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The construction of a biomaterial matrix with biological properties is of great importance to developing functional materials for clinical use. However, the site-specific immobilization of growth factors to endow materials with bioactivities has been a challenge to date. Considering the wide existence of glycosylation in mammalian proteins or recombinant proteins, we establish a bioaffinity-based protein immobilization strategy (bioanchoring method) utilizing the native sugar-lectin interaction between concanavalin A (Con A) and the oligosaccharide chain on glycosylated bone morphogenetic protein-2 (GBMP-2). The interaction realizes the site-specific immobilization of GBMP-2 to a substrate modified with Con A while preserving its bioactivity in a sustained and highly efficient way, as evidenced by its enhanced ability to induce osteodifferentiation compared with that of the soluble GBMP-2. Moreover, the surface with Con A-bioanchored GBMP-2 can be reused to stimulate multiple batches of C2C12 cells to differentiate almost to the same degree. Even after 4 month storage at 4 °C in phosphate-buffered saline (PBS), the Con A-bioanchored GBMP-2 still maintains the bioactivity to stimulate the differentiation of C2C12 cells. Furthermore, the ectopic ossification test proves the in vivo bioactivity of bioanchored GBMP-2. Overall, our results demonstrate that the tag-free and site (i.e., sugar chain)-specific protein immobilization strategy represents a simple and generic alternative, which is promising to apply for other glycoprotein immobilization and application. It should be noted that although the lectin we utilized can only bind to d-mannose/d-glucose, the diversity of the lectin family assures that a specific lectin could be offered for other sugar types, thus expanding the applicable scope further.

Fenton reaction, a typical inorganic reaction, is broadly utilized in the field of wastewater treatment. Recently In case of its ability to inhibit the growth of cancer cells, it has been frequently reported in cancer treatment. Using the unique tumor microenvironment in cancer cells, many iron-based nanoparticles have been developed to release iron ions in cancer cells to induce Fenton reaction. In this mini review, we outline several different types of iron-based nanoparticles and several main means to enhance Fenton reaction in cancer cells. Finally, we discussed the advantages and disadvantages of iron-based nanoparticles for cancer therapy, prospected the future development of iron-based nanoparticles. It is believed that iron-based nanoparticles can make certain contribution to the cause of human cancer in the future.

Casticin has wide-ranging functional activities, but its water solubility is poor in food products. Here, a nanoemulsion stabilized by Maillard whey protein isolate conjugates (MWPI) was fabricated to encapsulate casticin. The nanoemulsion, with an average diameter of 200 nm, possessed the capability to load 700 μg/g casticin. MWPI-stabilized nanoemulsion showed better stability than that of the WPI nanoemulsion during 4 weeks of storage. Both the inhibition effects of the casticin-loaded nanoemulsion on cancer cells and the process of cellular uptake were studied. Results revealed that the casticin-loaded nanoemulsion had better inhibitory activity in HepG2 and MCF-7 cells than free casticin. Cellular uptake of the nanoemulsion displayed a time-dependent manner. After the nanoemulsion passed into HepG2 and MCF-7 cells, it would locate in the lysosome but not in the nucleus. The main pathway for the nanoemulsion to enter HepG2 cells was pinocytosis, whereas, it entered MCF-7 predominantly through the clathrin-mediated pit. This work implies that MWPI-stabilized nanoemulsions could be utilized as an effective delivery system to load casticin and have the potential to be applied in the food and pharmaceutical industries.

The abundantly released tail-gas from lignocellulose pretreatment with phosphoric acid plus hydrogen peroxide (PHP) was found to accelerate the aging of latex/silicone textural accessories of the pretreatment device. Inspired by this, tail-gas was utilized to control organic pollutants. Methylene blue (MB), as a model pollutant, was rapidly decolorized by the tail-gas, and oxidative degradation was substantially proven by full-wavelength scanning with a UV–visible spectrometer. The tail-gas from six typical lignocellulosic feedstocks produced 68.0–98.3% MB degradation, suggesting its wide feedstock compatibility. Three other dyes, including rhodamine B, methyl orange and malachite green, obtained 97.5–99.5% degradation; moreover, tetracycline, resorcinol and hexachlorobenzene achieved 73.8–93.7% degradation, suggesting a superior pollutant compatibility. In a cytotoxicity assessment, the survival rate of the degraded MB was 103.5% compared with 80.4% for the untreated MB, implying almost no cytotoxicity after MB degradation. Mechanism investigations indicated that the self-exothermic reaction in PHP pretreatment drove the self-generated peroxy acids into tail-gas. Moreover, it heated the pollutant solution and thermally activated peroxy acids as free radicals for efficient pollutant degradation. Here, a brand-new technique for degrading organic pollutants with a “Win–Win–Win” concept was purposed for lignocellulose valorization, pollutant control by waste tail-gas, and biofuel production.

The secretions of the venom glands, dry skin and whole body of several Bufo species have been used as traditional medicines in East Asia to treat heart failure and cancer. Due to the highly similar morphological features of Bufo species and their derived commercial crude drugs, along with the high similarity of chemical composition of the secretions of venom glands, it is very challenging to identify the medicinal toads and the related crude drugs. The cyt-b sequences provide useful information to authenticate medicinal Bufo species. Based on the cyt-b sequences, a simple PCR-RFLP method was established for the identification of the medicinally used Bufo species as well as their derived crude drugs. The 23 specimens from three medicinally used Bufo species, B. bufo gargarizans (Bbg), B. melanostictus (Bm) and B. raddei (Br), were clearly divided into 3 groups according to the sequences of amplified cyt-b regions, which could be digested by specific restriction enzymes NcoI, EcoRV and BstXI, respectively. Then the specific PCR-RFLP method was further used to identify 9 samples of commercial crude drugs even with serious degradation of DNA, and all nine samples were identified as B. bufo gargarizans. The method is suitable for identification of medicinally used Bufo species and the related crude drugs.

Poor mechanical performances severely limit the application of hydrogels in vivo; for example, it is difficult to perform a very common suturing operation on hydrogels during surgery. There is a growing demand to improve the mechanical properties of hydrogels for broadening their clinical applications. Natural polyphenols can match the potential toughening sites in our previously reported PEG-lysozyme (LZM) hydrogel because polyphenols have unique structural units including a hydroxyl group and an aromatic ring that can interact with PEG via hydrogen bonding and form hydrophobic interactions with LZM. By utilizing polyphenols as noncovalent crosslinkers, the resultant PEG-LZM-polyphenol hydrogel presents super toughness and high elasticity in comparison to pristine PEG-LZM with no obvious changes in the initial shape, and it can even withstand the high pressure from sutures. At the same time, the mechanical properties could be widely adjusted by varying the polyphenol concentration. Interestingly, the PEG-LZM-polyphenol hydrogel has a higher water content than other polyphenol-toughened hydrogels, which may better meet the clinical needs for hydrogel materials. Besides, the introduction of polyphenols endows the hydrogel with improved antibacterial and anti-inflammatory abilities. Finally, the PEG-LZM-polyphenol (tannic acid) hydrogel was demonstrated to successfully patch a rabbit myocardial defect by suturing for 4 weeks and improve the wound healing and heart function recovery compared to autologous muscle patches.

Open wounds and burns are prone to infection and there remains considerable interest in developing safe and effective mechanisms to confer antimicrobial activities to wound dressings. We report a biomimetic wound dressing for the in situ and sustained generation of reactive oxygen species (ROS). Specifically, we fabricate a catechol-modified chitosan film that mimics features of the melanin capsule generated during an insect immune response to infection. We use an electrochemical reverse engineering approach to demonstrate that this catechol-chitosan film possesses redox-activities and can be repeatedly oxidized and reduced. In vitro tests demonstrate that this film catalyzes the transfer of electrons from physiological reductant ascorbate to O 2 for sustained ROS generation, and confers ascorbate-dependent antimicrobial activities. In vivo antimicrobial experiment with a rat subcutaneous model indicates the catechol-chitosan film at reduced state inhibits the bacterial growth and alleviates the infection of the incisions. Open wound healing tests with a mouse model indicate that the catechol-chitosan film suppresses the bacterial population at the wound site, induces less inflammation and promotes wound healing. We envision this biomimetic approach for the sustained, localized and in situ generation of ROS could provide new opportunities for wound management by protecting against pathogen infection and potentially even enlisting ROS-mediated wound healing mechanisms.

All-inorganic CsPbIBr2 perovskite has been regarded as a promising candidate for perovskite solar cells (PSCs) considering its suitable bandgap and high stability. However, the poor quality of CsPbIBr2 film greatly impedes the performance improvement of CsPbIBr2-based PSCs. Herein, we report a facile strategy to improve the quality of CsPbIBr2 perovskite film by introducing cellulose acetate (CA) into the perovskite precursor solution. The interaction between the oxygen functional groups of CA and Pb2+ and the increase of the precursor viscosity induced by CA addition can slow down the crystallization rate of CsPbIBr2 perovskite, which allows the perovskite films have enough time to form high-quality crystal structure. By optimizing the amount of CA (the optimal amount of CA is 2.5 wt%), a high-quality CsPbIBr2 perovskite film with high crystallinity, large grain size, and smooth surface is obtained. As consequence, the carbon-based PSC with a structure of FTO/TiO2/perovskite/carbon using the CsPbIBr2 perovskite film with 2.5 wt% CA achieves a champion efficiency of 7.52%, which is increased by 40.8% compared with the cell based on pure CsPbIBr2 perovskite film. In addition, the PSC based on CsPbIBr2 film with CA exhibits an excellent long-term stability under both ambient condition and high-humidity environment.

Zwitterionic polymers play an attractive role in the application of stealthy nanocarriers for their excellent antifouling property. Herein, a zwitterionic nanogel with temperature sensitivity and redox-responsive degradability prepared by copolymerization of N-vinylcaprolactam (VCL) and 2-(methacryloyloxy) ethyldimethyl-(3-sulfopropyl) ammonium hydroxide (DMAPS) via aqueous precipitation polymerization. The prepared nanogels own ultra-high colloidal stability and non-specific protein adsorption resistance as a result of the incorporation of zwitterionic groups. Meanwhile, they exhibit sensitive temperature-induced swelling/collapse transition in aqueous solution and excellent redox-degradability ascribed to the presence of disulfide bonds. The nanogels loaded with anticancer drug doxorubicin (DOX) exhibit low leakage of DOX under physiological conditions (merely 23.8 % within 24 h), whereas striking release amount of DOX under reducing conditions combined with elevated temperature (93.4 % within 24 h). The measurement of cell viability showed that the cytotoxicity of blank nanogels to tumor cells (HeLa cells) was negligible, while the nanogels loaded with DOX had a prominent inhibitory impact on tumor cells.

Reported herein is a chiral resolution polysulfone membrane prepared via mussel-inspired chemistry. Polysulfone membranes were modified with dopamine, which underwent in situ polymerization on the membrane substrate, and β-cyclodextrin was used as a chiral selector. The preparation conditions were optimized and the resultant membrane obtained under these conditions showed desirable water permeability (~ 24.0 L/(m 2 ·h·bar)) and surface hydrophilicity (contact angle is lower than 37.1 ± 3.4°). The polydopamine layer exhibited desirable stability in a series of aqueous solutions with pH values ranging from 4.0–6.0 or in isopropanol for less than an hour (detachment ratio was lower than 1.2%). Characterization of the surface morphology and XPS elemental analysis revealed that the membrane surface was fully coated by polydopamine and a β-cyclodextrin monolayer formed on the surface of the polydopamine coating. The grafting density of β-cyclodextrin calculated from the XPS results was ~ 11.5 mg/m 2 . The optimal pH value for the resolution of D - or L -tryptophan feed solution was 5.90 and a low concentration of the feed solution provided a high resolution efficiency. The enantiomeric excess (e.e.) value of the membrane for Trp racemic mixture achieved to ~ 3.2% with the feed solution of tryptophan racemic mixture was 5 × 10 − 5 mol/L and the operating pressure was 0.1 MPa. After 3 times of isopropanol-washed regeneration processes, the e.e. value was still stable around to ~ 3%. The mussel-inspired chemically modified membrane exhibited the same mechanical properties as the purely polysulfone-based membrane. The methods and results provided in this paper may facilitate the large-scale production of chiral resolution membranes or other chiral separation membranes with higher performance.

A novel multifunctional amphiphilic graft copolymer has been synthesized consisting of a biodegradable poly(l-aspartic acid) backbone that was decorated by water-soluble poly(ethylene glycol) (PEG) and pH-responsive poly(N,N-diethylaminoethyl methacrylate) (PDEAEMA) side-chains as well as thiol pendant groups. This graft copolymer together with doxorubicin (DOX) formed micelles in water at pH = 10.0 with PDEAEMA and DOX acting as the core and PEG serving as the micellar corona. Upon oxidation, the thiol groups dimerized to form disulfide bonds, thus “locking in” the micellar structure. These crosslinked micelles expanded as the pH was decreased from 7.4 to 5.0 or upon the addition, at pH = 7.4, of glutathione (GSH), a thiol-containing oligopeptide that is present in cancerous cells and cleaves disulfide bonds. At pH = 5.0, GSH addition triggered the disassembly of the micelles. The expansion and disassembly of the micelles have been determined via in vitro experiments to evaluate their DOX release behavior. More importantly, the graft copolymer micelles could enter cells by means of endocytosis and deliver DOX to the nuclei of ovarian cancer BEL-7402 cells. Thus, this polymer and its micelles are promising candidates for drug delivery applications. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 1536–1546

Considerable interest has been devoted to developing nanoscale biomass materials as adsorbents for wastewater treatment. A facile route was proposed to prepare cellulose-based composite nanofibers via electrospinning of cellulose acetate with organically modified montmorillonite, followed by deacetylation. The composite nanofibers are suitable for metal adsorption given their reasonably high selectivity in removing Cr 6+ ions from aqueous solution. The effects of experimental parameters, including solution pH, temperature, and contact time, on the removal of Cr 6+ ions were determined in a batch system to optimize the adsorption conditions. Results from this study may provide a promising biosorbent that can be used as an emerging material in large-scale adsorption of heavy metal ions.

Photothermal therapy (PTT) that utilizes phSUPPotothermal conversion agents (PTC) to ablate tumor under NIR light irradiation has attracted increasing attention due to its excellent therapeutic efficacy and improved target selectivity. Herein, a novel core-shell nanoparticle based on disulfide-crosslinked poly(methacrylic acid) (PMAA) layer coated polydopamine (PDA) particle has been successfully synthesized by precipitation polymerization. For these PDA@PMAA composite nanoparticles, PDA core exhibits high photothermal efficacy, meanwhile, the redox-labile PMAA shell serves as carriers to encapsulate anticancer drugs and selectively release them. Due to the characteristic of the disulfide bond, PMAA shell occurs at selective degradation as well as controlled drug release upon entering cancer cells. Moreover, the DOX-loaded PDA@PMAA nanoparticles demonstrated a synergistic effect, which shows a significantly improved inhibition effect against cancer cells by the combination of photothermal therapy and traditional chemotherapy with low drug dosage and short laser irradiation in an in vitro study. Electronic supplementary material The online version of this article (10.1186/s11671-019-3027-6) contains supplementary material, which is available to authorized users.

Membrane separation is recognized as one of the most effective strategies to treat the complicated wastewater system for economic development. However, serious membrane fouling has restricted its further application. Inspired by sphagnum, a 0D/2D heterojunction composite membrane is engineered by depositing graphitic carbon nitride nano/microspheres (CNMS) with plentiful wrinkles onto the polyacrylic acid functionalized carbon nanotubes (CNTs-PAA) membrane through hydrogen bond force. Through coupling unique structure and chemistry properties, the CNTs-PAA/CNMS heterojunction membrane presents superhydrophilicity and underwater superoleophobicity. Furthermore, thanks to the J-type aggregates during the solvothermal process, it is provided with a smaller bandgap (1.77 eV) than the traditional graphitic carbon nitride (g-C3 N4 ) sheets-based membranes (2.4-2.8 eV). This feature endows the CNTs-PAA/CNMS membrane with superior visible-light-driven self-cleaning ability, which can maintain its excellent emulsion separation (with a maximum flux of 5557 ± 331 L m-2 h-1 bar-1 and an efficiency of 98.5 ± 0.6%), photocatalytic degradation (with an efficiency of 99.7 ± 0.2%), and antibacterial (with an efficiency of ≈100%) ability even after cyclic experimental processes. The excellent self-cleaning performance of this all-in-one membrane represents its potential value for water purification.

Two new indole alkaloids, Bufotenidine B (2) and Bufocarboline A (6), along with seven known indole alkaloids (1, 3&ndash, 5, and 7&ndash, 9) and three organic acids (10&ndash, 12), were isolated from the water extract of toad venom. The structures of the new alkaloids were elucidated by extensive spectroscopic methods. The absolute configurations of 4, 6, and 8 were determined for the first time by electronic circular dichroism (ECD) calculations. The cytotoxic activity of all compounds was tested against human malignant melanoma cells A375 by the MTT method, and no antitumor activity was observed.

Uniaxially aligned cellulose nanofibers (CNFs), which are fabricated by electrospinning of cellulose acetate derived from bamboo cellulose (B-CA) followed by deacetylation, were used as reinforcements to make optically transparent composite films. We examined the effects of B-CA concentration and electrospinning parameters (e.g. spinning distance, and collection speed) on fiber morphology and orientation, which act on mechanical-to-optical properties of the CNFs-reinforced composites. Consequently, the resultant composite film exhibits high visible-light transmittance even with high fiber content, as well as improved mechanical properties. The understanding obtained from this study may facilitate the development of novel nanofibrous materials for various optical uses.

A ternary system thermoresponsive hydrogel, poly(N-isopropylacrylamide-co-hydroxyethyl methylacrylate polycaprolactone)/hydroxypropyl cellulose (or P(NIPAAm-co-HEMAPCL)/HPC), was prepared via "alkynyl/azide" click chemistry between the azide modified graft copolymer P(NIPAAm-co-HEMAPCL-N3) and the alkynyl modified HPC (or alkynyl-HPC). The structures of P(NIPAAm-co-HEMAPCL-N3) and alkynyl-HPC were characterized by (1)H NMR, SEC and FT-IR, and the results demonstrated that the mole ratio of the alkynyl and azide functional groups, and the feed ratios of HPC, PCL, and PNIPAAm could be easily adjusted. The incorporation of PCL and HPC dramatically enhanced the compression modulus of the P(NIPAAm-co-HEMAPCL)/HPC hydrogel, which ranged from 500 to 1000 g/cm(2). Due to the immiscibility of HPC and PCL, a heterogeneous and semicontinuous structure was observed via SEM. The incorporation of HPC accelerated the water absorption rate and enhanced the hydrogel's ability to shed water. The swelling-deswelling and compressive properties could also be adjusted by changing the feeding ratio. The hydrogel exhibited reversible swelling-deswelling behavior after three "swelling-deswelling" cycles.

Cellulose acetate derived from bamboo cellulose (B-CA) was prepared via a typical acetylation process and used to fabricate the aligned electrospun nanofibrous membranes (ENMs). A solvent post-treatment by soaking the B-CA ENMs in a mixture solution with different ethanol/acetone volume ratios was also performed to improve the mechanical properties of the membranes. In this study, we showed that this approach can enhance the bonding in the fiber membranes by solvent-induced fusion of inter-fiber junction points and change the degree of molecular orientation of the polymer, which are both considered to have important influences on the mechanical properties of ENMs. The treated membranes exhibited a significant enhancement in mechanical strength while retaining high hydraulic permeability. Increased performances will improve the prospects of ENMs as an emerging material in the filtration space for handling and scale-up manufacturing.

Electrical signals can be imposed with exquisite spatiotemporal control and provide exciting opportunities to create structure and confer function. Here, we report the use of electrical signals to program the fabrication of a chloramine wound dressing with high antimicrobial activity. This method involves two electrofabrication steps: (i) a cathodic electrodeposition of an aminopolysaccharide chitosan triggered by a localized region of high pH; and (ii) an anodic chlorination of the deposited film in the presence of chloride. This electrofabrication process is completed within several minutes and the chlorinated chitosan can be peeled from the electrode to yield a free-standing film. The presence of active N Cl species in this electrofabricated film was confirmed with chlorination occurring first on the amine groups and then on the amide groups when large anodic charges were used. Electrofabrication is quantitatively controllable as the cathodic input controls film growth during deposition and the anodic input controls film chlorination. In vitro studies demonstrate that the chlorinated chitosan film has antimicrobial activities that depend on the chlorination degree. In vivo studies with a MRSA infected wound healing model indicate that the chlorinated chitosan film inhibited bacterial growth, induced less inflammation, developed reorganized epithelial and dermis structures, and thus promoted wound healing compared to a bare wound or wound treated with unmodified chitosan. These results demonstrate the fabrication of advanced functional materials (i.e., antimicrobial wound dressings) using controllable electrical signals to both organize structure through non-covalent interactions (i.e., induce chitosan’s reversible self-assembly) and to initiate function-conferring covalent modifications (i.e., generate chloramine bonds). Potentially, electrofabrication may provide a simple, low cost and sustainable alternative for materials fabrication. Statement of Significance We believe this work is novel because this is the first report (to our knowledge) that electronic signals enable the fabrication of advanced antimicrobial dressings with controlled structure and biological performance. We believe this work is significant because electrofabrication enables rapid, controllable and sustainable materials construction with reduced adverse environmental impacts while generating high performance materials for healthcare applications. More specifically, we report an electrofbrication of antimicrobial film that can promote wound healing.

Vanadium carbide/titanium carbide (VC/TiC) superlattice films were synthesized by magnetron sputtering method. The effects of modulation period on the microstructure evolution and mechanical properties were investigated by EDXA, XRD, HRTEM and nano-indentation. The results reveal that the VC/TiC superlattice films form an epitaxial structure when their modulation period is less than a critical value, accompanied with a remarkable increase in hardness. Further increasing the modulation period, the hardness of superlattices decreases slowly to the rule-of-mixture value due to the destruction of epitaxial structures. The XRD results reveal that three-directional strains are generated in superlattices when the epitaxial structure is formed, which may change the modulus of constituent layers. This may explain the remarkable hardness enhancement of VC/TiC superlattices.

Wound dressings play important roles in the management of wounds, and calcium cross-linked alginate (Ca2+-Alg) is a commonly used hydrogel that is adapted for wound treatment. However, conventional methods for fabricating Ca2+-Alg hydrogels can be tedious and difficult to control because of the rapid Ca2+-induced gelation of alginate. In this study, An electrodeposition method was used to rapidly and controllably fabricate Ca2+-Alg films for wound treatment. Several measures of film growth (e.g., thickness and mass) are shown to linearly correlate to the imposed charge transfer at the electrode. Similarly, this charge transfer was also observed to control important physicochemical wound healing properties such as water uptake and retention capacity. Furthermore, a wound healing animal test was performed to evaluate the performance of this electro-fabricated calcium alginate film for wound treatment. This in vivo study demonstrated that wounds dressed with an electro-fabricated Ca2+-Alg film closed faster than that of untreated wounds. Further, the new dermis tissue that formed was composed of reorganized and stratified epithelial layer, with fully developed connective tissue, hair follicle, sebaceous glands as well as aligned collagen. Therefore, our study indicates that this electrofabrication method for the rapid and controlled preparation of alginate film could provide exciting opportunities for wound treatment. More broadly, this study demonstrates the potential of electrochemistry for the fabrication of high performance polymeric materials. Here we report a rapid and controllable fabrication of free-standing alginate films by coupling anodic electrodeposition with subsequent peeling of deposited materials for wound dressing.

In this study, starch with porous structures derived from purple sweet potato was prepared and used as a food-grade polymer for the microencapsulation of olive oil. The optimal reaction conditions for preparing porous starch were determined to improve its adsorption capacity as effective microcapsule-wall materials. Olive oil was then impregnated in microspheres, and loading ratio was optimized by investigating the restrictive factors, including the mass ratio of olive oil to porous starch, as well as the embedding temperature and time. The presence of olive oil in the starch matrix was confirmed by SEM, FTIR, and TGA. Results demonstrated that the porous starch-based microencapsulation exhibit a stable olive oil loading ratio and a significant improvement in oxidative stability compared with free olive oil. The newly-proposed process used in this work was easy to scale up for developing a new and attractive method for oil protection in the food industry.

Stearic and oleic acid-coated Fe3O4 nanoparticles were dispersed in decahydronaphthalene (DN). This oil phase was dispersed in water using ternary graft copolymer poly(glycidyl methacrylate)-graft-[polystyrene-ran-(methoxy polyethylene glycol)-ran-poly(2-cinnamoyloxyethyl methacrylate)] or PGMA-g-(PS-r-MPEG-r-PCEMA) to yield capsules. The walls of these capsules were composed of PCEMA chains that were soluble in neither water nor DN, and the DN-soluble PS chains stretched into the droplet phase and the water-soluble MPEG chains extended into the aqueous phase. Structurally stable capsules were prepared by photolyzing the capsules with UV light to cross-link the PCEMA layer. Both the magnetite particles and the magnetite-containing capsules were superparamagnetic. The sizes of the capsules increased as they were loaded with more magnetite nanoparticles, reaching a maximal loading of ~0.5 mg of ligated magnetite nanoparticles per mg of copolymer. But the radii of the capsules were always100 nm. Thus, a novel nanomaterial--superparamagnetic-oil-filled polymer nanocapsules--was prepared. The more heavily loaded capsules were readily captured by a magnet and could be redispersed via shaking. Although the cross-linked capsules survived this capturing and redispersing treatment many times, the un-cross-linked capsules ruptured after four cycles. These results suggest the potential to tailor-make capsules with tunable wall stability for magnetically controlled release applications.

A series of novel thermosensitive macroporous poly (ethylene glycol) (PEG)-co-poly(N-isopropylacrylamide) (PNIPAAm)-co-poly (e-caprolactone) (PCL) hydrogels were synthesized via in situ free radical polymerization. Poly(ethylene glycol diacrylate) (PEGDAc) and poly(e-caprolactone diacrylate) (PCLDAc) were prepared as macrocrosslinkers. All compounds were investigated by Nuclear Magnetic Resonance (NMR) and Fourier transform-infrared spectroscopy (FT-IR). Differential Scanning Calorimetry (DSC) results showed the lower critical solution temperatures (LCSTs) of the gels were at around 31°C. The macroporous gels not only had considerable swelling ratios, but also exhibited rapid swelling kinetics and response sensitivity. Above mentioned hydrogels showed a remarkable oscillatory swelling–deswelling transition, making them have potential application in long-term drug delivery. POLYM. ENG. SCI., 55:223–230, 2015. © 2014 Society of Plastics Engineers

Three ternary graft copolymers bearing polystyrene (PS), poly(ethylene glycol) methyl ether (MPEG), and poly(acrylic acid) (PAA) side chains were synthesized and characterized. At pH = 7.4, these copolymers stabilized doxorubicin (DOX)-containing benzyl benzoate (BBZ) nanoemulsion droplets in water and formed a compact polymer layer to inhibit DOX release. Upon lowering the solution pH to 5.0, the AA groups dissociated less and became less soluble. Moreover, the neutralized AA groups formed presumably H-bonded complexes with the EG units, reducing the solubility of the EG units. This dual action drastically shifted the hydrophilic and hydrophobic balance of the copolymer and caused the original stabilizing polymer layer to rupture and the nanoemulsion droplets to aggregate, releasing DOX. The rate and extent of DOX release could be increased by matching the numbers of PAA and MPEG chains per graft copolymer. In addition, these nanoemulsions were not toxic and entered human carcinoma cells, releasing DOX there. Thus, these nanoemulsions have potential as drug delivery vehicles.

An amphiphilic binary graft copolymer polysulfone-graft-[poly(methyl methacrylate)-random-poly(acrylic acid)], PSf-g-(PMMA-r-PAA), was synthesized via a combination of atom transfer radical polymerization (ATRP) and click chemistry. This copolymer and polysulfone (PSf) were used to prepare porous membranes through the phase inversion method, which involved dissolving the polymers in a common solvent N-methyl pyrrolidone (NMP), casting the solution onto a glass plate to obtain a film, and subsequently immersing this film into a coagulant (a mixture of dimethylformamide and water at a given pH). The surfaces of the membrane and its pore walls were covered by the copolymer, and these surfaces were enriched with PAA domains due to the immiscibility of PAA and PSf and the miscibility of PMMA and PSf. More specifically, while the hydrophobic PMMA component served as an anchor to fix the graft copolymer onto the PSf bulk substrate, the hydrophilic PAA component assembled and became exposed at the surfaces of the membrane and the pore walls. Factors influencing this surface AA concentration or carboxyl group content (CGC) enrichment and the surface and pore morphologies of the membranes include the ratio between the amount of the copolymer and PSf in the mixture, the solvent quality of the coagulant for PSf, and the temperature as well as the pH of the coagulant. These factors have been systematically adjusted to optimize the hydrophilization of the PSf membrane and the resultant membranes have been characterized by water contact angle (WCA) measurements, scanning electron microscopy (SEM), atomic force microscopy (AFM), and X-ray photoelectron spectroscopy (XPS). Optimization of the phase inversion process yielded membranes with nearly complete surface coverage by PAA, even when the graft copolymer represented only 8 wt% of the membrane's composition. The hydrophilized membranes exhibited increased water flux and even pH-responsive water flow without adversely affecting their mechanical properties. In addition, these hydrophilic membranes exhibited long-term stability. Therefore, this novel binary amphiphilic graft copolymer-based approach for membrane modification may be of commercial value.

A stimuli-responsive membrane exhibiting independent pH- and temperature-responsive behavior was fabricated from a blend of commercial polysulfone with a functional amphiphilic binary graft copolymer, namely, polysulfone-graft-(poly(isopropylacrylamide-co-acrylic acid)-random-poly(methyl acrylate)), denoted PSf-g-(P(NIPAAm-co-AA)-r-PMMA). Two graft copolymers with different lengths of P(NIPAAm-co-AA) side chains were designed and enriched on the membrane surface to serve as thermo- and pH-responsive on/off switches. The differences between the dual-responsive behaviors of the two kinds of polymer-blend membranes were studied by water-flux and contact-angle measurements. The PMMA side chains served to securely anchor the graft copolymers to the membrane substrate, and the blended membrane prepared from binary graft copolymer was more stable and exhibited more robust stimuli-responsive behavior than that prepared from mono-graft copolymer PSf-g-P(NIPAAm-co-AA).

Six novel europium complexes with phenanthroline derivatives as fluorescence sensor have been prepared, and their structures were characterized by FT-IR, UV–vis, 1 H NMR, 13 C NMR, ESI-MS, and element analysis. All complexes exhibited long luminescent lifetime and high luminescent quantum efficiency ( η ). Among these complexes, the complex (a) exhibited the lowest luminescent quantum efficiency and shortest lifetime, which was attributed to the presence of O H oscillators in the corresponding ligand HPIP. Spectroscopic studies, including UV–vis, PL and 1 H NMR spectra, showed that these sensors exhibited striking spectra changes in response to CH 3 COO − due to hydrogen bonding interaction of imidazolyl NH groups, aromatic and phenanthroline ring's protons with CH 3 COO − . Particularly, europium complexes (e) and (f) have a remarkable color changes (from transparent to light-yellow), and hence they were convenient to detect the CH 3 COO − with them by naked eye in DMSO solution.

Poly(N-isopropyl acrylamide) (PNIPAAm)-graft-poly(ethylene oxide) (PEO) hydrogels crosslinked by poly(ϵ-caprolactone) diacrylate were prepared, and their microstructures were investigated. The swelling/deswelling kinetics and compression strength were measured. The relationship between the structure and properties of hydrogel are discussed. It was found that the PEO comb-type grafted structure reduced the thermosensitivity and increased the compression strength. The addition of poly(ϵ-caprolactone) (PCL) accelerated the deswelling rate of the hydrogels. Meanwhile, the entanglement of PCL chains restrained the further swelling of the network of gels. The PCL crosslinking agent and PEO comb-type grafted structure made the behavior of the hydrogels deviate from the rubber elasticity equations. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013

In order to graft β-cyclodextrin onto chitosan fibers as more as possible, amino group of chitosan fibers should be protected by benzaldehyde firstly. Based on the similar structure of chitosan and cellulose fibers, different experimental programs were employed to discuss the possibility of β-cyclodextrin grafted onto chitosan fibers in the similar method. By infrared spectral and UV–visible spectroscopy analysis, the results showed although benzaldehyde could be grafted to chitosan fibers successfully to protect amino group, β-cyclodextrin could not be grafted further.

The aim of the study was to investigate the grafting process of β-cyclodextrin onto chitosan fibers via epichlorohydrin as a crosslinking agent. The parameters influencing the efficiency of the grafting reaction were studied by L9 (34) orthogonal test. The amounts of β-cyclodextrin grafting onto the treated fibers were estimated in terms of levofloxacin content. The optimum process was found to be epichlorohydrin 0.64 ml, temperature25°C, post-reaction time 48h, pre-reaction time 4.5h when chitosan fibers were 0.48g. In the case, the inclusion amount of levofloxacin was 1.792mg/g, and the releasing amount was 0.845mg/g at 35°C. The modified and unmodified fibers were characterized by FTIR Spectroscopy , which indicated that β-CD grafted with chitosan fibers were prepared successfully.

We report here a simple and reproducible strategy for fabricating highly durable and robust superhydrophobic cotton fabrics (SCFs) from a series of functional diblock copolymers. These diblock copolymers consisted of both poly(glycidyl methacrylate) (PGMA) and poly(2,2,2-trifluoroethyl methacrylate) (PTFEMA) blocks that were synthesized via sequential atom transfer radical polymerization (ATRP). While the PTFEMA block provides the low surface free energy, the PGMA block serves as an anchor and forms covalent bonds with the surfaces of cotton fibers. These covalent bonds are formed via the epoxy ring-opening reaction between the epoxy groups of the PGMA block and the hydroxyl groups on the surface of the cotton fiber, and self-crosslinking of epoxy groups from PGMA chains. Structures exhibiting nano- and microscale roughness were created in one-step by combining copolymer-based nanobumps onto surfaces of micro-sized fibers of the cotton fabric, as confirmed by SEM and AFM analysis. The modified cotton fabrics show excellent water repellency with water contact angles (WCAs) of ∼163° and water sliding angles (WSAs) of ∼3° under optimized conditions. Since the low-fluorinated PTFEMA chains are chemically bound to the cotton fibers, the SCFs possess long-term stability, ultra-high durability and robustness. In particular, these SCFs withstood mechanical abrasion by sandpaper, strong laundering conditions, ultrasonication treatment in tetrahydrofuran (THF) or trifluorotoluene (TFT), soaking in a wide range of organic solvents, as well as acidic and basic aqueous solutions, exposure to UV-irradiation and even refluxing in TFT or THF.