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Hen egg white lysozyme acted as the sole reducing agent and catalyzed the formation of silver nanoparticles in the presence of light. Stable silver colloids formed after mixing lysozyme and silver acetate in methanol and the resulting nanoparticles were concentrated and transferred to aqueous solution without any significant changes in physical properties. Activity and antimicrobial assays demonstrated lysozyme-silver nanoparticles retained the hydrolase function of the enzyme and were effective in inhibiting growth of Escherichia coli, Staphylococcus aureus, Bacillus anthracis, and Candida albicans. Remarkably, lysozyme-silver nanoparticles demonstrated a strong antimicrobial effect against silver-resistant Proteus mirabilis strains and a recombinant E. coli strain containing the multiple antibiotic- and silver-resistant plasmid, pMG101. Results of toxicological studies using human epidermal keratinocytes revealed that lysozyme-silver nanoparticles are nontoxic at concentrations sufficient to inhibit microbial growth. Overall, the ability of lysozyme to assemble silver nanoparticles in a one-step reaction offers a simple and environmentally friendly approach to form stable colloids of nontoxic silver nanoparticles that combine the antimicrobial properties of lysozyme and silver. The results expand the functionality of nanomaterials for biological systems and represent a novel antimicrobial composite for potential aseptics and therapeutic use in the future.
ACS Nano 2009 Apr 28
PMID:Lysozyme catalyzes the formation of antimicrobial silver nanoparticles. 1934 24

Understanding transport phenomena of fluids through nanotubes (NTs) is of great interest in order to enable potential application of NTs as separation devices, encapsulation media for molecule storage and delivery, and sensors. Single-walled metal oxide NTs are interesting materials because they present a well-defined solid-state structure, precisely tunable diameter and length, as well as a hydrophilic and functionalizable interior for tuning transport and adsorption selectivity. Here, we study the transport properties of hydrogen-bonding liquids (water, methanol, and ethanol) through a single-walled aluminosilicate NT to investigate the influence of liquid-surface and liquid-liquid interactions and the effects of competitive transport of different chemical species using molecular dynamics (MD) simulations. The self-diffusivities (D(s)) for all the three species decrease with increasing loading and are comparable to bulk liquid diffusivities at low molecular loadings. We show that the hydrogen-bond network associated with water makes its diffusion behavior different from methanol and ethanol. Mixtures of water and methanol show segregation in the NT, with water located closer to the tube wall and the alcohol molecules localized near the center of the NT. D(s) values of water in an analogous aluminogermanate NT are larger than those in the aluminosilicate NT due to a larger pore diameter.
ACS Nano 2009 Jun 23
PMID:Self-diffusion of water and simple alcohols in single-walled aluminosilicate nanotubes. 1954 68

Graphene nanosheet, the hottest material in physics and materials science, has been studied extensively because of its unique electronic, thermal, mechanical, and chemical properties arising from its strictly 2D structure and because of its potential technical applications. Particularly, these remarkable characteristics enable it to be a promising candidate as a new 2D support to load metal nanoparticles (NPs) for application in fuel cells. However, constructing high-quality graphene/bimetallic NP hybrids with high electrochemical surface area (ECSA) remains a great challenge to date. In this paper, we demonstrate for the first time a wet-chemical approach for the synthesis of high-quality three-dimensional (3D) Pt-on-Pd bimetallic nanodendrites supported on graphene nanosheets (TP-BNGN), which represents a new type of graphene/metal heterostructure. The resulting hybrids were characterized by atomic force microscopy (AFM), transmission electron microscopy (TEM), high-resolution TEM (HRTEM), energy-dispersive X-ray (EDX) spectroscopy, X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), Raman spectroscopy, and electrochemical technique. It is found that small single-crystal Pt nanobranches supported on Pd NCs with porous structure and good dispersion were directly grown onto the surface of graphene nanosheets, which exhibits high electrochemical active area. Furthermore, the number of nanobranches for Pt-on-Pd bimetallic nanodendrites on the surface of graphene nanosheets could be easily controlled via simply changing the synthetic parameters, thus resulting in the tunable catalytic properties. Most importantly, the electrochemical data indicate that the as-prepared graphene/bimetallic nanodendrite hybrids exhibited much higher electrocatalytic activity toward methanol oxidation reaction than the platinum black (PB) and commercial E-TEK Pt/C catalysts.
ACS Nano 2010 Jan 26
PMID:Three-dimensional Pt-on-Pd bimetallic nanodendrites supported on graphene nanosheet: facile synthesis and used as an advanced nanoelectrocatalyst for methanol oxidation. 2000 Aug 45

Dispersion of an aqueous H(2)PtCl(6) solution into a trifluorotoluene (TFT) solution of a polystyrene-block-poly(2-vinylpyridine)-block-poly(ethylene oxide) (PS-b-P2VP-b-PEO) triblock copolymer produced an emulsion-induced hollow micelle (EIHM), comprising a water nanodroplet stabilized by PEO, H(2)PtCl(6)/P2VP, and PS, sequentially. The following addition of an aqueous LiAuCl(4) solution into the dispersion led to a coordination of LiAuCl(4) and PEO. The resulting spherical EIHM structure was transformed to a hollow cylindrical micelle by the fusion of spherical EIHM with the addition of methanol. This structural transition was reversible by the alternative addition of methanol and TFT. Oxygen plasma was used to generate Pt/Au concentric spheres and hollow cylindrical Pt/Au nano-objects.
ACS Nano 2010 Feb 23
PMID:Fabrication of Pt/Au concentric spheres from triblock copolymer. 2011 65

Au-TiO2 snowman-like heterodimer nanoparticles were prepared by a surface sol-gel process based on gold Janus nanoparticles whose surface-protecting monolayers consisted of a hemisphere of hydrophobic 1-hexanethiolates and the other of hydrophilic 2-(2-mercaptoethoxy)ethanol. Transmission electron microscopic measurements showed that the resulting TiO2 nanoparticles (diameter 6 nm) exhibited well-defined lattice fringes that were consistent with the (101) diffraction planes of anatase TiO2. The heterodimer nanoparticles displayed apparent photoluminescence that was ascribed to electronic transitions involving trap states of TiO2 particles, and the photocatalytic activity was manifested by the oxidative conversion of methanol into formaldehyde, which was detected quantitatively by the Nash method. The enhanced photocatalytic performance, as compared to that of the TiO2 nanoparticles alone, was ascribed to the charge separation of photogenerated electrons and holes at the Au-TiO2 interface that was facilitated by the close proximity of the gold nanoparticles. These results suggested that (i) there were at least two possible pathways for photogenerated electrons at the TiO2 conduction band, decay to the trap states and transfer to the gold nanoparticles, and (ii) energy/electron transfer from the trap states to gold nanoparticles was less efficient. In essence, this study showed that the snowman-like heterodimers might be exploited as a homogeneous photocatalytic system for the preparation of functional molecules and materials.
ACS Appl Mater Interfaces 2009 Sep
PMID:Janus nanostructures based on Au-TiO2 heterodimers and their photocatalytic activity in the oxidation of methanol. 2035 33

Zinc, silicon, and steel superhydrophobic surfaces were prepared by a simple solution-immersion technique. In the case of zinc, the method consists of dipping of the substrate in a prehydrolyzed methanol solution of 1H,1H,2H,2H-(perfluorooctyl)trichlorosilane [CF(3)(CF(2))(5)(CH(2))(2)SiCl(3), PFTS] for 24 h at 50 degrees C. Micron-sized spheres (1.7-2 microm in diameter) were formed on the zinc substrate at 50 degrees C, while a featureless coating was obtained when the solution-immersion process was conducted at room temperature. When the reaction was performed at room temperature, the formation of superhydrophobic coatings took several days (up to 5 days). In contrast, immersion of silicon or steel substrates in the PFTS/methanol solution led to the formation of hydrophobic interfaces even for a prolonged immersion period at 50 degrees C. The formation of superhydrophobic surfaces on silicon and steel surfaces was only possible if a zinc foil was added in the PFTS/methanol solution containing the silicon or steel substrate. X-ray photoelectron spectroscopy analysis was used to characterize the resulting surfaces and to underline a plausible reaction mechanism.
ACS Appl Mater Interfaces 2009 Sep
PMID:Preparation of superhydrophobic coatings on zinc, silicon, and steel by a solution-immersion technique. 2035 37

Monodisperse polymer-mediated platinum (Pt) nanoparticles (NPs) have been synthesized by photoreduction in the presence of poly(ethylenimine) (PEI), a hyperbranched polymer. The formation process of the Pt NPs is pursued by UV-vis spectroscopy, and the formation mechanism is discussed. The morphology and size of the Pt NPs were characterized by transmission electron microscopy (TEM). TEM imaging shows that the Pt NPs' average diameter is 2.88 +/- 0.53 nm. The PEI/Pt NPs were immobilized on glassy carbon electrodes, and the electrocatalytic activity of the catalysts was investigated by cyclic voltammetry. PEI/Pt NPs exhibit very high catalytic activity for a methanol oxidation reaction. PEI/Pt NPs on glassy carbon electrodes are robust, showing good tolerance to poisoning even after many cycles. The electrocatalytic activity of PEI/Pt NPs compares favorably with other polymer-mediated Pt NPs. The results indicate that PEI is an appropriate complexing reducing agent for the photochemical production of Pt NPs and a good capping agent, allowing immobilization of the NPs on the working electrode.
ACS Appl Mater Interfaces 2009 Oct
PMID:Synthesis and electrocatalytic activity of photoreduced platinum nanoparticles in a poly(ethylenimine) matrix. 2035 66

Recently, organic-inorganic nanocomposite zwitterionic polymer electrolyte membranes (PEMs) have attracted remarkable interest for application to the direct methanol fuel cell (DMFC) operated at intermediate temperature (100-200 degrees C). In this paper, we report the synthesis of an organic-inorganic hybrid zwitterionomer silica precursor with ammonium and sulfonic acid functionality by the ring-opening of 3-propanesultone under mild heating conditions and the preparation procedure of a proton-conductive and stable organic-inorganic zwitterion-poly(vinyl alcohol) (PVA) cross-linked PEM by sol-gel in aqueous media. Developed PEMs were extensively characterized by studying their physicochemical and electrochemical properties under DMFC operating conditions. These membranes were designed to possess all of the required properties of a proton-conductive membrane, namely, reasonable swelling, good mechanical, dimensional, and oxidative strength, flexibility, and low methanol permeability along with reasonable proton conductivity (4.85 x 10(-2) S cm(-1)) due to zwitterionic functionality. Moreover, from the selectivity parameter among all developed membranes, ZI-70 [zwitterionomer membrane with 70 wt % of PVA of 3-[[3-(triethoxysilyl)propyl]amino]propane-1-sulfonic acid in the membrane matrix], exhibited the best results in comparison to the Nafion117 membrane for DMFC applications.
ACS Appl Mater Interfaces 2009 May
PMID:3-[[3-(Triethoxysilyl)propyl]amino]propane-1-sulfonic acid-poly(vinyl alcohol) cross-linked zwitterionic polymer electrolyte membranes for direct methanol fuel cell applications. 2035 85

Random disulfonated poly(arylene ether sulfone)-silica nanocomposite (FSPAES-SiO2) membranes were physicochemically tuned via surface fluorination. Surface fluorination for 30 min converted about 20% of the C-H bonds on the membrane surface into C-F bonds showing hydrophobicity and electronegativity at the same time. The membranes with hydrophobic surface properties showed high dimensional stability and low methanol permeability when hydrated for direct methanol fuel cell applications. In particular, the surface enrichment of fluorine atoms led to anisotropic swelling behavior, associated with a stable electrode interface formation. Interestingly, in spite of the use of a random copolymer as a polymer matrix, the low surface free energy of the C-F bonds induced a well-defined continuous ionic channel structure, similar to those of multiblock copolymers. In addition to the morphological transition, fluorine atoms with high electron-withdrawing capability promoted the dissociation of sulfonic acid (-SO3H) groups. Consequently, FSPAES-SiO2 membranes exhibited improved proton conductivity. Thus, FSPAES-SiO2 membranes exhibited significantly improved single-cell performances (about 200%) at a constant voltage of 0.4 V in comparison with those of Nafion 117 and nonfluorinated membranes. Surprisingly, their good electrochemical performances were maintained with very low nonrecovery loss over the time period of 1400 h and interfacial resistances 380% times lower than those of conventional membrane-electrode assemblies comprising the control hydrocarbon membrane and a Nafion binder for the electrodes.
ACS Appl Mater Interfaces 2009 May
PMID:Surface-fluorinated proton-exchange membrane with high electrochemical durability for direct methanol fuel cells. 2035 99

We report herein a simple procedure for the fabrication of TiO2 nanofibers by the combination of electrospinning and sol-gel techniques by using poly(vinylpyrrolidone) (PVP), titanium(IV) butoxide, and acetylacetone in methanol as a spinning solution. TiO2 nanofibers (260-355 nm in diameter), with a bundle of nanofibrils (20-25 nm in diameters) aligned in the fiber direction, or particle-linked structures were obtained from the calcination of as-spun TiO2/PVP composite fibers at temperatures ranging from 300 to 700 degrees C. These nanofibers were utilized as photocatalysts for hydrogen evolution. The nanofiber photocatalyst calcined at 450 degrees C showed the highest activity among the TiO2 nanofibers tested such as ones prepared by the hydrothermal method and anatase nanoparticles (Ishihara ST-01). These results indicate that one-dimensional electrospun nanofibers with highly aligned bundled nanofibrils are beneficial for enhancement of the crystallinity, large surface area, and higher photocatalytic activity.
ACS Appl Mater Interfaces 2009 May
PMID:Photocatalytic activity for hydrogen evolution of electrospun TiO2 nanofibers. 2035 2


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