Thermal‐Gated Polymer Electrolytes for Smart Zinc‐Ion Batteries

Smart self‐protection is essential for addressing safety issues of energy‐storage devices. However, conventional strategies based on sol‐gel transition electrolytes often suffer from unstable self‐recovery performance. Herein, smart separators based on thermal‐gated poly(N‐isopropylacrylamide) (PNIPAM) hydrogel electrolytes were developed for rechargeable zinc‐ion batteries (ZIBs). Such PNIPAM‐based separators not only display a pore structure evolution from opened to closed states, but also exhibit a surface wettability transition from hydrophilic to hydrophobic behaviors when the temperature rises. This behavior can suppress the migration of electrolyte ions across the separators, realizing the self‐protection of ZIBs at high temperatures. Furthermore, the thermal‐gated behavior is highly reversible, even after multiple heating/cooling cycles, because of the reversibility of temperature‐dependent structural evolution and hydrophilic/hydrophobic transition. This work will pave the way for designing thermal‐responsive energy‐storage devices with safe and controlled energy delivery.     

Mechanically strong Janus poly(<Emphasis Type="Italic">N</Emphasis>-isopropylacrylamide)/graphene oxide hydrogels as thermo-responsive soft robots

Simple preparation of stimuli-responsive hydrogels with good mechanical properties and mild stimuliresponsiveness is essential for their applications as smart soft robots. Mechanically strong Janus poly(N-isopropylacrylamide)/graphene oxide (PNIPAM/GO) nanocomposite hydrogels with stimuli-responsive bending behaviors are prepared through a simple one-step method by using molds made of a Teflon plate and a glass plate. Residual oxygen in the air bubbles on the Teflon plate surface affects the polymerization and hence the cross-linking density, leading to the different swelling/deswelling rates of the two sides of the gels. Therefore, the hydrogels exhibit bending/unbending behaviors upon heating/cooling in water. The incorporation of GO nanosheets dramatically enhances the mechanical properties of Janus hydrogels. Meanwhile, the photo-responsive property of the GO nanosheets also imparts the hydrogels with remotecontrollable deformation under IR irradiation. The application of the Janus PNIPAM/GO hydrogels as thermo-responsive grippers is demonstrated.     

Thermo‐Responsive MOF/Polymer Composites for Temperature‐Mediated Water Capture and Release

We report an in situ polymerization strategy to incorporate a thermo‐responsive polymer, poly(N‐isopropylacrylamide) (PNIPAM), with controlled loadings into the cavity of a mesoporous metal–organic framework (MOF), MIL‐101(Cr). The resulting MOF/polymer composites exhibit an unprecedented temperature‐triggered water capture and release behavior originating from the thermo‐responsive phase transition of the PNIPAM component. This result sheds light on the development of stimuli‐responsive porous adsorbent materials for water capture and heat transfer applications under relatively mild operating conditions.     

Amphiphilic copolymer grafted "smart surface" enhanced by surface roughness

Polystyrene-poly(acrylic acid) (PS-PAA) block copolymers polymerized by atom transfer radical polymerization were covalently grafted to both smooth and microtextured surfaces. These amphiphilic copolymers were utilized to create smart surfaces, which can be responsive to external stimuli, e.g., pH values or organic solvent. Atom force microscopy, field emission scanning electron microscopy, and contact angle measurements were employed to investigate the physiochemical features of the copolymer brushes. It was found that the wettability of surfaces depended on both the PS/PAA molar ratio and external solvent properties. Hydrophilic surfaces were obtained after treatment with basic solution, as well as a polar solvent, such as ethanol. With treatment with acidic solution or toluene, the surface could be reversibly turned relatively hydrophobic, probably due to the rearrangement or reorganization of polymer chains. Moreover, rougher surfaces, which were microtextured by ZnO nanorods, were incorporated into this adaptive system to enhance the tunable range of wettability.     

Adsorption isotherms and dissipation of adsorbed poly(N-isopropylacrylamide) in its swelling and collapsed states

Poly(N-isopropylacrylamide) (PNIPAM) physisorbed on gold surfaces in aqueous solutions has been studied using a quartz crystal microbalance with dissipation monitoring (QCM-D). The adsorption isotherms of the polymer, that is, the adsorbed mass versus the concentration of PNIPAM in solution, show distinctly different behaviors at temperatures below and above a lower critical solution temperature (LCST). Below the LCST, PNIPAM forms a single compact layer in solutions with concentrations up to 100 ppm in weight; above the LCST, much thicker films of PNIPAM form in the same concentration range. Changes in the dissipation factor versus solvent concentration show a behavior similar to those in the isotherms. The difference in the adsorption behavior below and above the LCST can be qualitatively explained in terms of the conformation difference of the polymer in its swelling and collapsed states.     

Fabrication and characterization of hierarchical nanostructured smart adhesion surfaces

The mechanics of fibrillar adhesive surfaces of biological systems such as a Lotus leaf and a gecko are widely studied due to their unique surface properties. The Lotus leaf is a model for superhydrophobic surfaces, self-cleaning properties, and low adhesion. Gecko feet have high adhesion due to the high micro/nanofibrillar hierarchical structures. A nanostructured surface may exhibit low adhesion or high adhesion depending upon fibrillar density, and it presents the possibility of realizing eco-friendly surface structures with desirable adhesion. The current research, for the first time uses a patterning technique to fabricate smart adhesion surfaces: single- and two-level hierarchical synthetic adhesive structure surfaces with various fibrillar densities and diameters that allows the observation of either the Lotus or gecko adhesion effects. Contact angles of the fabricated structured samples were measured to characterize their wettability, and contamination experiments were performed to study for self-cleaning ability. A conventional and a glass ball attached to an atomic force microscope (AFM) tip were used to obtain the adhesive forces via force-distance curves to study scale effect. A further increase of the adhesive forces on the samples was achieved by applying an adhesive to the surfaces.     

Mechanically Strong Janus Poly(N-isopropylacrylamide)/Graphene Oxide Hydrogels as Thermo-responsive Soft Robots

Simple preparation of stimuli-responsive hydrogels with good mechanical properties and mild stimuliresponsiveness is essential for their applications as smart soft robots.Mechanically strong Janus poly(Nisopropylacrylamide)/graphene oxide (PNIPAM/GO) nanocomposite hydrogels with stimuli-responsive bending behaviors are prepared through a simple one-step method by using molds made of a Teflon plate and a glass plate.Residual oxygen in the air bubbles on the Teflon plate surface affects the polymerization and hence the cross-linking density,leading to the different swelling/deswelling rates of the two sides of the gels.Therefore,the hydrogels exhibit bending/unbending behaviors upon heating/cooling in water.The incorporation of GO nanosheets dramatically enhances the mechanical properties of Janus hydrogels.Meanwhile,the photo-responsive property of the GO nanosheets also imparts the hydrogels with remotecontrollable deformation under IR irradiation.The application of the Janus PNIPAM/GO hydrogels as thermo-responsive grippers is demonstrated.     

Current Rectification in Temperature‐Responsive Single Nanopores

Herein we demonstrate a fully abiotic smart single‐nanopore device that rectifies ionic current in response to the temperature. The temperature‐responsive nanopore ionic rectifier can be switched between a rectifying state below 34 °C and a non‐rectifying state above 38 °C actuated by the phase transition of the poly(N‐isopropylacrylamide) [PNIPAM] brushes. On the rectifying state, the rectifying efficiency can be enhanced by the dehydration of the attached PNIPAM brushes below the LCST. When the PNIPAM brushes have sufficiently collapsed, the nanopore switches to the non‐rectifying state. The concept of the temperature‐responsive current rectification in chemically‐modified nanopores paves a new way for controlling the preferential direction of the ion transport in nanofluidics by modulating the temperature, which has the potential to build novel nanomachines with smart fluidic communication functions for future lab‐on‐chip devices.     

Reversibly Switchable Double‐Responsive Block Copolymer Brushes

Poly(2‐hydroxyethyl methacrylate)‐block‐poly(N‐isopropylacrylamide) (PHEMA‐b‐PNIPAM) was prepared by controlled surface‐initiated ATRP from silicon substrates, and the resulting block copolymers were successfully converted into the corresponding PSEMA‐b‐PNIPAM by esterification of the hydroxy groups on the PHEMA block using excess of succinic anhydride. The PSEMA‐b‐PNIPAM block copolymer brushes respond to both temperature and pH stimuli. The double‐responsive behavior of the block copolymer brushes in solution was investigated by height imaging and force–distance measurements of AFM. The results clearly show the responsive behavior of the smart block copolymer brushes.

     

Thermal-Gated Polymer Electrolytes for Smart Zinc-Ion Batteries

Smart self-protection is essential for addressing safety issues of energy-storage devices. However, conventional strategies based on sol-gel transition electrolytes often suffer from unstable self-recovery performance. Herein, smart separators based on thermal-gated poly(N-isopropylacrylamide) (PNIPAM) hydrogel electrolytes were developed for rechargeable zinc-ion batteries (ZIBs). Such PNIPAM-based separators not only display a pore structure evolution from opened to closed states, but also exhibit a surface wettability transition from hydrophilic to hydrophobic behaviors when the temperature rises. This behavior can suppress the migration of electrolyte ions across the separators, realizing the self-protection of ZIBs at high temperatures. Furthermore, the thermal-gated behavior is highly reversible, even after multiple heating/cooling cycles, because of the reversibility of temperature-dependent structural evolution and hydrophilic/hydrophobic transition. This work will pave the way for designing thermal-responsive energy-storage devices with safe and controlled energy delivery.     

Temperature-responsive polymer/carbon nanotube hybrids: smart conductive nanocomposite films for modulating the bioelectrocatalysis of NADH

A temperature-sensitive polymer/carbon nanotube interface with switchable bioelectrocatalytic capability was fabricated by self-assembly of poly(N-isopropylacrylamide)-grafted multiwalled carbon nanotubes (MWNT-g-PNIPAm) onto the PNIPAm-modified substrate. Electron microscopy and electrochemical measurements revealed that these fairly thick (>6?μm) and highly porous nanocomposite films exhibited high conductivity and electrocatalytic activity. The morphological transitions in both the tethered PNIPAm chains on a substrate and those polymers wrapping around the MWNT surface resulted in the opening, closing, or tuning of its permeability, and simultaneously an electron-transfer process took place through the channels formed in the nanostructure in response to temperature change. By combining the good electron-transfer and electrochemical catalysis capabilities, the large surface area, and good biocompatibility of MWNTs with the responsive features of PNIPAm, reversible temperature-controlled bioelectrocatalysis of 1,4-dihydro-β-nicotinamide adenine dinucleotide with improved sensitivity has been demonstrated by cyclic voltammetry and electrochemical impedance spectroscopy measurements. The mechanism behind this approach was studied by Raman spectroscopy, in situ attenuated total reflection FTIR spectroscopy, and contact angle measurements. The results also suggested that the synergetic or cooperative interactions of PNIPAm with MWNTs gave rise not only to an increase in surface wettability, but also to the enhancement of the interfacial thermoresponsive behavior. This bioelectrocatalytic "smart" system has potential applications in the design of biosensors and biofuel cells with externally controlled activity. Furthermore, this concept might be proposed for biomimetics, interfacial engineering, bioelectronic devices, and so forth.     

Synthesis and self‐assembly of thermoresponsive block‐graft fluoropolymer as well as its tunable wettability surface

Thermo‐responsive block‐graft fluoropolymer is synthesized and investigated the self‐assembly morphology and the tunable wettability surface on cotton fabric by dip‐coating into the micelles with different temperatures. Well‐defined block‐graft copolymer is prepared by click chemistry with poly(hexafluorobutyl methacrylate)‐block‐poly(glycidyl methacrylate) (PHFBMA‐b‐PGMA) and homopolymer poly(N‐isopropylacrylate) with alkyne on main chain (Alkynyl‐PNIPAM) to synthesize final block‐graft polymer PHFBMA‐b‐(PGMA‐g‐PNIPAM). The thermo‐responsive behaviors of block‐graft polymer prove that the diameter for fluoropolymer micelle is about 50–70 nm with uniform sphere shape at room temperature and bigger and broader at 40 °C. The surface of cotton fabric processed in micelle solution at room temperature is smooth and has good hydrophobic property, while it has the hydrophilic property dipped in high temperature micelle solution. This work may give valuable guidance for fabricating a facile strategy to establish controllable wettability surfaces on different substrates, which is a promising candidate for the coating materials and industrial fields. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 992–1002     

Photochemically and electrochemically triggered Au nanoparticles "sponges"

Stimuli-triggered wettability of surfaces and controlled uptake and release of substrates by "smart" materials are essential for drug delivery and microfluidic control. A composite "sponge" consisting of bis-aniline-bridged Au nanoparticles (NPs), functionalized with photoisomerizable nitrospiropyran/nitromerocyanine that includes selective imprinted molecular recognition sites for N,N'-bis(3-sulfonatopropyl)-4,4'-bipyridinium (PVS) was electropolymerized on a Au electrode. The system is triggered by photonic and/or electrical signals to yield four different states exhibiting variable binding/release capacities for PVS and controlled wettability of the surface. The electrical/optical uptake and release of PVS to and from the Au NPs "sponge", respectively, is followed by CdSe/ZnS quantum dots, acting as an auxiliary photonic label.     

Poly(N‐isopropylacrylamide) Phase Diagrams: Fifty Years of Research

In 1968, Heskins and Guillet published the first systematic study of the phase diagram of poly(N‐isopropylacrylamide) (PNIPAM), at the time a “young polymer” first synthesized in 1956. Since then, PNIPAM became the leading member of the growing families of thermoresponsive polymers and of stimuli‐responsive, “smart” polymers in general. Its thermal response is unanimously attributed to its phase behavior. Yet, in spite of 50 years of research, a coherent quantitative picture remains elusive. In this Review we survey the reported phase diagrams, discuss the differences and comment on theoretical ideas regarding their possible origins. We aim to alert the PNIPAM community to open questions in this reputably mature domain.     

智能蜂窝状有序多孔薄膜：体系构建、响应性能及应用探索

蜂窝状有序多孔膜是一种典型的具有微、纳米尺寸的图案化高分子薄膜材料,在超疏水表面、光电材料、组织工程、生物医学、传感器等领域都具有良好的应用前景。表面形貌或性质具有可逆刺激响应特性的智能型多孔膜不仅拥有常规多孔膜的性能,而且还拥有独特的"开-关"功能,因此受到广泛关注。本文回顾了智能有序多孔膜近年的研究进展,重点对其体系构建、响应方式、机理、性能和相关应用进行了归纳与分析,评述了不同刺激响应多孔膜的特点及优劣势,探讨了智能多孔膜的优化设计及提高响应性能等问题,指出了目前面临的挑战,并展望了未来的发展方向。     

Synthesis and "schizophrenic" micellization of double hydrophilic AB4 miktoarm star and AB diblock copolymers: structure and kinetics of micellization

Poly(N-isopropylacrylamide) (PNIPAM)-based tetrafunctional atom transfer radical polymerization (ATRP) macroinitiator (1b) was synthesized via addition reaction of mono-amino-terminated PNIPAM (1a) with glycidol, followed by esterification with excess 2-bromoisobutyryl bromide. Well-defined double hydrophilic miktoarm AB4 star copolymer, PNIPAM-b-(PDEA)4, was then synthesized by polymerizing 2-(diethylamino)ethyl methacrylate (DEA) via ATRP in 2-propanol at 45 degrees C using 1b, where PDEA was poly(2-(diethylamino)ethyl methacrylate). For comparison, PNIPAM-b-PDEA linear diblock copolymer with comparable molecular weight and composition to that of PNIPAM-b-(PDEA)4 was prepared via reversible addition-fragmentation chain transfer (RAFT) polymerization. The pH- and thermoresponsive "schizophrenic" micellization behavior of the obtained PNIPAM65-b-(PDEA63)4 miktoarm star and PNIPAM70-b-PDEA260 linear diblock copolymers were investigated by 1H NMR and laser light scattering (LLS). In acidic solution and elevated temperatures, PNIPAM-core micelles were formed; whereas at slightly alkaline conditions and room temperature, structurally inverted PDEA-core micelles were formed. The size of the PDEA-core micelles of PNIPAM65-b-(PDEA63)4 is much smaller than that of PNIPAM70-b-PDEA260. Furthermore, the pH-induced micellization kinetics of the AB4 miktoarm star and AB block copolymers were investigated by the stopped-flow light scattering technique upon a pH jump from 4 to 10. Typical kinetic traces for the micellization of both types of copolymers can be well fitted with double-exponential functions, yielding a fast (tau1) and a slow (tau2) relaxation processes. tau1 for both copolymers decreased with increasing polymer concentration. tau2 was independent of polymer concentration for PNIPAM65-b-(PDEA63)4, whereas it decreased with increasing polymer concentration for PNIPAM70-b-PDEA260. The chain architectural effects on the micellization properties and the underlying mechanisms were discussed in detail.     

Photoresponsive surfaces with controllable wettability

In this paper, current progress in the area of photoresponsive surfaces with controllable wettability is reviewed, including mainly surface conversion between wetting and anti-wetting, prepared from inorganic oxides (e.g., titanium dioxide, zinc oxide, and tungsten oxide) or/and photoactive organic molecules (e.g., azobenzene, and spiropyran), and movement of liquid droplets driven by molecular machines (e.g., molecular shuttles such as rotaxanes). Photoresponsive controllable wettability originates from a transition between the bistable states of photoresponsive materials. The exploration of the basic mechanisms provides a basis for the construction of novel smart responsive surfaces.     

绿色环保特殊浸润性纺织品的前沿进展

介绍了仿生超疏表面的工作机制以及疏水整理液的发展, 系统综述了近10年来特殊浸润性在开拓多功能绿色纺织领域的研究进展, 讨论了双面超疏、 超疏/超亲、 图案化及可响应浸润性纺织品的制备技术及应用, 介绍近几年在纺织品疏水化功能改性方面取得的前瞻性工作, 包括自清洁防污、 油水分离、 机械耐久、 图案化、 自修复、 单向运输等, 特别是在智能响应、 电子可穿戴、 能源等新兴领域方面的应用. 最后, 对超疏水纺织功能材料目前所面临的挑战及未来发展的方向进行了展望.     

Poly(N-isopropylacrylamide)-based thermo-responsive surfaces with controllable cell adhesion

Poly(N-isopropylacrylamide) (PNIPAAm)-based thermo-responsive surfaces can switch their wettability (from wettable to non-wettable) and adhesion (from sticky to non-sticky) according to external temperature changes. These smart surfaces with switchable interfacial properties are playing increasingly important roles in a diverse range of biomedical applications; these controlling cell-adhesion behavior has shown great potential for tissue engineering and disease diagnostics. Herein we reviewed the recent progress of research on PNIPAAm-based thermo-responsive surfaces that can dynamically control cell adhesion behavior. The underlying response mechanisms and influencing factors for PNIPAAm-based surfaces to control cell adhesion are described first. Then, PNIPAAm-modified two-dimensional flat surfaces for cell-sheet engineering and PNIPAAm-modified three-dimensional nanostructured surfaces for diagnostics are summarized. We also provide a future perspective for the development of stimuli-responsive surfaces.     

Surfaces Decorated with Polymeric Nanocompartments for pH Reporting

Here we present a novel active surface that demonstrates pH responsiveness and can be used as a platform for designing ‘smart labels’. To generate our active surfaces, we immobilized polymer nanocompartments onto glass surfaces using thiol–ene chemistry. Prior to surface attachment, a pH responsive model dye was encapsulated within nanocompartments at two different pH values. We confirmed the attachment and distribution of dye‐loaded polymersomes and established the pH responsiveness of the active surface construct. The strategy presented here was carefully chosen to obtain small sized functional surfaces from commercially available materials that can be easily integrated into intelligent packaging systems. The ability to miniaturize such smart labels, while still being able to detect their response to the environment, is a crucial step towards developing active surfaces suitable for food packaging applications.