Fabrication of a Dual-Stimuli-Responsive Supramolecular Micelle from a Pillar[5]arene-Based Supramolecular Diblock Copolymer for Photodynamic Therapy.

A pH and thermo dual-responsive supramolecular diblock copolymer is constructed by host-guest recognition of pillar[5]arene and viologen salt. The host polymer, poly(N,N-dimethylaminoethyl methacrylate) bearing pillar[5]arene as the terminal group (P[5]A-PDMAEMA) is synthesized by atom transfer radical polymerization (ATRP). Guest polymer, ethyl viologen-ended poly(N-isopropylacrylamide) (EV-PNIPAM) is prepared by reversible addition-fragmentation chain transfer polymerization. The supramolecular diblock copolymer can be self-assembled into stable supramolecular nanoparticles in aqueous solution at 40 °C, which show excellent pH and thermo responsiveness. The nanoparticles are further applied in the encapsulation of photosensitizers (pyropheophorbide-a, PhA) for photodynamic therapy (PDT). The dual-responsive nanoparticles can efficiently release PhA in acidic environment at 25 °C. Based on the result of cell experiments, PhA-loaded nanomicelles exhibit excellent PDT efficacy and low dark toxicity toward A549 cells. Thus, this supramolecular diblock copolymer enriches the methodology of constructing stimuli-responsive drug carriers and presents a great potential in PDT.

Phase inversion of ionomer-stabilized emulsions to form high internal phase emulsions (HIPEs).

Herein, we report the phase inversion of ionomer-stabilized emulsions to form high internal phase emulsions (HIPEs) induced by salt concentration and pH changes. The ionomers are sulfonated polystyrenes (SPSs) with different sulfonation degrees. The emulsion types were determined by conductivity measurements, confocal microscopy and optical microscopy, and the formation of HIPE organogels was verified by the tube-inversion method and rheological measurements. SPSs with high sulfonation degrees (water-soluble) and low sulfonation degrees (water-insoluble) can stabilize oil-in-water emulsions; these emulsions were transformed into water-in-oil HIPEs by varying salt concentrations and/or changing the pH. SPS, with a sulfonation degree of 11.6%, is the most efficient, and as low as 0.2 (w/v)% of the organic phase is enough to stabilize the HIPEs. Phase inversion of the oil-in-water emulsions occurred to form water-in-oil HIPEs by increasing the salt concentration in the aqueous phase. Two phase inversion points from oil-in-water emulsions to water-in-oil HIPEs were observed at pH 1 and 13. Moreover, synergetic effects between the salt concentration and pH changes occurred upon the inversion of the emulsion type. The organic phase can be a variety of organic solvents, including toluene, xylene, chloroform, dichloroethane, dichloromethane and anisole, as well as monomers such as styrene, butyl acrylate, methyl methacrylate and ethylene glycol dimethacrylate. Poly(HIPEs) were successfully prepared by the polymerization of monomers as the continuous phase in the ionomer-stabilized HIPEs.

Elastin and collagen enhances electrospun aligned polyurethane as scaffolds for vascular graft.

Mismatch in mechanical properties between synthetic vascular graft and arteries contribute to graft failure. The viscoelastic properties of arteries are conferred by elastin and collagen. In this study, the mechanical properties and cellular interactions of aligned nanofibrous polyurethane (PU) scaffolds blended with elastin, collagen or a mixture of both proteins were examined. Elastin softened PU to a peak stress and strain of 7.86 MPa and 112.28 % respectively, which are similar to those observed in blood vessels. Collagen-blended PU increased in peak stress to 28.14 MPa. The growth of smooth muscle cells (SMCs) on both collagen-blended and elastin/collagen-blended scaffold increased by 283 and 224 % respectively when compared to PU. Smooth muscle myosin staining indicated that the cells are contractile SMCs which are favored in vascular tissue engineering. Elastin and collagen are beneficial for creating compliant synthetic vascular grafts as elastin provided the necessary viscoelastic properties while collagen enhanced the cellular interactions.

Cellulose-based, flexible polyurethane polyHIPEs with quasi-closed-cell structures and high stability for thermal insulation.

Cellulose-based, closed-cell porous materials templated from emulsions are promising for thermal insulation, but their low stability imposed by physical interaction hinders the materials from real applications. Herein, we report the fabrication of cellulose-based, flexible polyurethane polyHIPEs with quasi-closed-cell structures, high stability and flexibility for thermal insulation. The polyHIPEs were prepared from cellulose-stabilized Pickering high internal phase emulsions through interfacial crosslinking using isocyanate. The resulting polyurethane polyHIPEs showed controllable external shapes, quasi-closed-cell structures, high flexibility, low density, and robust compression (without fracture even after compression to 30 % original height). The crosslinking enabled the polyHIPEs to show hydrophobicity, good stability (without breakage and dissolution observed after immersing in NaOH solution at pH 12, HCl solution at pH 1 and hot water at 100 °C, for 24 h) and decreased moisture uptake (below 1 %). The low density and quasi-closed-cell structures endowed the polyHIPEs with high thermal insulation, with thermal conductivity as low as 33.1 mW/(m K). These features make the cellulose-based, closed-cell polyHIPEs as an excellent candidate for thermal insulting.

Selective fluorescent sensing of α-amanitin in serum using carbon quantum dots-embedded specificity determinant imprinted polymers.

α-amanitin could make patients die of acute liver failure within a short time if suitable treatment is not provided in a timely fashion. This paper demonstrates a new strategy for direct detection of α-amanitin in serum using carbon quantum dots-embedded specificity determinant imprinted polymers. According to the structure of α-amanitin, we selected a proper moiety of α-amanitin as specificity determinant to synthesize template to prepare the MIPs. The computer simulation was used to screen out acidic methacrylic acid (MAA) and basic 4-vinyl pyridine (4-Vpy) together as functional monomers, and the experiments further proved that synergistic interaction of MAA and 4-Vpy was beneficial to enhance the recognition capability of MIPs for α-amanitin. Moreover, the fluorescence intensity showed good linear correlations with the concentration of α-amanitin from 0.05 to 4.0µgmL(-1). The detection limit for α-amanitin was 15ngmL(-1). The nanoparticles were employed to directly detect α-amanitin in serum without any pretreatment with recoveries of 97.8-100.9%.

An artificial receptor fabricated by target recognition determinant imprinting for selective capture of α-amanitin.

This is the first reported work of artificial α-amanitin receptors which are prepared using the design and synthesis of a template molecule based on an α-amanitin recognition determinant imprinting strategy. The resultant molecularly imprinted polymers (MIPs) are evaluated using high performance liquid chromatography (HPLC), binding experiment, nitrogen adsorption measurement, and solid-phase extraction. Experiment clearly demonstrates that the MIPs as the HPLC stationary phase can specifically recognize α-amanitin from analogues. The MIPs also successfully adsorb trace amounts of α-amanitin in spiked serum samples selectively pretreated and enriched through molecularly imprinted solid phase extraction. The limit of detection and recovery is 3.0 ng mL(-1) and 88.5-95.9%, respectively, for α-amanitin in serum samples. The high specific adsorption and excellent selectivity of the MIPs arises from imprinting effects related to the imprinting cavity of the polymeric matrix, the metal-coordination bond, and the hydrogen bond between the receptor and ligand.

Antimicrobial electrospun nanofibers of cellulose acetate and polyester urethane composite for wound dressing.

In this study, a series of nanofibrous membranes were prepared from cellulose acetate (CA) and polyester urethane (PEU) using coelectrospinning or blend-electrospinning. The drug release, in vitro antimicrobial activity and in vivo wound healing performance of the nanofiber membranes were evaluated for use as wound dressings. To prevent common clinical infections, an antimicrobial agent, polyhexamethylene biguanide (PHMB) was incorporated into the electrospun fibers. The presence of CA in the nanofiber membrane improved its hydrophilicity and permeability to air and moisture. CA fibers became slightly swollen upon contacting with liquid phase. CA not only increased the liquid uptake but also created a moist environment for the wound, which accelerated wound recovery. PHMB release dynamics of the membranes was controlled by the structure and component ratios of the membranes. The lower ratio of CA: PEU helped to preserve the physical and thermal properties of the membranes, and also reduced the burst release effectively and slowed down diffusion of PHMB during in vitro tests. The controlled-diffusion membranes exerted long-term antimicrobial effect for wound healing.