Lamellar Structure Research Articles

MgSiO3 Fiber Membrane Scaffold with Triggered Drug Delivery for Osteosarcoma Synergetic Therapy and Bone Regeneration.

In this research, a novel MgSiO3 fiber membrane (MSFM) loaded with indocyanine green (ICG) and doxorubicin (DOX) was prepared. Because of MgSiO3's unique lamellar structure composed of a silicon-oxygen tetrahedron, magnesium ion (Mg2+) moves easily and can be further replaced with other cations. Therefore, because of the positively charged functional group of ICG, MSFM has a rather high drug loading for ICG. In addition, there is electrostatic attraction between DOX (a cationic drug) and ICG (an anionic drug). Hence, after loading ICG, more DOX can be adsorbed into MSFM because of electrostatic interaction. The ICG endows the MSFM outstanding photothermal therapy (PTT) performance, and DOX as a chemotherapeutic drug can restrain tumor growth. On the one hand, H+ exchanged with the positively charged DOX based on the MgSiO3 special lamellar structure. On the other hand, the thermal effect could break the electrostatic interaction between ICG and DOX. Based on the above two points, both tumor acidic microenvironment and photothermal effect can trigger DOX release. What's more, in vitro and in vivo antiosteosarcoma therapy evaluations displayed a superior synergetic PTT-chemotherapy anticancer treatment and excellent biocompatibility of DOX&ICG-MSFM. Finally, the MSFM was proven to greatly promote cell proliferation, differentiation, and bone regeneration performance in vitro and in vivo. Therefore, MSFM provides a creative perspective in the design of multifunctional scaffolds and shows promising applications in controlled drug delivery, antitumor performance, and osteogenesis.

Effect of multiple laser remelting on microstructure and corrosion resistance of Fe0.5CoCrNi1.5Nb0.68Mo0.3 high entropy alloy coatings

High entropy alloy (HEA) coatings of Fe0.5CoCrNi1.5Nb0.68Mo0.3 was prepared on 304 stainless steel using laser cladding and subsequently remelted multiple times. The effects of multiple thermal cycles on the phase composition, grain size, microstructure evolution, and corrosion resistance of the coatings are thoroughly investigated. The original coating consisted of face-centered cubic (FCC), Laves, and NbC phases, and the phase composition does not change obviously, but the distribution and microstructure of the phase change significantly after multiple remelting. As the number of remelting times increased, the bar-like eutectic structure decreased while the lamellar eutectic structure became more prominent. Laser remelting induced dynamic recrystallization in the coating, resulting in a transformation from columnar grains to equiaxed grains, and then back to columnar grains. The grain size also changes significantly with different remelting times. Potentiodynamic polarization and electrochemical impact spectroscopy measurements were conducted in a 3.5 wt% NaCl solution to evaluate the corrosion resistance of the coating. The results revealed both the original coating and the once-remelted coating exhibited lower corrosion current density and higher corrosion potential, but the latter had a higher Faraday impedance. Additionally, immersion tests were performed in 10 wt% FeCl3 solution, which demonstrated that the once-remelted coating displayed fine and uniform corrosion pits with shallow depth. This study provides theoretical support for the regulation of microstructure and the optimization of coating performance. Furthermore, the microstructure evolution law discovered in this research is also applicable to additive manufacturing.

Modification Strategies of Hexagonal Boron Nitride Nanomaterials for Photocatalysis.

Although hexagonal boron nitride (h-BN) was initially considered a less promising photocatalyst due to its large band gap and apparent chemical inertness, its unique two-dimensional lamellar structure coupled with high stability and environmental friendliness, as the second largest van der Waals material after graphene, provides a unique platform for photocatalytic innovation. This review not only highlights the intrinsic qualities of h-BN with photocatalytic potentials, such as high stability, environmental compatibility, and tunable bandgap through various modification strategies but also provides a comprehensive overview of the recent advances in h-BN-based nanomaterials for environmental and energy applications, as well as an in-depth description of the modification methods and fundamental properties for these applications. In addition, we discuss the challenges and prospects of h-BN-based nanomaterials for future photocatalysis.

Morphology, functional groups, and CO2 adsorption performance of Cu2(OH)PO4: Effects of synthesis conditions

Global warming, primarily driven by emissions of greenhouse gases, particularly carbon dioxide, has emerged as a widely acknowledged concern. Hence, the development of novel carbon capture materials with high capacity and low cost holds substantial practical significance. This study investigates the influence of aging time, pH, and copper salt on the synthesis of Cu2(OH)PO4 and its CO2 adsorption performance. Cu2(OH)PO4 adsorbents were synthesized under various aging time, pH, and copper salt conditions, and their morphology and surface functional groups were characterized. Experimental findings indicate that excessively prolonged or abbreviated aging times adversely affect the formation of distinct, discernible lamellar structures within the material. Different pH levels influence the stacking configuration of the lamellae, impacting both their thickness and size. Under acidic conditions, lamellae exhibit dispersed three-dimensional stacking; under neutral conditions, lamellae notably enlarge and demonstrate two-dimensional stacking; at pH 9, lamellae stack three-dimensionally and aggregate. Additionally, the CO2 adsorption performance of Cu2(OH)PO4 adsorbents synthesized with different copper salts varies. By examining the relationship between surface functional group content and CO2 adsorption capacity, we deduced the mechanism by which various synthesis conditions affect both surface functional groups and adsorption capacity. Cu2(OH)PO4 synthesized with a 24 h aging time, pH 7, and CuSO4 as the copper salt exhibits the highest CO2 adsorption capacity, achieving 1.006 mmol/g.

Fabrication of high photocatalytic activity photocatalysts with TiO2 supported on lamellar BiOCl

A lamellar nanostructure consisting of anatase TiO2/BiOCl was effectively developed while employing the approach of solvothermal. The samples underwent comprehensive analysis of their phase structures, morphologies, surface areas, optical properties, and electronic states using various techniques including x-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), x-ray photoelectron spectroscopy (XPS), Brunauer–Emmett–Teller (BET) method, UV–vis diffuse reflectance spectra (UV–vis DRS), Fourier transform infrared spectroscopy (FTIR), and photoluminescence spectroscopy(PL). The photoelectrochemical data demonstrated that the incorporation of anatase TiO2 nanoparticles into the BiOCl lamellar structure significantly improved its photocatalytic efficiency to degrade Malachite Green (MG) in UV light, surpassing the performance of both pure BiOCl and anatase TiO2. Additionally, the study delved into the photocatalytic mechanism responsible for this enhanced performance. The superior photocatalytic efficiency of the anatase TiO2/BiOCl composites can be ascribed to higher surface area, smaller crystallite size, stronger light absorption and improved charge separation efficiency.

Eco-friendly MXene/enteromorpha prolifera biomass aerogel with excellent photothermal conversion and flame retardant properties for efficient separation of viscous oil/seawater mixture

Traditional adsorbents are often ineffective in cleaning up high-viscosity oil spills that cause harm to the marine environment. An efficient, safe and eco-friendly solution is urgently needed. Here, we prepare a superhydrophobic MXene/gelatin-enteromorpha prolifera biomass aerogel (H-MXene/G-EP) with excellent photothermal conversion and flame retardancy for solar-driven remediation of high-viscosity oil spills. The short-range aligned multidomain lamellar structure constructed through unidirectional freeze casting endows H-MXene/G-EP with compressibility and an adsorption capacity (63.7 g/g). Due to the excellent light responsiveness and full-spectrum high absorption of H-MXene/G-EP, it can reach a surface temperature 71.6 °C under 1 Sun (1.0 kW/m2), and an in-situ adsorption rate 367.40 g/h for viscous crude oil. The efficiency of separating O/W emulsions is up to 99.1%, which greatly broadens the range of applications for oil/water separation technology. Furthermore, the H-MXene/G-EP exhibits excellent flame retardancy, reducing the heat release rate by 89.59% and the total smoke production rate by 47.83%, respectively. This effectively reduces the probability of secondary marine fires. Thus, this novel biomass-derived aerogel provides a feasible and environmentally friendly solution for effective remediation of marine oil spills.

Insights into the adsorption performance and mechanism of novel 3D bimetallic MOF nanosheets for the high-efficient removal of 6PPD and 6PPD-quinone

N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine (6PPD) is commonly used as the tire rubber antioxidant, causing widespread contamination in water environments. Moreover, its derivative 6PPD-quinone (6PPD-Q) has been identified as highly toxic to aquatic organisms. Therefore, the urgent environmental concern revolves around the elimination of 6PPD and 6PPD-Q from aquatic settings. In this study, a highly effective 3D bimetallic nanosheet material was initially synthesized for the adsorptive removal of 6PPD and 6PPD-Q. The 3D bimetallic nanosheet materials, Al-TCPP-M (M = Co, Cu, Zn), were prepared by the two-step sequential process, displaying excellent adsorption performance with rates exceeding 97% and 98% for 6PPD and 6PPD-Q, respectively. The bimetallic and lamellar structure significantly enhanced the maximum adsorption capacities of Al-TCPP-M (M = Co, Cu, Zn) for 6PPD and 6PPD-Q reaching 331.9–355.9 mg/g and 260.6–335.0 mg/g, respectively. Findings from kinetics and thermodynamics suggested that monolayer adsorption was predominant, primarily driven by chemical adsorption. Additionally, the Al-TCPP-M nanosheets exhibited remarkable reusability and anti-interference ability, and achieved significant removal efficiencies for 6PPD and 6PPD-Q in real river water samples. Furthermore, probable adsorption mechanisms mainly involved hydrogen bonding, electrostatic interactions and π-π stacking. Density functional theory (DFT) calculations proved that the introduction of the second metal increased adsorption active sites of Al-TCPP-M through the formation of π-complexation between transition metals and 6PPD and 6PPD-Q. This research highlights the promising applications of 3D bimetallic MOF nanosheets in environmental remediation.

Evading the strength and toughness trade-off dilemma in Lu2Si2O7 environmental barrier coatings via micro-nano reinforcement

Lu2Si2O7 nanostructured environmental barrier coating was prepared using as–synthetic Lu2Si2O7 feedstock via atmospheric plasma spraying. The structure and mechanical performances of Lu2Si2O7 coatings were characterized in detail. Results indicate that nanostructured Lu2Si2O7 coating exhibits a bi-modal microstructure, lamella structure and unmelted particles. The phase components of nanostructured Lu2Si2O7 coatings consist of β-Lu2Si2O7 and a small number of X2-Lu2SiO5. Furthermore, the nanohardness and elastic modulus of Lu2Si2O7 coatings have the characterization of bi-modal properties via Weibull analysis, i.e., the large Weibull modulus and the small Weibull modulus represent molten lamella structure and unmelted particles, respectively. Meanwhile, the fracture toughness of nanostructured Lu2Si2O7 coatings is superior to conventional Lu2Si2O7 coatings, and the adhesion strength of Lu2Si2O7 coatings is about 22.6 MPa by pull-extend test. Results of research are helpful for the design and preparation of advanced thermal spray coating.

Microstructure, Hardness and EIS Evaluation of Ti-15Zr-5Nb Dental Alloy

Ti alloys have been widely used in biomedical applications due to their special properties. They have specific properties such as biocompatibility, biofunctionality and high corrosion resistance, which enable them to function inside the human body. Among them, Ti-6Al-4V is probably one of the most widely used alloys for implants. However, aluminum and vanadium ions have been reported to cause problems and adverse reactions in the human body over long periods. Thus, in the present study, Ti–15Zr–10Nb alloy synthesized by high vacuum melting was manufactured and characterized by different techniques. The phase composition was determined by XRD. This showed the presence of α and β phases in the alloy, consistent with the microstructural study. From a microstructural point of view, the alloy shows lamellar and acicular structures with α-grain boundaries. Vickers microhardness measurements showed an increased hardness compared to Ti-CP. Furthermore, the electrochemical behavior was evaluated using HCl as an electrolyte. The obtained results were compared to Ti-CP tested in the same electrochemical condition. The studies indicated that Ti-CP presents a nobler electrochemical behavior than Ti-15Zr-5Nb. Thus, despite the very good corrosion properties of Ti-15Zr-5Nb in a simulated oral environment and Ringer’s solutions, the present study reveals that the Ti-15Zr-5Nb alloy has lower corrosion resistance in aggressive media when compared to Ti-CP.

Hierarchically heterogeneous microstructure and mechanical properties in laser-directed energy deposition of γ-TiAl alloy through intrinsic cyclic heat treatment

The complex thermal effects of laser direct energy deposition (L-DED) provide significant advantages for production of high-performance γ-TiAl alloy, whereas challenges still exist in microstructure tailoring and mechanical properties. This work focuses on the influence of intrinsic cyclic heat treatment (ICHT) on the evolution of microstructures and mechanical properties in different building height regions of an L-DED TiAl alloy thin-wall sample. The results indicate that ICHT induces discontinuous coarsening (DC) effects by consuming the lamellar interface energy of the initial lamellae, resulting in grain refinement. With the increase in building height, the thermal accumulation leads to an increase in the initial lamellar spacing, which weakens the DC effect. At the top, insufficient thermal cycles prevent fine grain growth and erode coarse grains, hindering overall grain refinement. Ultimately, the hierarchically heterogeneous microstructure forms in the L-DED TiAl alloy, including refinement of hierarchical lamellar colony structure decorated with fine (α2+γ) lamellar structure and (α2+6H-LPS) lamellar structure (6H-LPS refers to 6H long-period structure phase). Specifically, the bottom region exhibits the best combination of ultimate tensile strength (706 ± 33 MPa) and strain (0.68 ± 0.05 %). The high tensile strength can be attributed to the hindrance of dislocation movement by the fine lamellae and the 6H-LPS phase ,caused by the high cooling rate of L-DED, while the elongation is attributed to the reduction in crack propagation energy due to the presence of fine grains.

Friction behavior and wear mechanism of laser cladded FeNiCr-WC composite coatings in comparison with different friction pairs

Complex formation structures lead to significant differences in the failure mechanisms of hobs. WC-reinforced medium entropy composite coatings exhibit excellent comprehensive properties. However, the wear mechanism of coatings in different formation structures is still unclear. In this study, FeNiCr-WCx (x = 0, 40, 50, 60 wt%) composite coatings were prepared on the surface of H13 steel using laser cladding technology. The friction and wear mechanism of FeNiCr-WC composite coatings under different friction pair conditions was discussed. The results show that FeNiCr-WC composite coatings mainly consist of reinforced phase, lamellar eutectic structure and solid solution phase. As the WC content increases, the content of M6C and carbide phases in these coatings increases. The average microhardness of 40WC, 50WC and 60WC coatings is 3.28 times, 3.61 times and 4.20 times that of H13 steel, respectively. The wear rates of 40WC, 50WC and 60WC coatings are respectively about 0.25, 0.10 and 0.06 times that of FeNiCr coating under Al2O3 friction pair conditions. Three-body wear and oxidation wear mainly occurred on the surface of FeNiCr-WC composite coatings. The wear rates of 40WC, 50WC and 60WC coatings are respectively about 0.34, 0.35 and 0.16 times that of FeNiCr coating under Si3N4 friction pair conditions. Glaze layers with high Si content were formed on the surface of 50WC and 60WC coatings. The glaze layer is prone to cracking and peeling, resulting in increased wear rates for both coatings. As the hardness of the coating increases, the GCr15 friction pair undergoes severe abrasive wear.

Holey Sheets Enhance the Packing and Osmotic Energy Harvesting of Graphene Oxide Membranes.

Layered membranes assembled from two-dimensional (2D) building blocks such as graphene oxide (GO) are of significant interest in desalination and osmotic power generation because of their ability to selectively transport ions through interconnected 2D nanochannels between stacked layers. However, architectural defects in the final assembled membranes (e.g., wrinkles, voids, and folded layers), which are hard to avoid due to mechanical compliant issues of the sheets during the membrane assembly, disrupt the ionic channel pathways and degrade the stacking geometry of the sheets. This leads to degraded ionic transport performance and the overall structural integrity. In this study, we demonstrate that introducing in-plane nanopores on GO sheets is an effective way to suppress the formation of such architectural imperfections, leading to a more homogeneous membrane. Stacking of porous GO sheets becomes significantly more compact, as the presence of nanopores makes the sheets mechanically softer and more compliant. The resulting membranes exhibit ideal lamellar microstructures with well-aligned and uniform nanochannel pathways. The well-defined nanochannels afford excellent ionic conductivity with an effective transport pathway, resulting in fast, selective ion transport. When applied as a nanofluidic membrane in an osmotic power generation system, the holey GO membrane exhibits higher osmotic power density (13.15 W m-2) and conversion efficiency (46.6%) than the pristine GO membrane under a KCl concentration gradient of 1000-fold.

Synthesis of sub‐micron sized SiC particles with high defect density by using polytetrafluoroethylene as an additive

AbstractA new preparation process for silicon carbide (SiC) powder is developed. In the Si–(C) –PTFE–Ar system, the grain size and morphology of the product 3C–SiC were controlled by adding a carbon source (graphite) and changing the percentage of polytetrafluoroethylene (PTFE) (0%, 10%, and 20%). The experimental results showed that the SiC powders prepared using a molar ratio of 1:1 silicon powder to graphite, plus 20% PTFE have a uniform particle size distribution (∼130 nm), a lamellar structure made of spherical particle stacking, a small bandgap (1.80 eV), a high carrier concentration, and a large number of lattice defects. These properties are expected to increase the electrical conductivity of 3C–SiC and decrease its thermal conductivity, thus providing a promising feedstock preparation option for SiC thermoelectric materials. In addition, the mechanism of PTFE in the preparation of SiC reactions was studied in detail.

ZnMn2O4/V2CTx Composites Prepared as an Anode Material via High-Temperature Calcination Method for Optimized Li-Ion Batteries.

The ZnMn2O4/V2CTx composites with a lamellar rod-like bond structure were successfully synthesized through high-temperature calcination at 300 °C, aiming to enhance the Li storage properties of spinel-type ZnMn2O4 anode materials for lithium-ion batteries. Moreover, even though the electrode of the composites obtained at 300 °C had a nominal specific capacity of 100 mAh g-1, it exhibited an impressive specific discharge capacity of 163 mAh g-1 after undergoing 100 cycles. This represents an approximate increase of 64% compared to that observed in the pure ZnMn2O4 electrode (99.5 mAh g-1). The remarkable performance of the composite can be credited to the collaborative impact between ZnMn2O4 and V2CTx, leading to a substantial improvement in its lithium ion storage capacity. Therefore, this study offers valuable insights into developing cost-effective, safe, and easily prepared anode materials.

Preparation and Application of Decanoic Acid/Arginine Hydrogels to a Transdermal Formulation.

We prepared a supramolecular hydrogel composed of decanoic acid and arginine (C10/Arg gel) and evaluated its application to a transdermal formulation. C10/Arg gel adjusted to pH 7 with 1 M NaOH aq or 1 M HCl aq provided a translucent hydrogel with a lamellar liquid crystal structure in the concentration region of decanoic acid ≥12% and arginine ≤9%. Rheological measurements showed that C10/Arg gel is a viscoelastic material with both solid and liquid properties, with elasticity being dominant over viscosity in the low shear stress region. The skin permeability of hydrocortisone (HC) and indomethacin (IM) from C10/Arg gels was investigated in vitro using hairless mouse skin and compared to control formulation drug suspensions (IM or HC) in water. The cumulative permeation amount of HC and IM from the C10/Arg gel at 10 h after application was approximately 16 and 11 times higher than that of the control, respectively. On the other hand, the flux of IM decreased with increasing arginine concentration, likely due to the acid-base interaction between Arg and IM in C10/Arg gel. Adequate drug skin permeation enhancement by C10/Arg gel requires optimizing the gel composition for each specific drug.

Mucoadhesive Chitosan Composite Sponge as a Carrier for β-Sitosterol Cubosomes for Thermal Burn Treatment

Our study aimed to explore the potential of using nanostructured lipid carriers (NLCs) to enhance the topical administration of β-sitosterol, a bioactive that is poorly soluble in water. Here, we have taken advantage of the unique characteristics that cubosomes have to provide as a drug delivery system. These characteristics include a large surface area, thermal stability, and the capacity to encapsulate molecules that are hydrophobic, amphiphilic, and hydrophilic. The cubosomal formulation was optimized by building a central composite design. The optimum dispersion exhibited a particle size of 88.3 nm, a zeta potential of -43, a polydispersity index of 0.358, and drug entrapment of 95.6%. It was composed of 15% w/w oleic acid and 5% w/w pluronic F127. The optimized cubosome dispersion was incorporated into a sponge formulation. The optimized cubosome sponge achieved a higher drug release compared with the cubosome dispersion. The SEM micrograph of the selected sponge showed that it has an interwoven irregular fibrous lamellar structure with low density and high porosity. The in-vivo data revealed that topical application of the β-sitosterol cubosomal sponge showed significant higher wound closure percentage relative to the β-sitosterol product (Mebo)®.Graphical

Lamellar structures in directionally solidified naphthalene suspensions

To investigate naphthalene as a suspending fluid for freeze-casting applications, sterically stabilized suspensions of copper microparticles suspended in liquid naphthalene are directionally solidified in a Bridgman furnace. Colonies of nearly particle-free naphthalene lamellae, interspersed with particle-enriched interlamellar regions, are predominantly aligned in the direction of the imposed thermal gradient. As furnace translation velocities decrease from 80 to 6.5 μm s−1, the thickness of naphthalene lamellae increases. For the lowest velocity, a transition to a lensing microstructure (with naphthalene bands aligned perpendicular to the solidification direction) is observed in central regions of samples. For all velocities, the naphthalene lamellae show (i) secondary dendritic arms on one of their sides and (ii) are thinnest within core regions relative to peripheral regions (closest to the crucible walls). Together, these observations suggest the presence of buoyancy-driven convection during solidification.Graphical

Hexagonal boron nitride nanosheets/graphene nanoplatelets/cellulose nanofibers-based multifunctional thermal interface materials enabling electromagnetic interference shielding and electrical insulation

Thermal interface materials (TIMs) that block electromagnetic interference (EMI) and current leakage are essential for high-density, high-power devices and compact form factors of electronic and mobility platforms. However, their coupled thermal-electrical-electromagnetic characteristics involve mismatches in thermal conductivity, electrical insulation, and EMI shielding, limiting the multifunctionality. Herein, a sandwich-like structural design that rationally combines graphene nanoplatelets (GNPs), hexagonal boron nitride nanosheets (BNNSs) and cellulose nanofibers (CNFs) is presented toward multifunctional trilayer TIMs enabling high thermal conductivity, EMI shielding, electrical insulation, mechanical compatibility and flame retardancy. The top and bottom BNNSs serve as electrically insulating yet thermally conductive layers while the GNPs in the central layer mitigate EMI and the CNFs as a binder complete the mechanical properties for the lamella-like trilayers. The resulting TIM exhibits a high in-plane thermal conductivity (25.5 W/m·K), and the LED cooling system using the TIM demonstrates the capability of reducing the operating temperature. Furthermore, it shows a high-volume resistivity (4.12 × 1013 Ω cm) and EMI shielding effectiveness (29.0 dB) at X-band frequencies. Its mechanical robustness is confirmed with tensile strength and elongation of 65.0 MPa and 2.36 %, and the high flame retardancy is validated. The outcomes will inspire tailoring multifunctional TIMs using lamellar structures that optimally combine micro/nanomaterials.

Compressible Hydrogels with Stabilized Chirality from Thermoresponsive Helical Dendronized Poly(phenylacetylene)s

AbstractFabrication of chiral hydrogels from thermoresponsive helical dendronized phenylacetylene copolymers (PPAs) carrying three‐fold dendritic oligoethylene glycols (OEGs) is reported. Three different temperatures, i.e. below or above cloud point temperatures (Tcps) of the copolymers, and under freezing condition, were utilized, affording thermoresponsive hydrogels with different morphologies and mechanical properties. At room temperature, transparent hydrogels were obtained through crosslinking among different copolymer chains. Differently, opaque hydrogels with much improved mechanical properties were formed at elevated temperatures through crosslinking from the thermally dehydrated and collapsed copolymer aggregates, leading to heterogeneity for the hydrogels with highly porous morphology. While crosslinking at freezing temperature synergistically through ice templating, these amphiphilic dendronized copolymers formed hydrogels with highly porous lamellar structures, which exhibited remarkable compressible properties as human articular cartilage with excellent fatigue resistance. Amphiphilicity of the dendronized copolymers played a pivotal role in modulating the network formation during the gelation, as well as morphology and mechanical performance of the resulting hydrogels. Through crosslinking, these dendronized copolymers featured with typical dynamic helical conformations were transformed into hydrogels with unprecedently stabilized helicities due to the restrained chain mobilities in the three‐dimensional networks.

Compressible Hydrogels with Stabilized Chirality from Thermoresponsive Helical Dendronized Poly(phenylacetylene)s.

Fabrication of chiral hydrogels from thermoresponsive helical dendronized phenylacetylene copolymers (PPAs) carrying three-fold dendritic oligoethylene glycols (OEGs) is reported. Three different temperatures, i.e. below or above cloud point temperatures (Tcps) of the copolymers, and under freezing condition, were utilized, affording thermoresponsive hydrogels with different morphologies and mechanical properties. At room temperature, transparent hydrogels were obtained through crosslinking among different copolymer chains. Differently, opaque hydrogels with much improved mechanical properties were formed at elevated temperatures through crosslinking from the thermally dehydrated and collapsed copolymer aggregates, leading to heterogeneity for the hydrogels with highly porous morphology. While crosslinking at freezing temperature synergistically through ice templating, these amphiphilic dendronized copolymers formed hydrogels with highly porous lamellar structures, which exhibited remarkable compressible properties as human articular cartilage with excellent fatigue resistance. Amphiphilicity of the dendronized copolymers played a pivotal role in modulating the network formation during the gelation, as well as morphology and mechanical performance of the resulting hydrogels. Through crosslinking, these dendronized copolymers featured with typical dynamic helical conformations were transformed into hydrogels with unprecedently stabilized helicities due to the restrained chain mobilities in the three-dimensional networks.