Pub Date : 2024-10-24DOI: 10.1021/accountsmr.4c0018710.1021/accountsmr.4c00187
Negar Rajabi, Matthew Gene Scarfo, Cole Martin Fredericks, Ramón Santiago Herrera Restrepo, Azin Adibi and Hamed Shahsavan*,
<p >Untethered small-scale (milli-, micro-, and nano-) soft robots promise minimally invasive and targeted medical procedures in tiny, flooded, and confined environments like inside the human body. Despite such potentials, small-scale robots have not yet found their way to real-world applications. This can be mainly attributed to the fundamental and technical challenges in the fabrication, powering, navigation, imaging, and closed-loop control of robots at submillimiter scales. Pertinent to this Account, the selection of building block materials of small-scale robots also poses a challenge that is directly related to their fabrication and function.</p><p >Early work in microrobotics focused on the mechanism of locomotion in fluids with low Reynolds number (<i>Re</i> ≪ 1), which was mainly inspired by the motility of cells and microorganisms. Looking closely at the motile cells and microorganisms, one can find both order and anisotropy within their microstructure, driving out-of-equilibrium asymmetric deformations of their soft bodies and appendages like cilia and flagella, resulting in locomotion and function in environments with low <i>Re</i> number. Microroboticists aim to mimic microorganisms’ locomotion and function in developing mobile small-scale robots. It is known that soft, ordered, and anisotropic microstructures of microorganisms are examples of liquid crystalline systems. With this in mind, we believe that liquid crystals are underutilized in the design of small-scale robots, even though they have remarkable similarities to biological materials and constructs.</p><p >In this Account, we have shed light on the role liquid crystals have played and can play in the design of small-scale robots. For this, we have first elaborated on the fundamentals of liquid crystals, which include a discussion of the various types of liquid crystals and their characteristics, their mesophase behavior, and their anisotropic properties. Then, we have discussed the applicability of anisotropic elastic networks of liquid crystals in the design of actuators which must satisfy all four programming pillars, including elasticity, alignment, responsiveness, and initial geometry. We have highlighted landmark reports where anisotropic elastic networks of liquid crystals, such as liquid crystal elastomers (LCEs), networks (LCNs), and hydrogels, are utilized as structural materials in the design of soft, small-scale actuators and robots. We point out the prevalence of the nematic phase and thermotropic liquid crystals utilized in these constructs over other mesophases and liquid crystal types as part of our discussion on the pros and cons of liquid crystals for microrobotics research. Finally, paths forward for the widespread applicability of liquid crystal microrobotics are envisaged. Specifically, the potential of soft robots constructed from elastic networks of chromonic and micellar lyotropic liquid crystals provides a substantial, yet daunting, opportunity f
{"title":"From Anisotropic Molecules and Particles to Small-Scale Actuators and Robots: An Account of Polymerized Liquid Crystals","authors":"Negar Rajabi, Matthew Gene Scarfo, Cole Martin Fredericks, Ramón Santiago Herrera Restrepo, Azin Adibi and Hamed Shahsavan*, ","doi":"10.1021/accountsmr.4c0018710.1021/accountsmr.4c00187","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00187https://doi.org/10.1021/accountsmr.4c00187","url":null,"abstract":"<p >Untethered small-scale (milli-, micro-, and nano-) soft robots promise minimally invasive and targeted medical procedures in tiny, flooded, and confined environments like inside the human body. Despite such potentials, small-scale robots have not yet found their way to real-world applications. This can be mainly attributed to the fundamental and technical challenges in the fabrication, powering, navigation, imaging, and closed-loop control of robots at submillimiter scales. Pertinent to this Account, the selection of building block materials of small-scale robots also poses a challenge that is directly related to their fabrication and function.</p><p >Early work in microrobotics focused on the mechanism of locomotion in fluids with low Reynolds number (<i>Re</i> ≪ 1), which was mainly inspired by the motility of cells and microorganisms. Looking closely at the motile cells and microorganisms, one can find both order and anisotropy within their microstructure, driving out-of-equilibrium asymmetric deformations of their soft bodies and appendages like cilia and flagella, resulting in locomotion and function in environments with low <i>Re</i> number. Microroboticists aim to mimic microorganisms’ locomotion and function in developing mobile small-scale robots. It is known that soft, ordered, and anisotropic microstructures of microorganisms are examples of liquid crystalline systems. With this in mind, we believe that liquid crystals are underutilized in the design of small-scale robots, even though they have remarkable similarities to biological materials and constructs.</p><p >In this Account, we have shed light on the role liquid crystals have played and can play in the design of small-scale robots. For this, we have first elaborated on the fundamentals of liquid crystals, which include a discussion of the various types of liquid crystals and their characteristics, their mesophase behavior, and their anisotropic properties. Then, we have discussed the applicability of anisotropic elastic networks of liquid crystals in the design of actuators which must satisfy all four programming pillars, including elasticity, alignment, responsiveness, and initial geometry. We have highlighted landmark reports where anisotropic elastic networks of liquid crystals, such as liquid crystal elastomers (LCEs), networks (LCNs), and hydrogels, are utilized as structural materials in the design of soft, small-scale actuators and robots. We point out the prevalence of the nematic phase and thermotropic liquid crystals utilized in these constructs over other mesophases and liquid crystal types as part of our discussion on the pros and cons of liquid crystals for microrobotics research. Finally, paths forward for the widespread applicability of liquid crystal microrobotics are envisaged. Specifically, the potential of soft robots constructed from elastic networks of chromonic and micellar lyotropic liquid crystals provides a substantial, yet daunting, opportunity f","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"5 12","pages":"1520–1531 1520–1531"},"PeriodicalIF":14.0,"publicationDate":"2024-10-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143127700","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}
Pub Date : 2024-10-23DOI: 10.1021/accountsmr.4c00258
Qi-Wen Chen, Xian-Zheng Zhang
Natural or bioengineered living organisms (including mammalian cells, bacteria, microalgaes, yeast, viruses, plant cells, and the multiple organism community) possess many intrinsic or artificial superiorities than the synthesized and inert biomaterials for application in many fields, especially biomedical applications. By leveraging the inherent or artificial therapeutic competences (e.g., disease chemotaxis, drugs production, intelligent delivery, immune activation and metabolic regulation), these living organisms have been developed as critical therapeutic formulations for biomedical applications to solve unmet medical needs. These living organisms are more intelligent, more easily available, more highly active, and more strongly curative than conventional inert formulations, such as inorganic nanocarriers, metal–organic chelating networks, polymeric nanovesicles and biomembrane biohybrids, etc. Nevertheless, nonspecific in vivo circulation, the diseased microenvironment-triggered inactivation, uncontrolled proliferation or colonization, unexpected side effects, and unsatisfactory therapeutic effect severely restricted their further research development and clinical approval. Living biomaterials, fabricated by integrating tailored functional materials with natural or bioengineered living organisms by chemical conjugation, physical assembly, and biological engineering strategies as well as advanced construction techniques, are rapidly developed to preserve or augment bioactivity and therapeutic properties of living organisms and even control their behaviors, decrease their biotoxicity, and impart them with new biofunctionalities, like stress resistance, bioactivity maintenance, safe trafficking, controllable proliferation and colonization, and evolved metabolism properties. These acquired capacities are especially beneficial to improve therapeutic potency and compliance, solve significant therapeutic restrictions, avoid biosafety questions, enhance therapeutic performances, and extend the boundaries of the fabricated living biomaterials on science research and practical biomedical applications. Additionally, the introduction of biocompatible and instructive functional materials, such as inorganic materials, synthetic polymers and polypeptides, functional proteins and enzymes, as well as biological component materials, can also promote the interaction of living biomaterials with the living body and provide feedback to further adapt the biofunctions of living organisms.
{"title":"Living Biomaterials: Fabrication Strategies and Biomedical Applications","authors":"Qi-Wen Chen, Xian-Zheng Zhang","doi":"10.1021/accountsmr.4c00258","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00258","url":null,"abstract":"Natural or bioengineered living organisms (including mammalian cells, bacteria, microalgaes, yeast, viruses, plant cells, and the multiple organism community) possess many intrinsic or artificial superiorities than the synthesized and inert biomaterials for application in many fields, especially biomedical applications. By leveraging the inherent or artificial therapeutic competences (e.g., disease chemotaxis, drugs production, intelligent delivery, immune activation and metabolic regulation), these living organisms have been developed as critical therapeutic formulations for biomedical applications to solve unmet medical needs. These living organisms are more intelligent, more easily available, more highly active, and more strongly curative than conventional inert formulations, such as inorganic nanocarriers, metal–organic chelating networks, polymeric nanovesicles and biomembrane biohybrids, etc. Nevertheless, nonspecific <i>in vivo</i> circulation, the diseased microenvironment-triggered inactivation, uncontrolled proliferation or colonization, unexpected side effects, and unsatisfactory therapeutic effect severely restricted their further research development and clinical approval. Living biomaterials, fabricated by integrating tailored functional materials with natural or bioengineered living organisms by chemical conjugation, physical assembly, and biological engineering strategies as well as advanced construction techniques, are rapidly developed to preserve or augment bioactivity and therapeutic properties of living organisms and even control their behaviors, decrease their biotoxicity, and impart them with new biofunctionalities, like stress resistance, bioactivity maintenance, safe trafficking, controllable proliferation and colonization, and evolved metabolism properties. These acquired capacities are especially beneficial to improve therapeutic potency and compliance, solve significant therapeutic restrictions, avoid biosafety questions, enhance therapeutic performances, and extend the boundaries of the fabricated living biomaterials on science research and practical biomedical applications. Additionally, the introduction of biocompatible and instructive functional materials, such as inorganic materials, synthetic polymers and polypeptides, functional proteins and enzymes, as well as biological component materials, can also promote the interaction of living biomaterials with the living body and provide feedback to further adapt the biofunctions of living organisms.","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"13 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142488032","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}
Pub Date : 2024-10-23DOI: 10.1021/accountsmr.4c0025810.1021/accountsmr.4c00258
Qi-Wen Chen, and , Xian-Zheng Zhang*,
<p >Natural or bioengineered living organisms (including mammalian cells, bacteria, microalgaes, yeast, viruses, plant cells, and the multiple organism community) possess many intrinsic or artificial superiorities than the synthesized and inert biomaterials for application in many fields, especially biomedical applications. By leveraging the inherent or artificial therapeutic competences (e.g., disease chemotaxis, drugs production, intelligent delivery, immune activation and metabolic regulation), these living organisms have been developed as critical therapeutic formulations for biomedical applications to solve unmet medical needs. These living organisms are more intelligent, more easily available, more highly active, and more strongly curative than conventional inert formulations, such as inorganic nanocarriers, metal–organic chelating networks, polymeric nanovesicles and biomembrane biohybrids, etc. Nevertheless, nonspecific <i>in vivo</i> circulation, the diseased microenvironment-triggered inactivation, uncontrolled proliferation or colonization, unexpected side effects, and unsatisfactory therapeutic effect severely restricted their further research development and clinical approval. Living biomaterials, fabricated by integrating tailored functional materials with natural or bioengineered living organisms by chemical conjugation, physical assembly, and biological engineering strategies as well as advanced construction techniques, are rapidly developed to preserve or augment bioactivity and therapeutic properties of living organisms and even control their behaviors, decrease their biotoxicity, and impart them with new biofunctionalities, like stress resistance, bioactivity maintenance, safe trafficking, controllable proliferation and colonization, and evolved metabolism properties. These acquired capacities are especially beneficial to improve therapeutic potency and compliance, solve significant therapeutic restrictions, avoid biosafety questions, enhance therapeutic performances, and extend the boundaries of the fabricated living biomaterials on science research and practical biomedical applications. Additionally, the introduction of biocompatible and instructive functional materials, such as inorganic materials, synthetic polymers and polypeptides, functional proteins and enzymes, as well as biological component materials, can also promote the interaction of living biomaterials with the living body and provide feedback to further adapt the biofunctions of living organisms.</p><p >In this Account, we present a brief overview of recent advances of living biomaterials in their fabrication strategies and biomedical applications, embracing living organism species as well as living organism communities. We introduce the typical and practicable methods and techniques for fabrication of living biomaterials, mainly including chemical conjugation, physical assembly, biological editing, and metabolic engineering. On the basis of these fabrication st
{"title":"Living Biomaterials: Fabrication Strategies and Biomedical Applications","authors":"Qi-Wen Chen, and , Xian-Zheng Zhang*, ","doi":"10.1021/accountsmr.4c0025810.1021/accountsmr.4c00258","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00258https://doi.org/10.1021/accountsmr.4c00258","url":null,"abstract":"<p >Natural or bioengineered living organisms (including mammalian cells, bacteria, microalgaes, yeast, viruses, plant cells, and the multiple organism community) possess many intrinsic or artificial superiorities than the synthesized and inert biomaterials for application in many fields, especially biomedical applications. By leveraging the inherent or artificial therapeutic competences (e.g., disease chemotaxis, drugs production, intelligent delivery, immune activation and metabolic regulation), these living organisms have been developed as critical therapeutic formulations for biomedical applications to solve unmet medical needs. These living organisms are more intelligent, more easily available, more highly active, and more strongly curative than conventional inert formulations, such as inorganic nanocarriers, metal–organic chelating networks, polymeric nanovesicles and biomembrane biohybrids, etc. Nevertheless, nonspecific <i>in vivo</i> circulation, the diseased microenvironment-triggered inactivation, uncontrolled proliferation or colonization, unexpected side effects, and unsatisfactory therapeutic effect severely restricted their further research development and clinical approval. Living biomaterials, fabricated by integrating tailored functional materials with natural or bioengineered living organisms by chemical conjugation, physical assembly, and biological engineering strategies as well as advanced construction techniques, are rapidly developed to preserve or augment bioactivity and therapeutic properties of living organisms and even control their behaviors, decrease their biotoxicity, and impart them with new biofunctionalities, like stress resistance, bioactivity maintenance, safe trafficking, controllable proliferation and colonization, and evolved metabolism properties. These acquired capacities are especially beneficial to improve therapeutic potency and compliance, solve significant therapeutic restrictions, avoid biosafety questions, enhance therapeutic performances, and extend the boundaries of the fabricated living biomaterials on science research and practical biomedical applications. Additionally, the introduction of biocompatible and instructive functional materials, such as inorganic materials, synthetic polymers and polypeptides, functional proteins and enzymes, as well as biological component materials, can also promote the interaction of living biomaterials with the living body and provide feedback to further adapt the biofunctions of living organisms.</p><p >In this Account, we present a brief overview of recent advances of living biomaterials in their fabrication strategies and biomedical applications, embracing living organism species as well as living organism communities. We introduce the typical and practicable methods and techniques for fabrication of living biomaterials, mainly including chemical conjugation, physical assembly, biological editing, and metabolic engineering. On the basis of these fabrication st","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"5 11","pages":"1440–1452 1440–1452"},"PeriodicalIF":14.0,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142691362","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}
Chemical bonding is fundamental in determining the physicochemical properties of the materials. Establishing correlations between chemical bonding and these properties may help identify potential materials with unique advantages or guide the composition design for improving the performance of functional materials. However, there is a lack of literature addressing this issue. This Account examines how chemical bonding engineering affects the performance optimization of four widely used or investigated functional materials that are applied in energy-storage/conversion fields, including thermoelectrics, piezoelectrics, lithium-ion batteries (LIBs), and catalysts. The key issues of these materials and correlations between chemical bonding and properties are briefly summarized.
{"title":"Chemical Bonding Engineering: Insights into Physicochemical Performance Optimization for Energy-Storage/Conversion","authors":"Zhifang Zhou, Rui Wei, Xuefan Zhou, Yuan Liu, Dou Zhang, Yuan-Hua Lin","doi":"10.1021/accountsmr.4c00243","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00243","url":null,"abstract":"Chemical bonding is fundamental in determining the physicochemical properties of the materials. Establishing correlations between chemical bonding and these properties may help identify potential materials with unique advantages or guide the composition design for improving the performance of functional materials. However, there is a lack of literature addressing this issue. This Account examines how chemical bonding engineering affects the performance optimization of four widely used or investigated functional materials that are applied in energy-storage/conversion fields, including thermoelectrics, piezoelectrics, lithium-ion batteries (LIBs), and catalysts. The key issues of these materials and correlations between chemical bonding and properties are briefly summarized.","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"24 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142440666","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}
<p >Chemical bonding is fundamental in determining the physicochemical properties of the materials. Establishing correlations between chemical bonding and these properties may help identify potential materials with unique advantages or guide the composition design for improving the performance of functional materials. However, there is a lack of literature addressing this issue. This Account examines how chemical bonding engineering affects the performance optimization of four widely used or investigated functional materials that are applied in energy-storage/conversion fields, including thermoelectrics, piezoelectrics, lithium-ion batteries (LIBs), and catalysts. The key issues of these materials and correlations between chemical bonding and properties are briefly summarized.</p><p >First, electron–phonon coupling hinders thermoelectric performance optimization, representing one of the main issues in the thermoelectric field that needs to be addressed. The role of chemical bonding engineering in electronic and phonon transport is discussed, highlighting how factors such as covalency, electronegativity differences, bond strength, and bond length affect carrier mobility and lattice thermal conductivity. We found that electronic and phonon transport properties can be tuned by modifying the chemical bonding of thermoelectric materials.</p><p >Second, the performance of perovskite piezoelectric materials is governed by their phase structure, which is closely associated with ABO<sub>3</sub> lattice distortion. However, clarifying the correlations between perovskite distortion and chemical bonding has long been challenging. The effects of chemical bonding on perovskite distortion and ferroelectric/piezoelectric response are summarized, focusing on lead-free piezoelectric materials. The roles of ionic radii and electronic structures in the ionocovalent bonding between A-/B-site cations and oxygen anions, as well as the stability of perovskite structures, are discussed. These factors are proven to significantly affect the phase structure and piezoelectric response.</p><p >Third, during LIB operation, various chemical reactions occur within the electrodes and at the electrode/electrolyte interface, leading to the formation of new reversible or irreversible products. These structural and compositional changes signify a continuous evolution of the chemical bonds within the LIB system. Strategies to enhance the stability of high-capacity electrodes through the development of chemical cross-linker binders are summarized. Additionally, the impact of chemical bonds on the electrochemical stability and lithium-transport capabilities of solid-state electrolytes is also explored. Consequently, deliberately controlling chemical bonds is crucial for optimizing the overall electrochemical performance of LIBs, including parameters such as energy density, cycling lifespan, and fast-charging capabilities.</p><p >Fourthly, improving the catalytic activity of catalysts fo
{"title":"Chemical Bonding Engineering: Insights into Physicochemical Performance Optimization for Energy-Storage/Conversion","authors":"Zhifang Zhou, Rui Wei, Xuefan Zhou, Yuan Liu, Dou Zhang and Yuan-Hua Lin*, ","doi":"10.1021/accountsmr.4c0024310.1021/accountsmr.4c00243","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00243https://doi.org/10.1021/accountsmr.4c00243","url":null,"abstract":"<p >Chemical bonding is fundamental in determining the physicochemical properties of the materials. Establishing correlations between chemical bonding and these properties may help identify potential materials with unique advantages or guide the composition design for improving the performance of functional materials. However, there is a lack of literature addressing this issue. This Account examines how chemical bonding engineering affects the performance optimization of four widely used or investigated functional materials that are applied in energy-storage/conversion fields, including thermoelectrics, piezoelectrics, lithium-ion batteries (LIBs), and catalysts. The key issues of these materials and correlations between chemical bonding and properties are briefly summarized.</p><p >First, electron–phonon coupling hinders thermoelectric performance optimization, representing one of the main issues in the thermoelectric field that needs to be addressed. The role of chemical bonding engineering in electronic and phonon transport is discussed, highlighting how factors such as covalency, electronegativity differences, bond strength, and bond length affect carrier mobility and lattice thermal conductivity. We found that electronic and phonon transport properties can be tuned by modifying the chemical bonding of thermoelectric materials.</p><p >Second, the performance of perovskite piezoelectric materials is governed by their phase structure, which is closely associated with ABO<sub>3</sub> lattice distortion. However, clarifying the correlations between perovskite distortion and chemical bonding has long been challenging. The effects of chemical bonding on perovskite distortion and ferroelectric/piezoelectric response are summarized, focusing on lead-free piezoelectric materials. The roles of ionic radii and electronic structures in the ionocovalent bonding between A-/B-site cations and oxygen anions, as well as the stability of perovskite structures, are discussed. These factors are proven to significantly affect the phase structure and piezoelectric response.</p><p >Third, during LIB operation, various chemical reactions occur within the electrodes and at the electrode/electrolyte interface, leading to the formation of new reversible or irreversible products. These structural and compositional changes signify a continuous evolution of the chemical bonds within the LIB system. Strategies to enhance the stability of high-capacity electrodes through the development of chemical cross-linker binders are summarized. Additionally, the impact of chemical bonds on the electrochemical stability and lithium-transport capabilities of solid-state electrolytes is also explored. Consequently, deliberately controlling chemical bonds is crucial for optimizing the overall electrochemical performance of LIBs, including parameters such as energy density, cycling lifespan, and fast-charging capabilities.</p><p >Fourthly, improving the catalytic activity of catalysts fo","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"5 12","pages":"1571–1582 1571–1582"},"PeriodicalIF":14.0,"publicationDate":"2024-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143127669","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}
Pub Date : 2024-10-14DOI: 10.1021/accountsmr.4c00172
Ludan Yue, Guocan Yu, Lang Rao, Ruibing Wang, Xiaoyuan Chen
Supramolecular chemistry is based on intermolecular bonds, where substances dynamically bind together through noncovalent interactions. These dynamic forces allow the macrocyclic molecules and guest molecules to form stable assemblies, with high stability under physiological conditions, making them suitable for in vivo drug delivery. These dynamic noncovalent bonds are easily influenced by external stimuli such as light, heat, pH, and oxidation; thus, the assemblies induced by supramolecular interactions exhibit high diversity and flexibility in response to external stimuli, providing an effective method for simulating natural and physiological processes. The host–guest interactions induced self-assemblies have been applied across multiple dimensions, ranging from the molecular level to the cellular level, for detoxification, targeted drug delivery, and therapeutic studies. At the molecular level, macrocyclic molecules can encapsulate toxic substances from the bloodstream, serving as a solution for emergency detoxification. At the nanoscale level, host–guest interactions can induce the formation of multiple nanostructures including nanomicelles, nanocapsules, nanovesicles, and nanoparticles. The host–guest interactions can enhance the stability of nanostructures and impart them with stimuli sensitivity, which is highly significant in specific microenvironments like tumors. Nanostructures induced by the host–guest interactions possess optimized drug release profiles and pharmacokinetic features, thereby enhancing the therapeutic efficacy while mitigating side effects. At the microscale level, the host–guest interactions can induce the formation of various microassemblies including hydrogels, microfibers, and microtube aggregates. Moreover, microassemblies show superior potential in morphology transformation for controlling cell activity and diseases. Additionally, at the level of biological components, host–guest interactions can induce the assembly of peptides and organelles within cells and having the cell–cell or cell–particle assemblies as hitchhikers at the cellular level. Therefore, this Account aims to summarize the applications of host–guest interactions induced self-assemblies at various levels and the latest research in supramolecular self-assembly, with a particular focus on the progress in our research group. We hope that this account not only reveals the applications of therapeutic supramolecular self-assemblies but also provides new insights into the design of smart drug delivery systems.
{"title":"Supramolecular Aggregates and Hitchhikers","authors":"Ludan Yue, Guocan Yu, Lang Rao, Ruibing Wang, Xiaoyuan Chen","doi":"10.1021/accountsmr.4c00172","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00172","url":null,"abstract":"Supramolecular chemistry is based on intermolecular bonds, where substances dynamically bind together through noncovalent interactions. These dynamic forces allow the macrocyclic molecules and guest molecules to form stable assemblies, with high stability under physiological conditions, making them suitable for <i>in vivo</i> drug delivery. These dynamic noncovalent bonds are easily influenced by external stimuli such as light, heat, pH, and oxidation; thus, the assemblies induced by supramolecular interactions exhibit high diversity and flexibility in response to external stimuli, providing an effective method for simulating natural and physiological processes. The host–guest interactions induced self-assemblies have been applied across multiple dimensions, ranging from the molecular level to the cellular level, for detoxification, targeted drug delivery, and therapeutic studies. At the molecular level, macrocyclic molecules can encapsulate toxic substances from the bloodstream, serving as a solution for emergency detoxification. At the nanoscale level, host–guest interactions can induce the formation of multiple nanostructures including nanomicelles, nanocapsules, nanovesicles, and nanoparticles. The host–guest interactions can enhance the stability of nanostructures and impart them with stimuli sensitivity, which is highly significant in specific microenvironments like tumors. Nanostructures induced by the host–guest interactions possess optimized drug release profiles and pharmacokinetic features, thereby enhancing the therapeutic efficacy while mitigating side effects. At the microscale level, the host–guest interactions can induce the formation of various microassemblies including hydrogels, microfibers, and microtube aggregates. Moreover, microassemblies show superior potential in morphology transformation for controlling cell activity and diseases. Additionally, at the level of biological components, host–guest interactions can induce the assembly of peptides and organelles within cells and having the cell–cell or cell–particle assemblies as hitchhikers at the cellular level. Therefore, this Account aims to summarize the applications of host–guest interactions induced self-assemblies at various levels and the latest research in supramolecular self-assembly, with a particular focus on the progress in our research group. We hope that this account not only reveals the applications of therapeutic supramolecular self-assemblies but also provides new insights into the design of smart drug delivery systems.","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"40 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142431479","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}
Black phosphorus (BP), a rediscovered two-dimensional (2D) material, has garnered significant interest due to its unique structure and physicochemical characteristics, including adjustable direct bandgaps, high carrier mobility, large specific surface area, and pronounced chemical reactivity. Distinct from the flat atomic structure of graphene, BP features a puckered honeycomb-like structure derived from sp3 hybridization. In addition to the three-coordination, each phosphorus atom possesses a lone pair of electrons, leading to an electron-rich nature. A variety of nanostructures such as nanosheets, nanoribbons, and quantum dots are developed from the bulk crystal of BP. The large surface area of nano BP provides numerous reactive sites that augment intralayer chemical interactions. Therefore, nano BP serves as a versatile scaffold for materials engineering, with potential applications across chemistry, catalysis, energy, and biomedicine. It is crucial to have a deep and systematic understanding of the hybridization interactions between BP and diverse molecules or materials, which is essential for functional design of BP-based materials for target applications.
Researchers have witnessed a surge in discussions surrounding the structure, physical properties, and synthesis methods of BP in recent years. However, the intrinsic reactivity of BP has received limited attention. The chemical properties of BP are usually associated with its environmental instability or degradation, and the main efforts are focused on its passivation rather than its exploitation. The intrinsic reactivity of BP facilitates a range of emerging applications including biomedicine, reducing agents, and composite construction. Notably, the controllable biodegradation of BP nanosheets can inhibit tumor growth, a phenomenon that has inspired the development of “bioactive phospho-therapy” as a cancer treatment strategy both in vitro and in vivo. In this Account, we first discuss the origin of BP’s chemical reactivity, and then categorize the typical types of chemical reactions, including redox reactions, covalent bonding, and noncovalent interactions. Each section is dedicated to a specific interaction type and is accompanied by relevant applications. These applications, which include catalysis, ion storage, sensors, and drug delivery, effectively demonstrate the structure–property–function relationships inherent in BP-based functional materials. Finally, a forward-looking perspective on the reactivity of BP is presented in the conclusion, which attempts to address the fundamental scientific questions and current technical challenges in this field. This Account is expected to encourage researchers to further explore the multifaceted potentials of BP across various areas.
{"title":"Understanding the Intrinsic Reactivity of Black Phosphorus","authors":"Haijiang Tian, Haoyu Wang, Jiahong Wang*, Guangbo Qu*, Xue-Feng Yu* and Guibin Jiang, ","doi":"10.1021/accountsmr.4c0014410.1021/accountsmr.4c00144","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00144https://doi.org/10.1021/accountsmr.4c00144","url":null,"abstract":"<p >Black phosphorus (BP), a rediscovered two-dimensional (2D) material, has garnered significant interest due to its unique structure and physicochemical characteristics, including adjustable direct bandgaps, high carrier mobility, large specific surface area, and pronounced chemical reactivity. Distinct from the flat atomic structure of graphene, BP features a puckered honeycomb-like structure derived from sp<sup>3</sup> hybridization. In addition to the three-coordination, each phosphorus atom possesses a lone pair of electrons, leading to an electron-rich nature. A variety of nanostructures such as nanosheets, nanoribbons, and quantum dots are developed from the bulk crystal of BP. The large surface area of nano BP provides numerous reactive sites that augment intralayer chemical interactions. Therefore, nano BP serves as a versatile scaffold for materials engineering, with potential applications across chemistry, catalysis, energy, and biomedicine. It is crucial to have a deep and systematic understanding of the hybridization interactions between BP and diverse molecules or materials, which is essential for functional design of BP-based materials for target applications.</p><p >Researchers have witnessed a surge in discussions surrounding the structure, physical properties, and synthesis methods of BP in recent years. However, the intrinsic reactivity of BP has received limited attention. The chemical properties of BP are usually associated with its environmental instability or degradation, and the main efforts are focused on its passivation rather than its exploitation. The intrinsic reactivity of BP facilitates a range of emerging applications including biomedicine, reducing agents, and composite construction. Notably, the controllable biodegradation of BP nanosheets can inhibit tumor growth, a phenomenon that has inspired the development of “bioactive phospho-therapy” as a cancer treatment strategy both in vitro and in vivo. In this Account, we first discuss the origin of BP’s chemical reactivity, and then categorize the typical types of chemical reactions, including redox reactions, covalent bonding, and noncovalent interactions. Each section is dedicated to a specific interaction type and is accompanied by relevant applications. These applications, which include catalysis, ion storage, sensors, and drug delivery, effectively demonstrate the structure–property–function relationships inherent in BP-based functional materials. Finally, a forward-looking perspective on the reactivity of BP is presented in the conclusion, which attempts to address the fundamental scientific questions and current technical challenges in this field. This Account is expected to encourage researchers to further explore the multifaceted potentials of BP across various areas.</p>","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"5 12","pages":"1472–1483 1472–1483"},"PeriodicalIF":14.0,"publicationDate":"2024-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143127567","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}
Black phosphorus (BP), a rediscovered two-dimensional (2D) material, has garnered significant interest due to its unique structure and physicochemical characteristics, including adjustable direct bandgaps, high carrier mobility, large specific surface area, and pronounced chemical reactivity. Distinct from the flat atomic structure of graphene, BP features a puckered honeycomb-like structure derived from sp3 hybridization. In addition to the three-coordination, each phosphorus atom possesses a lone pair of electrons, leading to an electron-rich nature. A variety of nanostructures such as nanosheets, nanoribbons, and quantum dots are developed from the bulk crystal of BP. The large surface area of nano BP provides numerous reactive sites that augment intralayer chemical interactions. Therefore, nano BP serves as a versatile scaffold for materials engineering, with potential applications across chemistry, catalysis, energy, and biomedicine. It is crucial to have a deep and systematic understanding of the hybridization interactions between BP and diverse molecules or materials, which is essential for functional design of BP-based materials for target applications.
黑磷（BP）是一种被重新发现的二维（2D）材料，由于其独特的结构和物理化学特性，包括可调节的直接带隙、高载流子迁移率、大比表面积和明显的化学反应活性，它引起了人们的极大兴趣。与石墨烯的平面原子结构不同，BP 具有由 sp3 杂化产生的皱褶蜂窝状结构。除了三配位外，每个磷原子还拥有一对孤对电子，因此具有富电子性。从 BP 的块状晶体中开发出了各种纳米结构，如纳米片、纳米带和量子点。纳米 BP 的大表面积提供了大量的反应位点，增强了层内的化学相互作用。因此，纳米 BP 可作为材料工程的多功能支架，在化学、催化、能源和生物医学等领域具有潜在的应用前景。深入、系统地了解 BP 与不同分子或材料之间的杂化相互作用至关重要，这对于为目标应用设计基于 BP 的功能材料至关重要。
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Pub Date : 2024-10-03DOI: 10.1021/accountsmr.4c00183
Wanpeng Lu, Dukula De Alwis Jayasinghe, Martin Schröder, Sihai Yang
Since the advent of the Haber–Bosch process in 1910, the global demand for ammonia (NH<sub>3</sub>) has surged, driven by its applications in agriculture, pharmaceuticals, and energy. Current methods of NH<sub>3</sub> storage, including high-pressure storage and transportation, present significant challenges due to their corrosive and toxic nature. Consequently, research has turned towards metal–organic framework (MOF) materials as potential candidates for NH<sub>3</sub> storage due to their potential high adsorption capacities and structural tunability. MOFs are coordination networks composed of metal nodes and organic linkers, offering unprecedented porosity and surface area, and allowing incorporation of various functional groups and metal sites that can enhance NH<sub>3</sub> adsorption. However, the stability of MOFs in the presence of NH<sub>3</sub> is a significant concern since many degrade upon exposure to NH<sub>3</sub>, primarily due to ligand displacement and framework collapse. To address this, recent studies have focused on the synthesis and postsynthetic modification of MOFs to enhance both NH<sub>3</sub> uptake and stability. In this Account, we summarize recent developments in the design and characterization of MOFs for NH<sub>3</sub> storage. The choice of metal centers in MOFs is crucial for stability and performance. High-valence metals such as Al<sup>III</sup> and Ti<sup>IV</sup> form strong metal–linker bonds, enhancing the stability of the framework to NH<sub>3</sub>. The MFM-300 series of materials composed of high-valence 3+ and 4+ metal ions and carboxylic linkers demonstrates high stability and high NH<sub>3</sub> uptake capacities. Ligand functionalization is another effective strategy for improving the NH<sub>3</sub> adsorption. Polar functional groups such as –NH<sub>2</sub>, –OH, and –COOH enhance the interaction between the framework and NH<sub>3</sub>, particularly at low partial pressures, while postsynthetic modification allows fine-tuning of these functionalities to optimize the framework for higher adsorption capacities and stability. For example, MFM-303(Al), incorporating free carboxylic acid groups, exhibits a high NH<sub>3</sub> packing density comparable to that of solid NH<sub>3</sub>. Creating defect sites by removing linkers or adding metal ions increases the number of active sites available for NH<sub>3</sub> adsorption and shows promise for enhancing uptake. UiO-66, a stable MOF framework, can be modified to include defect sites, significantly enhancing the level of NH<sub>3</sub> uptake. The full characterization of MOFs and especially their interactions with NH<sub>3</sub> are vital for understanding and improving their performance. Techniques such as neutron powder diffraction (NPD), inelastic neutron scattering (INS), diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), electron paramagnetic resonance (EPR) spectroscopy, and solid-state nuclear magnetic resonance (ssNMR) spectros
{"title":"Ammonia Storage in Metal–Organic Framework Materials: Recent Developments in Design and Characterization","authors":"Wanpeng Lu, Dukula De Alwis Jayasinghe, Martin Schröder, Sihai Yang","doi":"10.1021/accountsmr.4c00183","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00183","url":null,"abstract":"Since the advent of the Haber–Bosch process in 1910, the global demand for ammonia (NH<sub>3</sub>) has surged, driven by its applications in agriculture, pharmaceuticals, and energy. Current methods of NH<sub>3</sub> storage, including high-pressure storage and transportation, present significant challenges due to their corrosive and toxic nature. Consequently, research has turned towards metal–organic framework (MOF) materials as potential candidates for NH<sub>3</sub> storage due to their potential high adsorption capacities and structural tunability. MOFs are coordination networks composed of metal nodes and organic linkers, offering unprecedented porosity and surface area, and allowing incorporation of various functional groups and metal sites that can enhance NH<sub>3</sub> adsorption. However, the stability of MOFs in the presence of NH<sub>3</sub> is a significant concern since many degrade upon exposure to NH<sub>3</sub>, primarily due to ligand displacement and framework collapse. To address this, recent studies have focused on the synthesis and postsynthetic modification of MOFs to enhance both NH<sub>3</sub> uptake and stability. In this Account, we summarize recent developments in the design and characterization of MOFs for NH<sub>3</sub> storage. The choice of metal centers in MOFs is crucial for stability and performance. High-valence metals such as Al<sup>III</sup> and Ti<sup>IV</sup> form strong metal–linker bonds, enhancing the stability of the framework to NH<sub>3</sub>. The MFM-300 series of materials composed of high-valence 3+ and 4+ metal ions and carboxylic linkers demonstrates high stability and high NH<sub>3</sub> uptake capacities. Ligand functionalization is another effective strategy for improving the NH<sub>3</sub> adsorption. Polar functional groups such as –NH<sub>2</sub>, –OH, and –COOH enhance the interaction between the framework and NH<sub>3</sub>, particularly at low partial pressures, while postsynthetic modification allows fine-tuning of these functionalities to optimize the framework for higher adsorption capacities and stability. For example, MFM-303(Al), incorporating free carboxylic acid groups, exhibits a high NH<sub>3</sub> packing density comparable to that of solid NH<sub>3</sub>. Creating defect sites by removing linkers or adding metal ions increases the number of active sites available for NH<sub>3</sub> adsorption and shows promise for enhancing uptake. UiO-66, a stable MOF framework, can be modified to include defect sites, significantly enhancing the level of NH<sub>3</sub> uptake. The full characterization of MOFs and especially their interactions with NH<sub>3</sub> are vital for understanding and improving their performance. Techniques such as neutron powder diffraction (NPD), inelastic neutron scattering (INS), diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), electron paramagnetic resonance (EPR) spectroscopy, and solid-state nuclear magnetic resonance (ssNMR) spectros","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"21 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142374493","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}
Pub Date : 2024-09-29DOI: 10.1021/accountsmr.4c00186
Tong Wu, Xiaoran Li, Jiajia Xue, Younan Xia
As a ubiquitous feature of the biological world, gradation, in either composition or structure, is essential to many functions and processes. Taking protein gradation as an example, it plays a pivotal role in the development and evolution of human bodies, including stimulation and direction of the outgrowth of peripheral nerves in a developing fetus. It is also critically involved in wound healing by attracting and guiding immune cells to the site of injury or infection. Another good example can be found in the tendon-to-bone enthesis that relies on gradations in composition, structure, and cell phenotype to create a gradual change in mechanical stiffness. It is these unique gradations that eliminate the high level of stress at the interface, enabling the effective transfer of mechanical load from tendon to bone. How to fabricate and utilize graded surfaces and materials has been a constant theme of research in the context of materials science, chemistry, cell biology, and biomedical engineering. In cell biology, for example, graded surfaces are employed to investigate the fundamental mechanisms related to embryo development and to elucidate cell behaviors under chemo-, hapto-, or mechano-taxis. Scaffolds based upon graded materials have also been widely explored to enhance tissue repair or regeneration by accelerating cell migration and/or controlling stem cell differentiation.
{"title":"Rational Fabrication of Functionally-Graded Surfaces for Biological and Biomedical Applications","authors":"Tong Wu, Xiaoran Li, Jiajia Xue, Younan Xia","doi":"10.1021/accountsmr.4c00186","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00186","url":null,"abstract":"As a ubiquitous feature of the biological world, gradation, in either composition or structure, is essential to many functions and processes. Taking protein gradation as an example, it plays a pivotal role in the development and evolution of human bodies, including stimulation and direction of the outgrowth of peripheral nerves in a developing fetus. It is also critically involved in wound healing by attracting and guiding immune cells to the site of injury or infection. Another good example can be found in the tendon-to-bone enthesis that relies on gradations in composition, structure, and cell phenotype to create a gradual change in mechanical stiffness. It is these unique gradations that eliminate the high level of stress at the interface, enabling the effective transfer of mechanical load from tendon to bone. How to fabricate and utilize graded surfaces and materials has been a constant theme of research in the context of materials science, chemistry, cell biology, and biomedical engineering. In cell biology, for example, graded surfaces are employed to investigate the fundamental mechanisms related to embryo development and to elucidate cell behaviors under chemo-, hapto-, or mechano-taxis. Scaffolds based upon graded materials have also been widely explored to enhance tissue repair or regeneration by accelerating cell migration and/or controlling stem cell differentiation.","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"50 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142329288","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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