Silk-hydrogel Lenses for Light-emitting Diodes.

Today the high demand for electronics leads to massive production of waste, thus green materials based electronic devices are becoming more important for environmental protection and sustainability. The biomaterial based hydrogels are widely used in tissue engineering, but their uses in photonics are limited. In this study, silk fibroin protein in hydrogel form is explored as a bio-friendly alternative to conventional polymers for lens applications in light-emitting diodes. The concentration of silk fibroin protein and crosslinking agent had direct effects on optical properties of silk hydrogel. The spatial radiation intensity distribution was controlled via dome- and crater-type silk-hydrogel lenses. The hydrogel lens showed a light extraction efficiency over 0.95 on a warm white LED. The stability of silk hydrogel lens is enhanced approximately three-folds by using a biocompatible/biodegradable poly(ester-urethane) coating and more than three orders of magnitude by using an edible paraffin wax coating. Therefore, biomaterial lenses show promise for green optoelectronic applications.

Bioactive ZnO Coatings Deposited by MAPLE-An Appropriate Strategy to Produce Efficient Anti-Biofilm Surfaces.

Deposition of bioactive coatings composed of zinc oxide, cyclodextrin and cefepime (ZnO/CD/Cfp) was performed by the Matrix Assisted Pulsed Laser Evaporation (MAPLE) technique. The obtained nanostructures were characterized by X-ray diffraction, IR microscopy and scanning electron microscopy. The efficient release of cefepime was correlated with an increased anti-biofilm activity of ZnO/CD/Cfp composites. In vitro and in vivo tests have revealed a good biocompatibility of ZnO/CD/Cfp coatings, which recommend them as competitive candidates for the development of antimicrobial surfaces with biomedical applications. The release of the fourth generation cephalosporin Cfp in a biologically active form from the ZnO matrix could help preventing the bacterial adhesion and the subsequent colonization and biofilm development on various surfaces, and thus decreasing the risk of biofilm-related infections.

Governing the morphology of Pt-Au heteronanocrystals with improved electrocatalytic performance.

Platinum-gold heteronanostructures comprising either dimer (Pt-Au) or core-satellite (Pt@Au) configurations were synthesized by means of a seeded growth procedure using platinum nanodendrites as seeds. Careful control of the reduction kinetics of the gold precursor can be used to direct the nucleation and growth of gold nanoparticles on either one or multiple surface sites simultaneously, leading to the formation of either dimers or core-satellite nanoparticles, respectively, in high yields. Characterization by electron tomography and high resolution electron microscopy provided a better understanding of the actual three-dimensional particle morphology, as well as the Au-Pt interface, revealing quasi-epitaxial growth of Au on Pt. The prepared Pt-Au bimetallic nanostructures are highly efficient catalysts for ethanol oxidation in alkaline solution, showing accurate selectivity, high sensitivity, and improved efficiency by generating higher current densities than their monometallic counterparts.

MAPLE fabricated Fe3O4@Cinnamomum verum antimicrobial surfaces for improved gastrostomy tubes.

Cinnamomum verum-functionalized Fe3O4 nanoparticles of 9.4 nm in size were laser transferred by matrix assisted pulsed laser evaporation (MAPLE) technique onto gastrostomy tubes (G-tubes) for antibacterial activity evaluation toward Gram positive and Gram negative microbial colonization. X-ray diffraction analysis of the nanoparticle powder showed a polycrystalline magnetite structure, whereas infrared mapping confirmed the integrity of C. verum (CV) functional groups after the laser transfer. The specific topography of the deposited films involved a uniform thin coating together with several aggregates of bio-functionalized magnetite particles covering the G-tubes. Cytotoxicity assays showed an increase of the G-tube surface biocompatibility after Fe3O4@CV treatment, allowing a normal development of endothelial cells up to five days of incubation. Microbiological assays on nanoparticle-modified G-tube surfaces have proved an improvement of anti-adherent properties, significantly reducing both Gram negative and Gram positive bacteria colonization.

Spectroelectrochemistry of Silver Deposition on Single Gold Nanocrystals.

We report the electrodeposition of metallic silver onto gold nanostars adsorbed to ITO electrodes. The electrochemical process was studied at the single particle level by correlated in situ dark field spectroscopy and scanning electron microscopy (SEM). Underpotential deposition avoids bulk silver formation on the ITO substrates. SEM proves that deposition occurs on all surfaces of the gold nanostars when polyvinylpyrrolidone (PVP) is stabilizing the nanostars or preferentially at the nanostar tips when the ligand is removed. The surface plasmon resonance blue-shifts by more than 100 nm following the formation of a 5 nm Ag film on PVP stabilized gold nanostars, moving the scattered color from the near-infrared to red or orange. The spectral shifts can be accurately modeled using finite element simulations. These results demonstrate that the morphology and composition of individual bimetallic nanocrystals can be engineered electrochemically.

Dimethylformamide-mediated synthesis of water-soluble platinum nanodendrites for ethanol oxidation electrocatalysis.

Herein we describe the synthesis of water-soluble platinum nanodendrites in dimethylformamide (DMF), in the presence of polyethyleneimine (PEI) as a stabilizing agent. The average size of the dendrites is in the range of 20-25 nm while their porosity can be tuned by modifying the concentration of the metal precursor. Electron tomography revealed different crystalline orientations of nanocrystallites in the nanodendrites and allowed a better understanding of their peculiar branching and porosity. The high surface area of the dendrites (up to 22 m(2) g(-1)) was confirmed by BET measurements, while X-ray diffraction confirmed the abundance of high-index facets in the face-centered-cubic crystal structure of Pt. The prepared nanodendrites exhibit excellent performance in the electrocatalytic oxidation of ethanol in alkaline solution. Sensing, selectivity, cycleability and great tolerance toward poisoning were demonstrated by cyclic voltammetry measurements.

Gold nanowire networks: synthesis, characterization, and catalytic activity.

Gold nanowire networks (AuNWNs) with average widths of 17.74 nm (AuNWN(1)) or 23.54 nm (AuNWN(2)) were synthesized by direct reduction of HAuCl(4) with sodium borohydride powder in deep eutectic solvents, such as ethaline or reline, at 40 °C. Their width and length were dependent on the type of solvent and the NaBH(4)/HAuCl(4) molar ratio (32 in ethaline and 5.2 in reline). High resolution transmission electron microscopy (HR-TEM) analysis of the gold nanowire networks showed clear lattice fringes of polycrystalline nanopowder of d = 2.36, 2.04, 1.44, and 1.23 Å corresponding to the (111), (200), (220), or (311) crystallographic planes of face centered cubic gold. The purified AuNWNs were used as catalysts for the chemical reduction of p-nitroaniline to diaminophenylene with sodium borohydride in aqueous solution. The reaction was monitored in real time by UV-vis spectroscopy. The results show that the reduction process is six times faster in the presence of gold nanowire networks stabilized by urea from the reline (AuNWN(2)) than in the presence of gold nanowire networks stabilized by ethylene glycol from ethaline (AuNWN(1)). This is due to a higher number of corners and edges on the gold nanowires synthesized in reline than on those synthesized in ethaline as proven by X-ray diffraction (XRD) patterns recorded for both types of gold nanowire networks. Nevertheless, both types of nanomaterials determined short times of reaction and high conversion of p-nitroaniline to diaminophenylene. These gold nanomaterials represent a new addition to a new generation of catalysts: gold based catalysts.

Electrochemical study of ion transfer of acetylcholine across the interface of water and a lipid-modified 1,2-dichloroethane.

The ion transfer of acetylcholine (AcH(+)) ions across the unmodified and phospholipid-modified water|1,2-dichloroethane (DCE) interface has been studied by means of square-wave and cyclic voltammetry, as well as by electrochemical impedance spectroscopy. After being transferred in the organic phase, the AcH(+) ions undergo chemical reactions with the phospholipids. The overall behavior of the experimental system studied in the presence of phospholipids has been compared with the theoretical results of an ECrev reaction. The kinetic parameters of the chemical interactions between AcH(+) and the phospholipids have been determined from the voltammetric and impedance measurements. Additional characterization of those interactions has been made by using the surface tension measurements.

Electrochemical study of interfacial composite nanostructures: polyelectrolyte/gold nanoparticle multilayers assembled on phospholipid/dextran sulfate monolayers at a liquid-liquid interface.

The build up and electrochemical characterization of interfacial composite nanostructures containing a cationic polyelectrolyte and negatively charged mercaptosuccinic acid stabilized gold nanoparticles (AuNPs) is reported. The nanostructures were formed at the interface between two immiscible electrolyte solutions in which the organic phase is an immobilized 2-nitrophenyl octyl ether/PVC gel. The growth of the multilayer was verified with UV-vis spectra, and approximately a linear increase in UV-vis absorbance with increasing number of layers was observed. The interfacial capacitance of the multilayers was measured as a function of the potential and a theoretical model was developed to explain the results. The excellent agreement between theoretical and experimental capacitance curves allows us to conclude that nanocomposites behave similarly to polyelectrolyte multilayers, with the outmost layer determining the alternating sign of the outer surface charge density. Cyclic voltammograms were used to evaluate the transfer rate constant across the multilayers of a model drug, metoprolol, and the standard probe tetraethylammonium cation. The apparent rate constants were slightly larger than in other studies in the literature and decrease with the increasing number of layers.

Electrochemical characterization of polyelectrolyte/gold nanoparticle multilayers self-assembled on gold electrodes.

Polyelectrolyte/gold nanoparticle multilayers composed of poly(l-lysine) (pLys) and mercaptosuccinic acid (MSA) stabilized gold nanoparticles (Au NPs) were built up using the electrostatic layer-by-layer self-assembly technique upon a gold electrode modified with a first layer of MSA. The assemblies were characterized using UV-vis absorption spectroscopy, cyclic and square-wave voltammetry, electrochemical impedance spectroscopy, and atomic force microscopy. Charge transport through the multilayer was studied experimentally as well as theoretically by using two different redox pairs [Fe(CN)(6)](3-/4-) and [Ru(NH(3))(6)](3+/2+). This paper reports a large sensitivity to the charge of the outermost layer for the permeability of these assemblies to the probe ions. With the former redox pair, dramatic changes in the impedance response were obtained for thin multilayers each time a new layer was deposited. In the latter case, the multilayer behaves as a conductor exhibiting a strikingly lower impedance response, the electric current being enhanced as more layers are added for Au NP terminated multilayers. These results are interpreted quite satisfactorily by means of a capillary membrane model that encompasses the wide variety of behaviors observed. It is concluded that nonlinear slow diffusion through defects (pinholes) in the multilayer is the governing mechanism for the [Fe(CN)(6)](3-/4-) species, whereas electron transfer through the Au NPs is the dominant mechanism in the case of the [Ru(NH(3))(6)](3+/2+) pair.