Upper Critical Solution Temperature Research Articles

Thermal Responsiveness of 1,2,4-Triazolium-Based Poly(ionic liquid)s and Their Applications in Dye Extraction and Smart Switch.

Triazoliums are a family of five-membered heterocyclic cations that contain three nitrogen and two carbon atoms. In contrast to the widely studied imidazolium cations, triazoliums are less explored. In terms of the chemical structure, triazolium replaces a carbon atom in the imidazolium cation ring with an electron-withdrawing nitrogen atom, which makes the triazolium more polarized. Among the many physical properties, the thermal responsiveness of triazoliums is of particular interest to us but has been rarely investigated. In this contribution, we prepared a series of 1,2,4-triazolium-based poly(ionic liquid)s (PILs) with varying alkyl substituents and counteranions and studied their thermal-responsive behavior. We found that 1,2,4-triazolim-based PILs with a polymeric backbone structure similar to that of polyimidazoliums exhibited opposite thermal phase transition processes in solvents. For example, methyl-substituted 1,2,4-triazolium-based PILs exhibited an upper-critical-solution-temperature (UCST)-type phase transition in methanol when the counterion was I- and a lower-critical-solution-temperature (LCST)-type phase transition in acetone when the counterion was PF6 -. The thermal responsiveness was reversible and concentration-dependent. Interestingly, the thermal response of 1,2,4-triazolim-based PILs could be retained in the organogel form, which was applied in the pretreatment of anion-containing organic waste liquids and temperature-controlled "smart" switches.

Construction and Performance Study of an Injectable Dual-Network Hydrogel Dressing with Inherent Drainage Function.

With the widespread utilization of moist wound dressings, the extended healing time and increased risk of wound infection caused by excessively moist environments have garnered significant attention. The development of hydrogel dressings that can effectively control the wound moisture level and promote healing is very important. Inspired by the pore-opening perspiration effect of the skin, this study constructed an injectable dual-network hydrogel, CMCS-OSA/AG/MXene, by the composition of a dynamic covalent network of carboxymethyl chitosan and oxidized sodium alginate based on the Schiff base and hydrogen bond network of the thermosensitive low-melting-point agar with the advantage of the upper critical solution temperature (UCST) effect. Under near-infrared (NIR) light stimulation, the CMCS-OSA/AG/MXene hydrogel shows characteristics conducive to rapid removal of wound exudate while maintaining an appropriate moist environment for the wound and excellent antibacterial effects with its photothermal responses. The excellent conductivity of the hydrogel can also promote cell proliferation under external electrical stimulation (ES). Further validation through animal experiments on a full-thickness skin defect model demonstrates the excellent capability of CMCS-OSA/AG/MXene in accelerating wound healing. This work provides an innovative approach to the development of injectable hydrogel dressing materials with inherent drainage functionality and shows a new avenue to wound moisture control and wound healing promotion.

Robust, Switchable and Printable Underwater Adhesives Based on a Temperature‐Deactivated Design

AbstractConventional adhesives generally suffer from diminished adhesion in aqueous environments, posing significant challenges for their application in wet and submerged conditions. While extensive research efforts are directed toward enhancing the interfacial bonding, cohesive strength, and durability of adhesives in such environments, most existing underwater adhesives remain static and irreversible. This limitation hinders their reusability and often results in undesirable residues. Addressing the challenge of achieving strong underwater adhesion with on‐demand detachment remains crucial. This study introduces the development of temperature‐responsive underwater adhesives that demonstrate outstanding bonding strength, reversibility, and durability. Through the strategic integration of interfacial bonding, reinforced cross‐linking networks, dynamic hydrogen bonds, and upper critical solution temperature (UCST)‐driven phase transitions, one of the few temperature‐deactivated adhesives is created. The optimized adhesive is distinguished by its performance to achieve underwater adhesion strengths exceeding 1.4 MPa, nearly 100% switching efficiency and residue‐free adherend under mild thermal cycling. Beyond the template‐assisted fabrication of adhesive patches, 3D printable adhesives are achieved with programmable architectures via direct ink‐writing. This work highlights the development of temperature‐deactivated underwater adhesives activated by UCST‐type phase transitions, not only boosting adhesion strengths and switching efficiencies across various water conditions but also broadening their applicability with user‐defined and application‐specific functions.

Exploring LCST- and UCST-like Behavior of Branched Molecules Bearing Repeat Units of Elastin-like Peptides as Side Components.

Elastin-like peptides (ELPs) exhibit lower critical solution temperature (LCST)-type behavior, being soluble at low temperatures and insoluble at high temperatures. While the properties of linear, long-chain ELPs are well-studied, short-chain ELPs, especially those with branched architectures, have been less explored. Herein, to obtain further insights into multimeric short ELPs, we investigated the temperature-responsive properties of branched molecules composed of a repeating pentapeptide unit of short ELPs, Phe-Pro-Gly-Val-Gly, as side components and oligo(Glu) as a backbone structure. In turbidimetry experiments, the branched ELPs showed LCST-like behavior similar to conventional ELPs and upper critical solution temperature (UCST)-like behavior, which are rarely observed in ELPs. In addition, the morphological aspects and mechanisms underlying the temperature-responsiveness were investigated. We observed that spherical aggregates formed, and the branched ELPs underwent structural changes through the self-assembly process. This study demonstrates the unique temperature-responsiveness of branched short ELPs, providing new insights into the future development and use of ELPs with tailored properties.

Bidirectional Temperature‐Responsive Thermochromic Hydrogels With Adjustable Light Transmission Interval for Smart Windows

AbstractThermochromic smart windows have been widely developed for solar regulation to save building energy. However, most current smart windows still exhibit a single responsiveness to a specific temperature, which is not conducive to daytime energy saving or nighttime privacy protection. Herein, a low‐temperature response is achieved by pre‐initiation of the monomer acrylamide (AAm) and acrylic acid (AA) in the synthesis of P(AAm‐co‐AA). Then, N‐isopropyl acrylamide and AAm are introduced into P(AAm‐co‐AA) to form a pre‐polymerized precursor solution. The liquid precursor solution can be encapsulated within two quartz glasses and synthesized in situ to prepare smart windows, which exhibit a high visible light transmittance of 84.4%, excellent solar modulation of 69.5%, and bidirectional temperature responsiveness (cold and hot). In addition, the upper critical solution temperature and the lower critical solution temperature of the hydrogel and the light transmission interval between the two temperatures can be flexibly adjusted to adapt to different climates and individual user needs. The designed smart window maintains a high light transmission within the human body's comfort temperature range. The bidirectional temperature response window achieves the dual functions of energy saving and privacy protection, making it an ideal smart window candidate with good prospects for practical applications.

Innovative glycochenodeoxycholic Acid-Acrylamide Nanopolymer carriers: Regulating upper critical solution temperature on neurorehabilitation

Neurorehabilitation focuses on restoring function in patients with central and peripheral nervous system disorders, yet effective therapeutic options remain scarce. This study introduces a novel nanocopolymer, CaCO3-PAAm-GDCA, synthesized through reversible addition-fragmentation chain transfer polymerization of glycodeoxycholic acid, acrylamide, and CaCO3. This nanocopolymer exhibits a sharp and reversible insoluble-to-soluble transition in water at a temperature related to its upper critical solution temperature (UCST), which can be finely adjusted to a practical range around 37 °C, suitable for biomedical applications. The addition of β-cyclodextrin (β-CD) modulates this transition temperature by forming host-guest complexes, further enhancing the copolymer’s adaptability. When loaded with compound 1, the resulting CaCO3-PAAm-GDCA@1 significantly promoted the proliferation of damaged neuronal HT22 cells and inhibited ferroptosis through the modulation of Nrf2 and GPX4 pathways. This study provides a strong foundation for the development of neuroprotective drugs, highlighting the potential of tailored nanocopolymers in advanced neurorehabilitation therapies.

Exosome Loaded Protein Hydrogel for Enhanced Gelation Kinetics and Wound Healing.

Exosomes are being increasingly explored in biomedical research for wound healing applications. Exosomes can improve blood circulation and endocrine signaling, resulting in enhanced cell regeneration. However, exosome treatments suffer from low retention and bioavailability of exosomes at the wound site. Hydrogels are a popular tool for drug delivery due to their ability to encapsulate drugs in their network and allow for targeted release. Recently, hydrogels have proven to be an effective method to provide increased rates of wound healing when combined with exosomes that can be applied noninvasively. We have designed a series of single-domain protein-based hydrogels capable of physical cross-linking and upper critical solution temperature (UCST) behavior. Hydrogel variant Q5, previously designed with improved UCST behavior and a significantly enhanced gelation rate, is selected as a candidate for encapsulation release of exosomes dubbed Q5Exo. Q5Exo exhibits low critical gelation times and significant decreases in wound healing times in a diabetic mouse wound model showing promise as an exosome-based drug delivery tool and for future hybrid, noninvasive protein-exosome design.

Alteration of the upper critical solution temperature (UCST) behavior of the nonionic polymer poly(N-acryloyl-nipecotamide) by its terminal group

Influences of the terminal group of non-ionic polymer with upper critical solution temperature on cloud points (CPs) has been one of curious research topics, however, detailed investigation has not been conducted so far. This study investigates the effect of the terminal group of poly(N-acryloyl-nipecotamide)s (PNANAms) on their CPs in aqueous solution. PNANAms with different molecular weights (Mn) ranging from 4,100 to 34,300 and different terminal end groups were successfully synthesized via reversible addition–fragmentation chain transfer (RAFT) polymerization. The temperature-dependent optical transmittance of aqueous solutions of the PNANAms revealed that their CP was influenced by their terminal group, in addition to their Mn and polymer concentration. PNANAms with low Mn (Mn ≥ 7,500) and a hydrophobic (dodecyl) terminal group exhibited poor solubility, whereas PNANAms with a moderate Mn (Mn ≤ 10,200) and hydrophilic (maleimide or carboxylic) terminal groups were readily soluble in aqueous solution. However, PNANAms with a high Mn (Mn = 34,300) were hardly soluble in aqueous solution. The poor solubility of such PNANAms suggests that strong inter- and intramolecular hydrogen bonds were formed among the polymer chains, increasing their CP. PNANAm with a low Mn (Mn = 4,100) and the hydrophobic terminal and that with a moderate Mn (13,200 ≤ Mn ≤ 18,200) and hydrophilic terminal groups exhibited CPs in aqueous solution. The CP of PNANAms with carboxylic terminal groups was also influenced by the solution pH owing to the deprotonation of these groups. The size of polymeric aggregates was directly observed using phase-contrast microscopy, and the temperature-dependent aggregation and dispersion of the polymers were described in terms of the inter- and intramolecular hydrogen bonds formed among PNANAm chains. Finally, a cell viability assay was conducted to explore the possibility of the applications of PNANAm in the fields of biomaterials and regenerative therapy.

Novel amphiphilic multistimuli-responsive diblock copolymers and comparison between their self-assembly and controlled release behavior

Here, we reported three novel multistimuli-responsive copolymers prepared by reversible addition-fragmentation chain transfer (RAFT) polymerization. They have the same hydrophilic block and different hydrophobic block which contain azobenzene or ferrocene or both, thus leads to different stimuli-response. Poly[2-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)ethyl methacrylate]28-b-P[(E)-2-((2-(methacryloyloxy)ethyl)(methyl)amino)ethyl 4-(phenyldiazenyl) benzoate]38 (PMEO4MA28-b-P(Azo-N-MA)38) was temperature/pH/light-responsive with a lower critical solution temperature (LCST)-type cloud point (CP) of 68 °C and a critical pH of 3.5 in water, upper critical solution temperature (UCST) was shown in alcohols, and its light-response was confirmed by UV/vis absorption spectra by alternating UV/blue light radiation; Poly[2-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)ethyl methacrylate]28-b-P[2-((2-ferrocenyl ethyl ester) (methyl)amino)ethyl methacrylate]40 (PMEO4MA28-b-P(Fc-N-MA)40) was temperature/pH/redox-responsive and has a critical pH of 2.5 in water and an UCST-type CP in nPrOH, its redox-response was confirmed by UV/vis absorption spectra by addition of FeCl3 and VC. PMEO4MA28-b-[P(Azo-N-MA)–co-P(Fc-N-MA)]40 was temperature/pH/light/redox-responsive and has a critical pH of 3.0 in water and an UCST-type CP in nPrOH. The three copolymers can self-assemble into spherical, vesicular and spherical micelles in water, respectively. Evolution process of morphologies of micelles under different stimuli was then studied. Finally, by wrapping of Nile Red (NR), their controlled release behavior was compared and discussed. The three copolymers have simple synthesis steps, diverse and sensitive response, and have good application prospects in the field of self-assembly and drug release.

Ultrasound assisted upper critical solution temperature type switchable deep eutectic solvent based liquid-liquid microextraction for the determination of triazole in water

BackgroundThe use of pesticides to protect crops has long been an important measure to provide healthy and safe agricultural products, but excess pesticides flow into fields and rivers, causing environmental pollution. Earlier methods utilizing organic solvent liquid-liquid microextraction for pesticide residue detection were not environmentally friendly. Therefore, it is significant to find a greener and more convenient detection method to determine pesticide residues. ResultsA new method was established to detect three triazole fungicides (TFs), including myclobutanil, epoxiconazole and tebuconazole, in environmental water samples. And the determination was conducted using a high-performance liquid chromatography with the ultraviolet detector (HPLC-UV). The switchable deep eutectic solvent (SDES) can be reversibly switched between hydrophilic and hydrophobic states through temperature modulation. Additionally, the method exhibited excellent linearity for all target analytes within the concentration range of 10–2000 μg L−1, with satisfactory R2 values (≥0.9975). The limits of detection (LODs) ranged from 2.3 to 2.6 μg L−1, and the limits of quantification (LOQs) ranged from 7.8 to 8.7 μg L−1. The accuracy of the method was assessed through intra-day and inter-day precision tests, yielding relative standard deviations (RSDs) in the ranges of 2.8%–6.7% and 2.2%–7.5%, respectively. Density functional theory (DFT) results indicated that hydrogen bonding is a significant factor affecting the binding of DES with triazoles. Three different green assessment tools were used to prove that the SDES-HLLME method had good greenness and broad applicability. SignificanceThis is a homogeneous liquid-liquid microextraction (HLLME) method based on the upper critical solution temperature (UCST) type switchable deep eutectic solvent program, which can complete the extraction within a few minutes without dispersant. In terms of pesticide detection, the analytical method is simple and more conducive to environmental protection.

NIR-triggered and Thermoresponsive Core-shell nanoparticles for synergistic anticancer therapy

Recent advancements in cancer treatment have underscored the inadequacy of conventional monotherapies in addressing complex malignant tumors. Consequently, there is a growing interest in synergistic therapies capable of overcoming the limitations of monotherapies, leading to more personalized and effective approaches. Among these, the combination of photothermal therapy (PTT) and chemotherapy has emerged as a promising avenue for tumor management. In this study, we present a novel approach utilizing thermoresponsive mesoporous silica nanoparticles (MSN) as a delivery system for the chemotherapeutic drug doxorubicin. By incorporating photothermal agent copper sulfide (CuS) nanoparticles into the MSN, the resulting composite material exhibits potent photothermal properties. Furthermore, the integration of an upper critical solution temperature (UCST) polymer within the silica outer layer serves as a “gatekeeper”, enabling precise control over drug release kinetics. This innovative nanomaterial effectively merges thermoresponsive behavior with PTT, thereby minimizing the collateral damage associated with traditional chemotherapy on healthy tissues. Moreover, in both in vitro studies using mouse breast carcinoma cells (4 T1) and in vivo experiments utilizing a 4 T1 tumor-bearing mouse model, our nanomaterials demonstrated synergistic effects, enhancing the anti-tumor efficacy of combined PTT and chemotherapy. With its remarkable photothermal conversion efficiency, robust stability, and biocompatibility, the UCST-responsive nanoplatform holds immense potential for clinical applications.

Differential Effects of Sequence-Local versus Nonlocal Charge Patterns on Phase Separation and Conformational Dimensions of Polyampholytes as Model Intrinsically Disordered Proteins.

Conformational properties of intrinsically disordered proteins (IDPs) are governed by a sequence-ensemble relationship. To differentiate the impact of sequence-local versus sequence-nonlocal features of an IDP's charge pattern on its conformational dimensions and its phase-separation propensity, the charge "blockiness" κ and the nonlocality-weighted sequence charge decoration (SCD) parameters are compared for their correlations with isolated-chain radii of gyration (Rgs) and upper critical solution temperatures (UCSTs) of polyampholytes modeled by random phase approximation, field-theoretic simulation, and coarse-grained molecular dynamics. SCD is superior to κ in predicting Rg because SCD accounts for effects of contact order, i.e., nonlocality, on dimensions of isolated chains. In contrast, κ and SCD are comparably good, though nonideal, predictors of UCST because frequencies of interchain contacts in the multiple-chain condensed phase are less sensitive to sequence positions than frequencies of intrachain contacts of an isolated chain, as reflected by κ correlating better with condensed-phase interaction energy than SCD.

Asymmetrical surface-modified polyester/cotton fabrics for temperature-adaptive moisture and thermal management of human body

Personal moisture and thermal management fabrics that can regulate skin temperature are highly desired for improving human comfort and performance. Here, a symmetric surface modified polyester/cotton fabric (Janus T/C fabric) exhibiting exceptional temperature-adaptive personal moisture and thermal managements was developed. This was achieved by integrating two distinct temperature-sensitive hydrophobic/hydrophilic transition materials through single-sided spray coating technique and in-situ ultraviolet-induced free radical polymerization in 60/40 polyester/cotton blend fabric (T/C fabric, composed of 60 % cotton and 40 % polyester fibers). 2-(2-methoxyethoxy) ethoxyethyl-methacrylate (MEO2MA) was utilized to create lower critical solution temperature (LCST) polymer, while N, N-dimethyl (methacryloylethyl) ammonium propane sulfonate (DMAPS) formed an upper critical solution temperature (UCST) polymer on T/C fabric surface. Fabric’s surface demonstrated a reversible transition in hydrophobicity/hydrophilicity in response to environmental temperature changes. The distinct hydrophobic and hydrophilic surfaces configuration resulted in a remarkable wettability gradient, significantly increased moisture permeability to 6792.5 g/m2·24 h—an increase of 1132.1 g/m2·24 h compared to the 60/40 T/C fabric at 40 °C. Moreover, the Janus T/C fabric provided practical temperature adaptation benefits, offering a cooling effect of approximately 1.2 °C in hot environments and a warming effect of approximately 1.0 °C in cold conditions. These thermal responsive properties make the asymmetric surface-modified polyester/cotton fabric an ideal choice for personalized moisture and thermal management, ensuring optimal comfort across varying temperatures.

Hydrogen Bonding-Driven Self-Coacervation of Nonionic Homopolymers for Stimuli-Triggered Therapeutic Release.

Inspired by the unique functionalities of biomolecular membraneless organelles (MLOs) formed via liquid-liquid phase separation (LLPS) of intrinsically disordered proteins (IDPs) and nucleic acids, a great deal of effort has been devoted to devising phase-separated artificial subcellular dynamic compartments. These endeavors aim to unravel the molecular mechanism underlying the formation and intracellular delivery of susceptible macromolecular therapeutics. We report herein pyroglutamic acid (PGA)-based well-defined homopolymers featuring stimuli-tunable reversible self-coacervation ability. The polymer exhibits an upper critical solution temperature (UCST) transition in aqueous solutions and has the propensity to undergo cooling-induced LLPS, producing micrometer-sized liquid droplets. This phase separation phenomenon could be modulated by various factors, including polymer concentration, chain length, solution pH, and types and concentrations of different additives. These micrometer droplets are thermally reversible and encapsulate a wide variety of cargoes, including small hydrophobic fluorescent molecules, hydrophilic anticancer drugs, and fluorophore-labeled macromolecular proteins (bovine serum albumin and lysozyme). The payloads were released by exploiting the thermo/pH-mediated disassembly behavior of the coacervates, preserving the bioactivity of the sensitive therapeutics. This environmentally responsive, simple yet versatile artificial MLO model system will provide insights into the biomolecular nonionic condensates and pave the way for the de novo design of dynamic biomolecule depots.

Atomistic insights into the reentrant phase-transitions in polyuracil and polylysine mixtures.

The phase separation of protein and RNA mixtures underpins the assembly and regulation of numerous membraneless organelles in cells. The ubiquity of protein-RNA condensates in cellular regulatory processes is in part due to their sensitivity to RNA concentration, which affects their physical properties and stability. Recent experiments with poly-cationic peptide-RNA mixtures have revealed closed-loop phase diagrams featuring lower and upper critical solution temperatures. These diagrams indicate reentrant phase transitions shaped by biomolecular interactions and entropic forces such as solvent and ion reorganization. We employed atomistic simulations to study mixtures with various RNA-polylysine stoichiometries and temperatures to elucidate the microscopic driving forces behind reentrant phase transitions in protein-RNA mixtures. Our findings reveal an intricate interplay between hydration, ion condensation, and specific RNA-polylysine hydrogen bonding, resulting in distinct stoichiometry-dependent phase equilibria governing stabilities and structures of the condensate phase. Our simulations show that reentrant transitions are accompanied by desolvation around the phosphate groups of RNA, with increased contacts between phosphate and lysine side chains. In RNA-rich systems at lower temperatures, RNA molecules can form an extensive pi-stacking and hydrogen bond network, leading to percolation. In protein-rich systems, no such percolation-induced transitions are observed. Furthermore, we assessed the performance of three prominent water force fields-Optimal Point Charge (OPC), TIP4P-2005, and TIP4P-D-in capturing reentrant phase transitions. OPC provided a superior balance of interactions, enabling effective capture of reentrant transitions and accurate characterization of changes in solvent reorganization. This study offers atomistic insights into the nature of reentrant phase transitions using simple model peptide and nucleotide mixtures. We believe that our results are broadly applicable to larger classes of peptide-RNA mixtures exhibiting reentrant phase transitions.

Strong and Thermo-Switchable Gel Adhesion Based on UCST-Type Phase Transition in Deep Eutectic Solvent.

It remains a great challenge to achieve strong and reversible hydrogel adhesion. Hydrogel adhesives also suffer from poor environmental stability due to dehydration. To overcome these problems, here reversible adhesive gels are designed using a new switching mechanism and new solvent. For the first time, the study observes UCST (upper critical solution temperature)-type thermosensitive behaviors of poly(benzyl acrylate) (PBnA) polymer and gel in menthol:thymol deep eutectic solvents (DESs). The temperature-induced phase transition allows adjusting cohesive force, and hence adhesion strength of PBnA gels by temperature. To further improve the mechanical and adhesion properties, a peptide crosslinker is used to allow energy dissipation when deforming. The resulting eutectogel exhibits thermal reversible adhesion with a high switching ratio of 14.0. The adhesion strength at attachment state reaches 0.627MPa, which is much higher than most reversible adhesive hydrogels reported before. The low vapor pressure of DES endows the gel excellent environmental stability. More importantly, the gel can be repeatedly switched between attachment and detachment states. The strong and reversible gel adhesive is successfully used to design soft gripper for the transport of heavy cargos and climbing robot capable of moving on vertical and inverted surface in a manner similar to gecko.

Multistimuli responsive hydrogels with shape fix/memory capability fabricated from gold nanorod‐conjugated amino acid‐based vinyl polymer networks

AbstractFabricating robust shape‐memory hydrogels that respond to multiple external stimuli is an important challenge in facilitating gel technology for versatile applications. In this study, we report a simple approach for constructing thermo‐, redox‐, and photo‐responsive hydrogels with high mechanical strength and shape fix/memory capability. Upper critical solution temperature (UCST)‐type amino acid‐based hydrogels were facilely prepared by radical copolymerization of N‐acryloyl glycinamide (NAGAm) with cystine‐derived divinyl acrylamides (ionic cystine [NAC] or nonionic cystine‐methyl ester [NACMe]) units at different monomer concentrations (1/2 M). These hydrogels were transparent and exhibited good mechanical strength (tensile strength of 0.3–0.4 MPa and breaking elongation of 400%–700%). All hydrogels showed UCST‐type swelling‐shrinking behaviors based on thermo‐driven reversible hydrogen bonds among the PNAGAm units, and thus could be fixed into variety of shapes and recovered to the original shape by temperature manipulation. The cystine‐based crosslinkers having SS bonds served as efficient redox‐sensitive and gold‐nanorod‐(AuNR)‐adsorbing moieties; thus, AuNR could be conjugated stably and evenly into the PNAGAm/NAC hydrogel. Moreover, upon light‐irradiation, the AuNR‐conjugated hybrid hydrogel exhibited shape‐memory behavior owing to the photothermal effect of the AuNRs. These multiresponsive/functional hydrogels composed of amino acid units have considerable potential for various applications in the fields of soft actuators and biomedicines.

Biomimicking TRPM8: A Conversely Temperature-Dependent Nonionic Retrorse Nanochannel for Ion Flow Control.

Ion channels play a crucial role in the transmembrane transport and signal transmission of substances. In animals, transient receptor potential vanilloid 1 (TRPV1) and transient receptor potential melastatin 8 (TRPM8) serve as temperature-sensing units in sensory nerve endings. TRPV1 allows cells to sense heat, while TRPM8 enables them to detect cold, both serving to protect living organisms from harmful substances and environments. However, almost all studies on artificial nanochannels have mainly focused on TRPV1-like "forward nanochannels" thus far, which are incapable of "backward" responding to heat. So, we constructed an innovational TRPM8-inspired "retrorse nanochannel" through internal modification of poly(acrylamide-co-acrylonitrile) [P(AAm-co-AN)] with an upper critical solution temperature (UCST). Our results demonstrated that the internally modified nanochannels exhibited rapid, stable, and reversible heat-closing capability and converse temperature dependence within the typical temperature range of 25-40 °C. The biomimetic ion channel can effectively function as a facile, precise, and reversible thermal gate for controlling the transport of ions and substances. It also offers a promising microscopic technology for managing thermal effects on the substance, fluid, energy, and even signal delivery.

UCST-Type Thermoresponsive Sol-Gel Transition Triblock Copolymer Containing Zwitterionic Polymer Blocks.

Thermoresponsive sol-gel transition polymers are of significant interest because of their fascinating biomedical applications, including as drug reservoirs for drug delivery systems and scaffolds for tissue engineering. Although extensive research has been conducted on lower critical solution temperature (LCST)-type sol-gel transition polymers, there have been few reports on upper critical solution temperature (UCST)-type sol-gel transition polymers. In this study, we designed an ABA-type triblock copolymer composed of a poly(ethylene glycol) (PEG) block and zwitterionic polymer blocks that exhibit UCST-type thermoresponsive phase transitions. A sulfobetaine (SB) monomer with both ammonium and sulfonate (-SO3) groups in its side chain or a sulfabetaine (SaB) monomer with both ammonium and sulfate (-OSO3) groups in its side chain was polymerized from both ends of the PEG block via reversible addition-fragmentation chain-transfer (RAFT) polymerization to obtain PSB-PEG-PSB and PSaB-PEG-PSaB triblock copolymers, respectively. Although an aqueous solution containing the PSB-PEG-PSB triblock copolymer showed an increase in viscosity upon cooling, it did not undergo a sol-to-gel transition. In contrast, a sol-to-gel transition was observed when a phosphate-buffered saline containing PSaB-PEG-PSaB was cooled from 80 °C to 25 °C. The PSaB blocks with -OSO3 groups exhibited a stronger dipole-dipole interaction than conventional SB with -SO3 groups, leading to intermolecular association and the formation of a gel network composed of PSaB assemblies bridged with PEG. The fascinating UCST-type thermoresponsive sol-gel transition properties of the PSaB-PEG-PSaB triblock copolymer suggest that it can provide a useful platform for designing smart biomaterials, such as drug delivery reservoirs and cell culture scaffolds.

Cephalopod-Inspired Chemical-Gated Hydrogel Actuation Systems for Information 3D-Encoding Display.

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.