Injectable In Situ Photocrosslinked Hydrogel Dressing for Infected Wound Healing.

A traditional injectable photocrosslinked hydrogel had disadvantages of the residual photoinitiator and toxic crosslinker, slow in situ curing, and a complex preparation process. At the same time, hydrogels cannot act as artificial skin to restore skin sensory function during the wound healing cycle. In this work, an injectable photocrosslinked hydrogel was prepared which can be quickly in situ cured without photoinitiator. Oxidized sodium alginate was used as a natural macromolecular crosslinking agent to form an injectable hydrogel framework with the photosensitive polymer polyvinyl alcohol bearing styrylpyridinium group (PVA-SBQ). In addition, the hydrogel was endowed with photothermal therapy property after the introduction of biomass-like polydopamine particles. When used as a wound dressing, the hydrogel exhibited an excellent antibacterial property, with an antibacterial rate of 99.56% Escherichia coli and 97.96% Staphylococcus aureus. As a result, the hydrogel could significantly accelerate the repair of infected wounds, with a wound healing rate of 96.45% after 14 days. Moreover, the hydrogel exhibited a sensitive and stable sensing property, making it promising to reconstitute the sensory function of damaged skin during treatment. This work provides an idea for the development of injectable photocrosslinked hydrogel dressing.

A Review: Current Status and Emerging Developments on Natural Polymer-Based Electrospun Fibers.

In recent years, natural polymer-based electrospun fibers (EFs) with huge specific surface area, good biocompatibility, and biological activity obtained from electrospinning process exhibit tremendous vitality in the field of biomedical areas. Herein, the parameters of electrospinning from two perspectives, polymer solution such as solvent, polymeric relative molecular mass, concentration, viscosity, and conductivity of the solution, and electrospinning process such as spinning voltage, spinning flow rate, needle tip to collector distance, temperature, and humidity are first detailed. Next, the raw materials consisting of polysaccharides such as cellulose, hyaluronic acid, alginate, and chitosan as well as proteins such as collagen, gelatin, silk fibroin, and keratin are summarized. The preparation method and related characteristics of EFs with multistage structures such as porous, core-shell, Janus, bamboo-like and other structures are introduced. The biomedical applications of these natural polymer-based EFs mainly including tissue engineering, drug sustained release, wound dressings, and biomedical sensors are systematically recapitulated. Finally, the outlook on natural EFs is further proposed.

Polypropylene Hollow Fiber Membrane by Dissolution-Inducing Pore Methods.

Plasma leakage limits the development of polypropylene membranes as oxygenated membranes. Here, a new method named the dissolution-induced pore method was adapted to prepare polypropylene hollow fiber membranes: after polypropylene and polyvinyl chloride were melt-blended and extruded, the polyvinyl chloride was removed by N, N-dimethylacetamide to obtain a porous polypropylene membrane material. The variation of membranes has been explored in detail with respect to the influence of different parameters on the flux and mechanical properties of membranes and the feasibility of the polyvinyl chloride recovery. The resulting polypropylene hollow fiber membrane shows that plasma penetration was zero within 6 h of test, gas flux can reach 189,000 L/(m2·h·0.1 MPa), and its strength at break reaches 65 MPa and the elongation at break is 890%; polyvinyl chloride recovery achieves more than 99%. This research has developed a promising and low-cost extracorporeal membrane oxygenation material, which provides benefits for patients with less capacity for medical expenditure.

Polypropylene Hollow-Fiber Membrane Made Using the Dissolution-Induced Pores Method.

The efficient preparation of hydrophilic polypropylene membranes has always been a problem. Here, a twin-screw extruder was used to melt-blend ethylene-vinyl alcohol copolymer and polypropylene; then, hollow fibers were extrusion-molded with a spinneret and taken by a winder; after this, dimethyl sulfoxide was used to dissolve the ethylene-vinyl alcohol copolymer of the fiber to obtain a polypropylene hollow-fiber membrane. This procedure was used to study the effects of different contents and segment structure of ethylene-vinyl alcohol copolymer on the structure and filtration performance of the membranes; furthermore, the embedded factor and blocked factor were used to evaluate the ethylene-vinyl alcohol copolymer embedded in the matrix without dissolving and or being completely blocked in the matrix, respectively. The results show that the increase in ethylene-vinyl alcohol copolymer could reduce the embedded factor and increase the blocked factor. The increase in the polyethylene segments of ethylene-vinyl alcohol copolymer could increase both the embedded factor and blocked factor. The water permeation of the membrane reached 1300 Lm-2·h-1·bar-1 with a 100% rejection of ink (141 nm) and the elongation at break reached 188%, while the strength reached 22 MPa. The dissolution-induced pores method provides a completely viable alternative route for the preparation of polypropylene membranes.

Recoverable underwater superhydrophobicity from a fully wetted state via dynamic air spreading.

Maintaining the superhydrophobicity underwater offers drag resistance reduction, antifouling, anti-corrosion, noise reduction, and gas collection for boat hulls and submarine vehicles. However, superhydrophobicity typically does not last long underwater since the Cassie state is metastable. Here, we report a reversible and localized recovery of superhydrophobicity from the fully wetted state via air bubble spreading. Composed of sparse fluorinated chained nanoparticles, the submerged surface shows super-low energy barrier for bubble attachment. Especially the recovered plastron exhibits excellent longevity. Based on a simplified, truncated nanocone model, the dynamic spreading of bubbles is analyzed considering two basic parameters, i.e., surface geometric structure and surface energy (which appeared as intrinsic water contact angle). Numerical simulation results via COMSOL confirms the effect of geometric structure on bubble spreading. This investigation will not only offer new insights for the design of robust recoverable superhydrophobic surfaces but also broaden the applications of superhydrophobic coatings.

Fabrication of a Dual-Action Membrane with Both Antibacterial and Anticoagulant Properties via Cationic Polyelectrolyte-Induced Phase Separation.

The development of microorganisms and formation of thrombus on a biomaterial surface can seriously lead to device failure and threaten human health. Nonetheless, a surface that has both antibacterial and anticoagulant properties has scarcely been developed. Herein, a novel dual-action membrane composed of polyethersulfone (PES) bulk material and a hydrophilic anionic poly-2-acrylamido-2-methylpropanesulfonic acid (PAMPS) polymer has been prepared via the cationic antibacterial agent poly(hexamethylene biguanide) (PHMB)-induced phase separation technique. Interestingly, the resultant membrane can offer tunable antibacterial and anticoagulant properties, while maintaining satisfactory permeability and greatly increasing selectivity. The membrane also shows excellent hydrophilicity, a well-defined porous surface, and cross section with a sponge gradient structure. Furthermore, the PHMB-PAMPS complex formed on the membrane surface displays outstanding long-term stability, which is crucial for further practical applications. More importantly, the hollow fiber membrane fabricated by the cationic polyelectrolyte-induced phase separation technique confirms its capability to control the membrane permeability (257.4 L·m-2·h-1·bar-1) and selectivity (95.9%) without destroying the membrane structure. The present work opens a straightforward and efficient avenue for the rational design of a functional surface to fight biomedical material-associated infections.

Efficient removal of heavy metal ions by forward osmosis membrane with a polydopamine modified zeolitic imidazolate framework incorporated selective layer.

A novel thin film nanocomposite (TFN) forward osmosis (FO) membrane with a positively charged and nano-functional selective layer has been developed for effective heavy metal ions removal. The selective layer is constructed by penetrating the polydopamine modified zeolitic imidazolate framework (ZIF-8@PDA) in the poly(ethyleneimine)/1,3,5-benzenetricarboxylic acid chloride (PEI/TMC) crosslinked matrix. Compared with the pristine thin film composite (TFC) membrane, the thin film nanocomposite membrane (0.05 wt % nanofillers loading) exhibits a higher water flux (20.8 vs12.8 LMH) without losing of selectivity in terms of Js/Jw ratio (0.25 vs 0.20 g L-1) in FO mode. This improvement of the permeability is mainly attributed to the optimized selective layer with good wettability and loose structure. Besides, the modified PDA layer facilitates the affinity between the nanofillers and selective layer, which results in an ideal selectivity. In addition, this modified membrane shows a high heavy metal ion (Cu2+, and Ni2+ and Pb2+) rejection (>96%) in FO mode. Our finding offers a simple and efficient method to enhance the FO performance of membrane by designing the selective layer for treating heavy metal wastewater.

Fabrication of a loose nanofiltration candidate from Polyacrylonitrile/Graphene oxide hybrid membrane via thermally induced phase separation.

It is still a challenge to design and fabricate a robust nanoporous membrane in large scale and of fundamental importance for practical application. Here, a robust three/two-dimensional polyacrylonitrile/graphene oxide (PAN/GO) homogeneous nanoporous membrane is fabricated in large scale via thermally induced phase separation method, which guarantees the membrane with high mechanical strength and selective separation properties. Differing from conventional nanofiltration (NF) membrane with high rejection to both salt and dye, the resulting hybrid membrane is relative loose, which shows outstanding performances, i.e. high dye rejection and low salt rejection, high permeability and antifouling properties, acting as a promising candidate for dye/salt fractionation. The incorporation of 0.2 wt% GO endows membrane with excellent performance, where high tensile strength, high water permeability (33 L⋅ m-2⋅ h-1⋅ bar-1), selectivity (100% to methyl blue, 99.8% to acid red 18, 26.7% to magnesium sulfate and 10.9% to sodium chloride and flux recovery ratio of 84.4%) are perfectly balanced. Its homogeneous structure and high strength guarantee long term use without the peeling of thin active layer as encountered by conventional NF membranes. The successful fabrication of such a hybrid membrane provides an attractive opportunity for loose NF membrane preparation with performance enhancement in a feasible way for practical application.

Capsaicin-Inspired Thiol-Ene Terpolymer Networks Designed for Antibiofouling Coatings.

Novel photocurable ternary polymer networks were prepared by incorporating N-(4-hydroxy-3-methoxybenzyl)-acrylamide (HMBA) into a cross-linked thiol-ene network based on poly(ethylene glycol)diacrylate (PEGDA) and (mercaptopropyl)methylsiloxane homopolymers (MSHP). The ternary network materials displayed bactericidal activity against Escherichia coli and Staphylococcus aureus and reduced the attachment of marine organism Phaeodactylum tricornutum. Extensive soaking of the polymer networks in aqueous solution indicated that no active antibacterial component leached out of the materials, and thus the ternary thiol-ene coating killed the bacteria by surface contact. The surface structures of the polymer networks with varied content ratios were studied by sum frequency generation (SFG) vibrational spectroscopy. The results demonstrated that the PDMS Si-CH3 groups and mimic-capsaicine groups are predominantly present at the polymer-air interface of the coatings. Surface reorganization was apparent after polymers were placed in contact with D2O: the hydrophobic PDMS Si-CH3 groups left the surface and returned to the bulk of the polymer networks, and the hydrophilic PEG chains cover the polymer surfaces in D2O. The capasaicine methoxy groups are able to segregate to the surface in an aqueous environment, depending upon the ratio of HMBA/PEGDA. SFG measurements in situ showed that the antibacterial HMBA chains, rather than the nonfouling PEG, played a dominant role in mediating the antibiofouling performance in this particular polymer system.

Novel Anti-Biofouling Soft Contact Lens: l-Cysteine Conjugated Amphiphilic Conetworks via RAFT and Thiol-Ene Click Chemistry.

A unique l-cysteine conjugated antifouling amphiphilic conetwork (APCN) is synthesized through end-crosslinking of well-defined triblock copolymers poly(allyl methacrylate)-b-poly(ethylene glycol)-b-poly(allyl methacrylate) via a combination of reversible addition-fragmentation chain transfer (RAFT) polymerization and thiol-ene "click" chemistry. The synthesized poly(ethylene glycol) macro-RAFT agent initiates the polymerization of allyl methacrylate in a controlled manner. The vinyl pendant groups of the precursor partially conjugate with l-cysteine and the rest fully crosslink with mercaptopropyl-containing siloxane via thiol-ene click chemistry under UV irradiation into APCNs, which show distinguished properties, that is, excellent biocompatibility, more than 39.6% water content, 101 barrers oxygen permeability, optimized mechanical properties, and more than 93% visible light transmittance. What's more, the resultant APCNs exhibit eminent resistance to protein adsorption, where the bovine serum albumin and lysozyme adsorption are decreased to 12 and 21 µg cm-2 , respectively. The outstanding properties of APCNs depend on the RAFT controlled method, which precisely designs the hydrophilic/hydrophobic segments and eventually greatly improves the crosslinking efficiency and homogeneity. Meantime, the l-cysteine monolayer can effectively reduce the surface hydrophobicity and prevent protein adsorption, which exhibits the viability for antifouling surface over and under ophthalmic devices, suggesting a promising soft contact lens.

Constructing a novel zwitterionic surface of PVDF membrane through the assembled chitosan and sodium alginate.

A novel zwitterionic surface of PVDF membrane with significantly improved antifouling properties was prepared though pressure-assisted layer by layer self-assembly method based on the electrostatic interactions of chitosan (CS), sodium alginate (SA) and polyfunctional lysine. For the modified C-S-C-S-L membrane, the contact angle decreased to 35°, the bovine serum albumin (BSA) adsorption mass of static fouling on the membrane surface decreased to 10µg/cm(2), and the secondary water flux recovery rate (FRR) of dynamic fouling of BSA and humic acid (HA) pollutants increased to 98% and 99%, respectively, exhibiting excellent antifouling performance. The results demonstrated that using charged bio-macromolecules and amino acids to build zwitterionic surface was effective and convenient to change the interface properties of the separation membrane through the pressure-assisted self-assembly modification method, and provided a new way for the industrial scale hydrophilic modification of hydrophobic porous membrane materials.

Drawing dependent structures, mechanical properties and cyclization behaviors of polyacrylonitrile and polyacrylonitrile/carbon nanotube composite fibers prepared by plasticized spinning.

Drawing to change the structural properties and cyclization behaviors of the polyacrylonitrile (PAN) chains in crystalline and amorphous regions is carried out on PAN and PAN/carbon nanotube (CNT) composite fibers. Various characterization methods including Fourier transform infrared spectroscopy, differential scanning calorimetry, X-ray diffraction and thermal gravimetric analysis are used to monitor the structural evolution and cyclization behaviors of the fibers. With an increase of the draw ratio during the plasticized spinning process, the structural parameters of the fibers, i.e. crystallinity and planar zigzag conformation, are decreased at first, and then increased, which are associated with the heat exchange rate and the oriented-crystallization rate. A possible mechanism for plasticized spinning is proposed to explain the changing trends of crystallinity and planar zigzag conformation. PAN and PAN/CNT fibers exhibit various cyclization behaviors induced by drawing, e.g., the initiation temperature for the cyclization (Ti) of PAN fibers is increased with increasing draw ratio, while Ti of PAN/CNT fibers is decreased. Drawing also facilitates cyclization and lowers the percentage of ß-amino nitrile for PAN/CNT fibers during the stabilization.

Efficient Preparation of Super Antifouling PVDF Ultrafiltration Membrane with One Step Fabricated Zwitterionic Surface.

On the basis of the excellent fouling resistance of zwitterionic materials, the super antifouling polyvinylidene fluoride (PVDF) membrane was efficiently prepared though one-step sulfonation of PVDF and polyaniline blend membrane in situ. The self-doped sulfonated polyaniline (SPANI) was generated as a novel zwitterionic polymer to improve the antifouling property of PVDF ultrafiltration membrane used in sewage treatment. Surface attenuated total reflection Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, surface zeta potential, and water contact angle demonstrated the successful fabrication of zwitterionic interface by convenient sulfonation modification. The static adsorption fouling test showed the quantified adsorption mass of bovine serum albumin (BSA) pollutant on the PVDF/SPANI membrane surface decreases to 3(±2) µg/cm(2), and the water flux recovery ratio (FRR) values were no less than 95% for the three model pollutants of BSA, sodium alginate (SA), and humic acid (HA), which were corresponding hydrophobic, hydrophilic, and natural pollutants in sewage, respectively. This Research Article demonstrated the antifouling advantages of zwitterionic SPANI and aimed to provide a simple method for the large scale preparation of zwitterionic antifouling ultrafiltration membranes.

Engineering a Highly Hydrophilic PVDF Membrane via Binding TiO2Nanoparticles and a PVA Layer onto a Membrane Surface.

A highly hydrophilic PVDF membrane was fabricated through chemically binding TiO2 nanoparticles and a poly(vinyl alcohol) (PVA) layer onto a membrane surface simultaneously. The chemical composition of the modified membrane surface was determined by X-ray photoelectron spectroscopy, and the binding performance of TiO2 nanoparticles and the PVA layer was investigated by a rinsing test. The results indicated that the TiO2 nanoparticles were uniformly and strongly tailored onto the membrane surface, while the PVA layer was firmly attached onto the surface of TiO2 nanoparticles and the membrane by adsorption-cross-linking. The possible mechanisms during the modification process and filtration performance, i.e., water permeability and bovine serum albumin (BSA) rejection, were investigated as well. Furthermore, antifouling property was discussed through multicycles of BSA solution filtration tests, where the flux recovery ratio was significantly increased from 20.0% for pristine PVDF membrane to 80.5% for PVDF/TiO2/PVA-modified membrane. This remarkable promotion is mainly ascribed to the improvement of surface hydrophilicity, where the water contact angle of the membrane surface was decreased from 84° for pristine membrane to 24° for PVDF/TiO2/PVA membrane. This study presents a novel and varied strategy for immobilization of nanoparticles and PVA layer on substrate surface, which could be easily adapted for a variety of materials for surface modification.

"Near perfect" amphiphilic conetwork based on end-group cross-linking of polydimethylsiloxane triblock copolymer via atom transfer radical polymerization.

Novel amphiphilic conetworks (APCNs) with uniform channel size were synthesized through end-cross-linking of well-defined amphiphilic triblock copolymers via atom transfer radical polymerization (ATRP). A new ditelechelic polydimethylsiloxane macroinitiator was synthesized to initiate the polymerization of N,N-dimethylacrylamide. The resulting triblock copolymers show well-defined molecular weight with narrow polydisperisty, which are telechelic modified by allylamine and fully cross-linked with polyhydrosiloxanes through hydrosilylation. Transmission electron microscopy shows that the APCN has the behavior of microphase separation with small channel size and uniform phase domain. The resulting APCNs with idealized microstructure exhibit a combination of excellent properties, i.e., superhigh mechanical strength (4 ± 1 MPa) and elongation ratio (175 ± 25%), outstanding oxygen permeability (350 ± 150 barrers), a high water uptake property, and excellent biocompatibility, indicating that in this way, "near perfect" networks are obtained. These results are better than those reported in the literature, suggesting a promising semipermeable barrier for islet encapsulation in relative biomaterial fields.

Structure and properties of chitin whisker reinforced chitosan membranes.

In this paper, rod-like chitin whisker was used as a filler to reinforce the chitosan membrane, and a series of composite membranes were prepared by casting-evaporation method. Mechanical testing shows that tensile strength of the resulting composite membrane with 3 wt% chitin whisker content reaches up to 110.3 MPa, which is about 2.8 times than that of neat chitosan membrane (38.5 MPa), and moisture regain of all composite membranes presents a decreasing tendency with increasing content of chitin whisker. Furthermore, SEM was used to investigate the morphology difference between neat chitosan membrane and composite membranes, to understand the reinforce mechanism of chitin whisker. Wide angle x-ray diffraction and Fourier transform infrared spectroscopy were used to visualize the structure change before and after the compositing processes. Besides, the bacterostatic test shows that this composite membrane presents effective inhibitory effect on Staphylococcus aureus, Escherchia coli and Corinebaterium michiganence respectively, which indicates it a promising material for packaging and wound dressing.

High tenacity regenerated chitosan fibers prepared by using the binary ionic liquid solvent (Gly·HCl)-[Bmim]Cl.

A binary ionic liquid system was confirmed to be a promising solvent to dissolve chitosan, and the regenerated chitosan fibers were prepared by wet and dry-wet spinning technique respectively. The SEM results show that the chitosan fibers prepared by wet spinning technique present striated surface and round cross section, and the chitosan fibers prepared by dry-wet spinning technique present smooth surface and irregular cross section. The mechanical testing results show that the regenerated chitosan fibers present relatively high tenacity, especially, these prepared by dry-wet spinning process present excellent strength and initial modulus, i.e. 2.1cN/dtex and 83.5cN/dtex, which is stronger than that of most reported chitosan fibers. The FT-IR results show that the dissolution of chitosan in the binary ionic liquid system is due to the protonation of NH2 groups in the chitosan chains. Furthermore, a possible reaction during the dissolution and regeneration process is proposed.

A comparative study on the chitosan membranes prepared from glycine hydrochloride and acetic acid.

In this study, glycine hydrochloride (Gly·HCl) is confirmed to be a promising solvent for dissolving native chitosan and preparing regenerated chitosan membrane. As compared with the chitosan membrane prepared from traditional acetic acid, the membrane prepared from Gly·HCl by dry technique shows excellent tensile strength and initial modulus, i.e. 103.8MPa and 3.2GPa, respectively, which is superior to any chitosan membrane and most chitosan blend membranes reported in literatures. Besides, scanning electron microscopy (SEM), wide-angle X-ray diffraction (WAXD) and Fourier transform infrared spectroscopy (FT-IR) were used to visualize the difference between the two kind of regenerated chitosan membranes. The SEM results show that the membrane prepared from Gly·HCl by dry technique presents a novel structure, which ensures its high tenacity. Furthermore, the chitosan microporous membranes were also prepared using PEG as porogen.