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The low emission efficiency of clusteroluminogens restricts their practical applications in the fields of sensors and biological imaging. In this work, the clusteroluminescence of ordered/disordered polypeptides was observed, and the photoluminescence (PL) intensity of polypeptides can be modulated by the chirality of amino acid residues. Polyglutamates with different chiral compositions were synthesized, and the racemic polypeptides exhibited a significantly higher PL intensity than the enantiopure ones. This emission originates from the n-π* transition between CâO groups of polypeptides and is enhanced by clusterization of polypeptides. CD and Fourier transform infrared spectra demonstrated that the enantiopure and racemic polypeptides form α-helix and random coil structures, respectively. The disordered polypeptides can form more chain entanglements and interchain interactions because of their high flexibility, leading to more clusterizations and stronger PL intensity. The rigidity of ordered helical structures restrains the chain entanglements, and the formation of intrachain hydrogen bonds between amide groups of the backbone impairs the interchain interaction between polypeptides, resulting in lower PL intensity. The PL intensity of the polypeptides can also be manipulated by the addition of urea or trifluoroacetic acid. Our study not only elucidates the chirality/order-based structure-property relationship of clusteroluminescence in peptide-based polymers but also offers implications for the rational design of fluorescent peptides/proteins.
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Peptídeos , Proteínas , Estrutura Secundária de Proteína , Peptídeos/química , AminoácidosRESUMO
Most shape memory polymers apply glass transition or crystallization of domains to fix temporary shapes and shape recovery is induced by heating, which hinders their application under heat-intolerant conditions. Moreover, the permanent shapes of polymers normally cannot be altered arbitrarily after fabrication. Herein, we present a novel shape memory hydrogel with a remodelable permanent shape and programmable cold-induced shape recovery behavior. Poly(acrylic acid) (PAA) hydrogel is prepared in the presence of diethylenetriamine (DETA) and subsequently treated with calcium acetate (Ca(Ac)2). The charge-assisted hydrogen bonding between PAA and DETA imparts the hydrogel with remodelability, while the heat-induced hydrophobic aggregation of polymer chains and acetate groups results in shape fixation by heating and shape recovery by cooling. Afterwards, programmable deformable devices are obtained by assembling hydrogel blocks with different concentrations of Ca(Ac)2. This design strategy promotes the development of shape memory polymers with diverse potential applications.
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The phase separation behavior of biomacromolecules plays a key role in the fields of biology and medicine. In this work, we gain a deep insight into how the primary and secondary structures govern and regulate the phase separation behavior of polypeptides. To this end, we synthesized a series of polypeptides with tailorable hydroxyl-containing side chains. The secondary structure of polypeptides can be modulated by the local chemical environment and content of side chains. Interestingly, these polypeptides with different helical contents exhibited upper critical solution temperature behavior with marked differences in the cloud point temperature (Tcp) and the width of hysteresis. The phase transition temperature is highly relevant to the content of secondary structure and interchain interactions of polypeptides. The aggregation/deaggregation and the transition of secondary structure are completely reversible during heating-cooling cycles. Much to our surprise, the recovery rate of the α-helical structure governs the width of hysteresis. This work establishes the structure-property relationship between the secondary structure and phase separation behavior of the polypeptide and delivers new insight into the rational design of peptide-based materials with tailor-made phase separation behavior.
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Ácido Glutâmico , Peptídeos , Peptídeos/química , Estrutura Secundária de Proteína , Temperatura , Temperatura de TransiçãoRESUMO
The high-temperature durability of SiBCN ceramics is significantly influenced by the boron concentration and synthesis methods. Although single-source synthetic routes allow one to obtain homogeneous ceramics at the atomic level, the content of the boron element therein is limited by borane (BH3). In this study, the synthesis of carborane-substituted polyborosilazanes was performed via a simple one-pot reaction of polysilazanes with alkyne bonds on the main chain and decaborododecahydrodiacetonitrile complexes with different molar ratios. This enabled one to vary the boron content from â¼0 to 40.00 wt %. The ceramic yields were in the range of 50.92-90.81 wt %. Independently of the borane concentration, SiBCN ceramics started to crystallize at 1200 °C, and B4C appeared as a new crystalline phase with increasing boron content. The introduction of boron inhibited the crystallization of Si3N4 and increased the crystallization temperature of SiC. The presence of the B4C phase improved both thermal stability and functional properties such as neutron-shielding characteristics of the ceramics. Therefore, this research opens up new prospects for the design of novel polyborosilanzes with great application potential.
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This review summarizes recent progress in the synergistic design strategy for thermoresponsive polymers possessing an upper critical solution temperature (UCST) in aqueous systems. To achieve precise control of the responsive behavior of the UCST polymers, their molecular design can benefit from a synergistic effect of hydrogen bonding with other interactions or modification of the chemical structures. The combination of UCST behavior with other stimuli-responsive properties of the polymers may yield new functional materials with potential applications such as sensors, actuators, and controlled release devices. The advances in this area provide insight or inspiration into the understanding and design of functional UCST polymers for a wide range of applications.
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Polímeros , Água , Temperatura , Polímeros/química , Água/química , Ligação de HidrogênioRESUMO
Polymer-protein hybrids have been extensively used in biomedical fields. Polymers with upper critical solution temperature (UCST) behaviors can form a hydrated coacervate phase below the cloud point (Tcp), providing themselves the opportunity to directly capture hydrophilic proteins and form hybrids in aqueous solutions. However, it is always a challenge to obtain a UCST polymer that could aggregate at a high temperature at a relatively low concentration and also efficiently bind with proteins. In this work, a UCST polymer reactive with proteins was designed, and its temperature responsiveness and protein-capture ability were investigated in detail. The polymer was synthesized by the reversible addition-fragmentation chain transfer (RAFT) polymerization of acrylamide (AAm) and N-acryloxysuccinimide (NAS). Interestingly, taking advantage of the partial hydrolysis of NAS into acrylic acid (AAc), the obtained P(AAm-co-NAS-co-AAc) polymer exhibited an excellent UCST behavior and possessed good protein-capture ability. It showed a relatively higher Tcp (81 °C) at a lower concentration (0.1 wt %) and quickly formed polymer-protein hybrids with high protein loading and without losing protein bioactivity, and both the polymer and polymer-protein nanoparticles showed good cytocompatibility. All the findings are attributed to the unique structure of the polymer, which provided not only the strong and stable hydrogen bonds but also the quick and mild reactivity. The work offers an easy and mild strategy for polymer-protein hybridization directly in aqueous solutions, which may find applications in biomedical fields.
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Polímeros , Água , Acrilamida , Ligação de Hidrogênio , Polimerização , Polímeros/química , Temperatura , Água/químicaRESUMO
The synthesis of thermo-responsive polymers from non-responsive and water-soluble monomers has great practical advantages but significant challenges. Herein, the authors report a novel aqueous copolymerization strategy to prepare polymers with tunable upper critical solution temperature (UCST) or lower critical solution temperature (LCST) from non-responsive monomers. Acrylic acid (AAc), N-vinylpyrrolidone (NVP), and acrylamide (AAm) are copolymerized in water, yielding copolymers with UCST behavior. Interestingly, by simply replacing AAm with its methylated homologue, dimethyl acrylamide (DMA), the thermo-responsiveness of the copolymers is converted into LCST-type. The cloud points of the copolymers can be tuned rationally with their monomer ratios and the condition of the solvent. The UCST property of the poly(AAc-NVP-AAm) comes from the AAc-AAm and AAc-NVP hydrogen-bonds, while the LCST property of poly(AAc-NVP-DMA) originates from the hydrophobic aggregation of AAc-NVP complex and DMA, as indicated by temperature-dependent 1 H NMR and dynamic light scattering.
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Hidrogênio , Polímeros , Polimerização , Temperatura , ÁguaRESUMO
A self-healing hydrogel is prepared by crosslinking acrylamide with a host-guest macro-crosslinker assembled from poly(ß-cyclodextrin) nanogel and azobenzeneacrylamide. The photoisomerizable azobenzene moiety can change its binding affinity with ß-cyclodextrin, therefore the crosslinking density and rheology property of the hydrogel can be tuned with light stimulus. The hydrogel can repair its wound autonomously through the dynamic host-guest interaction. In addition, the wounded hydrogel will lose its ability of self-healing when exposed to ultraviolet light, and the self-healing behavior can be recovered upon the irradiation of visible light. The utilizing of host-guest macro-crosslinking approach manifests the as-prepared hydrogel reversible and light-switchable self-healing property, which would broaden the potential applications of self-healing polymers.
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Reagentes de Ligações Cruzadas/química , Hidrogel de Polietilenoglicol-Dimetacrilato/química , Hidrogel de Polietilenoglicol-Dimetacrilato/efeitos da radiação , Luz , Acrilamida/química , Hidrogel de Polietilenoglicol-Dimetacrilato/síntese química , Substâncias Macromoleculares/química , Estrutura MolecularRESUMO
In this study, mixed suspensions of large hard polystyrene microspheres and small soft poly(N-isopropylacrylamide) microgels are used as model systems to investigate the static and viscoelastic properties of suspensions which go through liquid to gel transitions. The microgels cause short-range attraction between microspheres through the bridging and depletion mechanism whose strength can be tuned by the microgel concentration. Rheological measurements are performed on suspensions with the volume fraction (Φ) of microspheres ranging from 0.02 to 0.15, and the transitions from liquid-like to solid-like behaviors triggered by the concentration of microgels are carefully identified. Two gel lines due to bridging attraction under unsaturated conditions are obtained. Ultra-small angle neutron scattering is used to probe the thermodynamic properties of suspensions approaching the liquid-solid transition boundaries. Baxter's sticky hard-sphere model is used to extract the effective inter-microsphere interaction introduced by the small soft microgels. It is found that the strength of attraction (characterized by a single stickiness parameter τ) on two gel lines formed by bridging is very close to the theoretical value for the spinodal line in the τ-Φ phase diagram predicted by Baxter's model. This indicates that the nature of the gel state may have the same thermodynamic origins, independent of the detailed mechanism of the short-range attraction. The relationship between the rheological criterion for the liquid-solid transition and the thermodynamic criterion for the equilibrium-nonequilibrium transition is also discussed.
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Gelation and glass transition in a mixed suspension of polystyrene (PS) microsphere and poly(N-isopropylacrylamide) (PNIPAM) microgel were studied as a function of the total colloid volume fraction and mixing ratio of these two components. The PNIPAM microgel, which is adsorbable on the PS microsphere surface, can induce bridging or stabilizing effect between microspheres depending on whether the volume fraction of microgel (ΦMG) is smaller or larger than the saturated adsorption concentration (Φ*MG) for a given volume fraction of the microsphere (ΦMS). Φ*MG is in a linear relationship with ΦMS, and the value of ΦMG/Φ*MG can be taken as an approximate measure of surface coverage. A state diagram of gelation and glass transition is constructed with the short-ranged attractive interaction, resulting from the well-defined bridging bonding. Keeping ΦMG/Φ*MG = 0.20 and increasing ΦMS from 0.25 to 0.55, the mixed suspension transforms from a bridging gel into an attractive glass; moreover, while keeping ΦMS = 0.45 and increasing ΦMG/Φ*MG from 0.20 to 1.2, the mixed suspension changes from a bridging gel into an attractive glass, and then to a repulsive glass. The bridging effect and the cage effect can be distinguished by the yielding behaviors in rheological measurements. In the nonlinear dynamic rheological experiments, one-step yielding, corresponding to the disconnecting of bridge network, is observed in the bridging gel, and one-step yielding, corresponding to the breaking of cage, is observed in the repulsive glass. However, a two-step yielding behavior is found in the bridging-induced attractive glass, which is attributed to the bridging effect of microgels and the caging effect of the dense environment.
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Bioadhesives have garnered widespread attention in the biomedical field, for wound healing and tissue sealing. However, challenges exist due to the inferior performance of bioadhesives, including weak adhesion, poor biocompatibility, or lack of biodegradability. In this work, we demonstrate the fabrication of hydrogel adhesive based on polypeptides composed of lysine and glutamic acid. The cation-π interaction between the ammonium cations and phenyl groups endows the hydrogel with strong cohesion, and the hydrophobicity of the phenyl group significantly enhances the interaction between polypeptides and the substrate interface, leading to excellent adhesive performance. The equivalent molar ratio of ammonium cations and the phenyl group is beneficial for the enhancement of adhesiveness. Furthermore, we discover that the polypeptides with an α-helix exhibit better adhesiveness than the polypeptides with a ß-sheet because the α-helical structure can increase the exposure of the side group on the polypeptide surface, which further strengthens the interaction between polypeptides and the substrate. Besides, this synthetic polypeptide adhesive can seal the tissue quickly and remain intact in water. This adhesive holds significant promise for application in wound healing and tissue sealing, and this study provides insight into the development of more peptide-based adhesives.
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Adesivos , Compostos de Amônio , Adesivos/química , Peptídeos/química , Hidrogéis/química , CátionsRESUMO
Cephalopods evolve the acetylcholine-gated actuation control function of their skin muscles, which enables their dynamic/static multimode display capacities for achieving perfectly spatial control over the colors/patterns on every inch of skin. Reproduction of artificial analogs that exhibit similar multimodal display is essential to reach advanced information three-dimensional (3D) encoding with higher security than the classic 2D-encoding strategy, but remains underdeveloped. The core difficulty is how to replicate such chemical-gated actuation control function into artificial soft actuating systems. Herein, this work proposes to develop azobenzene-functionalized poly(acrylamide) (PAAm) hydrogel systems, whose upper critical solution temperature (UCST) type actuation responsiveness can be intelligently programmed or even gated by the addition of hydrophilic α-cyclodextrin (α-CD) molecules for reversible association with pendant azobenzene moieties via supramolecular host-guest interactions. By employing such α-CD-gated hydrogel actuator as an analogue of cephalopods' skin muscle, biomimetic mechanically modulated multicolor fluorescent display systems are designed, which demonstrate a conceptually new α-CD-gated "thermal stimulation-hydrogel actuation-fluorescence output" display mechanism. Consequently, high-security 3D-encoding information carriers with an unprecedented combination of single-input multiple-output, dynamic/static dual-mode and spatially controlled display capacities are achieved. This bioinspired strategy brings functional-integrated features for artificial display systems and opens previously unidentified avenues for information security.
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The rheological property of mixed suspensions of silica colloid and hyperbranched polyethyleneimine (hPEI) was studied as functions of particle volume fraction, ratio of polymer to particle, and pH value. A mechanism of liquid-gel-liquid transition for this mixed system was proposed based on the amount and the conformation of polyelectrolyte bridges which were able to self-arrange with solution environments. The hPEI, which is adsorptive to the surface of silica colloid, can induce bridging or stabilizing effect between particles depending on whether the concentration of hPEI (Cp) is smaller or larger than the equilibrium adsorbed amount (Cp*) for a given volume fraction of particles. In dilute colloid suspensions, the Cp* can be determined by dynamic light scattering as the correlation function returns back to a narrow distributing single relaxation with increasing Cp. In concentrated colloid suspensions, the Cp* can be determined by rheological measurement as gel-liquid transition occurs with increasing Cp. The Cp* is an important concentration ratio of polymer to particle denoting the transition of irreversible and reversible bridging. For mixed suspensions at equilibrium adsorbed state (Cp ≈ Cp*), the adsorption-desorption of polymer bridges on the particles can reversibly take place, and shear thickening is observed under a steady shear flow as a result of rapid extension of bridges when the relaxation time scale of extension is shorter than that of desorption.
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The linear and nonlinear rheological measurements were utilized to study the mechanical response of concentrated mixtures of colloidal particles with opposite charges. The particle volume fraction (Φ) spans the region from low volume fraction (Φ = 0.18) gel to high volume fraction (Φ = 0.53) glass. In the linear viscoelastic region, the storage moduli G' exhibits deferent Φ dependence at low and high Φ's. It follows a power law relationship as G' ~ Φ(6.2±0.2) for Φ < 0.46, and follows an exponential relationship as G' ~ exp[(13.8 ± 0.6)Φ] for Φ ≥ 0.46. The difference can be taken as a distinction between a colloidal gel and an attractive glass (or dense gel) for the present system. The loss moduli G" is almost frequency independent within the whole experimental frequency range (10(-1)-10(2) rad∕s) for colloidal gel, and G" exhibits a weak minimum for attractive glass. In the nonlinear large amplitude rheological measurement, samples with Φ < 0.46 show one-step yielding, and samples with Φ ≥ 0.46 exhibit two-step yielding which is in agreement with numerous experiments in attractive glassy systems. The first yielding is due to the breaking of short range interactions which bond the interconnected clusters or local clusters, while the second yielding is attributed to the breaking of long range interaction, normally the caging forming or glass forming interactions. The qualitative distinction between attractive glass and gel in terms of their yielding behavior is consistent with the linear rheological results. The particle-particle interactions were modulated by salt concentration. It was found that, when the attraction interaction is enhanced, both yielding points in attractive glass shift to higher strain amplitude and the gap between the two yielding points become more separated.
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Poly(N-acryloyl glycinamide) (PNAGA) can form high-strength hydrogen bonds (H-bonds) through the dual amide motifs in the side chain, allowing the polymer to exhibit gelation behavior and an upper critical solution temperature (UCST) property. These features make PNAGA a candidate platform for biomedical devices. However, most applications focused on PNAGA hydrogels, while few focused on PNAGA nanoparticles. Improving the UCST tunability and bio-interfacial adhesion of the PNAGA nanoparticles may expand their applications in biomedical fields. To address the issues, we established a reactive H-bond-type P(NAGA-co-NAS) copolymer via reversible addition-fragmentation chain transfer polymerization of NAGA and N-acryloxysuccinimide (NAS) monomers. The UCST behaviors and the bio-interfacial adhesion toward the proteins and cells along with the potential application of the copolymer nanoparticles were investigated in detail. Taking advantage of the enhanced H-bonding and reactivity, the copolymer exhibited a tunable UCST in a broad temperature range, showing thermo-reversible transition between nanoparticles (PNPs) and soluble chains; the PNPs efficiently bonded proteins into nano-biohybrids while keeping the secondary structure of the protein, and more importantly, they also exhibited good adhesion ability to the cell membrane and significantly inhibited cell-specific propagation. These features suggest broad prospects for the P(NAGA-co-NAS) nanoparticles in the fields of biosensors, protein delivery, cell surface decoration, and cell-specific function regulation.
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Hidrogéis , Nanopartículas , Hidrogéis/química , Temperatura , Polímeros/química , Nanopartículas/químicaRESUMO
Schizophrenic copolymers are one type of the popular smart polymers that show invertible colloidal structures in response to temperature stimulus. However, the lack of principles to predict the phase transition temperature of a schizophrenic copolymer from its corresponding parent thermo-responsive polymers limits their development. Additionally, studies on their applications remain scarce. Herein, a series of schizophrenic copolymers were synthesized by polymerization of a RAFT-made polymer precursor poly(acrylamide-co-N-acryloxysuccinimide-co-acrylic acid) (P(AAm-co-NAS-co-AAc)) with the mixture of N-isopropylmethacrylamide (NIPAm) and acrylamide (AAm) in varying molar ratios. In aqueous solution, the block P(AAm-co-NAS-co-AAc) and the block poly(NIPAm-co-AAm) exhibited upper and lower critical solution temperature (UCST and LCST) behavior, respectively. The schizophrenic copolymers featured either UCST-LCST, LCST-UCST, or only LCST thermo-responsive transition. A preliminary correlation of phase transition between the schizophrenic copolymers and their parent polymers was summarized. Furthermore, the co-assembly of the schizophrenic copolymers and proteins were conducted and the kinetics of protein loading and protein activity were investigated, which showed that the schizophrenic copolymers were efficient platforms for protein co-assembly with ultra-high protein loading while preserving the protein bioactivities. Additionally, all the materials were non-toxic towards NIH 3T3 and MCF-7 cells. This work offers the prospects of the schizophrenic polymers in soft colloidal and assembly systems, particularly in guiding the design of new materials and their use in biomedical applications.
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Polímeros , Esquizofrenia , Humanos , Polímeros/química , Proteínas , Água , Temperatura , Acrilamidas/químicaRESUMO
The energy crisis is one of the most critical and urgent problems in modern society; thus, harvesting energy from ubiquitous low-grade heat energy with thermoelectric (TE) materials has become an available strategy in sustainable development. Recently, emerging ionic TE materials have been widely used to harvest low-grade heat energy, owing to their excellent performance in high ionic Seebeck coefficient, low thermal conductivity, and mechanical flexibility. However, the instability of ionic conductive materials in the underwater environment seriously suppresses underwater energy-harvesting, resulting in a waste of underwater low-grade heat energy. Herein, we developed a water-resistant TE ionogel (TEIG) with excellent long-term underwater stability utilizing a hydrophobic structure. Due to the hydrophobic polymer network and hydrophobic ionic liquid (IL), the TEIG exhibits high hydrophobicity and antiswelling capacity, which meets the requirement of environment stability for underwater thermoelectric application. Furthermore, the water resistance endows the TEIG with great thermoelectric performances in the underwater environment, including satisfactory ionic Seebeck coefficient, outstanding durability, and superior salt tolerance. Therefore, this investigation provides a promising strategy to design water-resistant TE materials, enabling a remarkable potential in harvesting low-grade heat energy under water.
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Polyborosilazanes with controllable B/N ratio were synthesized using high-boron-content m-carborane, dichloromethylsilane, and hexamethydisilazane. After high-temperature pyrolysis, Si-B-C-N quaternary ceramics with SiC and B4C as the main phases were obtained. The B/N ratio in the precursors corresponded to the change in the feeding ratio of carborane and dichloromethylsilane. The effects of boron content and B/N ratio on the ceramic precursors and microphase structure in Si-B-C-N quaternary ceramics were explored in detail through a series of analytical characterization methods. A high boron content results in a significant increase in the ceramic yield (up to 71 wt%) of polyborosilazanes, and at the same time, the B/N molar ratio was regulated from 28.4:1 to 1.62:1. The appearance of the B4C structure in the Si-B-C-N quaternary ceramics through the regulation of the B/N ratio, has rarely been reported.
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Thermoresponsive hydrogel actuators have attracted tremendous interest due to their promising applications in artificial muscles, soft robotics, and flexible electronics. However, most of these materials are based on polymers with lower critical solution temperature (LCST), while those from upper critical solution temperature (UCST) are rare. Herein, we report a multiple-responsive UCST hydrogel actuator based on the complex of poly(acrylic acid) (PAAc) and poly(acrylamide) (PAAm). By applying a heterogeneous photopolymerization, a bilayer hydrogel was obtained, including a layer of the interpenetrating network (IPN) of PAAm/PAAc and a layer of a single network of PAAm. When cooled down below the UCST, the PAAm/PAAc layer contracted due to the hydrogen bonding of the two polymers while the PAAm layer stays in swelling state, driving the hydrogel to curl. By adjusting the composition of the two layers, the amplitude of actuation behavior could be regulated. By creating patterned IPN domains with photomasks, the hydrogel could deform into complex two-dimensional (2D) and three-dimensional (3D) shapes. An active motion was realized in both water and oil bath, thanks to the internal water exchange between the two layers. Interestingly, the hydrogel actuator is also responsive to urea and salts (Na2SO4, NaCl, NaSCN), due to that the strength of the hydrogen bonds in the IPN changes with the additives. Overall, the current study realized an anisotropic UCST transition by introducing asymmetrically distributed polymer-polymer hydrogen bonds, which would inspire new inventions of intelligent materials.