Tuning the Functionality of a Carbon Nanofiber-Pt-RuO(2) System from Charge Storage to Electrocatalysis

Chemical-functionalization-induced switching in the property of a hybrid system composed of a hollow carbon nanofiber (CNF) and Pt and RuO(2) nanoparticles from charge storage to electrocatalysis is presented. The results of this study show how important it is to have a clear understanding of the nature of surface functionalities in the processes involving dispersion of more than one component on various substrates including carbon nanomorphologies. When pristine CNF is used to decorate Pt and RuO(2) nanoparticles, random dispersion occurs on the CNF surface (C-PtRuO(2)). This results in mainly phase-separated nanoparticles rich in RuO(2) characteristics. In contrast to this, upon moving from the pristine CNF to those activated by a simple H(2)O(2) treatment to create oxygen-containing surface functional groups, a material rich in Pt features on the surface is obtained (F-PtRuO(2)). This is achieved because of the preferential adsorption of RuO(2) by the functionalized surface of CNF. A better affinity of the oxygen-containing functional groups on CNF toward RuO(2) mobilizes relatively faster adsorption of this moiety, leading to a well-controlled segregation of Pt nanoparticles toward the surface. Further reorganization of Pt nanoparticles leads to the formation of a Pt nanosheet structure on the surface. The electrochemical properties of these materials are initially evaluated using cyclic voltammetric analysis. The cyclic voltammetric results indicate that C-PtRuO(2) shows a charge storage property, a typical characteristic of hydrous RuO(2), whereas F-PtRuO(2) shows an oxygen reduction property, which is the characteristic feature of Pt. This clear switch in the behavior from charge storage to electrocatalysis is further confirmed by galvanostatic charge-discharge and rotating-disk-electrode studies.     

Light-assisted synthesis and functionalization of silver nanoparticles with thiol derivative thioxanthones: new insights into the engineering of metal/chromophore nanoassemblies

Nanofluids are suspensions of nanometer-sized particles which significantly modify the properties of the base fluids. Nanofluids exhibit attractive properties, such as high thermal conductivity, tunable surface tension, viscosity, and rheology. Various attempts have been made to understand the mechanisms for these property modifications caused by adding nanoparticles; however, due to the lack of direct nanoscale evidence, these explanations are still controversial. This work calculated the surface tension, viscosity, and rheology of gold–water nanofluids using molecular dynamics simulations which provide a microscopic interpretation for the modified properties on the molecular level. The gold–water interaction potential parameters were changed to mimic various nanoparticle types. The results show that the nanoparticle wettability is responsible for the modified surface tension. Hydrophobic nanoparticles always tend to stay on the free surface so they behave like a surfactant to reduce the surface tension. Hydrophilic nanoparticles immersed into the bulk fluid impose strong attractive forces on the water molecules at the free surface which reduces the free surface thickness and increases the surface tension of the nanofluid. Solid-like absorbed water layers were observed around the nanoparticles which increase the equivalent nanoparticle radius and reduce the mobility of the nanoparticles within the base fluid which increases the nanofluid viscosity. The results show the water molecule solidification between two or many nanoparticles at high nanoparticle loadings, but the solidification effect is suppressed for shear rates greater than a critical shear rate; thus Newtonian nanofluids can present shear-thinning non-Newtonian behavior.     

One-dimensional confinement of a nanosized metal organic framework in carbon nanofibers for improved gas adsorption

The loading of a Zn-terephthalate based MOF in the inner cavity as well as on the outer walls of a hollow carbon nanofiber (CNF) creates MOF@CNF hybrids. This hybrid 'MOF@CNF' displayed improved thermal stability as well as gas adsorption compared to the individual counterparts.     

Neutral additives enhance the metal-chelate affinity adsorption of nucleic acids: role of water activity

Immobilized metal-chelate affinity chromatography has been widely used in the purification of proteins, and we have recently found that it can also be applied to purification of nucleic acids through interactions involving exposed bases, especially purines. Here we report that the inclusion of moderate quantities of neutral solutes in the buffer substantially enhances the binding affinity of nucleic acids for immobilized metal-chelate affinity adsorbents. Addition of 20% (v/v) of solutes such as ethanol, methanol, isopropanol, n-propanol, and dimethyl sulfoxide enhances the initial affinity of binding of total yeast RNA by 4.4-, 3.8-, 3.7-, 3.0-, and 2.8-fold, respectively for Cu(II)-iminodiacetic acid (IDA) agarose adsorbent, and the weaker adsorption by Cu(II)-nitrilotriacetic acid (NTA) agarose was even more strongly enhanced. The adsorption affinities of the smaller oligodeoxynucleotide molecules A20, G20, C20 and T20 also increase with the addition of ethanol, suggesting that the effect is not significantly mediated by conformational changes. Binding enhancement generally correlates with reduction of water activity by the various solutes, as predicted by several models of solution thermodynamics, consistent with an entropic contribution by displacement of waters from the metal-chelate. Interestingly, the enhancement was not seen with the proteins bovine serum albumin and lysozyme.     

Distinguished geodesics and jacobi fields on first order jet spaces

In the framework of jet spaces endowed with a non-linear connection, the special curves of these spaces (h-paths, v-paths, stationary curves and geodesics) which extend the corresponding notions from Riemannian geometry are characterized. The main geometric objects and the paths are described and, in the case when the vertical metric is independent of fiber coordinates, the first two variations of energy and the extended Jacobi field equations are derived.     

Synthesis of nanoscale antimony particles

For the search of new negative electrodes of Li-ion batteries, a low-temperature method has been developed for the preparation of nanoscale antimony particles which uses an alkoxide-activated sodium hydride as reducing agent of antimony pentachloride. X-ray diffraction and TEM studies confirm the obtaining of amorphous Sb nanoparticles dispersed in an organic matrix. ¹²¹Sb Mössbauer spectroscopy gives evidence for the occurrence of interactions between antimony and the matrix. These interactions are modified by the washing treatments.     

On signal reconstruction without phase

We will construct new classes of Parseval frames for a Hilbert space which allow signal reconstruction from the absolute value of the frame coefficients. As a consequence, signal reconstruction can be done without using phase or its estimation. This verifies a longstanding conjecture of the speech processing community.     

Stability theorems for Fourier frames and wavelet Riesz bases

In this paper we present two applications of a Stability Theorem of Hilbert frames to nonharmonic Fourier series and wavelet Riesz basis. The first result is an enhancement of the Paley-Wiener type constant for nonharmonic series given by Duffin and Schaefer in [6] and used recently in some applications (see [3]). In the case of an orthonormal basis, our estimate reduces to Kadec’ optimal 1/4 result. The second application proves that a phenomenon discovered by Daubechies and Tchamitchian [4] for the orthonormal Meyer wavelet basis (stability of the Riesz basis property under small changes of the translation parameter) actually holds for a large class of wavelet Riesz bases.     

Preparation of siloxane‐based urethane dimethacrylates carrying carboxylic groups and the effect of silver nanoparticles on the properties of composite polymer films

This work reports on the synthesis of three acid oligosiloxane‐urethane dimethacrylates and their use to obtain hybrid nanocomposite films, in which the presynthesized silver nanoparticles (NPs) were incorporated before photopolymerization, or produced via in situ photoreduction of the silver nitrate (AgNO₃) precursor into the formulation, without any conventional reducing agent. All samples were characterized by ¹H NMR, FT‐infrared and UV spectroscopies, photodifferential scanning calorimetry (photo‐DSC), transmission electron microscopy (TEM), and energy‐dispersive X‐ray (EDX) analysis. Fourier transformed infrared spectroscopy and photo‐DSC results showed that dimethacrylates having hydrophilic segment of poly(ethylene oxide) type in structure are more reactive than the acid oligosiloxane dimethacrylate. When another urethane dimethacrylate is taken as a comonomer, the photopolymerization rate (0.112–0.132 s^?1) and the degree of conversion (82–93%) significantly increased. Experimental evidence of the existence of nanosilver into the polymer matrix generated upon UV irradiation has been supported by UV spectroscopy, EDX and TEM analysis, the last allowing a visualization of the formation of silver NPs with size between 2 and 15 nm. Mechanical parameters and wettability of the photocrosslinked films are also discussed in the prospect of further potential applications in the biomedical field. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Histamine detection using functionalized porphyrin as electrochemical mediator

This study reports on deposition of asymmetrical substituted meso-phenyl porphyrin, 5-(4-carboxyphenyl)-10,15,20-triphenylporphyrin (CPTPP) thin films by matrix-assisted pulsed laser evaporation (MAPLE) on screen-printed electrodes, aiming for histamine detection. Raman spectrometry confirmed that CPTPP chemical structure was preserved in MAPLE-deposited thin films at 200 mJ/cm² laser fluence. Atomic force microscopy topography revealed that MAPLE-deposited thin films have a better coverage on the working electrode made of carbon compared to the ones obtained by dropcasting. Cyclic voltammetry demonstrated that CPTPP is an appropriate mediator for histamine detection in trichloroacetic acid solution. We proved that MAPLE serves as a soft technique in fabrication of porphyrin thin films and patterns.