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2024.12.19 Dr.Austin M.Evansが花王セミナーで講演しました 2024.04.22 Jerry Yang教授が花王セミナーで講演しました 2024.04.15 Dr. Phillip Szuromiが講演しました 2024.04.09 Tomas Torres Cebada教授が花王セミナーで講演しました 2024.04.08 Molly Stevens教授が花王セミナーで講演しました 2024.04.01 M1の服部君とSun君が新しく相田研に参加しました 2024.03.23 Farewell partyを行いました 2024.03.15 D1のFengさん、M1のHeくんとJiくんが新しく相田研に参加しました 2024.02.15 Shaodong Zhang教授が花王セミナーで講演しました 2024.02.09 Jounal Meetingでよい議論ができました 2023.01.31 D3のFuくんが新しく相田研に参加しました 2024.01.19 CEMSUPRAに参加しました
CEMSupraに参加しました
Image Credit: Bart van Overbeeke
重要な発見
Mechanically Strong yet Metabolizable Supramolecular Plastics
A strong, glassy supramolecular polymer has been shown to prevent the formation of marine microplastics by slowly dissolving in salt water into metabolizable compounds. Cheng et al. show that salt bridging between sodium hexametaphosphate or sulfated polysaccharides and guanidinium sulfates expels sodium sulfate to create a cross-linked network that is stable until the electrolytes are added back. The dried material is a moldable and recyclable thermoplastic that can be water stabilized with hydrophobic coatings.
Mechanically Robust, Readily Repairable Polymers via Tailored Noncovalent Cross-linking
The very long molecules found in synthetic polymers, and their tendency to entangle and partially crystallize, impart many of the polymers' useful properties. However, these same characteristics also mean that chain dynamics are slow, which impedes potential self-healing. Yanagisawa et al. developed a family of ether-thiourea linear polymers that form hydrogen-bonded networks and still manage to stay amorphous. The polymers are stiff, showing the strength of the hydrogen bonding; however, because these bonds can easily reform, the polymer is also able to self-heal when compressed.
Solvent-Free Autocatalytic Supramolecular Polymerization
Solvent-free chemical manufacturing is one of the awaited technologies for addressing an emergent issue of environmental pollution. Here, we report solvent-free autocatalytic supramolecular polymerization (SF-ASP), which provides an inhibition-free template-assisted catalytic organic transformation that takes great advantage of the fact that the product (template) undergoes a termination-free nucleation–elongation assembly (living supramolecular polymerization) under solvent-free conditions. SF-ASP allows for reductive cyclotetramerization of hydrogen-bonding phthalonitriles into the corresponding phthalocyanines in exceptionally high yields (>80%). SF-ASP requires the growing polymer to form hexagonally packed crystalline fibres, which possibly preorganize the phthalonitriles at their cross-sectional edges for their efficient transformation. With metal oleates, SF-ASP produces single-crystalline fibres of metallophthalocyanines again in exceptionally high yields, which grow in both directions without terminal coupling until the phthalonitrile precursors are completely consumed. By taking advantage of this living nature of polymerization, multistep SF-ASP without/with metal oleates allows for the precision synthesis of multi-block supramolecular copolymers.
Ultrafast Water Permeation through Nanochannels with a Densely Fluorous Interior Surface
Ultrafast water permeation in aquaporins is promoted by their hydrophobic interior surface. Polytetrafluoroethylene has a dense fluorine surface, leading to its strong water repellence. We report a series of fluorous oligoamide nanorings with interior diameters ranging from 0.9 to 1.9 nanometers. These nanorings undergo supramolecular polymerization in phospholipid bilayer membranes to form fluorous nanochannels, the interior walls of which are densely covered with fluorine atoms. The nanochannel with the smallest diameter exhibits a water permeation flux that is two orders of magnitude greater than those of aquaporins and carbon nanotubes. The proposed nanochannel exhibits negligible chloride ion (Cl–) permeability caused by a powerful electrostatic barrier provided by the electrostatically negative fluorous interior surface. Thus, this nanochannel is expected to show nearly perfect salt reflectance for desalination.
Accumulated Lattice Strain as an Internal Trigger for Spontaneous Pathway Selection
Multicomponent crystallization is universally important in various research fields including materials science as well as biology and geology, and presents new opportunities in crystal engineering. This process includes multiple kinetic and thermodynamic events that compete with each other, wherein “external triggers” often help the system select appropriate pathways for constructing desired structures. Here we report an unprecedented finding that a lattice strain accumulated with the growth of a crystal serves as an “internal trigger” for pathway selection in multicomponent crystallization. We discovered a “spontaneous” crystal transition, where the kinetically preferred layered crystal, initially formed by excluding the pillar component, carries a single dislocation at its geometrical center. This crystal “spontaneously” liberates a core region to relieve the accumulated lattice strain around the dislocation. Consequently, the liberated part becomes dynamic and enables the pillar ligand to invade the crystalline lattice, thereby transforming into a thermodynamically preferred pillared-layer crystal.
Ultrafast water permeation through nanochannels with a densely fluorous interior surface
We rarely board airplanes by joining the back of a single well-ordered line. More often, we jostle around in one of several bulging crowds that merge haphazardly near the gate. Roughly speaking, these processes are analogous to the chain growth and step growth mechanisms of polymer assembly at the molecular level. Kang et al. present a strategy to link molecular building blocks through hydrogen bonding in accord with the well-controlled chain growth model. The molecules start out curled inward, as they engage in internal hydrogen bonding, until an initiator pulls one open; that molecule is then in the right conformation to pull a partner into the growing chain, poising it to pull in yet another, and so forth down the line.
An Elastic Metal–Organic Crystal with a Densely Catenated Backbone
What particular mechanical properties can be expected for materials composed of interlocked backbones has been a long-standing issue in materials science since the first reports on polycatenane and polyrotaxane in the 1970s1,2,3. Here we report a three-dimensional porous metal–organic crystal, which is exceptional in that its warps and wefts are connected only by catenation. This porous crystal is composed of a tetragonal lattice and dynamically changes its geometry upon guest molecule release, uptake and exchange, and also upon temperature variation even in a low temperature range. We indented4 the crystal along its a/b axes and obtained the Young’s moduli of 1.77 ± 0.16 GPa in N,N-dimethylformamide and 1.63 ± 0.13 GPa in tetrahydrofuran, which are the lowest among those reported so far for porous metal–organic crystals5. To our surprise, hydrostatic compression showed that this elastic porous crystal was the most deformable along its c axis, where 5% contraction occurred without structural deterioration upon compression up to 0.88 GPa. The crystal structure obtained at 0.46 GPa showed that the catenated macrocycles move translationally upon contraction. We anticipate our mechanically interlocked molecule-based design to be a starting point for the development of porous materials with exotic mechanical properties. For example, squeezable porous crystals that may address an essential difficulty in realizing both high abilities of guest uptake and release are on the horizon.
Mechanically Strong yet Metabolizable Supramolecular Plastics
A strong, glassy supramolecular polymer has been shown to prevent the formation of marine microplastics by slowly dissolving in salt water into metabolizable compounds. Cheng et al. show that salt bridging between sodium hexametaphosphate or sulfated polysaccharides and guanidinium sulfates expels sodium sulfate to create a cross-linked network that is stable until the electrolytes are added back. The dried material is a moldable and recyclable thermoplastic that can be water stabilized with hydrophobic coatings.
Mechanically Robust, Readily Repairable Polymers via Tailored Noncovalent Cross-linking
The very long molecules found in synthetic polymers, and their tendency to entangle and partially crystallize, impart many of the polymers' useful properties. However, these same characteristics also mean that chain dynamics are slow, which impedes potential self-healing. Yanagisawa et al. developed a family of ether-thiourea linear polymers that form hydrogen-bonded networks and still manage to stay amorphous. The polymers are stiff, showing the strength of the hydrogen bonding; however, because these bonds can easily reform, the polymer is also able to self-heal when compressed.
Solvent-Free Autocatalytic Supramolecular Polymerization
Solvent-free chemical manufacturing is one of the awaited technologies for addressing an emergent issue of environmental pollution. Here, we report solvent-free autocatalytic supramolecular polymerization (SF-ASP), which provides an inhibition-free template-assisted catalytic organic transformation that takes great advantage of the fact that the product (template) undergoes a termination-free nucleation–elongation assembly (living supramolecular polymerization) under solvent-free conditions. SF-ASP allows for reductive cyclotetramerization of hydrogen-bonding phthalonitriles into the corresponding phthalocyanines in exceptionally high yields (>80%). SF-ASP requires the growing polymer to form hexagonally packed crystalline fibres, which possibly preorganize the phthalonitriles at their cross-sectional edges for their efficient transformation. With metal oleates, SF-ASP produces single-crystalline fibres of metallophthalocyanines again in exceptionally high yields, which grow in both directions without terminal coupling until the phthalonitrile precursors are completely consumed. By taking advantage of this living nature of polymerization, multistep SF-ASP without/with metal oleates allows for the precision synthesis of multi-block supramolecular copolymers.
Ultrafast Water Permeation through Nanochannels with a Densely Fluorous Interior Surface
Ultrafast water permeation in aquaporins is promoted by their hydrophobic interior surface. Polytetrafluoroethylene has a dense fluorine surface, leading to its strong water repellence. We report a series of fluorous oligoamide nanorings with interior diameters ranging from 0.9 to 1.9 nanometers. These nanorings undergo supramolecular polymerization in phospholipid bilayer membranes to form fluorous nanochannels, the interior walls of which are densely covered with fluorine atoms. The nanochannel with the smallest diameter exhibits a water permeation flux that is two orders of magnitude greater than those of aquaporins and carbon nanotubes. The proposed nanochannel exhibits negligible chloride ion (Cl–) permeability caused by a powerful electrostatic barrier provided by the electrostatically negative fluorous interior surface. Thus, this nanochannel is expected to show nearly perfect salt reflectance for desalination.
Accumulated Lattice Strain as an Internal Trigger for Spontaneous Pathway Selection
Multicomponent crystallization is universally important in various research fields including materials science as well as biology and geology, and presents new opportunities in crystal engineering. This process includes multiple kinetic and thermodynamic events that compete with each other, wherein “external triggers” often help the system select appropriate pathways for constructing desired structures. Here we report an unprecedented finding that a lattice strain accumulated with the growth of a crystal serves as an “internal trigger” for pathway selection in multicomponent crystallization. We discovered a “spontaneous” crystal transition, where the kinetically preferred layered crystal, initially formed by excluding the pillar component, carries a single dislocation at its geometrical center. This crystal “spontaneously” liberates a core region to relieve the accumulated lattice strain around the dislocation. Consequently, the liberated part becomes dynamic and enables the pillar ligand to invade the crystalline lattice, thereby transforming into a thermodynamically preferred pillared-layer crystal.
Ultrafast water permeation through nanochannels with a densely fluorous interior surface
We rarely board airplanes by joining the back of a single well-ordered line. More often, we jostle around in one of several bulging crowds that merge haphazardly near the gate. Roughly speaking, these processes are analogous to the chain growth and step growth mechanisms of polymer assembly at the molecular level. Kang et al. present a strategy to link molecular building blocks through hydrogen bonding in accord with the well-controlled chain growth model. The molecules start out curled inward, as they engage in internal hydrogen bonding, until an initiator pulls one open; that molecule is then in the right conformation to pull a partner into the growing chain, poising it to pull in yet another, and so forth down the line.
An Elastic Metal–Organic Crystal with a Densely Catenated Backbone
What particular mechanical properties can be expected for materials composed of interlocked backbones has been a long-standing issue in materials science since the first reports on polycatenane and polyrotaxane in the 1970s1,2,3. Here we report a three-dimensional porous metal–organic crystal, which is exceptional in that its warps and wefts are connected only by catenation. This porous crystal is composed of a tetragonal lattice and dynamically changes its geometry upon guest molecule release, uptake and exchange, and also upon temperature variation even in a low temperature range. We indented4 the crystal along its a/b axes and obtained the Young’s moduli of 1.77 ± 0.16 GPa in N,N-dimethylformamide and 1.63 ± 0.13 GPa in tetrahydrofuran, which are the lowest among those reported so far for porous metal–organic crystals5. To our surprise, hydrostatic compression showed that this elastic porous crystal was the most deformable along its c axis, where 5% contraction occurred without structural deterioration upon compression up to 0.88 GPa. The crystal structure obtained at 0.46 GPa showed that the catenated macrocycles move translationally upon contraction. We anticipate our mechanically interlocked molecule-based design to be a starting point for the development of porous materials with exotic mechanical properties. For example, squeezable porous crystals that may address an essential difficulty in realizing both high abilities of guest uptake and release are on the horizon.
Mechanically Strong yet Metabolizable Supramolecular Plastics
A strong, glassy supramolecular polymer has been shown to prevent the formation of marine microplastics by slowly dissolving in salt water into metabolizable compounds. Cheng et al. show that salt bridging between sodium hexametaphosphate or sulfated polysaccharides and guanidinium sulfates expels sodium sulfate to create a cross-linked network that is stable until the electrolytes are added back. The dried material is a moldable and recyclable thermoplastic that can be water stabilized with hydrophobic coatings.
Mechanically Robust, Readily Repairable Polymers via Tailored Noncovalent Cross-linking
The very long molecules found in synthetic polymers, and their tendency to entangle and partially crystallize, impart many of the polymers' useful properties. However, these same characteristics also mean that chain dynamics are slow, which impedes potential self-healing. Yanagisawa et al. developed a family of ether-thiourea linear polymers that form hydrogen-bonded networks and still manage to stay amorphous. The polymers are stiff, showing the strength of the hydrogen bonding; however, because these bonds can easily reform, the polymer is also able to self-heal when compressed.
Solvent-Free Autocatalytic Supramolecular Polymerization
Solvent-free chemical manufacturing is one of the awaited technologies for addressing an emergent issue of environmental pollution. Here, we report solvent-free autocatalytic supramolecular polymerization (SF-ASP), which provides an inhibition-free template-assisted catalytic organic transformation that takes great advantage of the fact that the product (template) undergoes a termination-free nucleation–elongation assembly (living supramolecular polymerization) under solvent-free conditions. SF-ASP allows for reductive cyclotetramerization of hydrogen-bonding phthalonitriles into the corresponding phthalocyanines in exceptionally high yields (>80%). SF-ASP requires the growing polymer to form hexagonally packed crystalline fibres, which possibly preorganize the phthalonitriles at their cross-sectional edges for their efficient transformation. With metal oleates, SF-ASP produces single-crystalline fibres of metallophthalocyanines again in exceptionally high yields, which grow in both directions without terminal coupling until the phthalonitrile precursors are completely consumed. By taking advantage of this living nature of polymerization, multistep SF-ASP without/with metal oleates allows for the precision synthesis of multi-block supramolecular copolymers.
Ultrafast Water Permeation through Nanochannels with a Densely Fluorous Interior Surface
Ultrafast water permeation in aquaporins is promoted by their hydrophobic interior surface. Polytetrafluoroethylene has a dense fluorine surface, leading to its strong water repellence. We report a series of fluorous oligoamide nanorings with interior diameters ranging from 0.9 to 1.9 nanometers. These nanorings undergo supramolecular polymerization in phospholipid bilayer membranes to form fluorous nanochannels, the interior walls of which are densely covered with fluorine atoms. The nanochannel with the smallest diameter exhibits a water permeation flux that is two orders of magnitude greater than those of aquaporins and carbon nanotubes. The proposed nanochannel exhibits negligible chloride ion (Cl–) permeability caused by a powerful electrostatic barrier provided by the electrostatically negative fluorous interior surface. Thus, this nanochannel is expected to show nearly perfect salt reflectance for desalination.
Accumulated Lattice Strain as an Internal Trigger for Spontaneous Pathway Selection
Multicomponent crystallization is universally important in various research fields including materials science as well as biology and geology, and presents new opportunities in crystal engineering. This process includes multiple kinetic and thermodynamic events that compete with each other, wherein “external triggers” often help the system select appropriate pathways for constructing desired structures. Here we report an unprecedented finding that a lattice strain accumulated with the growth of a crystal serves as an “internal trigger” for pathway selection in multicomponent crystallization. We discovered a “spontaneous” crystal transition, where the kinetically preferred layered crystal, initially formed by excluding the pillar component, carries a single dislocation at its geometrical center. This crystal “spontaneously” liberates a core region to relieve the accumulated lattice strain around the dislocation. Consequently, the liberated part becomes dynamic and enables the pillar ligand to invade the crystalline lattice, thereby transforming into a thermodynamically preferred pillared-layer crystal.
Ultrafast water permeation through nanochannels with a densely fluorous interior surface
We rarely board airplanes by joining the back of a single well-ordered line. More often, we jostle around in one of several bulging crowds that merge haphazardly near the gate. Roughly speaking, these processes are analogous to the chain growth and step growth mechanisms of polymer assembly at the molecular level. Kang et al. present a strategy to link molecular building blocks through hydrogen bonding in accord with the well-controlled chain growth model. The molecules start out curled inward, as they engage in internal hydrogen bonding, until an initiator pulls one open; that molecule is then in the right conformation to pull a partner into the growing chain, poising it to pull in yet another, and so forth down the line.
An Elastic Metal–Organic Crystal with a Densely Catenated Backbone
What particular mechanical properties can be expected for materials composed of interlocked backbones has been a long-standing issue in materials science since the first reports on polycatenane and polyrotaxane in the 1970s1,2,3. Here we report a three-dimensional porous metal–organic crystal, which is exceptional in that its warps and wefts are connected only by catenation. This porous crystal is composed of a tetragonal lattice and dynamically changes its geometry upon guest molecule release, uptake and exchange, and also upon temperature variation even in a low temperature range. We indented4 the crystal along its a/b axes and obtained the Young’s moduli of 1.77 ± 0.16 GPa in N,N-dimethylformamide and 1.63 ± 0.13 GPa in tetrahydrofuran, which are the lowest among those reported so far for porous metal–organic crystals5. To our surprise, hydrostatic compression showed that this elastic porous crystal was the most deformable along its c axis, where 5% contraction occurred without structural deterioration upon compression up to 0.88 GPa. The crystal structure obtained at 0.46 GPa showed that the catenated macrocycles move translationally upon contraction. We anticipate our mechanically interlocked molecule-based design to be a starting point for the development of porous materials with exotic mechanical properties. For example, squeezable porous crystals that may address an essential difficulty in realizing both high abilities of guest uptake and release are on the horizon.
Mechanically Strong yet Metabolizable Supramolecular Plastics
A strong, glassy supramolecular polymer has been shown to prevent the formation of marine microplastics by slowly dissolving in salt water into metabolizable compounds. Cheng et al. show that salt bridging between sodium hexametaphosphate or sulfated polysaccharides and guanidinium sulfates expels sodium sulfate to create a cross-linked network that is stable until the electrolytes are added back. The dried material is a moldable and recyclable thermoplastic that can be water stabilized with hydrophobic coatings.
Mechanically Robust, Readily Repairable Polymers via Tailored Noncovalent Cross-linking
The very long molecules found in synthetic polymers, and their tendency to entangle and partially crystallize, impart many of the polymers' useful properties. However, these same characteristics also mean that chain dynamics are slow, which impedes potential self-healing. Yanagisawa et al. developed a family of ether-thiourea linear polymers that form hydrogen-bonded networks and still manage to stay amorphous. The polymers are stiff, showing the strength of the hydrogen bonding; however, because these bonds can easily reform, the polymer is also able to self-heal when compressed.
Solvent-Free Autocatalytic Supramolecular Polymerization
Solvent-free chemical manufacturing is one of the awaited technologies for addressing an emergent issue of environmental pollution. Here, we report solvent-free autocatalytic supramolecular polymerization (SF-ASP), which provides an inhibition-free template-assisted catalytic organic transformation that takes great advantage of the fact that the product (template) undergoes a termination-free nucleation–elongation assembly (living supramolecular polymerization) under solvent-free conditions. SF-ASP allows for reductive cyclotetramerization of hydrogen-bonding phthalonitriles into the corresponding phthalocyanines in exceptionally high yields (>80%). SF-ASP requires the growing polymer to form hexagonally packed crystalline fibres, which possibly preorganize the phthalonitriles at their cross-sectional edges for their efficient transformation. With metal oleates, SF-ASP produces single-crystalline fibres of metallophthalocyanines again in exceptionally high yields, which grow in both directions without terminal coupling until the phthalonitrile precursors are completely consumed. By taking advantage of this living nature of polymerization, multistep SF-ASP without/with metal oleates allows for the precision synthesis of multi-block supramolecular copolymers.
Ultrafast Water Permeation through Nanochannels with a Densely Fluorous Interior Surface
Ultrafast water permeation in aquaporins is promoted by their hydrophobic interior surface. Polytetrafluoroethylene has a dense fluorine surface, leading to its strong water repellence. We report a series of fluorous oligoamide nanorings with interior diameters ranging from 0.9 to 1.9 nanometers. These nanorings undergo supramolecular polymerization in phospholipid bilayer membranes to form fluorous nanochannels, the interior walls of which are densely covered with fluorine atoms. The nanochannel with the smallest diameter exhibits a water permeation flux that is two orders of magnitude greater than those of aquaporins and carbon nanotubes. The proposed nanochannel exhibits negligible chloride ion (Cl–) permeability caused by a powerful electrostatic barrier provided by the electrostatically negative fluorous interior surface. Thus, this nanochannel is expected to show nearly perfect salt reflectance for desalination.
Accumulated Lattice Strain as an Internal Trigger for Spontaneous Pathway Selection
Multicomponent crystallization is universally important in various research fields including materials science as well as biology and geology, and presents new opportunities in crystal engineering. This process includes multiple kinetic and thermodynamic events that compete with each other, wherein “external triggers” often help the system select appropriate pathways for constructing desired structures. Here we report an unprecedented finding that a lattice strain accumulated with the growth of a crystal serves as an “internal trigger” for pathway selection in multicomponent crystallization. We discovered a “spontaneous” crystal transition, where the kinetically preferred layered crystal, initially formed by excluding the pillar component, carries a single dislocation at its geometrical center. This crystal “spontaneously” liberates a core region to relieve the accumulated lattice strain around the dislocation. Consequently, the liberated part becomes dynamic and enables the pillar ligand to invade the crystalline lattice, thereby transforming into a thermodynamically preferred pillared-layer crystal.
Ultrafast water permeation through nanochannels with a densely fluorous interior surface
We rarely board airplanes by joining the back of a single well-ordered line. More often, we jostle around in one of several bulging crowds that merge haphazardly near the gate. Roughly speaking, these processes are analogous to the chain growth and step growth mechanisms of polymer assembly at the molecular level. Kang et al. present a strategy to link molecular building blocks through hydrogen bonding in accord with the well-controlled chain growth model. The molecules start out curled inward, as they engage in internal hydrogen bonding, until an initiator pulls one open; that molecule is then in the right conformation to pull a partner into the growing chain, poising it to pull in yet another, and so forth down the line.
An Elastic Metal–Organic Crystal with a Densely Catenated Backbone
What particular mechanical properties can be expected for materials composed of interlocked backbones has been a long-standing issue in materials science since the first reports on polycatenane and polyrotaxane in the 1970s1,2,3. Here we report a three-dimensional porous metal–organic crystal, which is exceptional in that its warps and wefts are connected only by catenation. This porous crystal is composed of a tetragonal lattice and dynamically changes its geometry upon guest molecule release, uptake and exchange, and also upon temperature variation even in a low temperature range. We indented4 the crystal along its a/b axes and obtained the Young’s moduli of 1.77 ± 0.16 GPa in N,N-dimethylformamide and 1.63 ± 0.13 GPa in tetrahydrofuran, which are the lowest among those reported so far for porous metal–organic crystals5. To our surprise, hydrostatic compression showed that this elastic porous crystal was the most deformable along its c axis, where 5% contraction occurred without structural deterioration upon compression up to 0.88 GPa. The crystal structure obtained at 0.46 GPa showed that the catenated macrocycles move translationally upon contraction. We anticipate our mechanically interlocked molecule-based design to be a starting point for the development of porous materials with exotic mechanical properties. For example, squeezable porous crystals that may address an essential difficulty in realizing both high abilities of guest uptake and release are on the horizon.
Mechanically Strong yet Metabolizable Supramolecular Plastics
A strong, glassy supramolecular polymer has been shown to prevent the formation of marine microplastics by slowly dissolving in salt water into metabolizable compounds. Cheng et al. show that salt bridging between sodium hexametaphosphate or sulfated polysaccharides and guanidinium sulfates expels sodium sulfate to create a cross-linked network that is stable until the electrolytes are added back. The dried material is a moldable and recyclable thermoplastic that can be water stabilized with hydrophobic coatings.
Mechanically Robust, Readily Repairable Polymers via Tailored Noncovalent Cross-linking
The very long molecules found in synthetic polymers, and their tendency to entangle and partially crystallize, impart many of the polymers' useful properties. However, these same characteristics also mean that chain dynamics are slow, which impedes potential self-healing. Yanagisawa et al. developed a family of ether-thiourea linear polymers that form hydrogen-bonded networks and still manage to stay amorphous. The polymers are stiff, showing the strength of the hydrogen bonding; however, because these bonds can easily reform, the polymer is also able to self-heal when compressed.
Solvent-Free Autocatalytic Supramolecular Polymerization
Solvent-free chemical manufacturing is one of the awaited technologies for addressing an emergent issue of environmental pollution. Here, we report solvent-free autocatalytic supramolecular polymerization (SF-ASP), which provides an inhibition-free template-assisted catalytic organic transformation that takes great advantage of the fact that the product (template) undergoes a termination-free nucleation–elongation assembly (living supramolecular polymerization) under solvent-free conditions. SF-ASP allows for reductive cyclotetramerization of hydrogen-bonding phthalonitriles into the corresponding phthalocyanines in exceptionally high yields (>80%). SF-ASP requires the growing polymer to form hexagonally packed crystalline fibres, which possibly preorganize the phthalonitriles at their cross-sectional edges for their efficient transformation. With metal oleates, SF-ASP produces single-crystalline fibres of metallophthalocyanines again in exceptionally high yields, which grow in both directions without terminal coupling until the phthalonitrile precursors are completely consumed. By taking advantage of this living nature of polymerization, multistep SF-ASP without/with metal oleates allows for the precision synthesis of multi-block supramolecular copolymers.
Ultrafast Water Permeation through Nanochannels with a Densely Fluorous Interior Surface
Ultrafast water permeation in aquaporins is promoted by their hydrophobic interior surface. Polytetrafluoroethylene has a dense fluorine surface, leading to its strong water repellence. We report a series of fluorous oligoamide nanorings with interior diameters ranging from 0.9 to 1.9 nanometers. These nanorings undergo supramolecular polymerization in phospholipid bilayer membranes to form fluorous nanochannels, the interior walls of which are densely covered with fluorine atoms. The nanochannel with the smallest diameter exhibits a water permeation flux that is two orders of magnitude greater than those of aquaporins and carbon nanotubes. The proposed nanochannel exhibits negligible chloride ion (Cl–) permeability caused by a powerful electrostatic barrier provided by the electrostatically negative fluorous interior surface. Thus, this nanochannel is expected to show nearly perfect salt reflectance for desalination.
Accumulated Lattice Strain as an Internal Trigger for Spontaneous Pathway Selection
Multicomponent crystallization is universally important in various research fields including materials science as well as biology and geology, and presents new opportunities in crystal engineering. This process includes multiple kinetic and thermodynamic events that compete with each other, wherein “external triggers” often help the system select appropriate pathways for constructing desired structures. Here we report an unprecedented finding that a lattice strain accumulated with the growth of a crystal serves as an “internal trigger” for pathway selection in multicomponent crystallization. We discovered a “spontaneous” crystal transition, where the kinetically preferred layered crystal, initially formed by excluding the pillar component, carries a single dislocation at its geometrical center. This crystal “spontaneously” liberates a core region to relieve the accumulated lattice strain around the dislocation. Consequently, the liberated part becomes dynamic and enables the pillar ligand to invade the crystalline lattice, thereby transforming into a thermodynamically preferred pillared-layer crystal.
Ultrafast water permeation through nanochannels with a densely fluorous interior surface
We rarely board airplanes by joining the back of a single well-ordered line. More often, we jostle around in one of several bulging crowds that merge haphazardly near the gate. Roughly speaking, these processes are analogous to the chain growth and step growth mechanisms of polymer assembly at the molecular level. Kang et al. present a strategy to link molecular building blocks through hydrogen bonding in accord with the well-controlled chain growth model. The molecules start out curled inward, as they engage in internal hydrogen bonding, until an initiator pulls one open; that molecule is then in the right conformation to pull a partner into the growing chain, poising it to pull in yet another, and so forth down the line.
An Elastic Metal–Organic Crystal with a Densely Catenated Backbone
What particular mechanical properties can be expected for materials composed of interlocked backbones has been a long-standing issue in materials science since the first reports on polycatenane and polyrotaxane in the 1970s1,2,3. Here we report a three-dimensional porous metal–organic crystal, which is exceptional in that its warps and wefts are connected only by catenation. This porous crystal is composed of a tetragonal lattice and dynamically changes its geometry upon guest molecule release, uptake and exchange, and also upon temperature variation even in a low temperature range. We indented4 the crystal along its a/b axes and obtained the Young’s moduli of 1.77 ± 0.16 GPa in N,N-dimethylformamide and 1.63 ± 0.13 GPa in tetrahydrofuran, which are the lowest among those reported so far for porous metal–organic crystals5. To our surprise, hydrostatic compression showed that this elastic porous crystal was the most deformable along its c axis, where 5% contraction occurred without structural deterioration upon compression up to 0.88 GPa. The crystal structure obtained at 0.46 GPa showed that the catenated macrocycles move translationally upon contraction. We anticipate our mechanically interlocked molecule-based design to be a starting point for the development of porous materials with exotic mechanical properties. For example, squeezable porous crystals that may address an essential difficulty in realizing both high abilities of guest uptake and release are on the horizon.
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