Polymer‐Based Stimuli‐Responsive Recyclable Catalytic Systems for Organic Synthesis

The introduction of stimuli‐responsive polymers into the study of organic catalysis leads to the generation of a new kind of polymer‐based stimuli‐responsive recyclable catalytic system. Owing to their reversible switching properties in response to external stimuli, these systems are capable of improving the mass transports of reactants/products in aqueous solution, modulating the chemical reaction rates, and switching the catalytic process on and off. Furthermore, their stimuli‐responsive properties facilitate the separation and recovery of the active catalysts from the reaction mixtures. As a fascinating approach of the controllable catalysis, these stimuli‐responsive catalytic systems including thermoresponsive, pH‐responsive, chemo‐mechano‐chemical, ionic strength‐responsive, and dual‐responsive, are reviewed in terms of their nanoreactors and mechanisms.     

Thermoreversible Morphology and Conductivity of a Conjugated Polymer Network Embedded in Block Copolymer Self‐Assemblies

Self‐assembly of block copolymers provides numerous opportunities to create functional materials, utilizing self‐assembled microdomains with a variety of morphology and periodic architectures as templates for functional nanofillers. Here new progress is reported toward the fabrication of thermally responsive and electrically conductive polymeric self‐assemblies made from a water‐soluble poly(thiophene) derivative with short poly(ethylene oxide) side chains and Pluronic L62 block copolymer solution in water. The structural and electrical properties of conjugated polymer‐embedded self‐assembled architectures are investigated by combining small‐angle neutron and X‐ray scattering, coarse‐grained molecular dynamics simulations, and impedance spectroscopy. The L62 solution template organizes the conjugated polymers by stably incorporating them into the hydrophilic domains thus inhibiting aggregation. The changing morphology of L62 during the micellar‐to‐lamellar phase transition defines the embedded conjugated polymer network. As a result, the conductivity is strongly coupled to the structural change of the templating L62 phase and exhibits thermally reversible behavior with no signs of quenching of the conductivity at high temperature. This study shows promise for enabling more flexibility in processing and utilizing water‐soluble conjugated polymers in aqueous solutions for self‐assembly based fabrication of stimuli‐responsive nanostructures and sensory materials.     

Benzoboroxole‐Functionalized Magnetic Core/Shell Microspheres for Highly Specific Enrichment of Glycoproteins under Physiological Conditions

Efficient enrichment of specific glycoproteins from complex biological samples is of great importance towards the discovery of disease biomarkers in biological systems. Recently, phenylboronic acid‐based functional materials have been widely used for enrichment of glycoproteins. However, such enrichment was mainly carried out under alkaline conditions, which is different to the status of glycoproteins in neutral physiological conditions and may cause some unpredictable degradation. In this study, on‐demand neutral enrichment of glycoproteins from crude biological samples is accomplished by utilizing the reversible interaction between the cis‐diols of glycoproteins and benzoboroxole‐functionalized magnetic composite microspheres (Fe₃O₄/PAA‐AOPB). The Fe₃O₄/PAA‐AOPB composite microspheres are deliberately designed and constructed with a high‐magnetic‐response magnetic supraparticle (MSP) core and a crosslinked poly(acrylic acid) (PAA) shell anchoring abundant benzoboroxole functional groups on the surface. These nanocomposites possessed many merits, such as large enrichment capacity (93.9 mg/g, protein/beads), low non‐specific adsorption, quick enrichment process (10 min) and magnetic separation speed (20 s), and high recovery efficiency. Furthermore, the as‐prepared Fe₃O₄/PAA‐AOPB microspheres display high selectivity to glycoproteins even in the E. coli lysate or fetal bovine serum, showing great potential in the identify of low‐abundance glycoproteins as biomarkers in real complex biological systems for clinical diagnoses.     

Diameter‐ and Metallicity‐Selective Enrichment of Single‐Walled Carbon Nanotubes Using Polymethacrylates with Pendant Aromatic Functional Groups

Current methods for the synthesis of single‐walled nanotubes (SWNTs) produce mixtures of semiconducting (sem‐) and metallic (met‐) nanotubes. Most approaches to the chemical separation of sem‐/met‐SWNTs are based on small neutral molecules or conjugated aromatic polymers, which characteristically have low separation/dispersion efficiencies or present difficulties in the postseparation removal of the polymer so that the resulting field‐effect transistors (FETs) have poor performance. In this Full Paper, the use of three polymethacrylates with different pendant aromatic functional groups to separate cobalt–molybdenum catalyst (CoMoCAT) SWNTs according to their metallicity and diameters is reported. UV/Vis/NIR spectroscopy indicates that poly(methyl‐methacrylate‐co‐fluorescein‐o‐acrylate) (PMMAFA) and poly(9‐anthracenylmethyl‐methacrylate) (PAMMA) preferentially disperse semiconducting SWNTs while poly(2‐naphthylmethacrylate) (PNMA) preferentially disperses metallic SWNTs, all in dimethylforamide (DMF). Photoluminescence excitation (PLE) spectroscopy indicates that all three polymers preferentially disperse smaller‐diameter SWNTs, particularly those of (6,5) chirality, in DMF. When chloroform is used instead of DMF, the larger‐diameter SWNTs (8,4) and (7,6) are instead selected by PNMA. The solvent effects suggest that diameter selectivity and change of polymer conformation is probably responsible. Change of the polymer fluorescence upon interaction with SWNTs indicates that metallicity selectivity presumably results from the photon‐induced dipole–dipole interaction between polymeric chromophore and SWNTs. Thin‐film FET devices using semiconductor‐enriched solution with PMMAFA have been successfully fabricated and the device performance confirms the sem‐SWNTs enrichment with a highly reproducible on/off ratio of about 10³.     

Thermo‐Switchable Materials Prepared Using the OEGMA‐Platform

We describe here the advantages of oligo(ethylene glycol)‐based (co)polymers for preparing thermoresponsive materials as diverse as polymer‐enzyme bio‐hybrids, injectable hydrogels, capsules for drug‐release, modified magnetic particles for in vivo utilization, cell‐culture substrates, antibacterial surfaces, or stationary phases for bioseparation. Oligo(ethylene glycol) methacrylates (OEGMAs) can be (co)polymerized using versatile and widely‐applicable methods of polymerization such as atom transfer radical polymerization (ATRP) of reversible addition‐fragmentation chain‐transfer (RAFT) polymerization. Thus, the molecular structure and therefore the stimuli‐responsive properties of these polymers can be precisely controlled. Moreover, these stimuli‐responsive macromolecules can be easily attached to–or directly grown from–organic, inorganic or biological materials. As a consequence, the OEGMA synthetic platform is today a popular option for materials design. The present research news summaries the progress of the last two years.     

Thermal‐Responsive Polymers for Enhancing Safety of Electrochemical Storage Devices

Thermal runway constitutes the most pressing safety issue in lithium‐ion batteries and supercapacitors of large‐scale and high‐power density due to risks of fire or explosion. However, traditional strategies for averting thermal runaway do not enable the charging–discharging rate to change according to temperature or the original performance to resume when the device is cooled to room temperature. To efficiently control thermal runaway, thermal‐responsive polymers provide a feasible and reversible strategy due to their ability to sense and subsequently act according to a predetermined sequence when triggered by heat. Herein, recent research progress on the use of thermal‐responsive polymers to enhance the thermal safety of electrochemical storage devices is reviewed. First, a brief discussion is provided on the methods of preventing thermal runaway in electrochemical storage devices. Subsequently, a short review is provided on the different types of thermal‐responsive polymers that can efficiently avoid thermal runaway, such as phase change polymers, polymers with sol–gel transitions, and polymers with positive temperature coefficients. The results represent the important development of thermal‐responsive polymers toward the prevention of thermal runaway in next‐generation smart electrochemical storage devices.     

Self‐Collapsing of Single Molecular Poly‐Propylene Oxide (PPO) in a 3D DNA Network

On the basis of DNA self‐assembly, a thermal responsive polymer polypropylene oxide (PPO) is evenly inserted into a rigid 3D DNA network for the study of single molecular self‐collapsing process. At low temperature, PPO is hydrophilic and dispersed uniformly in the network; when elevating temperature, PPO becomes hydrophobic but can only collapse on itself because of the fixation and separation of DNA rigid network. The process has been characterized by rheological test and Small Angle X‐Ray Scattering test. It is also demonstrated that this self‐collapsing process is reversible and it is believed that this strategy could provide a new tool to study the nucleation‐growing process of block copolymers.     

Proteolytically Degradable Photo‐Polymerized Hydrogels Made From PEG–Fibrinogen Adducts

We develop a biomaterial based on protein–polymer conjugates where poly(ethylene glycol) (PEG) polymer chains are covalently linked to multiple thiols on denatured fibrinogen. We hypothesize that conjugation of large diacrylate‐functionalized linear PEG chains to fibrinogen could govern the molecular architecture of the polymer network via a unique protein–polymer interaction. The hypothesis is explored using carefully designed shear rheometry and swelling experiments of the hydrogels and their precursor PEG/fibrinogen conjugate solutions. The physical properties of non‐cross‐linked and UV cross‐linked PEGylated fibrinogen having PEG molecular weights ranging from 10 to 20 kDa are specifically investigated. Attaching multiple hydrophilic, functionalized PEG chains to the denatured fibrinogen solubilizes the denatured protein and enables a rapid free‐radical polymerization cross‐linking reaction in the hydrogel precursor solution. As expected, the conjugated protein‐polymer macromolecular complexes act to mediate the interactions between radicals and unsaturated bonds during the free‐radical polymerization reaction, when compared to control PEG hydrogels. Accordingly, the cross‐linking kinetics and stiffness of the cross‐linked hydrogel are highly influenced by the protein–polymer conjugate architecture and molecular entanglements arising from hydrophobic/hydrophilic interactions and steric hindrances. The proteolytic degradation products of the protein–polymer conjugates proves to be were different from those of the non‐conjugated denatured protein degradation products, indicating that steric hindrances may alter the proteolytic susceptibility of the PEG–protein adduct. A more complete understanding of the molecular complexities associated with this type of protein‐polymer conjugation can help to identify the full potential of a biomaterial that combines the advantages of synthetic polymers and bioactive proteins.     

Solvent‐Induced Self‐Assembly Strategy to Synthesize Well‐Defined Hierarchically Porous Polymers

Porous polymers with well‐orchestrated nanomorphologies are useful in many fields, but high surface area, hierarchical structure, and ordered pores are difficult to be satisfied in one polymer simultaneously. Herein, a solvent‐induced self‐assembly strategy to synthesize hierarchical porous polymers with tunable morphology, mesoporous structure, and microporous pore wall is reported. The poly(ethylene oxide)‐b‐polystyrene (PEO‐b‐PS) diblock copolymer micelles are cross‐linked via Friedel–Crafts reaction, which is a new way to anchor micelles into porous polymers with well‐defined structure. Varying the polarity of the solvent has a dramatic effect upon the oleophobic/oleophylic interaction, and the self‐assembly structure of PEO‐b‐PS can be tailored from aggregated nanoparticles to hollow spheres even mesoporous bulk. A morphological phase diagram is accomplished to systematically evaluate the influence of the composition of PEO‐b‐PS and the mixed solvent component on the pore structure and morphology of products. The hypercrosslinked hollow polymer spheres provide a confined microenvironment for the in situ reduction of K₂PdCl₄ to ultrasmall Pd nanoparticles, which exhibit excellent catalytic performance in solvent‐free catalytic oxidation of hydrocarbons and alcohols.     

Stimuli‐Responsive,Shape‐Transforming Nanostructured Particles

Development of particles that change shape in response to external stimuli has been a long‐thought goal for producing bioinspired, smart materials. Herein, the temperature‐driven transformation of the shape and morphology of polymer particles composed of polystyrene‐b‐poly(4‐vinylpyridine) (PS‐b‐P4VP) block copolymers (BCPs) and temperature‐responsive poly(N‐isopropylacrylamide) (PNIPAM) surfactants is reported. PNIPAM acts as a temperature‐responsive surfactant with two important roles. First, PNIPAM stabilizes oil‐in‐water droplets as a P4VP‐selective surfactant, creating a nearly neutral interface between the PS and P4VP domains together with cetyltrimethylammonium bromide, a PS‐selective surfactant, to form anisotropic PS‐b‐P4VP particles (i.e., convex lenses and ellipsoids). More importantly, the temperature‐directed positioning of PNIPAM depending on its solubility determines the overall particle shape. Ellipsoidal particles are produced above the critical temperature, whereas convex lens‐shaped particles are obtained below the critical temperature. Interestingly, given that the temperature at which particle shape change occurs depends solely on the lower critical solution temperature (LCST) of the polymer surfactants, facile tuning of the transition temperature is realized by employing other PNIPAM derivatives with different LCSTs. Furthermore, reversible transformations between different shapes of PS‐b‐P4VP particles are successfully demonstrated using a solvent‐adsorption annealing with chloroform, suggesting great promise of these particles for sensing, smart coating, and drug delivery applications.     

The Continuous Exudation of Micro‐Meniscus Capsules by Polymer Perspiration

Perspiration is a common phenomenon in many natural creatures in order to maintain their steady state. Here, through the facile use of a linear polymer of polymethylmethacrylate (PMMA) and an incompatible polymer of cross‐linked polydimethylsiloxane (PDMS) under an organic‐solvent atmosphere, the polymer system undergoes an analogous perspiration phenomenon as a result of the macroscopic phase separation between the two polymers. The resulting “sweat,” consisting of PMMA and solvent, are solidified into extraordinary micro‐meniscus capsules on the PDMS surface, which does not rely on the shape and topography of the PDMS substrates. Perspiration continues until the sweat of PMMA is exhausted, enabling the production of recoverable microstructures without complicated manufacturing processes. A thorough assessment of the influencing factors for the perspiration reveals that the formation of micro‐meniscus capsules follows a process of protrusion, ripening, and solidification. The micro‐meniscus capsules are primarily evaluated for applications in light scattering, in organic‐vapor sensing, and in bio‐macromolecular immobilization.     

Tough Self‐Healing Elastomers by Molecular Enforced Integration of Covalent and Reversible Networks

Self‐healing polymers crosslinked by solely reversible bonds are intrinsically weaker than common covalently crosslinked networks. Introducing covalent crosslinks into a reversible network would improve mechanical strength. It is challenging, however, to apply this concept to “dry” elastomers, largely because reversible crosslinks such as hydrogen bonds are often polar motifs, whereas covalent crosslinks are nonpolar motifs. These two types of bonds are intrinsically immiscible without cosolvents. Here, we design and fabricate a hybrid polymer network by crosslinking randomly branched polymers carrying motifs that can form both reversible hydrogen bonds and permanent covalent crosslinks. The randomly branched polymer links such two types of bonds and forces them to mix on the molecular level without cosolvents. This enables a hybrid “dry” elastomer that is very tough with fracture energy 13500 Jm^?2 comparable to that of natural rubber. Moreover, the elastomer can self‐heal at room temperature with a recovered tensile strength 4 MPa, which is 30% of its original value, yet comparable to the pristine strength of existing self‐healing polymers. The concept of forcing covalent and reversible bonds to mix at molecular scale to create a homogenous network is quite general and should enable development of tough, self‐healing polymers of practical usage.     

Dynamic Coordination of Eu–Iminodiacetate to Control Fluorochromic Response of Polymer Hydrogels to Multistimuli

New fluorochromic materials that reversibly change their emission properties in response to their environment are of interest for the development of sensors and light‐emitting materials. A new design of Eu‐containing polymer hydrogels showing fast self‐healing and tunable fluorochromic properties in response to five different stimuli, including pH, temperature, metal ions, sonication, and force, is reported. The polymer hydrogels are fabricated using Eu–iminodiacetate (IDA) coordination in a hydrophilic poly(N,N‐dimethylacrylamide) matrix. Dynamic metal–ligand coordination allows reversible formation and disruption of hydrogel networks under various stimuli which makes hydrogels self‐healable and injectable. Such hydrogels show interesting switchable ON/OFF luminescence along with the sol–gel transition through the reversible formation and dissociation of Eu–IDA complexes upon various stimuli. It is demonstrated that Eu‐containing hydrogels display fast and reversible mechanochromic response as well in hydrogels having interpenetrating polymer network. Those multistimuli responsive fluorochromic hydrogels illustrate a new pathway to make smart optical materials, particularly for biological sensors where multistimuli response is required.     

Molecular transport characteristics of poly (ethylene‐co‐vinyl acetate) membranes in the presence of normal alkanes

Solvent transport into poly (ethylene‐co‐vinyl acetate) membranes exposed to n‐alkanes has been studied in the temperature interval of 30–60°C. Pure and cross‐linked membranes were prepared. Membranes with different loading of cross‐linking agent were also prepared. It was found that for all liquids, the equilibrium penetrant uptake was influenced by the introduction of cross links. The mechanism of transport has been found to deviate from the regular Fickian behaviour. Transport parameters such as diffusion coefficient, sorption constant and permeability coefficient have been calculated. The influence of temperature on transport was analysed. Transport parameters and activation parameters for the process of diffusion have been calculated. The transport coefficients and the activation parameters showed a dependence on cross‐link density. The Van't Hoff's relationship was used to compute the entropy change. The values of polymer–solvent interaction parameters have been used to calculate the molar mass between cross links of the network polymer. The phantom and affine models were used to analyse the deformation of the networks during swelling. A correlation between theoretical and experimental results was also done. Copyright © 2007 John Wiley & Sons, Ltd.     

A Highly Reversible Long‐Life Li–CO2 Battery with a RuP2‐Based Catalytic Cathode

Rechargeable Li–CO₂ batteries have attracted worldwide attention due to the capability of CO₂ capture and superhigh energy density. However, they still suffer from poor cycling performance and huge overpotential. Thus, it is essential to explore highly efficient catalysts to improve the electrochemical performance of Li–CO₂ batteries. Here, phytic acid (PA)‐cross‐linked ruthenium complexes and melamine are used as precursors to design and synthesize RuP₂ nanoparticles highly dispersed on N, P dual‐doped carbon films (RuP₂‐NPCFs), and the obtained RuP₂‐NPCF is further applied as the catalytic cathode for Li–CO₂ batteries. RuP₂ nanoparticles that are uniformly deposited on the surface of NPCF show enhanced catalytic activity to decompose Li₂CO₃ at low charge overpotential. In addition, the NPCF its with porous structure in RuP₂‐NPCF provides superior electrical conductivity, high electrochemical stability, and enough ion/electron and space for the reversible reaction in Li–CO₂ batteries. Hence, the RuP₂‐NPCF cathode delivers a superior reversible discharge capacity of 11951 mAh g^?1, and achieves excellent cyclability for more than 200 cycles with low overpotentials (<1.3 V) at the fixed capacity of 1000 mAh g^?1. This work paves a new way to design more effective catalysts for Li–CO₂ batteries.     

Ordered‐Assembly Conductive Nanowires Array with Tunable Polymeric Structure for Specific Organic Vapor Detection

An artificial organic vapor sensor based on a finite number of 1D nanowires arrays can provide a strategy to allow classification and identification of different analytes with high efficiency, but fabricating a 1D nanowires array is challenging. Here, a coaxial Ag/polymer nanowires array is prepared as an organic vapor sensor with specific recognition, using a strategy combining superwettability‐based nanofabrication and polymeric swelling‐induced resistance change. Such organic vapor sensor containing commercial polymers can successfully classify and identify various organic vapors with good separation efficiency. An Ag/polymer nanowires array with synthetic polyethersulfone polymers is also fabricated, through molecular structure modification of the polymers, to distinguish the similar organic vapors of methanol and ethanol. Theoretical simulation results demonstrate introduction of specific molecular interaction between the designed polymers and organic vapors can improve the specific recognition performance of the sensors.     

An All‐Integrated Anode via Interlinked Chemical Bonding between Double‐Shelled–Yolk‐Structured Silicon and Binder for Lithium‐Ion Batteries

The concept of an all‐integrated design with multifunctionalization is widely employed in optoelectronic devices, sensors, resonator systems, and microfluidic devices, resulting in benefits for many ongoing research projects. Here, maintaining structural/electrode stability against large volume change by means of an all‐integrated design is realized for silicon anodes. An all‐integrated silicon anode is achieved via multicomponent interlinking among carbon@void@silica@silicon (CVSS) nanospheres and cross‐linked carboxymethyl cellulose and citric acid polymer binder (c‐CMC‐CA). Due to the additional protection from the silica layer, CVSS is superior to the carbon@void@silicon (CVS) electrode in terms of long‐term cyclability. The as‐prepared all‐integrated CVSS electrode exhibits high mechanical strength, which can be ascribed to the high adhesivity and ductility of c‐CMC‐CA binder and the strong binding energy between CVSS and c‐CMC‐CA, as calculated based on density functional theory (DFT). This electrode exhibits a high reversible capacity of 1640 mA h g^?1 after 100 cycles at a current density of 1 A g^?1, high rate performance, and long‐term cycling stability with 84.6% capacity retention after 1000 cycles at 5 A g^?1.     

Antibody‐Free Hydrogel with the Synergistic Effect of Cell Imprinting and Boronate Affinity: Toward the Selective Capture and Release of Undamaged Circulating Tumor Cells

The selective and highly efficient capture of circulating tumor cells (CTCs) from blood and their subsequent release without damage are very important for the early diagnosis of tumors and for understanding the mechanism of metastasis. Herein, a universal strategy is proposed for the fabrication of an antibody‐free hydrogel that has a synergistic effect by featuring microinterfaces obtained by cell imprinting and molecular recognition conferred by boronate affinity. With this artificial antibody, highly efficient capture of human hepatocarcinoma SMMC‐7721 cells is achieved: as many as 90.3 ± 1.4% (n = 3) cells are captured when 1 × 10⁵ SMMC‐7721 cells are incubated on a 4.5 cm² hydrogel, and 99% of these captured cells are subsequently released without any loss of proliferation ability. In the presence of 1000 times as many nontarget cells, namely, leukaemia Jurkat cells, the SMMC‐7721 cells can be captured with an enrichment factor as high as 13.5 ± 3.2 (n = 3), demonstrating the superior selectivity of the artificial antibody for the capture of the targeted CTCs. Most importantly, the SMMC‐7721 cells can be successfully captured even when spiked into whole blood, indicating the great promise of this approach for the further molecular characterization of CTCs.     

Interphase Induced Dynamic Self‐Stiffening in Graphene‐Based Polydimethylsiloxane Nanocomposites

The ability to rearrange microstructures and self‐stiffen in response to dynamic external mechanical stimuli is critical for biological tissues to adapt to the environment. While for most synthetic materials, subjecting to repeated mechanical stress lower than their yield point would lead to structural failure. Here, it is reported that the graphene‐based polydimethylsiloxane (PDMS) nanocomposite, a chemically and physically cross‐linked system, exhibits an increase in the storage modulus under low‐frequency, low‐amplitude dynamic compressive loading. Cross‐linking density statistics and molecular dynamics calculations show that the dynamic self‐stiffening could be attributed to the increase in physical cross‐linking density, resulted from the re‐alignment and re‐orientation of polymer chains along the surface of nano‐fillers that constitute an interphase. Consequently, the interfacial interaction between PDMS‐nano‐fillers and the mobility of polymer chain, which depend on the degree of chemical cross‐linking and temperature, are important factors defining the observed performance of self‐stiffening. The understanding of the dynamic self‐stiffening mechanism lays the ground for the future development of adaptive structural materials and bio‐compatible, load‐bearing materials for tissue engineering applications.     

Composite Microgels Created by Complexation between Polyvinyl Alcohol and Graphene Oxide in Compressed Double‐Emulsion Drops

Microgels, microparticles made of hydrogels, show fast diffusion kinetics and high reconfigurability while maintaining the advantages of hydrogels, being useful for various applications. Here, presented is a new microfluidic strategy for producing polymer‐graphene oxide (GO) composite microgels without chemical cues or a temperature swing for gelation. As a main component of microgels, polymers that are able to form hydrogen bonds, such as polyvinyl alcohol (PVA), are used. In the mixture of PVA and GO, GO is tethered by PVA through hydrogen bonding. When the mixture is rapidly concentrated in the core of double‐emulsion drops by osmotic‐pressure‐driven water pumping, PVA‐tethered GO sheets form a nematic phase with a planar alignment. In addition, the GO sheets are linked by additional hydrogen bonds, leading to a sol–gel transition. Therefore, the PVA–GO composite remains undissolved when it is directly exposed to water by oil‐shell rupture. These composite microgels can be also produced using poly(ethylene oxide) or poly(acrylic acid), instead of PVA. In addition, the microgels can be functionalized by incorporating other polymers in the presence of the hydrogel‐forming polymers. It is shown that the multicomponent microgels made from a mixture of polyacrylamide, PVA, and GO show an excellent adsorption capacity for impurities.