Zheng
Elevated levels of carbon dioxide (CO2) in the atmosphere and the diminishing reserves of fossil fuels have raised profound concerns regarding the resulting consequences of global climate change and the future supply of energy. Hence, the reduction and transformation of CO2 not only mitigates environmental pollution but also generates value-added chemicals, providing a dual remedy to address both energy and environmental challenges. Despite notable advancements, the low conversion efficiency of CO2 remains a major obstacle, largely attributed to its inert chemical nature. It is imperative to engineer catalysts/materials that exhibit high conversion efficiency, selectivity, and stability for CO2 transformation. With unparalleled precision at the atomic level, atomic layer deposition (ALD) and molecular layer deposition (MLD) methods utilize various strategies, including ultrathin modification, overcoating, interlayer coating, area-selective deposition, template-assisted deposition, and sacrificial-layer-assisted deposition, to synthesize numerous novel metal-based materials with diverse structures. These materials, functioning as active materials, passive materials or modifiers, have contributed to the enhancement of catalytic activity, selectivity, and stability, effectively addressing the challenges linked to CO2 transformation. Herein, this review focuses on ALD and MLD's role in fabricating materials for electro-, photo-, photoelectro-, and thermal catalytic CO2 reduction, CO2 capture and separation, and electrochemical CO2 sensing. Significant emphasis is dedicated to the ALD and MLD designed materials, their crucial role in enhancing performance, and exploring the relationship between their structures and catalytic activities for CO2 transformation. Finally, this comprehensive review presents the summary, challenges and prospects for ALD and MLD-designed materials for CO2 transformation.
{"title":"Atomic/molecular layer deposition strategies for enhanced CO2 capture, utilisation and storage materials","authors":"Joshua O. Olowoyo, Vahid Shahed Gharahshiran, Yimin Zeng, Yang Zhao and Ying Zheng","doi":"10.1039/D3CS00759F","DOIUrl":"10.1039/D3CS00759F","url":null,"abstract":"<p >Elevated levels of carbon dioxide (CO<small><sub>2</sub></small>) in the atmosphere and the diminishing reserves of fossil fuels have raised profound concerns regarding the resulting consequences of global climate change and the future supply of energy. Hence, the reduction and transformation of CO<small><sub>2</sub></small> not only mitigates environmental pollution but also generates value-added chemicals, providing a dual remedy to address both energy and environmental challenges. Despite notable advancements, the low conversion efficiency of CO<small><sub>2</sub></small> remains a major obstacle, largely attributed to its inert chemical nature. It is imperative to engineer catalysts/materials that exhibit high conversion efficiency, selectivity, and stability for CO<small><sub>2</sub></small> transformation. With unparalleled precision at the atomic level, atomic layer deposition (ALD) and molecular layer deposition (MLD) methods utilize various strategies, including ultrathin modification, overcoating, interlayer coating, area-selective deposition, template-assisted deposition, and sacrificial-layer-assisted deposition, to synthesize numerous novel metal-based materials with diverse structures. These materials, functioning as active materials, passive materials or modifiers, have contributed to the enhancement of catalytic activity, selectivity, and stability, effectively addressing the challenges linked to CO<small><sub>2</sub></small> transformation. Herein, this review focuses on ALD and MLD's role in fabricating materials for electro-, photo-, photoelectro-, and thermal catalytic CO<small><sub>2</sub></small> reduction, CO<small><sub>2</sub></small> capture and separation, and electrochemical CO<small><sub>2</sub></small> sensing. Significant emphasis is dedicated to the ALD and MLD designed materials, their crucial role in enhancing performance, and exploring the relationship between their structures and catalytic activities for CO<small><sub>2</sub></small> transformation. Finally, this comprehensive review presents the summary, challenges and prospects for ALD and MLD-designed materials for CO<small><sub>2</sub></small> transformation.</p>","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":null,"pages":null},"PeriodicalIF":46.2,"publicationDate":"2024-04-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140808437","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Eun Joo Park, Patric Jannasch, Kenji Miyatake, Chulsung Bae, Kevin Noonan, Cy Fujimoto, Steven Holdcroft, John R. Varcoe, Dirk Henkensmeier, Michael D. Guiver and Yu Seung Kim
Anion exchange polymers (AEPs) play a crucial role in green hydrogen production through anion exchange membrane water electrolysis. The chemical stability of AEPs is paramount for stable system operation in electrolysers and other electrochemical devices. Given the instability of aryl ether-containing AEPs under high pH conditions, recent research has focused on quaternized aryl ether-free variants. The primary goal of this review is to provide a greater depth of knowledge on the synthesis of aryl ether-free AEPs targeted for electrochemical devices. Synthetic pathways that yield polyaromatic AEPs include acid-catalysed polyhydroxyalkylation, metal-promoted coupling reactions, ionene synthesis via nucleophilic substitution, alkylation of polybenzimidazole, and Diels–Alder polymerization. Polyolefinic AEPs are prepared through addition polymerization, ring-opening metathesis, radiation grafting reactions, and anionic polymerization. Discussions cover structure–property–performance relationships of AEPs in fuel cells, redox flow batteries, and water and CO2 electrolysers, along with the current status of scale-up synthesis and commercialization.
{"title":"Aryl ether-free polymer electrolytes for electrochemical and energy devices†","authors":"Eun Joo Park, Patric Jannasch, Kenji Miyatake, Chulsung Bae, Kevin Noonan, Cy Fujimoto, Steven Holdcroft, John R. Varcoe, Dirk Henkensmeier, Michael D. Guiver and Yu Seung Kim","doi":"10.1039/D3CS00186E","DOIUrl":"10.1039/D3CS00186E","url":null,"abstract":"<p >Anion exchange polymers (AEPs) play a crucial role in green hydrogen production through anion exchange membrane water electrolysis. The chemical stability of AEPs is paramount for stable system operation in electrolysers and other electrochemical devices. Given the instability of aryl ether-containing AEPs under high pH conditions, recent research has focused on quaternized aryl ether-free variants. The primary goal of this review is to provide a greater depth of knowledge on the synthesis of aryl ether-free AEPs targeted for electrochemical devices. Synthetic pathways that yield polyaromatic AEPs include acid-catalysed polyhydroxyalkylation, metal-promoted coupling reactions, ionene synthesis <em>via</em> nucleophilic substitution, alkylation of polybenzimidazole, and Diels–Alder polymerization. Polyolefinic AEPs are prepared through addition polymerization, ring-opening metathesis, radiation grafting reactions, and anionic polymerization. Discussions cover structure–property–performance relationships of AEPs in fuel cells, redox flow batteries, and water and CO<small><sub>2</sub></small> electrolysers, along with the current status of scale-up synthesis and commercialization.</p>","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":null,"pages":null},"PeriodicalIF":46.2,"publicationDate":"2024-04-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/cs/d3cs00186e?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140648654","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Catenanes, a distinctive category of mechanically interlocked molecules composed of intertwined macrocycles, have undergone significant advancements since their initial stages characterized by inefficient statistical synthesis methods. Through the aid of molecular recognition processes and principles of self-assembly, a diverse array of catenanes with intricate structures can now be readily accessed utilizing template-directed synthetic protocols. The rapid evolution and emergence of this field have catalyzed the design and construction of artificial molecular switches and machines, leading to the development of increasingly integrated functional systems and materials. This review endeavors to explore the pivotal advancements in catenane synthesis from its inception, offering a comprehensive discussion of the synthetic methodologies employed in recent years. By elucidating the progress made in synthetic approaches to catenanes, our aim is to provide a clearer understanding of the future challenges in further advancing catenane chemistry from a synthetic perspective.
{"title":"Advancements and strategic approaches in catenane synthesis","authors":"Qing Chen and Kelong Zhu","doi":"10.1039/D3CS00499F","DOIUrl":"10.1039/D3CS00499F","url":null,"abstract":"<p >Catenanes, a distinctive category of mechanically interlocked molecules composed of intertwined macrocycles, have undergone significant advancements since their initial stages characterized by inefficient statistical synthesis methods. Through the aid of molecular recognition processes and principles of self-assembly, a diverse array of catenanes with intricate structures can now be readily accessed utilizing template-directed synthetic protocols. The rapid evolution and emergence of this field have catalyzed the design and construction of artificial molecular switches and machines, leading to the development of increasingly integrated functional systems and materials. This review endeavors to explore the pivotal advancements in catenane synthesis from its inception, offering a comprehensive discussion of the synthetic methodologies employed in recent years. By elucidating the progress made in synthetic approaches to catenanes, our aim is to provide a clearer understanding of the future challenges in further advancing catenane chemistry from a synthetic perspective.</p>","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":null,"pages":null},"PeriodicalIF":46.2,"publicationDate":"2024-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140642797","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Hai-Yu Li, Xiang-Jing Kong, Song-De Han, Jiandong Pang, Tao He, Guo-Ming Wang and Xian-He Bu
Metalation of metal–organic frameworks (MOFs) has been developed as a prominent strategy for materials functionalization for pore chemistry modulation and property optimization. By introducing exotic metal ions/complexes/nanoparticles onto/into the parent framework, many metallized MOFs have exhibited significantly improved performance in a wide range of applications. In this review, we focus on the research progress in the metalation of metal–organic frameworks during the last five years, spanning the design principles, synthetic strategies, and potential applications. Based on the crystal engineering principles, a minor change in the MOF composition through metalation would lead to leveraged variation of properties. This review starts from the general strategies established for the incorporation of metal species within MOFs, followed by the design principles to graft the desired functionality while maintaining the porosity of frameworks. Facile metalation has contributed a great number of bespoke materials with excellent performance, and we summarize their applications in gas adsorption and separation, heterogeneous catalysis, detection and sensing, and energy storage and conversion. The underlying mechanisms are also investigated by state-of-the-art techniques and analyzed for gaining insight into the structure–property relationships, which would in turn facilitate the further development of design principles. Finally, the current challenges and opportunities in MOF metalation have been discussed, and the promising future directions for customizing the next-generation advanced materials have been outlined as well.
{"title":"Metalation of metal–organic frameworks: fundamentals and applications","authors":"Hai-Yu Li, Xiang-Jing Kong, Song-De Han, Jiandong Pang, Tao He, Guo-Ming Wang and Xian-He Bu","doi":"10.1039/D3CS00873H","DOIUrl":"10.1039/D3CS00873H","url":null,"abstract":"<p >Metalation of metal–organic frameworks (MOFs) has been developed as a prominent strategy for materials functionalization for pore chemistry modulation and property optimization. By introducing exotic metal ions/complexes/nanoparticles onto/into the parent framework, many metallized MOFs have exhibited significantly improved performance in a wide range of applications. In this review, we focus on the research progress in the metalation of metal–organic frameworks during the last five years, spanning the design principles, synthetic strategies, and potential applications. Based on the crystal engineering principles, a minor change in the MOF composition through metalation would lead to leveraged variation of properties. This review starts from the general strategies established for the incorporation of metal species within MOFs, followed by the design principles to graft the desired functionality while maintaining the porosity of frameworks. Facile metalation has contributed a great number of bespoke materials with excellent performance, and we summarize their applications in gas adsorption and separation, heterogeneous catalysis, detection and sensing, and energy storage and conversion. The underlying mechanisms are also investigated by state-of-the-art techniques and analyzed for gaining insight into the structure–property relationships, which would in turn facilitate the further development of design principles. Finally, the current challenges and opportunities in MOF metalation have been discussed, and the promising future directions for customizing the next-generation advanced materials have been outlined as well.</p>","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":null,"pages":null},"PeriodicalIF":46.2,"publicationDate":"2024-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140640421","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
It has been shown that both the electron-transfer rate constant of an electrochemical reaction and the conductance quantum are correlated with the concept of quantum capacitance. This simple association between the two separate concepts has an entirely quantum rate basis that encompasses the electron-transfer rate theory as originally proposed by Rudolph A. Marcus whether statistical mechanics is appropriately taken into account. I have prepared a concise review of the quantum mechanical rate theory principles focused on its quantum electrodynamics character to demonstrate that it can reconcile the conflicting views established on attempting to use the super-exchange (supported on electron transfer) or ‘metallic-like’ (supported on conductance quantum) mechanisms separately to explain the highly efficient long-range electron transport observed in the respiratory processes of living cells. The unresolved issues related to long-range electron transport are clarified in light of the quantum rate theory with a discussion focused on Geobacter sulfurreducens films as a reference standard of the respiration chain. Theoretical analyses supported by experimental data suggest that the efficiency of respiration within a long-range electron transport path is intrinsically a quantum mechanical event that follows relativistic quantum electrodynamics principles as addressed by quantum rate theory.
研究表明,电化学反应的电子转移速率常数和电导量子都与量子电容的概念相关。这两个独立概念之间的简单联系完全以量子速率为基础,包括鲁道夫-马库斯(Rudolph A. Marcus)最初提出的电子转移速率理论(无论是否适当考虑了统计力学)。我对量子力学速率理论原理进行了简明扼要的评述,重点关注其量子电动力学特性,以证明它可以调和试图分别使用超交换(以电子转移为基础)或 "类金属"(以电导量子为基础)机制来解释活细胞呼吸过程中观察到的高效长程电子传递所产生的相互冲突的观点。根据量子速率理论澄清了与长程电子传递有关的未决问题,并重点讨论了作为呼吸链参考标准的硫化酵母菌薄膜。实验数据支持的理论分析表明,长程电子传递路径中的呼吸效率本质上是一个量子力学事件,遵循量子速率理论所涉及的相对论量子电动力学原理。
{"title":"On the fundamentals of quantum rate theory and the long-range electron transport in respiratory chains†","authors":"Paulo Roberto Bueno","doi":"10.1039/D3CS00662J","DOIUrl":"10.1039/D3CS00662J","url":null,"abstract":"<p >It has been shown that both the electron-transfer rate constant of an electrochemical reaction and the conductance quantum are correlated with the concept of quantum capacitance. This simple association between the two separate concepts has an entirely quantum rate basis that encompasses the electron-transfer rate theory as originally proposed by Rudolph A. Marcus whether statistical mechanics is appropriately taken into account. I have prepared a concise review of the quantum mechanical rate theory principles focused on its quantum electrodynamics character to demonstrate that it can reconcile the conflicting views established on attempting to use the super-exchange (supported on electron transfer) or ‘metallic-like’ (supported on conductance quantum) mechanisms separately to explain the highly efficient long-range electron transport observed in the respiratory processes of living cells. The unresolved issues related to long-range electron transport are clarified in light of the quantum rate theory with a discussion focused on <em>Geobacter sulfurreducens</em> films as a reference standard of the respiration chain. Theoretical analyses supported by experimental data suggest that the efficiency of respiration within a long-range electron transport path is intrinsically a quantum mechanical event that follows relativistic quantum electrodynamics principles as addressed by quantum rate theory.</p>","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":null,"pages":null},"PeriodicalIF":46.2,"publicationDate":"2024-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140637665","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}