<p >Porous organic polymers (POPs) are organic networks distinguished by their highly cross-linked structures and their intrinsic porosity. The growing emphasis on POPs is driven by their exceptional hydrothermal stability and diverse application prospects. However, traditional metal-catalyzed high-temperature reactions using rigid building units yield POPs in insoluble powder form, posing challenges for processing into different shapes for device integration and optoelectronic applications. The successful fabrication of a soluble porous organic polymer relies on the employment of specific design strategies and reaction conditions to restrict the molecular weight and extensive cross-linking. In recent decades, researchers have been actively exploring various design strategies, such as limiting molecular weight through hyperbranching and employing controlled polymer growth strategies, to produce solution processable amorphous porous organic polymers. However, targeted synthesis for specific applications remains underdeveloped, justifying the need for an in-depth deliberation of currently available strategies and possible future avenues. In this context, this Account highlights the advancements in the field of solution processable amorphous cross-linked porous organic polymers (SCPOPs), describing diverse design strategies and function-led applications. In order to address the challenges associated with the solution processing of amorphous cross-linked POPs, our research group has focused on fine-tuning the noncovalent interactions among the molecular building blocks, the key to achieving both porosity and solubility in the resultant porous polymer. Following this principle, we introduce long alkyl chains as flexible groups in the monomer and comonomer units that offer a high degree of rotational freedom and a substantial twist angle. This approach facilitates alleviation of the pronounced π–π stacking interaction and extensive cross-linking, thereby enhancing the solubility of the porous polymer. As a result, the facile interaction between the analytes and inefficiently packed polymer chains with aromatic building units in SCPOPs opens the scope for fluorescence-based nitroaromatic sensing in solution. Further, a stable dispersion of fluorescent porous polymer nanoparticles could be an attractive platform for analyte detection in water with enhanced sensitivity. The porous nature of the fluorescent SCPOPs enables the encapsulation of diverse dye molecules, and controlling the energy transfer efficiency from polymer to dyes results in fluorescence tuning, leading to the emission of white light in solution, nanoparticles, gel, and a thin transparent film. Furthermore, we demonstrate that incorporating alternate donor–acceptor units into the cross-linked polymer leads to the optimum band positions for light-driven redox reactions, such as photooxidation of benzylamine and hydrogen evolution. We investigated a biphasic catalysis route employing soluti
{"title":"Intriguing Facets of Solution Processable Cross-Linked Porous Organic Polymers","authors":"Madhurima Sarkar, Suprabhat Sarkar, Monisha Saha, Khushi Luvani and Abhijit Patra*, ","doi":"10.1021/accountsmr.4c0019710.1021/accountsmr.4c00197","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00197https://doi.org/10.1021/accountsmr.4c00197","url":null,"abstract":"<p >Porous organic polymers (POPs) are organic networks distinguished by their highly cross-linked structures and their intrinsic porosity. The growing emphasis on POPs is driven by their exceptional hydrothermal stability and diverse application prospects. However, traditional metal-catalyzed high-temperature reactions using rigid building units yield POPs in insoluble powder form, posing challenges for processing into different shapes for device integration and optoelectronic applications. The successful fabrication of a soluble porous organic polymer relies on the employment of specific design strategies and reaction conditions to restrict the molecular weight and extensive cross-linking. In recent decades, researchers have been actively exploring various design strategies, such as limiting molecular weight through hyperbranching and employing controlled polymer growth strategies, to produce solution processable amorphous porous organic polymers. However, targeted synthesis for specific applications remains underdeveloped, justifying the need for an in-depth deliberation of currently available strategies and possible future avenues. In this context, this Account highlights the advancements in the field of solution processable amorphous cross-linked porous organic polymers (SCPOPs), describing diverse design strategies and function-led applications. In order to address the challenges associated with the solution processing of amorphous cross-linked POPs, our research group has focused on fine-tuning the noncovalent interactions among the molecular building blocks, the key to achieving both porosity and solubility in the resultant porous polymer. Following this principle, we introduce long alkyl chains as flexible groups in the monomer and comonomer units that offer a high degree of rotational freedom and a substantial twist angle. This approach facilitates alleviation of the pronounced π–π stacking interaction and extensive cross-linking, thereby enhancing the solubility of the porous polymer. As a result, the facile interaction between the analytes and inefficiently packed polymer chains with aromatic building units in SCPOPs opens the scope for fluorescence-based nitroaromatic sensing in solution. Further, a stable dispersion of fluorescent porous polymer nanoparticles could be an attractive platform for analyte detection in water with enhanced sensitivity. The porous nature of the fluorescent SCPOPs enables the encapsulation of diverse dye molecules, and controlling the energy transfer efficiency from polymer to dyes results in fluorescence tuning, leading to the emission of white light in solution, nanoparticles, gel, and a thin transparent film. Furthermore, we demonstrate that incorporating alternate donor–acceptor units into the cross-linked polymer leads to the optimum band positions for light-driven redox reactions, such as photooxidation of benzylamine and hydrogen evolution. We investigated a biphasic catalysis route employing soluti","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"5 11","pages":"1353–1365 1353–1365"},"PeriodicalIF":14.0,"publicationDate":"2024-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142691378","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 : 2024-09-17DOI: 10.1021/accountsmr.4c0016010.1021/accountsmr.4c00160
Qingxin Yang*, and , Evgenii V. Kondratenko*,
<p >The conversion of carbon dioxide (CO<sub>2</sub>) with hydrogen (H<sub>2</sub>), generated by renewable energy sources, into value-added products is a promising approach to meet future demands for sustainable development. In this context, the hydrogenation of CO<sub>2</sub> (CO<sub>2</sub>-FTS) to higher hydrocarbons (C<sub>2+</sub>), lower olefins, and fuels should be mentioned in particular. These products are used in our daily lives but are currently produced by energy-intensive and CO<sub>2</sub>-emitting oil-based cracking processes. The environmental compatibility and abundance of iron (Fe) used in CO<sub>2</sub>-FTS catalysts are also relevant to sustainable development. The CO<sub>2</sub>-FTS reaction was inspired by the experience accumulated in long-term research on Fischer–Tropsch synthesis with CO (CO-FTS). A simple grafting of catalyst formulations and reaction mechanisms from CO-FTS to CO<sub>2</sub>-FTS has, however, been proven unsatisfactory, likely due to differences in surface adsorbates, chemical potentials of CO and CO<sub>2</sub>, and H<sub>2</sub>O partial pressure. These characteristics affect both the catalyst structure and the reaction pathways. Consequently, CO<sub>2</sub>-FTS provides higher CH<sub>4</sub> selectivity but lower C<sub>2+</sub>-selectivity than does CO-FTS, which appeals to fundamental research to hinder CH<sub>4</sub> formation.</p><p >In this Account, our recent progress in identifying descriptors for purposeful catalyst design is highlighted. Different from the trial-and-error methods and chemist’s intuition strategies commonly used for catalyst design, our initial efforts were devoted to a meta-analysis of literature data to identify catalyst property–performance relationships in CO<sub>2</sub>-FTS. The resulting hypotheses were experimentally validated and provided the basis for catalyst development. Our other distinguishing strategy is spatially resolved analyses of reaction-induced catalyst restructuring and reaction kinetics. As the catalyst composition changes downstream of the catalyst bed, it is critical to consider the respective profiles to establish proper correlations between the working catalyst phase and species and the kinetics of the formation of selective and unselective reaction products. The importance of in situ characterization studies for understanding reaction-induced catalyst restructuring is especially highlighted. We also demonstrate the power of transient kinetic methods, i.e., temporal analysis of products (TAP) and steady-state isotopic transient kinetic analysis (SSITKA), to identify the mechanism and microkinetics of the activation of CO<sub>2</sub>, CO, and H<sub>2</sub> that characterize the efficiency of iron carbides for CO<sub>2</sub> hydrogenation. The SSITKA method is also instrumental in quantifying the abundance and lifetime of surface intermediates, leading to CO or CH<sub>4</sub>. The global network of product formation is further established by analyzing
{"title":"From Understanding of Catalyst Functioning toward Controlling Selectivity in CO2 Hydrogenation to Higher Hydrocarbons over Fe-Based Catalysts","authors":"Qingxin Yang*, and , Evgenii V. Kondratenko*, ","doi":"10.1021/accountsmr.4c0016010.1021/accountsmr.4c00160","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00160https://doi.org/10.1021/accountsmr.4c00160","url":null,"abstract":"<p >The conversion of carbon dioxide (CO<sub>2</sub>) with hydrogen (H<sub>2</sub>), generated by renewable energy sources, into value-added products is a promising approach to meet future demands for sustainable development. In this context, the hydrogenation of CO<sub>2</sub> (CO<sub>2</sub>-FTS) to higher hydrocarbons (C<sub>2+</sub>), lower olefins, and fuels should be mentioned in particular. These products are used in our daily lives but are currently produced by energy-intensive and CO<sub>2</sub>-emitting oil-based cracking processes. The environmental compatibility and abundance of iron (Fe) used in CO<sub>2</sub>-FTS catalysts are also relevant to sustainable development. The CO<sub>2</sub>-FTS reaction was inspired by the experience accumulated in long-term research on Fischer–Tropsch synthesis with CO (CO-FTS). A simple grafting of catalyst formulations and reaction mechanisms from CO-FTS to CO<sub>2</sub>-FTS has, however, been proven unsatisfactory, likely due to differences in surface adsorbates, chemical potentials of CO and CO<sub>2</sub>, and H<sub>2</sub>O partial pressure. These characteristics affect both the catalyst structure and the reaction pathways. Consequently, CO<sub>2</sub>-FTS provides higher CH<sub>4</sub> selectivity but lower C<sub>2+</sub>-selectivity than does CO-FTS, which appeals to fundamental research to hinder CH<sub>4</sub> formation.</p><p >In this Account, our recent progress in identifying descriptors for purposeful catalyst design is highlighted. Different from the trial-and-error methods and chemist’s intuition strategies commonly used for catalyst design, our initial efforts were devoted to a meta-analysis of literature data to identify catalyst property–performance relationships in CO<sub>2</sub>-FTS. The resulting hypotheses were experimentally validated and provided the basis for catalyst development. Our other distinguishing strategy is spatially resolved analyses of reaction-induced catalyst restructuring and reaction kinetics. As the catalyst composition changes downstream of the catalyst bed, it is critical to consider the respective profiles to establish proper correlations between the working catalyst phase and species and the kinetics of the formation of selective and unselective reaction products. The importance of in situ characterization studies for understanding reaction-induced catalyst restructuring is especially highlighted. We also demonstrate the power of transient kinetic methods, i.e., temporal analysis of products (TAP) and steady-state isotopic transient kinetic analysis (SSITKA), to identify the mechanism and microkinetics of the activation of CO<sub>2</sub>, CO, and H<sub>2</sub> that characterize the efficiency of iron carbides for CO<sub>2</sub> hydrogenation. The SSITKA method is also instrumental in quantifying the abundance and lifetime of surface intermediates, leading to CO or CH<sub>4</sub>. The global network of product formation is further established by analyzing","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"5 11","pages":"1314–1328 1314–1328"},"PeriodicalIF":14.0,"publicationDate":"2024-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/accountsmr.4c00160","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142691377","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-09-17DOI: 10.1021/accountsmr.4c00160
Qingxin Yang, Evgenii V. Kondratenko
The conversion of carbon dioxide (CO2) with hydrogen (H2), generated by renewable energy sources, into value-added products is a promising approach to meet future demands for sustainable development. In this context, the hydrogenation of CO2 (CO2-FTS) to higher hydrocarbons (C2+), lower olefins, and fuels should be mentioned in particular. These products are used in our daily lives but are currently produced by energy-intensive and CO2-emitting oil-based cracking processes. The environmental compatibility and abundance of iron (Fe) used in CO2-FTS catalysts are also relevant to sustainable development. The CO2-FTS reaction was inspired by the experience accumulated in long-term research on Fischer–Tropsch synthesis with CO (CO-FTS). A simple grafting of catalyst formulations and reaction mechanisms from CO-FTS to CO2-FTS has, however, been proven unsatisfactory, likely due to differences in surface adsorbates, chemical potentials of CO and CO2, and H2O partial pressure. These characteristics affect both the catalyst structure and the reaction pathways. Consequently, CO2-FTS provides higher CH4 selectivity but lower C2+-selectivity than does CO-FTS, which appeals to fundamental research to hinder CH4 formation.
{"title":"From Understanding of Catalyst Functioning toward Controlling Selectivity in CO2 Hydrogenation to Higher Hydrocarbons over Fe-Based Catalysts","authors":"Qingxin Yang, Evgenii V. Kondratenko","doi":"10.1021/accountsmr.4c00160","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00160","url":null,"abstract":"The conversion of carbon dioxide (CO<sub>2</sub>) with hydrogen (H<sub>2</sub>), generated by renewable energy sources, into value-added products is a promising approach to meet future demands for sustainable development. In this context, the hydrogenation of CO<sub>2</sub> (CO<sub>2</sub>-FTS) to higher hydrocarbons (C<sub>2+</sub>), lower olefins, and fuels should be mentioned in particular. These products are used in our daily lives but are currently produced by energy-intensive and CO<sub>2</sub>-emitting oil-based cracking processes. The environmental compatibility and abundance of iron (Fe) used in CO<sub>2</sub>-FTS catalysts are also relevant to sustainable development. The CO<sub>2</sub>-FTS reaction was inspired by the experience accumulated in long-term research on Fischer–Tropsch synthesis with CO (CO-FTS). A simple grafting of catalyst formulations and reaction mechanisms from CO-FTS to CO<sub>2</sub>-FTS has, however, been proven unsatisfactory, likely due to differences in surface adsorbates, chemical potentials of CO and CO<sub>2</sub>, and H<sub>2</sub>O partial pressure. These characteristics affect both the catalyst structure and the reaction pathways. Consequently, CO<sub>2</sub>-FTS provides higher CH<sub>4</sub> selectivity but lower C<sub>2+</sub>-selectivity than does CO-FTS, which appeals to fundamental research to hinder CH<sub>4</sub> formation.","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"7 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142235485","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 : 2024-09-16DOI: 10.1021/accountsmr.4c0018210.1021/accountsmr.4c00182
Zhen Zhang, Ravikumar R. Gowda and Eugene Y.-X. Chen*,
<p >Aliphatic polyesters consisting of hydrolytically and/or enzymatically degradable ester bonds in each repeating unit possess diverse thermomechanical properties and desired biodegradability and biocompatibility, thus, finding broad applications in biomedical fields. Among them, poly(4-hydroxybutyrate) (P4HB) is a biomaterial receiving particular attention, due to its proper thermal transition temperatures (<i>T</i><sub>g</sub> ∼ – 50 °C, <i>T</i><sub>m</sub> ∼ 60 °C) relative to the environment of living systems, excellent mechanical properties (high toughness and extensibility when molar mass is sufficiently high), and facile degradability in aqueous media where living systems function. The production of P4HB has long relied on biological fermentation, where it is stored in fermented cells and extracted at the end of the fermentation. However, the high production cost of the fermentation process, associated with its slow reaction kinetics and presently limited production volume, hinders broader implementations of P4HB. In addition, biological routes typically produce P4HB with poor control over the polymer molar mass and dispersity, and postfermentation treatment is employed to offer various molar mass P4HB formulations. Considering that chemical catalysis generally offers faster reaction kinetics, more rapid catalyst tuning, a higher degree of control, and better scalability, it would be desirable to develop a chemocatalytic route to access P4HB more rapidly, at scale, and on-demand for tailorable chain lengths and architectures. In this context, developing the effective and efficient chemocatalytic synthesis of P4HB through ring-opening polymerization (ROP) of γ-butyrolactone (γBL), which is bioderived and available at scale, is of great interest and significance.</p><p >The ROP of γBL was first attempted in 1932 and followed subsequently using various conditions, but those attempts only led to the formation of oligomers, due to the negligible ring strain of the five-membered lactone ring that renders γBL (commonly referred to as) “nonpolymerizable”. Ten years ago, we first isolated the semicrystalline, chemosynthetic P4HB from the ROP of γBL and then in 2016 reported the first effective chemocatalytic synthesis of P4HB with useful molar mass of <i>M</i><sub>n</sub> ∼ 30 kDa, through investigating the thermodynamics of the polymerization to identify appropriate conditions for the effective ROP, exploring the catalysts to enhance the ROP rate and selectivity, and optimizing the reaction/process conditions to continuously perturb the thermodynamic equilibrium for achieving high monomer conversions far exceeding the thermodynamic limit. Since then, the field of chemosynthetic P4HB has witnessed significant advances contributed by many research groups worldwide. In this Account, we will describe the recent advances made in the catalyzed ROP of γBL, which have culminated with the achievement previously thought not possible: high-molar-mass P4HB
{"title":"Chemosynthetic P4HB: A Ten-Year Journey from a “Non-Polymerizable” Monomer to a High-Performance Biomaterial","authors":"Zhen Zhang, Ravikumar R. Gowda and Eugene Y.-X. Chen*, ","doi":"10.1021/accountsmr.4c0018210.1021/accountsmr.4c00182","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00182https://doi.org/10.1021/accountsmr.4c00182","url":null,"abstract":"<p >Aliphatic polyesters consisting of hydrolytically and/or enzymatically degradable ester bonds in each repeating unit possess diverse thermomechanical properties and desired biodegradability and biocompatibility, thus, finding broad applications in biomedical fields. Among them, poly(4-hydroxybutyrate) (P4HB) is a biomaterial receiving particular attention, due to its proper thermal transition temperatures (<i>T</i><sub>g</sub> ∼ – 50 °C, <i>T</i><sub>m</sub> ∼ 60 °C) relative to the environment of living systems, excellent mechanical properties (high toughness and extensibility when molar mass is sufficiently high), and facile degradability in aqueous media where living systems function. The production of P4HB has long relied on biological fermentation, where it is stored in fermented cells and extracted at the end of the fermentation. However, the high production cost of the fermentation process, associated with its slow reaction kinetics and presently limited production volume, hinders broader implementations of P4HB. In addition, biological routes typically produce P4HB with poor control over the polymer molar mass and dispersity, and postfermentation treatment is employed to offer various molar mass P4HB formulations. Considering that chemical catalysis generally offers faster reaction kinetics, more rapid catalyst tuning, a higher degree of control, and better scalability, it would be desirable to develop a chemocatalytic route to access P4HB more rapidly, at scale, and on-demand for tailorable chain lengths and architectures. In this context, developing the effective and efficient chemocatalytic synthesis of P4HB through ring-opening polymerization (ROP) of γ-butyrolactone (γBL), which is bioderived and available at scale, is of great interest and significance.</p><p >The ROP of γBL was first attempted in 1932 and followed subsequently using various conditions, but those attempts only led to the formation of oligomers, due to the negligible ring strain of the five-membered lactone ring that renders γBL (commonly referred to as) “nonpolymerizable”. Ten years ago, we first isolated the semicrystalline, chemosynthetic P4HB from the ROP of γBL and then in 2016 reported the first effective chemocatalytic synthesis of P4HB with useful molar mass of <i>M</i><sub>n</sub> ∼ 30 kDa, through investigating the thermodynamics of the polymerization to identify appropriate conditions for the effective ROP, exploring the catalysts to enhance the ROP rate and selectivity, and optimizing the reaction/process conditions to continuously perturb the thermodynamic equilibrium for achieving high monomer conversions far exceeding the thermodynamic limit. Since then, the field of chemosynthetic P4HB has witnessed significant advances contributed by many research groups worldwide. In this Account, we will describe the recent advances made in the catalyzed ROP of γBL, which have culminated with the achievement previously thought not possible: high-molar-mass P4HB","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"5 11","pages":"1340–1352 1340–1352"},"PeriodicalIF":14.0,"publicationDate":"2024-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142691376","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 : 2024-09-16DOI: 10.1021/accountsmr.4c00182
Zhen Zhang, Ravikumar R. Gowda, Eugene Y.-X. Chen
Aliphatic polyesters consisting of hydrolytically and/or enzymatically degradable ester bonds in each repeating unit possess diverse thermomechanical properties and desired biodegradability and biocompatibility, thus, finding broad applications in biomedical fields. Among them, poly(4-hydroxybutyrate) (P4HB) is a biomaterial receiving particular attention, due to its proper thermal transition temperatures (Tg ∼ – 50 °C, Tm ∼ 60 °C) relative to the environment of living systems, excellent mechanical properties (high toughness and extensibility when molar mass is sufficiently high), and facile degradability in aqueous media where living systems function. The production of P4HB has long relied on biological fermentation, where it is stored in fermented cells and extracted at the end of the fermentation. However, the high production cost of the fermentation process, associated with its slow reaction kinetics and presently limited production volume, hinders broader implementations of P4HB. In addition, biological routes typically produce P4HB with poor control over the polymer molar mass and dispersity, and postfermentation treatment is employed to offer various molar mass P4HB formulations. Considering that chemical catalysis generally offers faster reaction kinetics, more rapid catalyst tuning, a higher degree of control, and better scalability, it would be desirable to develop a chemocatalytic route to access P4HB more rapidly, at scale, and on-demand for tailorable chain lengths and architectures. In this context, developing the effective and efficient chemocatalytic synthesis of P4HB through ring-opening polymerization (ROP) of γ-butyrolactone (γBL), which is bioderived and available at scale, is of great interest and significance.
{"title":"Chemosynthetic P4HB: A Ten-Year Journey from a “Non-Polymerizable” Monomer to a High-Performance Biomaterial","authors":"Zhen Zhang, Ravikumar R. Gowda, Eugene Y.-X. Chen","doi":"10.1021/accountsmr.4c00182","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00182","url":null,"abstract":"Aliphatic polyesters consisting of hydrolytically and/or enzymatically degradable ester bonds in each repeating unit possess diverse thermomechanical properties and desired biodegradability and biocompatibility, thus, finding broad applications in biomedical fields. Among them, poly(4-hydroxybutyrate) (P4HB) is a biomaterial receiving particular attention, due to its proper thermal transition temperatures (<i>T</i><sub>g</sub> ∼ – 50 °C, <i>T</i><sub>m</sub> ∼ 60 °C) relative to the environment of living systems, excellent mechanical properties (high toughness and extensibility when molar mass is sufficiently high), and facile degradability in aqueous media where living systems function. The production of P4HB has long relied on biological fermentation, where it is stored in fermented cells and extracted at the end of the fermentation. However, the high production cost of the fermentation process, associated with its slow reaction kinetics and presently limited production volume, hinders broader implementations of P4HB. In addition, biological routes typically produce P4HB with poor control over the polymer molar mass and dispersity, and postfermentation treatment is employed to offer various molar mass P4HB formulations. Considering that chemical catalysis generally offers faster reaction kinetics, more rapid catalyst tuning, a higher degree of control, and better scalability, it would be desirable to develop a chemocatalytic route to access P4HB more rapidly, at scale, and on-demand for tailorable chain lengths and architectures. In this context, developing the effective and efficient chemocatalytic synthesis of P4HB through ring-opening polymerization (ROP) of γ-butyrolactone (γBL), which is bioderived and available at scale, is of great interest and significance.","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"32 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142235486","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 : 2024-09-13DOI: 10.1021/accountsmr.4c0021610.1021/accountsmr.4c00216
Guang Chu*,
<p >Cellulose is widely distributed in nature and imparts structural integrity and mechanical support to the cell walls of plants, algae, and some bacteria. It has gained significant attention due to the growing demand for the fabrication of sustainable and high-performance materials. Various types of cellulosic materials are involved, among which cellulose nanocrystals (CNCs) emerge as a compelling next-gen material extracted from bulk cellulose, attracting considerable attention from both industry and academia. These rodlike colloidal materials exhibit remarkable mechanical, optical, and thermal properties due to their high aspect ratio, biodegradability, and renewable nature, providing promising opportunities for sustainable solutions to modern complex technological and societal challenges. Particularly noteworthy is the inherent chirality of CNC that triggers spontaneous self-assembly into left-handed helicoidal arrangements, termed cholesteric organization and sustained in both suspension and solid films. This unique property begets long-range ordered liquid crystallinity and polarization-sensitive structural color, highlighting the potential of CNC as a versatile platform for the design and fabrication of artificial functional materials with naturally derived alternatives. Benefiting from the robust self-assembly power of CNC, there is a burgeoning development in the creation of innovative nanocellulose-based materials.</p><p >This Account delineates our recent strides in controlled CNC self-assembly strategies, serving as colloidal structural building blocks in sculpting cholesteric liquid crystal functional materials, with a focal point residing in custom-tailored photonics and complex soft matter. Through the evaporation-induced self-assembly process, we present a general overview of CNC-based photonic materials, delving into guest–host coassembly with functional additives and top-down micronano manufacturing techniques. We probe the origin of chiral light–matter interactions, encompassing diverse optical mechanisms such as chiral plasmonics, circularly polarized luminescence, or circularly polarized diffraction. The resulting optical phenomena encompass the tunable photonic band gap inherent in the cholesteric cellulose matrix, alongside external optical signals arising from guest functional additives or hierarchical surface topography. Apart from evaporation, control over CNC self-assembly can be extended to fluidic conditions, facilitating the construction of diverse complex soft matter, including liquid crystal foams, emulsions, aerogels, and active matter. We have explored the confined CNC self-assembly under permeable and nonpermeable interfaces and optimized the assembly mode and structure–performance relationship between colloidal particles, thereby enabling the construction of various multiphase soft matter. Moreover, we establish CNC self-assembly within a nonequilibrium system, shedding light on the mechanisms underlying liq
{"title":"Controlled Self-Assembly of Cellulose Nanocrystal as Custom-Tailored Photonics and Complex Soft Matter","authors":"Guang Chu*, ","doi":"10.1021/accountsmr.4c0021610.1021/accountsmr.4c00216","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00216https://doi.org/10.1021/accountsmr.4c00216","url":null,"abstract":"<p >Cellulose is widely distributed in nature and imparts structural integrity and mechanical support to the cell walls of plants, algae, and some bacteria. It has gained significant attention due to the growing demand for the fabrication of sustainable and high-performance materials. Various types of cellulosic materials are involved, among which cellulose nanocrystals (CNCs) emerge as a compelling next-gen material extracted from bulk cellulose, attracting considerable attention from both industry and academia. These rodlike colloidal materials exhibit remarkable mechanical, optical, and thermal properties due to their high aspect ratio, biodegradability, and renewable nature, providing promising opportunities for sustainable solutions to modern complex technological and societal challenges. Particularly noteworthy is the inherent chirality of CNC that triggers spontaneous self-assembly into left-handed helicoidal arrangements, termed cholesteric organization and sustained in both suspension and solid films. This unique property begets long-range ordered liquid crystallinity and polarization-sensitive structural color, highlighting the potential of CNC as a versatile platform for the design and fabrication of artificial functional materials with naturally derived alternatives. Benefiting from the robust self-assembly power of CNC, there is a burgeoning development in the creation of innovative nanocellulose-based materials.</p><p >This Account delineates our recent strides in controlled CNC self-assembly strategies, serving as colloidal structural building blocks in sculpting cholesteric liquid crystal functional materials, with a focal point residing in custom-tailored photonics and complex soft matter. Through the evaporation-induced self-assembly process, we present a general overview of CNC-based photonic materials, delving into guest–host coassembly with functional additives and top-down micronano manufacturing techniques. We probe the origin of chiral light–matter interactions, encompassing diverse optical mechanisms such as chiral plasmonics, circularly polarized luminescence, or circularly polarized diffraction. The resulting optical phenomena encompass the tunable photonic band gap inherent in the cholesteric cellulose matrix, alongside external optical signals arising from guest functional additives or hierarchical surface topography. Apart from evaporation, control over CNC self-assembly can be extended to fluidic conditions, facilitating the construction of diverse complex soft matter, including liquid crystal foams, emulsions, aerogels, and active matter. We have explored the confined CNC self-assembly under permeable and nonpermeable interfaces and optimized the assembly mode and structure–performance relationship between colloidal particles, thereby enabling the construction of various multiphase soft matter. Moreover, we establish CNC self-assembly within a nonequilibrium system, shedding light on the mechanisms underlying liq","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"5 11","pages":"1388–1400 1388–1400"},"PeriodicalIF":14.0,"publicationDate":"2024-09-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142691375","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 : 2024-09-13DOI: 10.1021/accountsmr.4c00216
Guang Chu
Cellulose is widely distributed in nature and imparts structural integrity and mechanical support to the cell walls of plants, algae, and some bacteria. It has gained significant attention due to the growing demand for the fabrication of sustainable and high-performance materials. Various types of cellulosic materials are involved, among which cellulose nanocrystals (CNCs) emerge as a compelling next-gen material extracted from bulk cellulose, attracting considerable attention from both industry and academia. These rodlike colloidal materials exhibit remarkable mechanical, optical, and thermal properties due to their high aspect ratio, biodegradability, and renewable nature, providing promising opportunities for sustainable solutions to modern complex technological and societal challenges. Particularly noteworthy is the inherent chirality of CNC that triggers spontaneous self-assembly into left-handed helicoidal arrangements, termed cholesteric organization and sustained in both suspension and solid films. This unique property begets long-range ordered liquid crystallinity and polarization-sensitive structural color, highlighting the potential of CNC as a versatile platform for the design and fabrication of artificial functional materials with naturally derived alternatives. Benefiting from the robust self-assembly power of CNC, there is a burgeoning development in the creation of innovative nanocellulose-based materials.
{"title":"Controlled Self-Assembly of Cellulose Nanocrystal as Custom-Tailored Photonics and Complex Soft Matter","authors":"Guang Chu","doi":"10.1021/accountsmr.4c00216","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00216","url":null,"abstract":"Cellulose is widely distributed in nature and imparts structural integrity and mechanical support to the cell walls of plants, algae, and some bacteria. It has gained significant attention due to the growing demand for the fabrication of sustainable and high-performance materials. Various types of cellulosic materials are involved, among which cellulose nanocrystals (CNCs) emerge as a compelling next-gen material extracted from bulk cellulose, attracting considerable attention from both industry and academia. These rodlike colloidal materials exhibit remarkable mechanical, optical, and thermal properties due to their high aspect ratio, biodegradability, and renewable nature, providing promising opportunities for sustainable solutions to modern complex technological and societal challenges. Particularly noteworthy is the inherent chirality of CNC that triggers spontaneous self-assembly into left-handed helicoidal arrangements, termed cholesteric organization and sustained in both suspension and solid films. This unique property begets long-range ordered liquid crystallinity and polarization-sensitive structural color, highlighting the potential of CNC as a versatile platform for the design and fabrication of artificial functional materials with naturally derived alternatives. Benefiting from the robust self-assembly power of CNC, there is a burgeoning development in the creation of innovative nanocellulose-based materials.","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"300 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-09-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142231429","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 : 2024-09-12DOI: 10.1021/accountsmr.4c00215
Yan-Xi Tan, Xiang Zhang, Yaobing Wang, Jiannian Yao
Natural photosynthesis has produced most of the energy that fuels human society and sustains life on earth. However, with an ever-growing demand for energy, urgent efforts are required to develop artificial systems that mimic the essential processes of natural photosynthesis, including light harvesting/charge separation, photocatalytic water oxidation, energy storage, and catalytic CO2 reduction. Recent advancements have seen the development of nanoscale photoelectrochemical materials that integrate light absorbers with cocatalysts or redox units for artificial photosynthetic systems. However, the potential of molecular photoelectrochemical materials, which couple electron donor–acceptor (D-A) structures with catalytic or redox-active moieties into a periodic porous aggregate, remains largely underexplored. By combining D–A structures with redox moieties, these materials can enable solar-to-electrochemical energy storage process, while the further incorporation of catalytic sites can extend their application to photo(electro)catalytic water oxidation or CO2 reduction, thus enabling customized artificial systems. On the other hand, they can enhance energy efficiency by molecular-scale in situ photogenerated charge separation coupled with redox reactions─an exciton-involved redox mechanism─to circumvent the energy losses typically associated with charge carrier transport in nanoscale counterparts. Despite these merits, critical challenges remain with a limited understanding of the structure–functional motif relationship at the molecular level and a shortage of molecular assemblies to enable multifunctional motifs necessary for overall natural photosynthesis mimicry.
{"title":"Molecular Assembly of Functional Motifs for Artificial Photosynthesis","authors":"Yan-Xi Tan, Xiang Zhang, Yaobing Wang, Jiannian Yao","doi":"10.1021/accountsmr.4c00215","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00215","url":null,"abstract":"Natural photosynthesis has produced most of the energy that fuels human society and sustains life on earth. However, with an ever-growing demand for energy, urgent efforts are required to develop artificial systems that mimic the essential processes of natural photosynthesis, including light harvesting/charge separation, photocatalytic water oxidation, energy storage, and catalytic CO<sub>2</sub> reduction. Recent advancements have seen the development of nanoscale photoelectrochemical materials that integrate light absorbers with cocatalysts or redox units for artificial photosynthetic systems. However, the potential of molecular photoelectrochemical materials, which couple electron donor–acceptor (D-A) structures with catalytic or redox-active moieties into a periodic porous aggregate, remains largely underexplored. By combining D–A structures with redox moieties, these materials can enable solar-to-electrochemical energy storage process, while the further incorporation of catalytic sites can extend their application to photo(electro)catalytic water oxidation or CO<sub>2</sub> reduction, thus enabling customized artificial systems. On the other hand, they can enhance energy efficiency by molecular-scale in situ photogenerated charge separation coupled with redox reactions─an exciton-involved redox mechanism─to circumvent the energy losses typically associated with charge carrier transport in nanoscale counterparts. Despite these merits, critical challenges remain with a limited understanding of the structure–functional motif relationship at the molecular level and a shortage of molecular assemblies to enable multifunctional motifs necessary for overall natural photosynthesis mimicry.","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"30 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-09-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142171232","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 : 2024-09-12DOI: 10.1021/accountsmr.4c0021510.1021/accountsmr.4c00215
Yan-Xi Tan, Xiang Zhang, Yaobing Wang* and Jiannian Yao,
<p >Natural photosynthesis has produced most of the energy that fuels human society and sustains life on earth. However, with an ever-growing demand for energy, urgent efforts are required to develop artificial systems that mimic the essential processes of natural photosynthesis, including light harvesting/charge separation, photocatalytic water oxidation, energy storage, and catalytic CO<sub>2</sub> reduction. Recent advancements have seen the development of nanoscale photoelectrochemical materials that integrate light absorbers with cocatalysts or redox units for artificial photosynthetic systems. However, the potential of molecular photoelectrochemical materials, which couple electron donor–acceptor (D-A) structures with catalytic or redox-active moieties into a periodic porous aggregate, remains largely underexplored. By combining D–A structures with redox moieties, these materials can enable solar-to-electrochemical energy storage process, while the further incorporation of catalytic sites can extend their application to photo(electro)catalytic water oxidation or CO<sub>2</sub> reduction, thus enabling customized artificial systems. On the other hand, they can enhance energy efficiency by molecular-scale in situ photogenerated charge separation coupled with redox reactions─an exciton-involved redox mechanism─to circumvent the energy losses typically associated with charge carrier transport in nanoscale counterparts. Despite these merits, critical challenges remain with a limited understanding of the structure–functional motif relationship at the molecular level and a shortage of molecular assemblies to enable multifunctional motifs necessary for overall natural photosynthesis mimicry.</p><p >In this Account, we introduce the general concept of molecular photoelectrochemical materials for artificial photosynthesis, emphasizing their structural advantages in enabling diverse functional motifs. We also outline fundamental design principles and operational mechanisms of these motifs at the molecular level. Furthermore, we present three specific cases of molecular assembly targeting different functional motifs: (1) a donor (photocatalytic water oxidation)–acceptor (reduction) functional motif for solar-to-chemical conversion; (2) a donor (oxidation)–acceptor (reduction) motif for solar-to-electrochemical energy storage; and (3) a donor (oxidation)–acceptor (photocatalytic CO<sub>2</sub> reduction) motif for solar-to-electrochemical energy storage and conversion. The essential role of intramolecular photoinduced PCET during the operation of each functional motif is also discussed. Finally, we conclude with an overview of major challenges and future prospects for modulating molecular assemblies to achieve high energy conversion efficiency, along with a perspective on the design of versatile molecular materials and the implementation of photoinduced PCET to couple multifunctional motifs for overall natural photosynthesis mimicry. We hope that this A
{"title":"Molecular Assembly of Functional Motifs for Artificial Photosynthesis","authors":"Yan-Xi Tan, Xiang Zhang, Yaobing Wang* and Jiannian Yao, ","doi":"10.1021/accountsmr.4c0021510.1021/accountsmr.4c00215","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00215https://doi.org/10.1021/accountsmr.4c00215","url":null,"abstract":"<p >Natural photosynthesis has produced most of the energy that fuels human society and sustains life on earth. However, with an ever-growing demand for energy, urgent efforts are required to develop artificial systems that mimic the essential processes of natural photosynthesis, including light harvesting/charge separation, photocatalytic water oxidation, energy storage, and catalytic CO<sub>2</sub> reduction. Recent advancements have seen the development of nanoscale photoelectrochemical materials that integrate light absorbers with cocatalysts or redox units for artificial photosynthetic systems. However, the potential of molecular photoelectrochemical materials, which couple electron donor–acceptor (D-A) structures with catalytic or redox-active moieties into a periodic porous aggregate, remains largely underexplored. By combining D–A structures with redox moieties, these materials can enable solar-to-electrochemical energy storage process, while the further incorporation of catalytic sites can extend their application to photo(electro)catalytic water oxidation or CO<sub>2</sub> reduction, thus enabling customized artificial systems. On the other hand, they can enhance energy efficiency by molecular-scale in situ photogenerated charge separation coupled with redox reactions─an exciton-involved redox mechanism─to circumvent the energy losses typically associated with charge carrier transport in nanoscale counterparts. Despite these merits, critical challenges remain with a limited understanding of the structure–functional motif relationship at the molecular level and a shortage of molecular assemblies to enable multifunctional motifs necessary for overall natural photosynthesis mimicry.</p><p >In this Account, we introduce the general concept of molecular photoelectrochemical materials for artificial photosynthesis, emphasizing their structural advantages in enabling diverse functional motifs. We also outline fundamental design principles and operational mechanisms of these motifs at the molecular level. Furthermore, we present three specific cases of molecular assembly targeting different functional motifs: (1) a donor (photocatalytic water oxidation)–acceptor (reduction) functional motif for solar-to-chemical conversion; (2) a donor (oxidation)–acceptor (reduction) motif for solar-to-electrochemical energy storage; and (3) a donor (oxidation)–acceptor (photocatalytic CO<sub>2</sub> reduction) motif for solar-to-electrochemical energy storage and conversion. The essential role of intramolecular photoinduced PCET during the operation of each functional motif is also discussed. Finally, we conclude with an overview of major challenges and future prospects for modulating molecular assemblies to achieve high energy conversion efficiency, along with a perspective on the design of versatile molecular materials and the implementation of photoinduced PCET to couple multifunctional motifs for overall natural photosynthesis mimicry. We hope that this A","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"5 11","pages":"1377–1387 1377–1387"},"PeriodicalIF":14.0,"publicationDate":"2024-09-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142685216","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 : 2024-09-10DOI: 10.1021/accountsmr.4c00149
Jia Lv, Xun Liu, Lichen Yin, Yiyun Cheng
Protein therapeutics holds enormous promise for the treatment of various diseases but is limited to extracellular targets because of the membrane impermeable nature of most proteins. Cytosolic protein delivery systems are of great importance in the development of next-generation protein therapeutics. Since proteins are biomacromolecules characterized with limited binding sites, chemical modification or genetic engineering of cargo proteins is usually required to strengthen their binding affinity with the delivery carriers, which, however, may irreversibly impair their bioactivities. As thus, protein delivery systems that can efficiently transport native proteins into the cytosol of living cells with uncompromised bioactivities are highly desired.
{"title":"Rational Engineering of Cytosolic Delivery Systems for Protein Therapeutics","authors":"Jia Lv, Xun Liu, Lichen Yin, Yiyun Cheng","doi":"10.1021/accountsmr.4c00149","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00149","url":null,"abstract":"Protein therapeutics holds enormous promise for the treatment of various diseases but is limited to extracellular targets because of the membrane impermeable nature of most proteins. Cytosolic protein delivery systems are of great importance in the development of next-generation protein therapeutics. Since proteins are biomacromolecules characterized with limited binding sites, chemical modification or genetic engineering of cargo proteins is usually required to strengthen their binding affinity with the delivery carriers, which, however, may irreversibly impair their bioactivities. As thus, protein delivery systems that can efficiently transport native proteins into the cytosol of living cells with uncompromised bioactivities are highly desired.","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"59 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142161065","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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