Fabrication of Ag-doped ZnO/PAN composite nanofibers by electrospinning: Photocatalytic and antiviral activities.

Ag-doped ZnO nanoparticles (AZNs) were directly synthesized using sol-gel method to embed into polyacrylonitrile (PAN) nanofibers by electrospinning. The synthesized AZNs were optically and structurally characterized by UV-VIS spectroscopy, photoluminescence spectroscopy, high resolution HR-TEM and XRD. The photocatalytic activity of the AZNs was examined by photocatalytic degradation of methylene blue to correlate with their antiviral efficacy in PAN nanofibers fabricated via electrospinning technique. The PAN nanofibers containing AZNs were characterized using SEM and EDS. Finally, antiviral activity of AZNs/PAN nanofibers was investigated by using virus ϕx174 under visible light irradiation. As a result, the antiviral efficacy of nanofibers increased as the concentration of Ag in AZNs increased. The results show that better antiviral efficacy was obtained in AZNs/PAN nanofibers prepared with AZNs of higher photocatalytic performance.

Alcohol-Treated Porous PTFE Substrate for the Penetration of PTFE-Incompatible Hydrocarbon-Based Ionomer Solutions.

For a mechanically tough proton exchange membrane, a composite membrane incorporated with a porous polymer substrate is of great interest to suppress the ionomer swelling and to improve the dimensional stability and mechanical strength of the ionomers. For the composite membranes, good impregnation of substrate-incompatible ionomer solution into the substrate pores still remains one of the challenges to be solved. Here, we demonstrated a facile process (surface treatment with solvents compatible with both substrate and the ionomer solution) for the fabrication of the composite membranes using polytetrafluoroethylene (PTFE) as a porous substrate and poly(arylene ether sulfone) (SPAES) as a hydrocarbon-based (HC) ionomer. Appropriate solvents for the surface treatment were sought through the contact angle measurement, and it was found that alcohol solvents effectively tuned the surface property of PTFE pores to facilitate the penetration of the SPAES/N-methyl-2-pyrrolidone (NMP) solution into ∼300 nm pores of the substrate. Using this simple alcohol treatment, the SPAES/NMP contact angle was reduced in half, and we could fabricate the mechanically tough PTFE/HC composite membranes, which were apparently translucent and microscopically almost void-free composite membranes.

Antimelanogenic Efficacy of Melasolv (3,4,5-Trimethoxycinnamate Thymol Ester) in Melanocytes and Three-Dimensional Human Skin Equivalent.

BACKGROUND/AIMS: Excessive melanogenesis often causes unaesthetic hyperpigmentation. In a previous report, our group introduced a newly synthesized depigmentary agent, Melasolv™ (3,4,5-trimethoxycinnamate thymol ester). In this study, we demonstrated the significant whitening efficacy of Melasolv using various melanocytes and human skin equivalents as in vitro experimental systems. METHODS: The depigmentary effect of Melasolv was tested in melan-a cells (immortalized normal murine melanocytes), α-melanocyte-stimulating hormone (α-MSH)-stimulated B16 murine melanoma cells, primary normal human melanocytes (NHMs), and human skin equivalent (MelanoDerm). The whitening efficacy of Melasolv was further demonstrated by photography, time-lapse microscopy, Fontana-Masson (F&M) staining, and 2-photon microscopy. RESULTS: Melasolv significantly inhibited melanogenesis in the melan-a and α-MSH-stimulated B16 cells. In human systems, Melasolv also clearly showed a whitening effect in NHMs and human skin equivalent, reflecting a decrease in melanin content. F&M staining and 2-photon microscopy revealed that Melasolv suppressed melanin transfer into multiple epidermal layers from melanocytes as well as melanin synthesis in human skin equivalent. CONCLUSION: Our study showed that Melasolv clearly exerts a whitening effect on various melanocytes and human skin equivalent. These results suggest the possibility that Melasolv can be used as a depigmentary agent to treat pigmentary disorders as well as an active ingredient in cosmetics to increase whitening efficacy.

Fabrication of biodegradable cellulose acetate nanofibers containing Rose Bengal dye by electrospinning technique and their antiviral efficacy under visible light irradiation.

Biodegradable cellulose acetate (CA) nanofibers containing Rose Bengal (RB) dye were fabricated by electrospinning technique. RB dye, an anionic photosensitizer, has been used in photodynamic therapy due to its excellent biocompatibility and ability to absorb light to generate reactive oxygen species (ROS), but has a decisive disadvantage of water solubility on infection prevention. Firstly, water-insoluble RB dye was synthesized through complexation with cationic ionic liquid (IL) for antiviral agents. The synthesized water-insoluble RB dyes were embedded into biodegradable CA nanofibers by electrospinning. The electrospun nanofibers passed both antiviral test for φx174 virus under visible light irradiation and biodegradability-test using enzymes. The fabricated RB nanofibers absorbed light and generated ROS to inactivate the virus. As a result, the log reduction (-Log10(N/N0)) of φx174 titer under visible light reached a detection limit of 5.00 within 30 min. Also, the fabricated nanofibers were degraded up to 34 wt % in 9 weeks by lipase and cellulase enzymes compared with non-biodegradable nanofibers.

Fabrication of ZnO Nanoparticle-Decorated Nanofiber Mat with High Uniformity Protected by Constructing Tri-Layer Structure.

We demonstrate a sequential electrospinning process involving the adsorption of ZnO nanoparticles on the surface of bio-based polyester, which is a terpolyester of a renewable isosorbide (ISB) monomer, ethylene glycol, 1,4-cyclohexane dimethanol, and terephthalic acid, the-so-called PEICT, to fabricate stable ZnO nanoparticles/PEICT nanofiber composite system protected with other two PEICT nanofiber mats. We found that post-electrospinning treatment with a particular solvent was effective to remove a residual solvent molecule in the PEICT nanofibers, which induced significant aggregation of the nanoparticles, leading to non-uniform distribution of the particles on the surface. Sequential electrospinning of the PEICT solution to sandwich ZnO nanoparticle-decorated PEICT nanofiber mat enabled to attain protected the inorganic/organic hybrid nanofiber mat, improving the long-term stability, and the reproducibility of the inorganic particles decorated nanofiber fabrication.

Well-organized highly efficient white organic light emitting diodes using fluorescent emitting materials.

New type of White-Light Emitting Diode (WOLED) that emits three primary colors of red, green and blue has been demonstrated. WOLED is properly laid out with emitting layers so that all three wavelengths of light can be emitted by using fit energy level, and the organic functional layer named white balanced layer (WBL) is introduced. As for the material used as WBL, the experiment used NPB that has electron blocking effect with its large LUMO value. The color purity of such WOLED can be easily adjusted through the adjustment of the number of electron carriers injected into light emitting layer. Therefore, the experiment organized WOLED by using doping concentration of highest efficiency demonstrated by RGB single color device, and adjusted color purity of white color through the adjustment of WBL thickness adjustment. In the case of WOLED device that possesses the device structure of ITO/m-MTDATA 40 nm/NPB 5 nm/NPB + P-1 (3%) 3 nm/NPB 0.1 nm/Alq3 + C-545T(5%) 0.5 nm/IDE-120 + IDE-105(7%) 35 nm/LiF 1 nm/Al 150 nm in this study, color coordinate was (0.341, 0.424) and light emitting efficiency was 16.5 cd/A at current density 10 mA/cm2, so the WOLED demonstrated highly efficient characteristics of over commercial level.

Reinforced anion exchange membrane based on thermal cross-linking method with outstanding cell performance for reverse electrodialysis.

A poly(ethylene)-reinforced anion exchange membrane based on cross-linked quaternary-aminated polystyrene and quaternary-aminated poly(phenylene oxide) was developed for reverse electrodialysis. Although reverse electrodialysis is a clean and renewable energy generation system, the low power output and high membrane cost are serious obstacles to its commercialization. Herein, to lower the membrane cost, inexpensive polystyrene and poly(phenylene oxide) were used as ionomer backbones. The ionomers were impregnated into a poly(ethylene) matrix supporter and were cross-linked in situ to enhance the mechanical and chemical properties. Pre-treatment of the porous PE matrix membrane with atmospheric plasma increased the compatibility between the ionomer and matrix membrane. The fabricated membranes showed outstanding physical, chemical, and electrochemical properties. The area resistance of the fabricated membranes (0.69-1.67 Ω cm2) was lower than that of AMV (2.58 Ω cm2). Moreover, the transport number of PErC(5)QPS-QPPO was comparable to that of AMV, despite the thinness (51 µm) of the former. The RED stack with the PErC(5)QPS-QPPO membrane provided an excellent maximum power density of 1.82 W m-2 at a flow rate of 100 mL min-1, which is 20.7% higher than that (1.50 W m-2) of the RED stack with the AMV membrane.

Antibacterial efficacy of poly(vinyl alcohol) composite nanofibers embedded with silver-anchored silica nanoparticles.

Silver has been widely used as an effective antibacterial agent especially for treating burns and wounds. However, release of silver from materials often arouse side effects due to toxicity of silver towards mammalian cells. Argyria and argyrosis are well known problems of acute toxicity of silver towards human body. Immobilization of silver is an effective approach to reduce silver release. Herein, we present poly(vinyl alcohol) (PVA) composite nanofibers embedded with silver-anchored silica nanoparticles (SSNs) as a novel antibacterial material. Silver nanoparticles anchored on silica nanoparticles were prepared and incorporated into PVA nanofibers to fabricate silver-silica embedded PVA nanofibers (SSN-PVA) by electrospinning. Incorporation of SSNs into PVA was confirmed by TEM and SEM results revealed regular nanofibers whose diameter increased with successive addition of SSNs. The SSN-PVA nanofibers showed significant antibacterial efficacy against both Gram-negative and Gram-positive bacteria. Our research results demonstrated SSN-embedded polymeric nanofibers can open up a promising prospect for the prevention of bacterial infection in diverse biomedical fields including wound dressing. © 2017 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 106B: 1121-1128, 2018.

Development of efficient adeno-associated virus (AAV)-mediated gene delivery system with a phytoactive material for targeting human melanoma cells.

We exploited the emerging potential of gene therapy strategies to design a powerful therapeutic system that combines two key components-AAV vector and [6]-gingerol. In this study, we created an AAV2 construct expressing the proapoptotic protein BIM, which uses HSPG as its primary receptor, to target HSPG-overexpressing melanoma cells. This combination treatment showed promising results in vitro, inducing apoptosis in human melanoma cells. This new platform technology will make a significant contribution to numerous therapeutic applications, most notably for melanoma, including overcoming resistance to conventional anticancer therapies.

Effect of BMP-2 Delivery Mode on Osteogenic Differentiation of Stem Cells.

Differentiation of stem cells is an important strategy for regeneration of defective tissue in stem cell therapy. Bone morphogenetic protein-2 (BMP-2) is a well-known osteogenic differentiation factor that stimulates stem cell signaling pathways by activating transmembrane type I and type II receptors. However, BMPs have a very short half-life and may rapidly lose their bioactivity. Thus, a BMP delivery system is required to take advantage of an osteoinductive effect for osteogenic differentiation. Previously, BMP delivery has been designed and evaluated for osteogenic differentiation, focusing on carriers and sustained release system for delivery of BMPs. The effect of the delivery mode in cell culture plate on osteogenic differentiation potential was not evaluated. Herein, to investigate the effect of delivery mode on osteogenic differentiation of BM-MSCs in this study, we fabricated bottom-up release and top-down release systems for culture plate delivery of BMP-2. And also, we selected Arg-Gly-Asp- (RGD-) conjugated alginate hydrogel for BMP-2 delivery because alginate is able to release BMP-2 in a sustained manner and it is a biocompatible material. After 7 days of culture, the bottom-up release system in culture plate significantly stimulated alkaline phosphate activity of human bone marrow-mesenchymal stem cells. The present study highlights the potential value of the tool in stem cell therapy.

Loading of gold nanoparticles inside the DPPC bilayers of liposome and their effects on membrane fluidities.

Gold nanoparticles were loaded in the bilayer of dipalmitoylphosphatidylcholine (DPPC) liposomes, named as gold-loaded liposomes. Above the gel to liquid-crystalline phase transition temperature, membrane fluidities of DPPC liposomes were changed by loading the gold nanoparticles. Compared with liposomes without loading the gold nanoparticles, gold-loaded liposomes showed the lower fluorescence anisotropy values. That is, the membrane fluidities of DPPC bilayer were increased by loading the gold nanoparticles. The membrane fluidities were increased as the amount of gold nanoparticles increased. The existence of gold nanoparticles in the DPPC bilayer was observed by transmission electron microscopy. Through the energy dispersive X-ray spectrometer, the particles in DPPC bilayer were confirmed to be gold nanoparticles.

New approach to the immobilization of glucose oxidase on non-porous silica microspheres functionalized by (3-aminopropyl)trimethoxysilane (APTMS).

The immobilization and encapsulation of glucose oxidase (GOD) onto the mesoporous and the non-porous silica spheres prepared by co-condensation of tetraethylorthosilicate (TEOS) and (3-aminopropyl)trimethoxysilane (APTMS) in the water-in-oil (W/O) emulsion system were studied. The terminal amine group was used as the important functionality for GOD immobilization on the silica substrate. When only TEOS is used as a silica source, the disordered mesoporous silica microspheres are obtained. As the molar ratio of APTMS to TEOS (R(AT)) increases, the surface area and pore volume of the silica particles measured by nitrogen adsorption and desorption method and SEM decrease rapidly. Particularly, the largest change of the surface morphology is observed between R(AT)=0.20 and R(AT)=0.25. The amount and the adsorption time of immobilized enzyme were measured by UV spectroscopy. About 20wt% of GOD was immobilized into the silica substrates above R(AT)=0.60 and was completely adsorbed into the substrate of R(AT)=0.80 with lapse of 4h after addition. In the measurement of the thermal stability, GOD dissolved in buffer solution loses nearly all of its activity after 30 min at 65 degrees C. In contrast, GOD immobilized on the surface-modified silica particles still retains about 90% of its activity after the same treatment. At this temperature, the immobilized glucose oxidase retained half of its initial activity after 4h. It is shown that the suitable usage of functionalizing agent like APTMS as well as the control of surface morphology is very important on the immobilization of enzyme.

A novel preparation route for platinum-polystyrene heterogeneous nanocomposite particles using alcohol-reduction method.

Platinum nanoparticles are homogeneously immobilized onto the polystyrene surface using alcohol-reduction method for the first time. Sulfonate groups were employed as a chemical protocol to make a binding between platinum nanoparticle and polystyrene surface. A large number of quasi-spherical platinum nanoparticles with a size of approximately 5 nm in diameter are formed and strongly attached to the polystyrene surface modified with sulfonate groups. The formation mechanism of composite materials was discussed briefly. The most distinguished features of this novel preparation route include simple operation, and absence of the toxic reducing agent. In addition, this novel preparation route can be extended to the preparation of other noble metal-polymer heterogeneous nanocomposites such as silver, gold, palladium, iridium and ruthenium.

The Chemical Deposition Method for the Decoration of Palladium Particles on Carbon Nanofibers with Rapid Conductivity Changes.

Palladium (Pd) metal is well-known for hydrogen sensing material due to its high sensitivity and selectivity toward hydrogen, and is able to detect hydrogen at near room temperature. In this work, palladium-doped carbon nanofibers (Pd/CNFs) were successfully produced in a facile manner via electrospinning. Well-organized and uniformly distributed Pd was observed in microscopic images of the resultant nanofibers. Hydrogen causes an increment in the volume of Pd due to the ability of hydrogen atoms to occupy the octahedral interstitial positions within its face centered cubic lattice structure, resulting in the resistance transition of Pd/CNFs. The resistance variation was around 400%, and it responded rapidly within 1 min, even in 5% hydrogen atmosphere conditions at room temperature. This fibrous hybrid material platform will open a new and practical route and stimulate further researches on the development of hydrogen sensing materials with rapid response, even to low concentrations of hydrogen in an atmosphere.

Controlled release of retinol from silica particles prepared in O/W/O emulsion: the effects of surfactants and polymers.

Spherical silica particles containing retinol were fabricated by using O/W/O multiple emulsion and sol-gel method. In this study, when both hydroxypropyl cellulose (HPC) and surfactants such as Tween 20 and Span 80 were used, multiple emulsion encapsulating retinol was prepared successfully. The size of water droplets and the amount of released retinol depended on the concentration of surfactants and PEG polymer. In addition, PEG, PVP, and Pluronic P123 were introduced as a stabilizer in the water phase to investigate the effect of polymers on the encapsulation efficiency. In the case of PVP, encapsulation efficiency of retinol in the silica particles was 7.35% and the lowest. On the other hand, in the case of Pluronic P123, it was 30.89% and the highest among obtained silica particles. The morphologies of multiple emulsion and silica particles were observed by optical microscope (OM) and field emission scanning electronic microscope (FE-SEM). In vitro release test and encapsulation efficiency were characterized by HPLC.

Effects of silver nanoparticles on the fluidity of bilayer in phospholipid liposome.

This paper describes the formation and characterization of liposome entrapping the silver nanoparticles in bilayer. Silver nanoparticles were entrapped in the bilayer of dipalmitoylphosphatidylcholine (DPPC) liposome, named as silver-loaded liposome. Specifically, above the gel to liquid-crystalline phase transition temperature of this lipid (i.e., 41 degrees C), it was observed that membrane fluidities of silver-loaded liposomes were increased, and fluorescence anisotropy values were reduced from 0.114 to 0.097. This might be due to the structural modifications and interactions between DPPC molecules and silver nanoparticles within the bilayer. It was also confirmed that silver nanoparticles were entrapped in hydrophobic region of lipid bilayer with transmission electron microscopy (TEM) and electron energy loss spectroscopy (EELS) measurements.

Preparation and antibacterial effects of Ag-SiO2 thin films by sol-gel method.

In the present study, silver-doped silica thin films were successfully prepared by sol-gel method to apply for antibacterial materials. The starting solution was prepared from 1:0.24:3.75:2.2 molar ratios of Si(OC2H5)4):AgNO3:H2O:C2H5OCH2CH2OH and then the pH value controlled at 3 with 0.5 N HNO3 solution. The formation of silver-doped glassy silica thin films at various temperatures was investigated through infrared spectroscopy, ultraviolet-visible, scanning electron microscopy and X-ray diffraction. From these analysis data, it was found that silver ions were completely trapped in the silica matrix and their reduction could be achieved at 600 degrees C annealing temperature. The antibacterial effects of silica thin films against Escherichia coli and Staphylococcus aureus were examined by film attachment method. The coating films had an excellent antibacterial performance.

Analysis of trihalomethanes in drinking water using headspace-SPME technique with gas chromatography.

In many drinking water treatment plants, the chlorination process is one of the main techniques used for the disinfection of water. This disinfecting treatment leads to the formation of trihalomethanes (THMs) such as chloroform, dichlorobromomethane, chlorodibromomethane and bromoform. In this study, headspace-solid-phase microextraction (HS-SPME, 85 microm carboxen/polydimethylsiloxane fiber) technique was applied for the analysis of THMs in drinking water. The effects of experimental parameters such as kinds of SPME fiber, the volume ratio of sample to headspace, the addition of salts, magnetic stirring, extraction temperature, extraction time and desorption time on the analysis were investigated. Analytical parameters such as linearity, repeatability and limit of detection were also evaluated. The results of THMs from the survey of Seongnam (Korea) drinking water samples showed that the highest total trihalomethane and chloroform were 24.03 and 13.34 microg/l, which were well within the Korean drinking water quality standard of 100 and 80 microg/l, respectively.

Preparation of hollow silica microspheres in W/O emulsions with polymers.

Micrometer-sized hollow silica particles were synthesized by sol-gel reaction in water-in-oil emulsion. To obtain hollow structures in silica particles, the viscosity of water droplets in W/O emulsion was controlled with polyethylene glycol (PEG) or polyvinylpyrrolidone (PVP). To stabilize the emulsion structure, hydroxypropyl cellulose (HPC) was added to the oil phase. Without HPC, the particles have an irregular shape and hardly have a particulate form. As the concentration of HPC increased from 0.8 to 1.4 wt%, the size of silica particles decreased from 10 to 1 microm. But above 1.4 wt%, the solution was very viscous, so that it was difficult to handle. Especially, the role of PEG or PVP in the water phase was very important, not only because it stabilized the W/O emulsion structure, but also because it influenced the formation of hollow structure. Interestingly, the hollow silica particles were formed when the molar ratio of water to TEOS (Rw) was 4 and the concentrations of PEG and HPC were 6 and 1.4 wt%, respectively. Also, when PEG was replaced with polyvinylpyrrolidone (PVP), hollow silica particles ranging from 3 to 7 microm were formed.

Distribution of macropores in silica particles prepared by using multiple emulsions.

The distribution of macropores in silica particles prepared by the hydrolysis and condensation of TEOS in a hexane/water/decyl alcohol (O(1)/W/O(2)) multiple emulsion was investigated. To stabilize the emulsion structure, hydroxypropyl cellulose (HPC) was added into the O(2) phase and polyethylene glycol (PEG) was added into the water phase. Without HPC, the particles have an irregular shape and hardly have particulate forms. As the concentration of HPC increases, the shape of particles becomes more and more spherical and the size decreases. The size of silica particles was varied from 5 to 1 microm as the concentration of HPC increased from 0.5 to 0.7 wt%. The number and size of the macropores in silica particles were affected by PEG polymer concentration. With the variation in the concentration of PEG, macropores in silica particles were located at the surface of or inside the particles. At high concentrations of PEG, the macropores in particles were located inside the particles, but at low concentrations of PEG the macropores were located at the surfaces of particles. Interestingly, the particles of dimpled surfaces were formed when the molar ratio of water to TEOS (R(w)) was 4.0 and the concentrations of PEG and HPC were 2.0 and 0.7 wt% respectively. The surface areas of dimpled silica particles and completely spherical particles, measured by the BET method, were 409 and 433 m(2)/g respectively.