Preparation of silk fibroin/hyaluronic acid composite hydrogel based on thiol-ene click chemistry. / 基于巯基-çƒ¯ç‚¹å‡»åŒ–å­¦åˆ¶å¤‡ä¸ç´ è›‹ç™½/é€æ˜Žè´¨é ¸å¤åˆæ°´å‡èƒ¶.

OBJECTIVES: To design and prepare silk fibroin/hyaluronic acid composite hydrogel. METHODS: The thiol modified silk fibroin and the double-bond modified hyaluronic acid were rapidly cured into gels through thiol-ene click polymerization under ultraviolet light condition. The grafting rate of modified silk fibroin and hyaluronic acid was characterized by 1H NMR spectroscopy; the gel point and the internal microstructure of hydrogels were characterized by rheological test and scanning electron microscopy; the mechanical properties were characterized by compression test; the swelling rate and degradation rate were determined by mass method. The hydrogel was co-cultured with the cells, the cytotoxicity was measured by the lactate dehydrogenase method, the cell adhesion was measured by the float count method, and the cell growth and differentiation on the surface of the gel were observed by scanning electron microscope and fluorescence microscope. RESULTS: The functional group substitution degrees of modified silk fibroin and hyaluronic acid were 17.99% and 48.03%, respectively. The prepared silk fibroin/hyaluronic acid composite hydrogel had a gel point of 40-60 s and had a porous structure inside the gel. The compressive strength was as high as 450 kPa and it would not break after ten cycles. The water absorption capacity of the composite hydrogel was 4-10 times of its own weight. Degradation experiments showed that the hydrogel was biodegradable, and the degradation rate reached 28%-42% after 35 d. The cell biology experiments showed that the cytotoxicity of the composite gel was low, the cell adhesion was good, and the growth and differentiation of the cells on the surface of the gel were good. CONCLUSIONS: The photocurable silk fibroin/hyaluronic acid composite hydrogel can form a gel quickly, and has excellent mechanical properties, adjustable swelling rate and degradation degree, good biocompatibility, so it has promising application prospects in biomedicine.

Click-Chemistry Approach toward Antibacterial and Degradable Hybrid Hydrogels Based on Octa-Betaine Ester Polyhedral Oligomeric Silsesquioxane.

An efficient process for the synthesis of degradable hydrogels containing octa-betaine ester polyhedral oligomeric silsesquioxane (POSS) through efficient thiol-ene and Menschutkin click reactions was developed. The hydrogels exhibited a yield strength of 0.36 MPa and a compressive modulus of 4.38 MPa and displayed excellent flexibility as well as torsion resistance. Antibacterial efficacy of hydrogels (and degradation products) was evaluated using Escherichia coli (Gram-negative) and Staphylococcus aureus (Gram-positive). Efficacy was found to increase with the concentration of cetyl chloroacetate (CCA) in the hydrogel network, reaching 93% and 99% for Escherichia coli and Staphylococcus aureus, respectively. Degradation of hydrogels was observed in weak alkali conditions (pH = 8) and at physiological conditions (pH = 7.4). The degradation time of the hydrogels could be finely tuned by variation of the CCA content in the hydrogel and environmental stimulus. The tunable degradation behavior under physiological conditions combined with high antibacterial efficacy could render the presented materials interesting for tissue engineering applications.

Electric Assisted Salt-Responsive Bacterial Killing and Release of Polyzwitterionic Brushes in Low-Concentration Salt Solution.

Polyzwitterionic brushes with strong antipolyelectrolyte effects have shown great potential as versatile platforms for the development of switchable friction/lubrication and bacterial absorption/desorption surfaces. However, the surface property switches of these brushes are usually triggered by high salt concentrations (>0.53 M), thereby greatly limiting their applications in biological fields where the salt concentration for mammals is ?0.15 M. To solve this problem, an electric field was used to assist the salt-responsive process of the polyzwitterionic brushes to achieve bacterial release at low concentrations of the salt solution. Briefly, poly(3-(dimethyl (4-vinylbenzyl) ammonium) propyl sulfonate) (polyDVBAPS) brushes grafted on ITO surfaces were prepared by surface initiated atom transfer radical polymerization. The bacterial release of this surface was conducted under an electric field, where anions were migrated and enriched around the brush-grafted ITO surface as anode. The local high concentration ion led to the conformation change of the brush and release of the attached bacteria. The effect of salt type, salt concentration, electric field strength, and conducting time on the bacterial release properties were investigated. The results indicated that under an electrical field of 3 V/mm, polyDVBAPS showed release capacities of ?93% for E. coli and ?81% for S. aureus in 0.12 M NaCl electrolyte solution. Furthermore, by the introduction of a bactericidal agent, i.e., Triclosan (TCS), an antibacterial surface with dual functions of killing and release was fabricated. This surface could kill ?90% and release 95% of attached E. coli in a 0.12 M NaCl solution by the application of a 3 V/mm electric field. This work demonstrated the feasibility of triggering a salt-responsive behavior of polyzwitterionic at low salt concentration by assistance of electric field, which would greatly extend the applications of polyzwitterionic, in particular in biological applications.

Structural Dependence of Salt-Responsive Polyzwitterionic Brushes with an Anti-Polyelectrolyte Effect.

Some polyzwitterionic brushes exhibit a strong "anti-polyelectrolyte effect" and ionic specificity that make them versatile platforms to build smart surfaces for many applications. However, the structure-property relationship of zwitterionic polymer brushes still remains to be elucidated. Herein, we aim to study the structure-dependent relationship between different zwitterionic polymers and the anti-polyelectrolyte effect. To this end, a series of polyzwitterionic brushes with different cationic moieties (e.g., imidazolium, ammonium, and pyridinium) in their monomeric units and with different carbon spacer lengths (e.g., CSL = 1, 3, and 4) between the cation and anion were designed and synthesized to form polymer brushes via the surface-initiated atom transfer radical polymerization. All zwitterionic brushes were carefully characterized for their surface morphologies, compositions, wettability, and film thicknesses by atomic force microscopy, contact angle measurement, and ellipsometry, respectively. The salt-responsiveness of all zwitterionic brushes to surface hydration and friction was further examined and compared both in water and in salt solutions with different salt concentrations and counterion types. The collective data showed that zwitterionic brushes with different cationic moieties and shorter CSLs in salt solution induced higher surface friction and lower surface hydration than those in water, exhibiting strong anti-polyelectrolyte effect salt-responsive behaviors. By tuning the CSLs, cationic moieties, and salt concentrations and types, the surface wettability can be changed from a highly hydrophobic surface (∼60°) to a highly hydrophilic surface (∼9°), while interfacial friction can be changed from ultrahigh friction (µ ≈ 4.5) to superior lubrication (µ ≈ 10-3). This work provides important structural insights into how subtle structural changes in zwitterionic polymers can yield great changes in the salt-responsive properties at the interface, which could be used for the development of smart surfaces for different applications.

Enhanced energy density and thermal conductivity in poly(fluorovinylidene-co-hexafluoropropylene) nanocomposites incorporated with boron nitride nanosheets exfoliated under assistance of hyperbranched polyethylene.

Polymer dielectric film with a large dielectric constant, high energy density and enhanced thermal conductivity are of significance for the development of impulse capacitors. However, the fabrication of polymer dielectrics combining high energy density and thermal conductivity is still a challenge at the moment. Here we demonstrate the facile exfoliation of hexagonal boron nitride nanosheets (BNNSs) in common organic solvents under sonication with the assistance of hyperbranched polyethylene (HBPE). The noncovalent CH-π interactions between the nanosheets and HBPE ensure the dispersion of BNNSs in organic solvents with high concentrations, because of the highly branched chain structure of HBPE. Subsequently, the resultant BNNSs with a few defects are distributed uniformly in the poly(fluorovinylidene-co-hexafluoropropylene) (P(VDF-HFP)) nanocomposite films prepared via simple solution casting. The BNNS/P(VDF-HFP) nanocomposite exhibits outstanding dielectric properties, high energy density and high thermal conductivity. The dielectric constant of the 0.5 wt% nanocomposite film is 35.5 at 100 Hz with an energy density of 5.6 J cm-3 at 325 MV m-1 and a high charge-discharge efficiency of 79% due to the depression of the charge injection and chemical species ionization in a high field. Moreover, a thermal conductivity of 1.0 wt% nanocomposite film reaches 0.91 W·m-1 · K-1, which is 3.13 times higher than that of the fluoropolymer matrix. With dipole accumulation and orientation in the interfacial zone, lightweight, flexible BNNS/P(VDF-HFP) nanocomposite films with high charge-discharge performance and thermal conductivity, exhibit promising applications in relatively high-temperature electronics and energy storage devices.

Salt-Induced Regenerative Surface for Bacteria Killing and Release.

Antibacterial surfaces with both bacteria killing and release functions show great promise in biological and biomedical applications, in particular for reusable medical devices. However, these surfaces either require a sophisticated technique to create delicate structures or need rigorous stimuli to trigger the functions, greatly limiting their practical application. In this study, we made a step forward by developing a simple system based on a salt-responsive polyzwitterionic brush. Specifically, the salt-responsive brush of poly(3-(dimethyl (4-vinylbenzyl) ammonium) propyl sulfonate) (polyDVBAPS) was endowed with bactericidal function by grafting an effective bactericide, i.e., triclosan (TCS). This simple functionalization successfully integrated the bacteria attach/release function of polyDVBAPS and bactericidal function of TCS. As a result, the surface could kill more than 95% attached bacteria and, subsequently, could rapidly detach ∼97% bacteria after gently shaking in 1.0 M NaCl for 10 min. More importantly, such high killing efficiency and release rate could be well retained (unchanged effectiveness of both killing and release after four severe killing/release cycles), indicating the highly efficient regeneration and long-term reusability of this system. This study not only contributes zwitterionic polymers by conferring new functions but also provides a new, highly efficient and reliable surface for "killing-release" antibacterial strategy.

Salt-Responsive Zwitterionic Polymer Brushes with Tunable Friction and Antifouling Properties.

Development of smart, multifunction materials is challenging but important for many fundamental and industrial applications. Here, we synthesized and characterized zwitterionic poly(3-(1-(4-vinylbenzyl)-1H-imidazol-3-ium-3-yl)propane-1-sulfonate) (polyVBIPS) brushes as ion-responsive smart surfaces via the surface-initiated atom transfer radical polymerization. PolyVBIPS brushes were carefully characterized for their surface morphologies, compositions, wettability, and film thicknesses by atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), contact angle, and ellipsometer, respectively. Salt-responsive, switching properties of polyVBIPS brushes on surface hydration, friction, and antifouling properties were further examined and compared both in water and in salt solutions with different salt concentrations and counterion types. Collective data showed that polyVBIPS brushes exhibited reversible surface wettability switching between in water and saturated NaCl solution. PolyVBIPS brushes in water induced the larger protein absorption, higher surface friction, and lower surface hydration than those in salt solutions, exhibiting "anti-polyelectrolyte effect" salt responsive behaviors. At appropriate ionic conditions, polyVBIPs brushes were able to switch to superlow fouling surfaces (<0.3 ng/cm(2) protein adsorption) and superlow friction surfaces (u ∼ 10(-3)). The relationship between brush structure and its salt-responsive performance was also discussed. This work provides new zwitterionic surface-responsive materials with controllable antifouling and friction capabilities for multifunctional applications.

Risk Factors of Hidden Blood Loss in Unilateral Biportal Endoscopic Surgery for Patients with Lumbar Spinal Stenosis.

OBJECTIVE: Unilateral biportal endoscopic (UBE) surgery has recently been used as a minimally invasive procedure for the treatment of lumbar spinal stenosis and is associated with less perioperative blood loss. However, perioperative hidden blood loss (HBL) may be neglected during UBE. This study aimed to examine the volume of HBL and discuss the influential risk factors for HBL during unilateral biportal endoscopic surgery. METHODS: From January 2022 to August 2022, 51 patients underwent percutaneous unilateral biportal endoscopic surgery for lumbar spinal stenosis at the Department of Spinal Surgery of the Affiliated Traditional Chinese Medicine Hospital of Southwest Medical University and were enrolled in this study. The data included general indicators (age, sex and body mass index [BMI]), underlying disease (hypertension and diabetes), laboratory test results (prothrombin time [PT], activated partial thromboplastin time [APTT], fibrinogen [Fbg]), and preoperative and postoperative hematocrit and hemoglobin), related imaging parameters (severity of intervertebral disc [IVD] degeneration and soft tissue thickness of the interlaminar approach), number of operated vertebrae and operation time. Total blood loss (TBL) and HBL during surgical procedures were measured via the Gross formula. Influential factors were further analyzed by multivariate linear regression analysis and t-tests. RESULTS: The mean HBL was 257.89 ± 190.66 mL for single-operation patients and 296.58 ± 269.75 mL for two-operation patients. Patients with lower PT (p = 0.044), deeper tissue thickness (p = 0.047), and diabetes mellitus were determined to have more HBL during UBE. The operation time might also be an important factor (p = 0.047). However, sex (p = 0.265), age (p = 0.771/0.624), BMI (p = 0.655/0.664), APTT (p = 0.545/0.751), degree of degenerated IVD (p = 0.932/0.477), and hypertension (p = 0.356/0.896) were not related to HBL. CONCLUSION: This study determined the different influential factors of HBL during UBE. PT, tissue thickness, and diabetes mellitus are the independent risk factors that affect HBL incidence. Long PT may decrease the volume of HBL within a certain range. Tissue thickness and diabetes mellitus can lead to an increased volume of HBL.

Graphene/poly(vinylidene fluoride) composites with high dielectric constant and low percolation threshold.

In aiming to obtain highly flexible polymer composites with high dielectric performance, graphene/poly(vinylidene fluoride) (PVDF) composites with a multi-layered structure were proposed and prepared. Graphene sheets were prepared by reducing graphene oxide using phenylhydrazine, which could effectively alleviate aggregation of the graphene sheets. A two-step method, including solution casting and compression molding, was employed to fabricate the graphene/PVDF composites. The composites showed an alternative multi-layered structure of graphene sheets and PVDF. Due to their unique structure, the composites had an extremely low percolation threshold (0.0018 volume fraction of graphene), which was the lowest percolation threshold ever reported among PVDF-based polymer composites. A high dielectric constant of more than 340 at 100 Hz could be obtained within the vicinity of the percolation threshold when the graphene volume fraction was 0.00177. Above the percolation threshold, the dielectric constant continued to increase and a maximum value of as high as 7940 at 100 Hz was observed when the graphene volume fraction was 0.0177.

Fabrication of polyethylene surface with stable superhydrophobicity by nanoparticle assisted thermal micromolding process.

Superhydrophobic surface with lotus leaf effect has many practical and potential applications in different fields. In this paper, a novel process based on nanoparticle assisted thermal micromolding was developed to create polyethylene superhydrophobic surface. Briefly, a thin layer of TiO2 nanoparticles was first coated on the featured surface of the poly(dimethylsiloxane) (PDMS) stamp replicated from a fresh lotus leaf. Then low-density polyethylene (LDPE) was thermally pressed onto such TiO2 coated stamp. A control process was also performed by thermally pressing TiO2/LDPE nanocomposite material onto a blank PDMS stamp. Scanning electron microscopy (SEM) imaging and contact angle measurements showed that the surfaces of LDPE films replicated from stamp coated with TiO2 had more delicate nano-structures and higher water contact angles (> or = 155 degrees) than those replicated from the blank stamp. Moreover, the superhydrophobic surface formed by TiO2 assisted micromolding was relatively stable under water stream with high pressure. This study shows that nanoparticle assisted micromolding is an alternative technique to other techniques for large scale production of superhydrophobic polymeric films.

The Injected Foaming Study of Polypropylene/Multiwall Carbon Nanotube Composite with In Situ Fibrillation Reinforcement.

This paper explored the injection foaming process of in situ fibrillation reinforced polypropylene composites. Using polypropylene (PP) as the continuous phase, polytetrafluoroethylene (PTFE) as the dispersed phase, multi-wall carbon nanotubes (MWCNTs) as the conductive filler, and PP grafted with maleic anhydride (PP-g-MA) as the compatibilizer, a MWCNTs/PP-g-MA masterbatch was prepared by using a solution blending method. Then, a lightweight, conductive PP/PTFE/MWCNTs composite foam was prepared by means of extruder granulation and supercritical nitrogen (ScN2) injection foaming. The composite foams were studied in terms of rheology, morphological, foaming behavior and mechanical properties. The results proved that the in situ fibrillation of PTFE can have a remarkable effect on melt strength and viscoelasticity, thus improving the foaming performance; we found that PP/3% PTFE showed excellent performance. Meanwhile, the addition of MWCNTs endows the material with conductive properties, and the conductivity reached was 2.73 × 10-5 S/m with the addition of 0.2 wt% MWCNTs. This study's findings are expected to be applied in the lightweight, antistatic and high-performance automotive industry.

GO@Fe3O4@CuSilicate Composite with a Hierarchical Structure: Fabrication, Microstructure, and Highly Electromagnetic Shielding Performance.

Two nanocomposites with a hierarchical structure (GO@CuSilicate@Fe3O4 and GO@Fe3O4@CuSilicate) were fabricated in this paper. These as-synthesized nanocomposites were analyzed for their structural, compositional, and morphological features by X-ray diffraction, scanning electron microscopy (SEM), Raman spectroscopy, and Brunauer-Emmett-Teller methods. SEM images showed that both nanocomposites had a core-shell structure, and their shells were composed of CuSilicate nanoneedle arrays. Further, their total electromagnetic shielding efficiency was measured and compared in a wide frequency range of 8-12 GHz (X-band). Because of the "antenna" role of CuSilicate nanoneedle arrays and the polarization at the interface between graphene oxide (GO) and Fe3O4, GO@Fe3O4@CuSilicate showed higher electromagnetic shielding performance than that of GO@CuSilicate@Fe3O4. With 1 mm thickness, GO@Fe3O4@CuSilicate showed a high electromagnetic shielding efficiency (over 40 dB) in the whole X-band (8.2-12.4 GHz) and reached a maximum value (41.8 dB) at 8.2 GHz. Its total electromagnetic shielding efficiency was mainly contributed by absorption rather than reflection. This study provided an idea for the structural design of high-performance electromagnetic shielding materials in the GHz frequency range (X band).

Adjustable and ultrafast light-cured hyaluronic acid hydrogel: promoting biocompatibility and cell growth.

Bio-sourced hydrogels are attractive materials for diagnosing, repairing and improving the function of human tissues and organs. However, their mechanical strength decreases with an increase in water content. Furthermore, it is challenging to mold these hydrogels with high precision, which significantly limits their applications. Herein, we modified a biocompatible and biodegradable material, hyaluronic acid, with methacrylic anhydride and then cured it with a four-arm star structure cross-linking agent under ultraviolet light. The hyaluronic acid hydrogel was finally cured within 15 s with an adjustable cross-linking degree. The results demonstrated that the developed gel maintained good mechanical strength with a water content of 90%, while achieving micropatterns at a precision of 20 µm. The biological experiments showed that it could effectively promote the release of vascular endothelial growth factor (VEGF), which contributed to promoting cell growth, and has favorable biocompatibility. Overall, this hyaluronic acid hydrogel is a promising biomedical material with high forming accuracy, excellent mechanical properties, and favorable biocompatibility, which indicate its potential value in a variety of tissue engineering and biomedical applications.

Novel Salt-Responsive SiO2@Cellulose Membranes Promote Continuous Gradient and Adjustable Transport Efficiency.

Continuously growing interest in the controlled and tunable transport or separation of target molecules has attracted more attention recently. However, traditional "on-off" stimuli-responsive membranes are limited to nongradient feedback, which manifests as filtration efficiency that cannot be increased or decreased gradually along with the different stimuli conditions; indeed, only the transformation of on/off state is visible. Herein, we design and fabricate a series of robust salt-responsive SiO2@cellulose membranes (SRMs) by simply combining salt-responsive poly[3-(dimethyl(4-vinylbenzyl)ammonium)propyl sulfonate] (polyDVBAPS)-modified SiO2 nanoparticles and cellulose membranes under negative-pressure filtering. The antipolyelectrolyte effect induces stretch/shrinkage of polyDVBAPS chains inside the channels and facilities the directional aperture size and surface wettability variation, greatly enhancing the variability of interfacial transport and separation efficiency. Due to the linear salt-responsive feedback mechanism, the optimal SRMs achieve highly efficient target macromolecule separation (>75%) and rapid oil/saline separation (>97%) with a continuous gradient and adjustable permeability, instead of simply an "on-off" switch. The salt-responsive factors (SiO2-polyDVBAPS) could be reversibly separated or self-assembled to membrane substrates; thus, SRMs achieved unprecedented repeatability and reusability even after long-term cyclic testing, which exceeds those of currently reported membranes. Such SRMs possess simultaneously a superfast responsive time, a controllable gradient permeability, a high gating ratio, and an excellent reusability, making our strategy a potentially exciting approach for efficient osmotic transportation and target molecule separation in a more controllable manner.

Synthesis and characterization of a novel ruthenium(ii) trisbipyridine complex magnetic nanocomposite for the selective oxidation of phenols.

Anchoring ruthenium(ii) trisbipyridine complex [Ru(Bpy)3]2+ into a magnetic dendritic fibrous silica nanostructure produces an unprecedented strong nanocatalyst, FeNi3/DFNS/[Ru(Bpy)3]2+. Impressive oxidation of phenols to 1,4-benzoquinones catalyzed by FeNi3/DFNS/[Ru(Bpy)3]2+ is obtained in acetonitrile and water solution with molecular dioxygen as oxidant. Exclusively, apparently inert phenols such as phenol itself and mono-alkyl-substituted phenols are impressively oxidized to produce 1,4-benzoquinones through activation of the C-H bond in the position para to the carbon-oxygen bond under mild conditions. In addition, the production of industrially significant quinones that are known intermediates for vitamin combinations is investigated and studied FeNi3/DFNS/[Ru(Bpy)3]2+ magnetic nanoparticles were produced, and their properties were investigated by AFM, FTIR, XRD, TGA, SEM, TEM, and VSM.

Super Hydrophilic Semi-IPN Fluorescent Poly(N-(2-hydroxyethyl)acrylamide) Hydrogel for Ultrafast, Selective, and Long-Term Effective Mercury(II) Detection in a Bacteria-Laden System.

Convenient, low-cost chemosensors for hazardous mercury ion detection have been receiving more and more attention in recent studies. However, most of these practical studies are based on an ideal sterile detecting atmosphere and ignore the role of bacteria in actual Hg(II) analytes. Herein, we demonstrate a new type of hydrophilic semi-IPN fluorescent polyHEAA hydrogel chemosensors fabricated by UV polymerization in situ interpenetrating fluorescent polymer PA-NDBCB with a polyHEAA network. Because of specific intermolecular interaction, i.e., hydrogen bonding between hydrophilic fluorescent polymer and polyHEAA matrix comprising a distinct semi-IPN structure, the mechanical property of bulk fluorescent hydrogels can be greatly improved over that of pure polyHEAA hydrogels. Moreover, the design of the hydrogel chemosensors rely on the highly efficient cyclization reaction between Hg(II) ions and the thiourea moieties that induce a visible "green-to-blue" fluorescence color change. On account of the hydrophilic porous structures, these hydrogel chemosensors achieve ultrafast, sensitive, selective Hg(II) detection (detection limit of 0.067 µM) and enable facile ratiometric actual detection in real-world aqueous system. Notably, they maintain fluorescence emission and detection property even under long-term coculture in a complex E. coli bacteria-laden environment. This novel strategy could inspire future construction of soft interfaces/fluorescent apparatus for hazardous Hg(II) detection in a complex real-world system.

Extrusion Foaming of Lightweight Polystyrene Composite Foams with Controllable Cellular Structure for Sound Absorption Application.

Polymer foams are promising for sound absorption applications. In order to process an industrial product, a series of polystyrene (PS) composite foams were prepared by continuous extrusion foaming assisted by supercritical CO2. Because the cell size and cell density were the key to determine the sound absorption coefficient at normal incidence, the bio-resource lignin was employed for the first time to control the cellular structure on basis of hetero-nucleation effect. The sound absorption range of the PS/lignin composite foams was corresponding to the cellular structure and lignin content. As a result, the maximum sound absorption coefficient at normal incidence was higher than 0.90. For a comparison, multiwall carbon nanotube (MWCNT) and micro graphite (mGr) particles were also used as the nucleation agent during the foaming process, respectively, which were more effective on the hetero-nucleation effect. The mechanical property and thermal stability of various foams were measured as well. Lignin showed a fire retardant effect in PS composite foam.

One-Pot and One-Step Fabrication of Salt-Responsive Bilayer Hydrogels with 2D and 3D Shape Transformations.

Bilayer hydrogels are one of the most promising materials for use as soft actuators, artificial muscles, and soft robotic elements. Therefore, the development of new and simple methods for the fabrication of such hydrogels is of particular importance for both academic research and industrial applications. Herein, a facile, one-pot, and one-step methodology was used to prepare bilayer hydrogels. Specifically, several common monomers, including N-isopropyl acrylamide, acrylamide, and N-(2-hydroxyethyl)acrylamide, as well as two salt-responsive zwitterionic monomers, 3-(1-(4-vinylbenzyl)-1H-imidazol-3-ium-3-yl)propane-1-sulfonate (VBIPS) and dimethyl-(4-vinylphenyl)ammonium propane sulfonate (DVBAPS), were chosen and employed with different combinations and ratios to understand the formation and structural tunability of the bilayer hydrogels. The results indicated that a salt-responsive zwitterionic-enriched copolymer, which could precipitate from water, plays a dominant role in the formation of the bilayer structure and that the ratio between the common monomer and the zwitterionic monomer had a significant effect on the structure. Due to the salt-responsive properties of polyVBIPS and polyDVBAPS, the resultant bilayer hydrogels exhibited excellent bidirectional bending properties in response to the salt solution. With the optimal monomer pair and ratio determined, the bend of the hydrogel could be reversed from ∼-360 to ∼266° in response to a switch between water and a 1.0 M NaCl solution. Additionally, this method was further used to fabricate small-scaled patterns with structural and compositional distinction in two-dimensional hydrogel sheets. These two-dimensional hydrogel sheets exhibited complex and reversible three-dimensional shape transformations due to the different bending behaviors of the patterned hydrogel stripes under the action of an external stimulus. This work provides greater insight into the mechanism of the one-step, one-pot method fabrication of bilayer hydrogels, demonstrates the ability of this method for the preparation of small-scale patterns in hydrogel sheets to endow the complex with a three-dimensional shape transformation capability, and hopefully opens up a new pathway for the design and fabrication of smart hydrogels.

Design of salt-responsive and regenerative antibacterial polymer brushes with integrated bacterial resistance, killing, and release properties.

The development of smart materials and surfaces with multiple antibacterial actions is of great importance for both fundamental research and practical applications, but this has proved to be extremely challenging. In this work, we proposed to integrate salt-responsive polyDVBAPS (poly(3-(dimethyl(4-vinylbenzyl) ammonio)propyl sulfonate)), antifouling polyHEAA (poly(N-hydroxyethyl acrylamide)), and bactericidal TCS (triclosan) into single surfaces by polymerizing and grafting polyDVBAPS and polyHEAA onto the substrate in a different way to form two types of polyDVBAPS/poly(HEAA-g-TCS) and poly(DVBAPS-b-HEAA-g-TCS) brushes with different hierarchical structures, as confirmed by X-ray photoelectron spectroscopy (XPS), atom force microscopy (AFM), and ellipsometry. Both types of polymer brushes demonstrated their tri-functional antibacterial activity to resist bacterial attachment by polyHEAA, to release ∼90% of dead bacteria from the surface by polyDVBAPS, and to kill ∼90% of bacteria on the surface by TCS. Comparative studies also showed that removal of any component from polyDVBAPS/poly(HEAA-g-TCS) and poly(DVBAPS-b-HEAA-g-TCS) compromised the overall antibacterial performance, further supporting a synergistic effect of the three compatible components. More importantly, the presence of salt-responsive polyDVBAPS allowed both brushes to regenerate with almost unaffected antibacterial capacity for reuse in multiple kill-and-release cycles. The tri-functional antibacterial surfaces present a promising design strategy for further developing next-generation antibacterial materials and coatings for antibacterial applications.

Preparation of carbon-based hybrid particles and their application in microcellular foaming and flame-retardant materials.

Polymeric microcellular foams with high strength and light weight are very important for industrial applications. However, regulating their cell structure and their weak flame retardancy are problematic. We designed single-arm POSS-based ionic liquids ([bel-POSS][PF6]), and constructed hybrid composites based on physical interaction between ionic liquids and carbon-based materials in PS microcellular foaming. Ionization of bel-POSS could result in a quaternary ammonium reaction and ion-exchange reaction, and the carbon materials exhibit good dispersion through blending. The prepared hybrid composites showed high CO2 adsorption. Conical calorimeter tests showed that PS composite materials could reduce the heat release rate, total heat release, toxic gases (CO2 and CO) release, and amount of smoke generated. These carbon materials could affect PS micropore structure, including the cell diameter and density. Upon addition of 5 wt% of carbon materials, the hole diameter decreased by >50%, and the hole density increased nearly ten folds.