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Block copolymer self-assembly affords diverse nanostructures, spanning from spheres and cylinders to networks, offering meticulous control over properties and functionalities at the nanoscale. However, creating thermodynamically stable network structures with high packing frustration remains a challenge. In this study, we report a methodology to access diverse network structures such as gyroid, diamond, and primitive phases from diblock copolymers using end group and linker chemistry. The stability of the medial packing of polymer chain ends (plumber's nightmare structure) over skeletal aggregation (gyroid) is attributed to the interplay between the strength of the end-end interactions and the initial shape of the curvature. Our study establishes an approach to develop tailored network structures from block copolymers, providing an important platform for using block copolymers in nanotechnology applications.
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We present a strategic approach for enhancing the ionic conductivity of block copolymer electrolytes. This was achieved by introducing mixed ionic liquids (ILs) with varying molar ratios, wherein the imidazolium cation was paired with either tetrafluoroborate (BF4) anion or bis(trifluoromethylsulfonyl)imide (TFSI) anion. Two polymer matrices, poly(4-styrenesulfonate)-b-polymethylbutylene (SSMB) and poly(4-styrenesulfonyl (trifluoromethanesulfonyl)imide)-b-polymethylbutylene (STMB), were synthesized for this purpose. All the SSMB and STMB containing mixed ILs showed hexagonal cylindrical structures, but the type of tethered acid group significantly influenced the interfacial properties. STMB electrolytes demonstrated enhanced segregation strength, which was attributed to strengthened Coulomb and hydrogen bonding interactions in the ionic domains, where the ILs were uniformly distributed. In contrast, the SSMB electrolytes exhibited increased concentration fluctuations because the BF4 anions were selectively sequestered at the block interfaces. This resulted in the effective confinement of imidazolium TFSI along the ionic domains, thereby preventing ion trapping in dead zones and facilitating rapid ion diffusion. Consequently, the SSMB electrolytes with mixed ILs demonstrated significantly improved ionic conductivities, surpassing the expected values based on the arithmetic average of the conductivities of each IL, whereas the ionic conductivity of the STMB was aligned with the expected average. The methodology explored in this study holds great promise for the development of solid-state polymer electrolytes.
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We designed solid-state hybrid electrolytes with single-ion conducting properties by co-assembling binary core-shell polymer nanoparticles. By controlling the nanoparticle size and number, we created superlattices that optimized the Li+ concentration and transport. The electrolytes exhibited a remarkable ionic conductivity (10-4 S cm-1), lithium transference number (0.94), electrochemical stability (up to 6 V), and modulus (0.12 GPa) at 25 °C. The mechanical strength of these electrolytes depended minimally on temperature at 25-150 °C because of the robustness of the cores. When implemented in Li-S batteries with no liquids, they demonstrated an initial discharge capacity of 1090 mA h g-1 at 0.05C, a cycle life of over 200 cycles, and a rate capability with a discharge capacity of 627 mA h g-1 at 3C.
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Achieving superionic conductivity from solid-state polymer electrolytes is an important task in the development of future energy storage and conversion technologies. Herein, a platform for innovative electrolyte technologies based on a bifunctional polymer, poly(3-hydroxy-4-sulfonated styrene) (PS-3H4S), is presented. By incorporating OH and SO3 H functional groups at adjacent positions in the styrene repeating unit, "intra-monomer" hydrogen bonds are formed to effectively weaken the electrostatic interactions of the SO3 - moieties in the polymer matrix with embedded ions, promoting rich structural and dynamic heterogeneity in the PS-3H4S electrolyte. Upon the incorporation of an ionic liquid, interconnected rod-like ion channels, which allow the decoupling of ion relaxation from polymer relaxation, are formed in the stiff motif of the polymeric domains passivated by interfacial ionic layers. This results in accelerated proton hopping through the glassy polymer matrix, and proton hopping becomes more pronounced at cryogenic temperatures down to -35 °C. The PS-3H4S/ionic liquid composite electrolytes exhibit a high ionic conductivity of 10-3 S cm-1 and high storage modulus of ≈100 MPa at 25 °C, and can be successfully applied in soft actuators and lithium-metal batteries.
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Under strong laser fields, electrons in solids radiate high-harmonic fields by travelling through quantum pathways in Bloch bands in the sub-laser-cycle timescales. Understanding these pathways in the momentum space through the high-harmonic radiation can enable an all-optical ultrafast probe to observe coherent lightwave-driven processes and measure electronic structures as recently demonstrated for semiconductors. However, such demonstration has been largely limited for semimetals because the absence of the bandgap hinders an experimental characterization of the exact pathways. In this study, by combining electrostatic control of chemical potentials with HHG measurement, we resolve quantum pathways of massless Dirac fermions in graphene under strong laser fields. Electrical modulation of HHG reveals quantum interference between the multi-photon interband excitation channels. As the light-matter interaction deviates beyond the perturbative regime, elliptically polarized laser fields efficiently drive massless Dirac fermions via an intricate coupling between the interband and intraband transitions, which is corroborated by our theoretical calculations. Our findings pave the way for strong-laser-field tomography of Dirac electrons in various quantum semimetals and their ultrafast electronics with a gate control.
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We developed a method for producing porous charged polymer nanosheets using frozen ice containing microplastics. Upon assessing SARS-CoV-2 filtration using nanosheets with 100 nm-sized pores, a high rejection rate of 96% was achieved. The charged surfaces of nanosheets further enabled the electrophoretic capture of the virus using a portable battery with additional real-time sensing capability.
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COVID-19 , Microplásticos , Humanos , Porosidade , Plásticos , Polímeros , Gelo , SARS-CoV-2 , COVID-19/diagnósticoRESUMO
Conducting polymers have been studied widely over the past decades for use as organic electrode materials owing to their high electrical conductivity and low-cost synthesis. Among the various synthesis methods reported, the recently established ice-assisted approach for developing conducting polymer nanosheets is regarded as an advanced technology that allows for easy fabrication in an eco-friendly manner. However, the role of the crystallinity of the underlying ice surface in determining the physicochemical properties of the conducting polymers remains unclear. Here, the electronic properties and packing structures of polyaniline (PANI) nanosheets formed on ice surfaces are studied by controlling the ice crystallinity. Intriguingly, the crystallinity of the PANI nanosheets resembles that of the ice surfaces, in that the anisotropic growth of the PANI crystals with a face-on orientation occurs preferentially on high-crystalline ice surfaces. In addition, it is found that the development of highly crystalline PANI nanosheets results in efficient charge transport, owing to polaron delocalization in PANI with extended chain conformations and the improvement in the degree of backbone ordering because of the preorganized aniline moieties on the ice surface.
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Gelo , Polímeros , Condutividade Elétrica , Eletrônica , PesquisaRESUMO
To fulfill the insatiable demand for wearable technologies, ionic electroactive polymer actuators have been entrenched as promising candidates that can convert low-input-voltage energy into high mechanical throughput. However, a ubiquitous trilayer design of actuators allows exclusively bending deformation and their highly nonlinear response restricts the true potential of low-voltage actuators for next-generation technology. Herein, we report an unprecedented multilayer design for soft actuators that enables complex deformations shown by skeletal muscles, mechanoreceptors, and plant roots in response to various environmental stimuli. Hierarchically ordered pores in a stretchable interlayer provide excellent electromechanical properties and fast charging kinetics, which enable linear motion by soft actuators at 3 V and under ambient conditions. Our actuators demonstrate astonishing levels of performance, including a 6.5% linear actuation strain, 0.8 s rapid switching speed, and 5000 cycle stable performance in air, producing a 4.2 mN linear blocking force at a ±3 V alternating square-wave voltage. This actuator design demonstrating a walkable spider capable of controlled back-and-forth propelling motion at low driving voltages provides the platform to envision a complex functionality using a portable battery as a power source for soft robotics, wearable exosuits, and biomimetic technologies.
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Materiais Biomiméticos/química , Polímeros/química , Robótica , Materiais Biomiméticos/síntese química , Humanos , Cinética , Teste de Materiais , Polímeros/síntese químicaRESUMO
Charged block copolymers are promising materials for next-generation battery technologies and soft electronics. Although once it was only possible to prepare randomly organized structures, nowadays, well-ordered charged block copolymers can be prepared. In addition, theoretical and experimental analyses of the thermodynamic properties of charged polymers have provided insights into how to control nanostructures via electrostatic interactions and improve the ionic conductivity without compromising mechanical strength, which is crucial for practical applications. In this Account, we discuss methods to control the self-assembly and ion diffusion behavior of charged block copolymers by varying the type of tethered ionic moieties, local concentration of embedded ions with controlled electrostatic interactions, and nanoscale morphology. We discuss with particular emphasis on the structure-transport relationship of charged block copolymers using various ionic additives to control the phase behavior electrostatically as well as the ion transport properties. Through this, we establish the role of interconnected ionic channels in promoting ion-conduction and the importance of developing three-dimensional interconnected morphologies such as gyroid, orthorhombic Fddd (O70) networks, body-centered cubic (bcc), face-centered cubic (fcc), and A15 structures with well-defined interfaces in creating less tortuous ion-conduction pathways. Our prolonged surge and synthetic advances are pushing the frontiers of charged block copolymers to have virtually homogeneous ionic domains with suppressed ion agglomeration via the nanoconfinement of closely bound ionic moieties, resulting in efficient ion conduction and high mechanical strength.Subsequently, we discuss how, by using zwitterions, we have radically improved the ionic conductivity of single-ion conducting polymers, which have potential for use in next-generation electrochemical devices owing to the constrained anion depletion. Key to the improvement stems from hierarchically ordered ionic crystals in nanodomains of the single-ion block copolymers through the self-organization of the dipolar/ionic moieties under confinement. By precisely tuning the distances between ionic sites and the dipolar orientation in the ionic domains with varied zwitterion contents, unprecedented dielectric constants close to those of aqueous electrolytes have been achieved, leading to the development of high-conductivity solid-state single-ion conducting polymers with leak-free characteristics. Further, using these materials, low-voltage-driven artificial muscles have been prepared that show a large bending strain and millisecond-scale mechanical deformations at 1 V in air without fatigue, exceeding the performance of previously reported polymer actuators. Finally, smart multiresponsive actuators based on tailor-made charged polymers capable of programmable deformation with high force and self-locking without power consumption are suggested as candidates for use in soft robotics.
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Recently, the interest in charged polymers has been rapidly growing due to their uses in energy storage and transfer devices. Yet, polymer electrolyte-based devices are not on the immediate horizon because of the low ionic conductivity. In the present study, we developed a methodology to enhance the ionic conductivity of charged block copolymers comprising ionic liquids through the electrostatic control of the interfacial layers. Unprecedented reentrant phase transitions between lamellar and A15 structures were seen, which cannot be explained by well-established thermodynamic factors. X-ray scattering experiments and molecular dynamics simulations revealed the formation of fascinating, thin ionic shell layers composed of ionic complexes. The ionic liquid cations of these complexes predominantly presented near the micellar interfaces if they had strong binding affinity with the charged polymer chains. Therefore, the interfacial properties and concentration fluctuations of the A15 structures were crucially dependent on the type of tethered acid groups in the polymers. Overall, the stabilization energies of the A15 structures were greater when enriched, attractive electrostatic interactions were present at the micellar interfaces. Contrary to the conventional wisdom that block copolymer interfaces act as "dead zone" to significantly deteriorate ion transport, this study establishes a prospective avenue for advanced polymer electrolyte having tailor-made interfaces.
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The discovery of peculiar quasi-liquid layers on ice surfaces marks a major breakthrough in ice-related sciences, as the facile tuning of the reactions and morphologies of substances in contact with these layers make ice-assisted chemistry a low-cost, environmentally benign, and ubiquitous methodology for the synthesis of nanomaterials with improved functionality. Ice-templated synthesis of porous materials offers the appealing features of rapid self-organization and remarkable property changes arising from confinement effects and affords materials that have found a diverse range of applications such as batteries, supercapacitors, and gas separation. Moreover, much attention has been drawn to the acceleration of chemical reactions and transformations on the ice surface due to the freeze concentration effect, fast self-diffusion of surface water, and modulated surface potential energy. Some of these results are related to the accumulation of inorganic contaminants in glaciers and the blockage of natural gas pipelines. As an emerging theme in nanomaterial design, the dimension-controlled synthesis of hybrid materials with unprecedentedly enhanced properties on ice surfaces has attracted much interest. However, a deep understanding of quasi-liquid layer characteristics (and hence, the development of cutting-edge analytical technologies with high surface sensitivity) is required to achieve the current goal of ice-assisted chemistry, namely the preparation of tailor-made materials with the desired properties.
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Advances in lithium battery technologies necessitate improved energy densities, long cycle lives, fast charging, safe operation, and environmentally friendly components. This study concerns lithium-organic batteries comprising bioinspired poly(4-vinyl catechol) (P4VC) cathode materials and single-ion conducting polymer nanoparticle electrolytes. The controlled synthesis of P4VC results in a two-step redox reaction with voltage plateaus at around 3.1 and 3.5â V, as well as a high initial specific capacity of 352â mAh g-1 . The use of single-ion nanoparticle electrolytes enables high electrochemical stabilities up to 5.5â V, a high lithium transference number of 0.99, high ionic conductivities, ranging from 0.2×10-3 to 10-3 â S cm-1 , and stable storage moduli of >10â MPa at 25-90 °C. Lithium cells can deliver 165â mAh g-1 at 39.7â mA g-1 for 100 cycles and stable specific capacities of >100â mAh g-1 at a high current density of 794â mA g-1 for 500â cycles. As the first successful demonstration of solid-state single-ion polymer electrolytes in environmentally benign and cost-effective lithium-organic batteries, this work establishes a future research avenue for advancing lithium battery technologies.
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Scientific research on advanced polymer electrolytes has led to the emergence of all-solid-state energy storage/transfer systems. Early research began with acid-tethered polymers half a century ago, and research interest has gradually shifted to high-precision polymers with controllable acid functional groups and nanoscale morphologies. Consequently, various self-assembled acid-tethered block polymer morphologies have been produced. Their ion properties are profoundly affected by the multiscale intermolecular interactions in confinements. The creation of hierarchically organized ion/dipole arrangements inside the block copolymer nanostructures has been highlighted as a future method for developing advanced single-ion polymers with decoupled ion dynamics and polymer chain relaxation. Several emerging practical applications of the acid-tethered block copolymers have been explored to draw attention to the challenges and opportunities in developing state-of-the-art electrochemical systems.
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The performance limits of conventional super engineering plastics with inorganic nanofillers are surpassed by all-organic nanocomposites prepared via in situ SNAr polymerization of polysulfone (PSU) in the presence of a highly dispersed aramid nanofiber (ANF) solution. The latter is directly used, bypassing the energy-consuming, nanostructure-damaging workup process. Using only a 0.15 wt % nanofiller, the all-organic nanocomposite shows an ultimate tensile strength 1.6× higher and 3.4× tougher than neat PSU and its blending counterpart due to the mutually interactive filler and maximally homogenized matrix. The exceptional toughness of the ANF/PSU nanocomposite originates from the grafted PSU on the surface of ANF; it drives stress-delocalized deformation, as revealed by stress-absorbable viscoelastic behavior and ductile elongation of materials. This material is a promising candidate for use as a filler-interactive, high-performance nanocomposite.
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Polymerizing monomers on an atomically flat solid surface and air/water, solid/liquid, or liquid/liquid interface is now a rapidly emerging frontier. Dimension-controlled synthesis of π-conjugated polymers is of particular interest, which can be achieved by precise control of monomer distribution during the polymerization. The surface of ice allows rapid polymerization of monomers in the plane direction along the air-water interface to yield large-area two-dimensional sheet-like poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (2D sheet-like PEDOT:PSS) films with a thickness of ca. 30 nm. The persuasive role of ice chemistry is reflected in the high degree of crystallinity and superior conductivity of resultant PEDOT:PSS films. Excellent photoelectrochemical features were further disclosed when the ice-templated PEDOT:PSS films were coupled to quantum dots. Utilization of these polymer films in photovoltaic devices also resulted in excellent current density and power conversion efficiency. This work presents an innovative material technology that goes beyond traditional and ubiquitous inorganic 2D materials such as graphene and MoS2 for integrated electronic applications.
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Emulation of human sensory and motor functions becomes a core technology in bioinspired electronics for next-generation electronic prosthetics and neurologically inspired robotics. An electronic synapse functionalized with an artificial sensory receptor and an artificial motor unit can be a fundamental element of bioinspired soft electronics. Here, we report an organic optoelectronic sensorimotor synapse that uses an organic optoelectronic synapse and a neuromuscular system based on a stretchable organic nanowire synaptic transistor (s-ONWST). The voltage pulses of a self-powered photodetector triggered by optical signals drive the s-ONWST, and resultant informative synaptic outputs are used not only for optical wireless communication of human-machine interfaces but also for light-interactive actuation of an artificial muscle actuator in the same way that a biological muscle fiber contracts. Our organic optoelectronic sensorimotor synapse suggests a promising strategy toward developing bioinspired soft electronics, neurologically inspired robotics, and electronic prostheses.
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Nanofios/química , Junção Neuromuscular/fisiologia , Monitoração Neuromuscular/instrumentação , Polímeros/química , Sinapses/fisiologia , Transistores Eletrônicos , Dispositivos Eletrônicos Vestíveis , Eletrônica , Humanos , Modelos NeurológicosRESUMO
The synthesis of high-conductivity solid-state electrolyte materials with eliminated polarization loss is a great challenge. Here we show a promising potential of single-ion block copolymers with crystalline protogenic channels as efficient proton conductors. Through the self-organization of zwitterion, imidazole, and polystyrene sulfonate with controlled dipolar interactions therein, the distance between neighboring proton donors and acceptors in ionic crystals, as well as the dipolar orientation in nanoscale ionic phases was precisely tuned. This allowed a markedly high static dielectric constant comparable to water and fast structural diffusion of protons with a low potential barrier for single-ion polymers. The optimized sample exhibited a high proton diffusion coefficient of 2.4 × 10-6 cm2 s-1 under anhydrous conditions at 90 °C.
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Soft actuators based on electroactive polymers (EAPs) are the core constituents of future soft robots owing to their fascinating properties such as lightweight, compactness, easy fabrication into various forms, and low cost. Ionic EAP actuators are particularly attractive owing to the low driving voltages (<3 V) as compared to those of electronic EAP actuators (usually kilovolts). This paper presents a brief overview of the recent progress in a range of EAP actuators by focusing on low voltage operation, in addition to the challenges and future strategies for their wide applicability in artificial muscles and various innovative soft robot technologies.
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Natural double-layered structures observed in living organisms are known to exhibit asymmetric volume changes with environmental triggers. Typical examples are natural roots of plants, which show unique self-organized bending behavior in response to environmental stimuli. Herein, light- and electro-active polymer (LEAP) based actuators with a double-layered structure are reported. The LEAP actuators exhibit an improvement of 250% in displacement and hold an object three times heavier as compared to that in the case of conventional electro-active polymer actuators. Most interestingly, the bending motion of the LEAP actuators can be effectively locked for a few tens of minutes even in the absence of a power supply. Further, the self-locking LEAP actuators show a large and reversible bending strain of more than 2.0% and require only 6.2 mW h cm-2 of energy to hold an object for 15 min at an operating voltage of 3 V. These novel self-locking soft actuators should find wide applicability in artificial muscles, biomedical microdevices, and various innovative soft robot technologies.
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Miktoarm star copolymers composed of three poly(ethylene oxide) (PEO) arms connected to one polystyrene (PS) chain, i.e., PS-(PEO)3, demonstrated synergistic improvements in the ionic conductivity and mechanical strength by factors of 2-30 compared to those shown by PS-PEO diblock copolymers. Entropic constraints for the chain stretching of (PEO)3 gave rise to notably reduced domain sizes of PS-(PEO)3 electrolytes, compared with the values of PS-PEO analogues. Further, the melting transition of PS-(PEO)3 with PEO molecular weight of Mn = 2 kg mol-1 was vanished with lithium salt doping at [Li]/[EO] = 0.06 under such confinements, resulting in an order of magnitude increase in the room temperature conductivity. The fact that lithium ion transport in PEO-based copolymers can be tunable by the way PEO chains are connected to hard polymers can lead to innovative designs for solid-state polymer electrolytes.