Colorless, Transparent, and High-Performance Polyurethane with Intrinsic Ultraviolet Resistance and Its Anti-UV Mechanism.

Polyurethane (PU) is a widely used polymer material that will age under prolonged exposure to ultraviolet (UV) light, shortening the service life. Several methods have been used to prepare the anti-UV PU, including adding nonreactive anti-UV additives, functional fillers, and biological antioxidant molecules. However, the nonreactive anti-UV additives may migrate during long-term use, the functional fillers may damage the mechanical properties and seriously reduce the light transmittance of the sample, and the biological antioxidant molecules will inevitably color the sample. To solve these problems, in this work, a benzotriazole UV absorber (Chiguard R-455) was introduced into the PU molecular chains by in situ polymerization to prepare the nonmigrating intrinsic anti-UV PU sample with high performance and colorless transparency. The anti-UV PU samples exhibit light transmittance of over 88% in the visible range and superior mechanical properties with tensile strength higher than 65 MPa and elongation at break higher than 900%. After 24 h UV irradiation (200 W, 365 nm), the tensile strength and elongation at break of pure PU sample are significantly reduced to only 8.9 and 15.8% of the original one, respectively. On the contrary, the addition of Chiguard R-455 will endow the PU sample with excellent anti-UV performance. After 24 h UV irradiation, the tensile strength (67.2 ± 1.6 MPa) and elongation at break (917.4 ± 30.0%) of PU-0.5% (the content of Chiguard R-455 is only 0.5 wt %) have changed little compared with the sample without irradiation (67.4 ± 3.5 MPa and 919.4 ± 26.5%). Additionally, the anti-UV mechanism of the PU sample is systematically studied. This work provides a feasible method for preparing colorless, transparent, high-performance, nonmigrating intrinsic UV-shielding PU samples, which can be used as a UV light-shielding material in various fields with visible and aesthetic requirements, such as protection fields and wearable products.

Thermal/Near-Infrared Light Dual-Responsive Reconfigurable and Recyclable Polythiourethane/CNT Composite with Simultaneously Enhanced Strength and Toughness.

Thermoset polymers cross-linked by dynamic covalent bonds are recyclable and reconfigurable based on solid-state plasticity, resulting in less waste and environmental pollution. However, most thermoset polymers previously reported show thermal-responsive solid-state plasticity, depending much on external conditions and not allowing for local shape modulation. Herein, the isocyanate modified carbon nanotubes (CNTs-NCO) are introduced into the polythiourethane (PCTU) network with multiple dynamic covalent bonds by in situ polymerization to prepare the composite with thermal/light dual-responsive solid-state plasticity, reconfigurability, and recyclability. The introduction of CNTs-NCO simultaneously strengthens and toughens the PCTU composite. Moreover, based on the photothermal properties and light-responsive solid-state plasticity, the PCTU/CNTs composite or bilayer sample can achieve complex permanent shape by locally precise shape regulation without affecting other parts. This work provides a simple and reliable method for preparing high-performance polymer composite with light-responsive solid-state plasticity, which may be applied in the fields of sensing and flexible electronics.

Transparent, photothermal and stretchable alginate-based hydrogels for remote actuation and human motion sensing.

Multifunctional hydrogels show potential applications in actuators and wearable sensors. However, it is still a challenge to develop a photothermal responsive conductive hydrogel with high transparency, mechanical properties, broad sensing range, and low-temperature resistance. In this work, a transparent, photothermal responsive, and highly stretchable alginate-based hydrogels was feasibly constructed by adding two-dimensional non-layered molybdenum dioxide nanosheets (2D-MoO2) to sodium alginate/polyacrylamide mixture and then soaking into the calcium chloride solution. The introduction of 2D-MoO2 renders the hydrogels excellent photothermal properties and controllable photomechanical deformation under near-infrared irradiation, while maintaining high transparency (~60 %).The calcium ions give the hydrogel excellent mechanics, conductivity, and freezing tolerance concurrently. The transparent hydrogel-based sensor shows wide sensing range (0-1800 %) and cycling stability in detecting deformations and real-time human motions even in harsh environments. Therefore, this work provides a new route for generating transparent multifunctional hydrogels towards the applications of remote actuation and strain sensing.

Arbitrarily Reconfigurable and Thermadapt Reversible Two-Way Shape Memory Poly(thiourethane) Accomplished by Multiple Dynamic Covalent Bonds.

The fabrication of a single polymer network that exhibits a good reversible two-way shape memory effect (2W-SME), can be formed into arbitrarily complex three-dimensional (3D) shapes, and is recyclable remains a challenge. Herein, we design and fabricate poly(thiourethane) (PTU) networks with an excellent thermadapt reversible 2W-SME, arbitrary reconfigurability, and good recyclability via the synergistic effects of multiple dynamic covalent bonds (i.e., ester, urethane, and thiourethane bonds). The PTU samples with good mechanical performance simultaneously demonstrate a maximum tensile stress of 29.7 ± 1.1 MPa and a high strain of 474.8 ± 7.5%. In addition, the fraction of reversible strain of the PTU with 20 wt % hard segment reaches 22.4% during the reversible 2W-SME, where the fraction of reversible strain is enhanced by self-nucleated crystallization of the PTU. A sample with arbitrarily complex permanent 3D shapes can be realized via the solid-state plasticity, and that sample also exhibits excellent reversible 2W-SME. A smart light-responsive actuator with a double control switch is fabricated using a reversible two-way shape memory PTU/MXene film. In addition, the PTU networks are de-cross-linked by alcohol solvolysis, enabling the recovery of monomers and the realization of recyclability. Therefore, the present study involving the design and fabrication of a PTU network for potential applications in intelligent actuators and multifunctional shape-shifting devices provides a new strategy for the development of thermadapt reversible two-way shape memory polymers.

Rapid Photothermal Responsive Conductive MXene Nanocomposite Hydrogels for Soft Manipulators and Sensitive Strain Sensors.

Stimulus-responsive hydrogels are of great significance in soft robotics, wearable electronic devices, and sensors. Near-infrared (NIR) light is considered an ideal stimulus as it can trigger the response behavior remotely and precisely. In this work, a smart flexible stimuli-responsive hydrogel with excellent photothermal property and decent conductivity are prepared by incorporating MXene nanosheets into the physically cross-linked poly(N-isopropyl acrylamide) hydrogel matrix. Because of outstanding photothermal effect and dispersion of MXene, the composite hydrogel exhibits rapid photothermal responsiveness and excellent photothermal stability under the NIR irradiation. Furthermore, the anisotropic bilayer hydrogel actuator shows fast and controllable light-driven bending behavior, which can be used as a light-controlled soft manipulator. Meanwhile, the hydrogel sensor exhibits cycling stability and good durability in detecting various deformation and real-time human activities. Therefore, the present study involving the fabrication of MXene nanocomposite hydrogels for potential applications in remotely controlled actuator and wearable electronic device provides a new method for the development of photothermal responsive conductive hydrogels.

Two-Dimensional MoO2 Nanosheet Composite Hydrogels with High Transmittance and Excellent Photothermal Property for Near-Infrared Responsive Actuators and Microvalves.

Stimulus-responsive intelligent hydrogel actuators have highly promising applications in the fields of soft robotics, smart manipulators, and flexible devices. Near-infrared (NIR) light is considered an ideal method to trigger the response behavior remotely and precisely. In order to realize the excellent optical transmittance and photothermal property of NIR-responsive hydrogels at the same time, two-dimensional nonlayered MoO2 nanosheets (2D-MoO2) with excellent photothermal efficiency (62% under an NIR light irradiation of 808 nm), splendid chemistry stability, and low preparation cost are used as photothermal agents and incorporated into the poly(N-isopropylacrylamide) (PNIPAM) hydrogel network, forming the 2D-MoO2/Laponite/PNIPAM ternary nanocomposite hydrogel (TN hydrogel). It is remarkable that compared with the GO and MXene hydrogels with the same agent content (1.0 mg mL-1) and thickness (1 mm) whose transmittance values are only ∼5% at 600 nm, the TN hydrogel shows a similar NIR-responsive temperature, but much higher optical transmittance (∼53%). Besides, of the three hydrogels with similar transmittance, the TN hydrogel shows a much higher NIR-responsive temperature. The TN hydrogel with a low loading of 2D-MoO2 (1.5 mg mL-1) can produce a significant temperature increase of ∼30 °C after the application of 0.8 W cm-2 NIR light irradiation for 15 s. Impressively, the TN hydrogel exhibits excellent anti-fatigue property, keeping a fast response and temperature rise behavior even after 50 times of heating-cooling cycles. The flexibly controllable and reversible deformation is realized by a well-designed bilayer structure even in harsh environments. The transparent and asymmetric bilayer hydrogel is further used as a soft manipulator to capture objects visually and accurately. The NIR light-controlled microvalve based on this composite hydrogel is also demonstrated. This work provides a novel kind of transparent hybrid NIR response hydrogel for the further development of smart, programmable, reversible hydrogel-based actuators and soft robotics.

Interference with KCNJ2 inhibits proliferation, migration and EMT progression of apillary thyroid carcinoma cells by upregulating GNG2 expression.

Papillary thyroid carcinoma is a common malignant tumor of the endocrine system. The specific role and molecular mechanism of potassium inwardly rectifying channel subfamily J member 2 (KCNJ2) in papillary thyroid carcinoma remain unknown. In the present study, the underlying mechanism of KCNJ2 in papillary thyroid carcinoma was explored. KCNJ2 expression in thyroid cancer tissues was predicted using the Gene Expression Profiling Interactive Analysis database, and reverse transcription­quantitative PCR and western blot analyses were performed to detect KCNJ2 expression in papillary thyroid carcinoma cell lines. Cell transfection was performed to inhibit KCNJ2 and G protein subunit Î³2 (GNG2) expression. In addition, cell proliferation was detected via the colony formation and MTT assays. The wound healing and Transwell assays were performed to assess cell migration and invasion, respectively. Western blot analysis was performed to detect the expression levels of transport­related proteins and interstitial related proteins. The StarBase database was used to detect GNG2 expression in thyroid cancer. The results demonstrated that KCNJ2 expression was upregulated in papillary thyroid carcinoma cells. In addition, interfering with KCNJ2 expression inhibited the proliferation, invasion and migration of papillary thyroid carcinoma cells, and inhibited the epithelial­to­mesenchymal transition (EMT). These processes may be influenced by the upregulation of GNG2 expression induced by KCNJ2 knockdown. Overall , the results of the present study demonstrated that interference with KCNJ2 inhibited proliferation, migration and EMT progression of papillary thyroid carcinoma cells by upregulating GNG2 expression.

Thermal/Near-Infrared Light Dual-Responsive Reversible Two-Way Shape Memory cEVA/2D-MoO2 Composite for Multifunctional Applications.

Light-responsive reversible two-way shape memory polymers (2W-SMPs) are highly promising for many fields due to indirect heating, clean, and remote control. In this work, a composite with both thermal- and near-infrared (NIR) light-induced reversible two-way shape memory effect (2W-SME) is prepared by doping extremely little quantities of 2D non-layered molybdenum dioxide nanosheets (2D-MoO2 ) into semicrystalline poly(ethylene-co-vinyl acetate) (EVA) networks. This is the first report on light-induced reversible two-way shape memory composites employing 2D-MoO2 as photothermal fillers. Upon switching the NIR light on and off, due to the excellent photothermal feature and stability of 2D-MoO2 , the composite exhibits remarkable light-induced reversible 2W-SME. A light-driven actuator for sensing applications is designed based on the composite and the circuit, where the lamp acting as an alarm can raise and fade upon responding to NIR light. A completely flexible, fuel-free self-walking soft robot is designed based on the advantages of the light-responsive reversible 2W-SMPs. Additionally, the composite acting as a light-fueled crane is able to lift and lower a load that is 3846 times its own weight. The results demonstrate that the prepared composite has a promising prospect for applications as actuators, self-walking soft robot and crane.

Morphology and transport characterization of solution-processed rubrene thin films on polymer-modified substrates.

In this report, the morpho-structural peculiarities and the crystallization mechanisms in solution-processed, solvent vapor annealed (SVA) thin films of rubrene (5,6,11,12-tetraphenylnaphthacene) on different substrates were investigated. The high-quality rubrene crystal films with a triclinic crystal structure were successfully prepared on the FTO substrates (glass slide coated with fluorine-tin-oxide) modified by PLA (polylactic acid) for the first time. The area coverage of rubrene crystal and the sizes of rubrene dendritic crystals increased with increasing thickness of PLA film and concentration of rubrene solution. For rubrene molecules, FTO wafers with rough surface provided the possibility of heterogeneous nucleation. During the SVA process, there were two kinds of forces acting on the diffusion of rubrene molecules: one force was provided by the residual chloroform solvent, which was perpendicular to the substrate, and the other force was provided by gaseous dichloromethane, which was parallel to the substrate. The synergy of these two forces was proposed to explain the nucleation and the crystallization processes of rubrene films. The higher nucleus of PLA/rubrene dendrites and the layer-by-layer stacking of needle-shaped nanocrystalline PLA/rubrene were important for exploring their kinetic formation process.

Amphiphilic poly(caprolactone-b-N-hydroxyethyl acrylamide) micelles for controlled drug delivery.

To increase the bioavailability and water solubility of hydrophobic medicine, an amphiphilic block copolymer, polycaprolactone-block-polyhydroxyethyl acrylamide (PCL-b-PHEAA), was synthesized. The copolymer can self-assemble into micelles by dialysis. The micelles were characterized by the Tyndall effect, static drop method, fluorescence spectrometry, dynamic light scattering, scanning electron microscopy and transmission electron microscopy. Ibuprofen was encapsulated inside the micelles by dialysis as a model medicine. The results show that the amphiphilic copolymer forms a uniform micelle system, with spherical micelles dispersed well in solution which have a low critical micelle concentration. In addition, the system shows good amphipathic behavior. Average particle size of a micelle is 104 nm, which increases a lot after drug loading and standing for half a month. In the first few hours, the cumulative release of the drug increases gradually; the rate of increase in the first ten hours is faster, then reaching a plateau which tends to be flat finally. It is similar under two different pH conditions. This biocompatible, biodegradable amphiphilic block copolymer has potential applications in the biomedical field.

Colorless, Transparent, Robust, and Fast Scratch-Self-Healing Elastomers via a Phase-Locked Dynamic Bonds Design.

Robust self-healing thermoplastic elastomers are expected to have repeated healing capability, remarkable mechanical properties, transparency, and superior toughness. The phase-locked design in this work provides excellent tensile mechanical properties and efficient healability at a moderate temperature due to the dynamic disulfide bonds embedded in the hard segments and mainly being locked in the viscoelastic hard microphase region. The self-healing elastomers exhibit a maximum tensile stress of 25 MPa and a fracture strain of over 1600%, which are quite prominent compared to previous reports. The nanoscale domains of the elastomer are smaller than the wavelength of visible light by microphase separation control resulting in colorless, nearly 100% transparency, and are as good as quartz glasses. The high dynamics of the phase-locked disulfide bonds renders a high healing efficiency of scratches on the surface within 60 s at 70 °C. The rapid scratch healing and complete transparency recovery of the elastomers provide new avenues in the highly transparent surface or protective films which finds potential applications for precision optical lenses, flexible display screens, and automobile or aircraft lighting finishes.

Double Crystalline Multiblock Copolymers with Controlling Microstructure for High Shape Memory Fixity and Recovery.

The shape memory performance of double crystalline poly(butylene succinate)-co-poly(ε-caprolactone) (PBS-co-PCL) multiblock copolymers with controlling microstructure was studied, and the corresponding microstructure origin was further quantitatively analyzed by wide and small-angle X-ray scattering (WAXS and SAXS) experiments. It was found that the multiblock copolymer with higher PCL content, proper deformation strain, and inhibited crystallization of PBS (lower crystallinity and smaller crystal size, which could be realized by quenching from the melt) would exhibit better shape memory fixity and recovery performance. WAXS and SAXS results revealed that the shape fixity ratio (Rf) was closely related with the relative crystallinity of the PCL component, while the shape recovery ratio (Rr) strongly relied on the deformation and recovery behavior of the PBS and PCL components that changed along with compositions and deformation strains. For the copolymer with higher PCL content (BS30CL70), at the lower deformation strain (0% ∼ 90%), both the PBS and PCL components after recovery had no orientation (labeled as stage I), resulting in almost complete recovery; with the deformation strain increasing (90% ∼ 200%), it was the irreversible deformation of the PCL component that largely took responsibility for the decreased Rr (stage II). On the contrary, when the PCL content decreased to 50 wt % (BS50CL50), stage I (0% ∼ 50%) and stage II (50% ∼ 100%) appeared in much lower strains; with the deformation strain increasing (100% ∼ 200%), the irreversible deformation of both PBS and PCL components was mainly responsible for the further reduction of Rr (stage III). It could exhibit excellent shape memory performance for biodegradable double crystalline multiblock copolymers by controlling the composition, deformation strain, and crystallization, which might have wide application prospects in biomedical areas.

Self-Associated Polyamide Alloys with Tailored Polymorphism Transition and Lamellar Thickening for Advanced Mechanical Application.

Long chain polyamides with various number of methylene units in recurring amide groups, PA1012 and PA612, were blended to combine their unique advantages. The Brill transition and accompanied lamellar thickening were investigated by in situ wide angle X-ray scattering (WAXS) and small angle X-ray scattering. From WAXS patterns, the transformation from the α- to γ-crystalline phase, known as "Brill transition", can be independently observed in the constituent phases of the long chain polyamide alloys (LCPAs) during heating. A constant Tb (ca., 100 °C) irrespective of the blend composition and proportional variations of the phase content was obtained. Additionally, with elevated temperature, a gradual increase in both the crystalline layer (Lc) and amorphous layer (La) was detected in constituent polyamides. The compositional independence of the Brill transition in LCPAs and similar lamellar thickening originate from the complete immiscibility of both polyamides, which share stronger intramolecular rather than intermolecular hydrogen-bonding interaction and hence exhibit self-association. Contributed by the γ phase, with less extended structure and increased lamellar thickness with compact stacking, LCPAs with controlled strength and flexible features can be achieved, which can be utilized in advanced mechanical applications, particularly for hoses of automobiles. The unusually linear compositional dependence of mechanical parameters makes it possible to tailor the polymorphic and tensile properties.

Dually actuated triple shape memory polymers of cross-linked polycyclooctene-carbon nanotube/polyethylene nanocomposites.

In this work, electrically and thermally actuated triple shape memory polymers (SMPs) of chemically cross-linked polycyclooctene (PCO)-multiwalled carbon nanotube (MWCNT)/polyethylene (PE) nanocomposites with co-continuous structure and selective distribution of fillers in PCO phase are prepared. We systematically studied not only the microstructure including morphology and fillers' selective distribution in one phase of the PCO/PE blends, but also the macroscopic properties including thermal, mechanical, and electrical properties. The co-continuous window of the immiscible PCO/PE blends is found to be the volume fraction of PCO (vPCO) of ca. 40-70 vol %. The selective distribution of fillers in one phase of co-continuous blends is obtained by a masterbatch technique. The prepared triple SMP materials show pronounced triple shape memory effects (SMEs) on the dynamic mechanical thermal analysis (DMTA) and the visual observation by both thermal and electric actuations. Such polyolefin samples with well-defined microstructure, electrical actuation, and triple SMEs might have potential applications as, for example, multiple autochoke elements for engines, self-adjusting orthodontic wires, and ophthalmic devices.