Pd-coated Ni nanoparticles by the polyol method: an efficient hydrogenation catalyst

Pd-coated Ni nanoparticles of 50 +/- 15 nm size are prepared by the polyol method and characterized by X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy and thermogravimetry analysis. Surface coverage of Pd on Ni particles is less than a monolayer for 0.5 and 1 at% Pd-coated Ni. Quantitative conversion of nitrobenzene to aniline is observed over these Pd-coated Ni particles at 27degreesC under one atmospheric pressure of hydrogen. 0.5 and 1 at% Pd-coated Ni exhibits 10 times greater activity than that of typical colloidal palladium and platinum catalysts and 2.5 times higher activity than commercial 5 wt% Pd/C.

Self-assembled molecular films of tetraamino metal (Co, Cu, Fe) phthalocyanines on gold and silver. Electrochemical and spectroscopic characterization

The formation of molecular films of 2,9,16,23-tetraamino metal phthalocyanines [TAM(II)Pc; M (II) = Co, Cu, and TAM(III)Pc; M = Fe] by spontaneous adsorption on gold and silver surfaces is described. The properties of these films have been investigated by cyclic voltammetry, impedance, and FT-Raman spectroscopy. The charge associated with Co(II) and Co(I) redox couple in voltammetric data leads to a coverage of (0.35+/-0.05) x 10(-10) mol cm(-2), suggesting that the tetraamino cobalt phthalocyanine is adsorbed as a monolayer with an almost complete coverage. The blocking behavior of the films toward oxygen and Fe(CN)(6)(3-/4-) redox couple have been followed by cyclic voltammetry and impedance measurements. This leads to an estimate of the coverage of about 85 % in the case of copper and the iron analogs. FT-Raman studies show characteristic bands around 236 cm(-1) revealing the interaction between the metal substrate and the nitrogen of the -NH2 group on the phthalocyanine molecules.

Stress induced phase transition in a monomolecular perfluroalkylsilane film self assembled on aluminium surface

We control the stiffnesses of two dual double cantelevers placed in series to control penetration into a perflurooctyltrichlorosilane monolayer self assembled on aluminium and silicon substrates. The top cantilever which carries the probe is displaced with respect to the bottom cantilever which carries the substrate, the difference in displacement recorded using capacitors gives penetration. We further modulate the input displacement sinusoidally to deconvolute the viscoelastic properties of the monolayer. When the intervention is limited to the terminal end of the molecule there is a strong viscous response in consonance with the ability of the molecule to dissipate energy by the generation of gauche defects freely. When the intervention reaches the backbone, at a contact mean pressure of 0.2GPa the damping disappears abruptly and the molecule registers a steep rise in elastic modulus and relaxation time constant, with increasing contact pressure. We offer a physical explanation of the process and describe this change as due to a phase transition from a liquid like to a solid like state.

Nature of Electronic States in Atomically Thin MoS(2) Field-Effect Transistors

We present low-temperature electrical transport experiments in five field-effect transistor devices consisting of monolayer, bilayer, and trilayer MoS(2) films, mechanically exfoliated onto Si/SiO(2) substrate. Our experiments reveal that the electronic states In all films are localized well up to room temperature over the experimentally accessible range of gate voltage. This manifests in two-dimensional (2D) variable range hopping (VRH) at high temperatures, while below similar to 30 K, the conductivity displays oscillatory structures In gate voltage arising from resonant tunneling at the localized sites. From the correlation energy (T(0)) of VRH and gate voltage dependence of conductivity, we suggest that Coulomb potential from trapped charges In the substrate is the dominant source of disorder in MoS(2) field-effect devices, which leads to carrier localization, as well.

SOS films and interfaces: chemical aspects

The possible chemical reactions that take place during the growth of single crystal films of silicon on sapphire (SOS) are analyzed thermodynamically. The temperature for the growth of good quality epitaxial films is dependent on the extent of water vapor present in the carrier gas. The higher the water vapor content the higher the temperature needed to grow SOS films. Due to the interaction of silicon with sapphire at elevated temperatures, SOS films are doped with aluminum. The extent of doping is dependent on the conditions of film growth. The doping by aluminum from the substrate increases with increasing growth temperatures and decreasing growth rates. The equilibrium concentrations of aluminum at the silicon-sapphire interface are calculated as a function of deposition temperature, assuming that SiO2 or Al6Si2O13 are the products of reaction. It is most likely that the product could be a solid solutio n of Al2O3 in SiO2. The total amount of aluminum released due to the interaction between silicon and sapphire will account only for the formation of not more than one monolayer of reaction product unless the films are annealed long enough at elevated temperatures. This value is in good agreement with the recently reported observations employing high resolution transmission electron microscopy.

Scale effects on buckling analysis of orthotropic nanoplates based on nonlocal two-variable refined plate theory

This article presents the buckling analysis of orthotropic nanoplates such as graphene using the two-variable refined plate theory and nonlocal small-scale effects. The two-variable refined plate theory takes account of transverse shear effects and parabolic distribution of the transverse shear strains through the thickness of the plate, hence it is unnecessary to use shear correction factors. Nonlocal governing equations of motion for the monolayer graphene are derived from the principle of virtual displacements. The closed-form solution for buckling load of a simply supported rectangular orthotropic nanoplate subjected to in-plane loading has been obtained by using the Navier's method. Numerical results obtained by the present theory are compared with first-order shear deformation theory for various shear correction factors. It has been proven that the nondimensional buckling load of the orthotropic nanoplate is always smaller than that of the isotropic nanoplate. It is also shown that small-scale effects contribute significantly to the mechanical behavior of orthotropic graphene sheets and cannot be neglected. Further, buckling load decreases with the increase of the nonlocal scale parameter value. The effects of the mode number, compression ratio and aspect ratio on the buckling load of the orthotropic nanoplate are also captured and discussed in detail. The results presented in this work may provide useful guidance for design and development of orthotropic graphene based nanodevices that make use of the buckling properties of orthotropic nanoplates.

Surface chemical and adsorption studies using Thiobacillus ferrooxidans with reference to bacterial adhesion to sulfide minerals

Adhesion of Thiobacillus ferrooxidans to pyrite and chalcopyrite in relation to its importance in bioleaching and bioflotation has been studied. Electrokinetic studies as well as FT-IR spectra suggest that the surface chemistry of Thiobacillus ferrooxidans depends on bacterial growth conditions. Sulfur-,Pyrite- and chalcopyrite-grown Thiobacillus ferrooxidans were found to be relatively more hydrophobic. The altered surface chemistry of Thiobacillus ferrooxidans was due to secretion of newer and specific proteinaceous compounds. The adsorption density corresponds to a monolayer coverage in a horizontal orientation of the cells. The xanthate flotation of pyrite in presence of Thiobacillus ferrooxidans is strongly depressed where as the cells have insignificant effect on chalcopyrite flotation. This study demonstrate that: (a)Thiobacillus ferrooxidans cells can be used for selective flotation of chalcopyrite from pyrite and importantly at natural pH values. (b)Sulfur-grown cells exhibits higher leaching kinetics than ferrous ion-grown cells.

Janus Hybramers: Self-Adapting Amphiphilic Hyperbranched Polymers

Janus structures have attracted a great deal of interest because of their fascinating properties and potential for applications. In this study, we demonstrate that hyperbranched polymers, bearing randomly placed docosyl (C22 alkyl segment) and PEG segments on their periphery, can readily reconfigure so as to segregate the alkyl and PEG segments, thereby generating Janus-type structures that we have termed Janus hybramers. DSC studies clearly reveal an endothermic transition that corresponds to the melting of the docosyl domains, while Langmuir isotherms demonstrate that these polymers form stable monolayers that appear to undergo a slight densification beyond a critical surface pressure; this suggested possible crystallization of the docosyl segments at the air-water interface. AFM studies of the transferred monolayers reveal various interesting aggregate morphologies at different surface pressures suggestive of island formation at the air-water interface; at the same time they also provided an estimate of the monolayer thickness. These Janus HBPs also form vesicles as evident from TEM and AFM studies; the AFM height of the deposited vesicles, as expected, was roughly 4 times that of the monolayer. SAXS studies revealed the formation of lamellar structures; the interlamellar spacing was largest when the relative mole fractions of docosyl and PEG segments were similar, but the spacing decreased when the mole fraction of either of these peripheral segments is substantially smaller; this suggested the possible presence of interdigitation within the domains of the minor component.

Nanosphere Templated Metallic Grating Assisted Enhanced Fluorescence

In this paper, enhanced fluorescence from a silver film coated nanosphere templated grating is presented. Initially, numerical simulation was performed to determine the plasmon resonance wavelength by varying the thickness of the silver film on top of a monolayer of 400 nm nanospheres. The simulation results are verified experimentally and tested for enhancing fluorescence from fluorescein isothiocyanate whose excitation wavelength closely matches with the plasmon resonance wavelength of the substrate with 100 nm silver film over nanosphere. The 12 times enhancement in the intensity is attributed to the local field enhancement in addition to the excitation of surface plasmon polaritons along the surface.

Serine/Threonine/Tyrosine Protein Kinase Phosphorylates Oleosin, a Regulator of Lipid Metabolic Functions

Plant oils are stored in oleosomes or oil bodies, which are surrounded by a monolayer of phospholipids embedded with oleosin proteins that stabilize the structure. Recently, a structural protein, Oleosin3 (OLE3), was shown to exhibit both monoacylglycerol acyltransferase and phospholipase A(2) activities. The regulation of these distinct dual activities in a single protein is unclear. Here, we report that a serine/threonine/tyrosine protein kinase phosphorylates oleosin. Using bimolecular fluorescence complementation analysis, we demonstrate that this kinase interacts with OLE3 and that the fluorescence was associated with chloroplasts. Oleosin-green fluorescent protein fusion protein was exclusively associated with the chloroplasts. Phosphorylated OLE3 exhibited reduced monoacylglycerol acyltransferase and increased phospholipase A(2) activities. Moreover, phosphatidylcholine and diacylglycerol activated oleosin phosphorylation, whereas lysophosphatidylcholine, oleic acid, and Ca2+ inhibited phosphorylation. In addition, recombinant peanut (Arachis hypogaea) kinase was determined to predominantly phosphorylate serine residues, specifically serine-18 in OLE3. Phosphorylation levels of OLE3 during seed germination were determined to be higher than in developing peanut seeds. These findings provide direct evidence for the in vivo substrate selectivity of the dual-specificity kinase and demonstrate that the bifunctional activities of oleosin are regulated by phosphorylation.

Thermoelectricity in graphene: Effects of a gap and magnetic fields

We calculate the thermopower of monolayer graphene in various circumstances. We consider acoustic phonon scattering which might be the operative scattering mechanism in freestanding films and predict that the thermopower will be linear in any induced gap in the system. Further, the thermopower peaks at the same value of chemical potential (tunable by gate voltage) independent of the gap. We show that in the semiclassical approximation, the thermopower in a magnetic field saturates at high field to a value which can be calculated exactly and is independent of the details of the scattering. This effect might be observable experimentally. We also note that a Yukawa scattering potential can be used to fit experimental data for the thermopower for reasonable values of the screening length parameter.

Role of Specific Cations and Water Entropy on the Stability of Branched DNA Motif Structures

DNA three-way junctions (TWJs) are important intermediates in various cellular processes and are the simplest of a family of branched nucleic acids being considered as scaffolds for biomolecular nanotechnology. Branched nucleic acids are stabilized by divalent cations such as Mg2+, presumably due to condensation and neutralization of the negatively charged DNA backbone. However, electrostatic screening effects point to more complex solvation dynamics and a large role of interfacial waters in thermodynamic stability. Here, we report extensive computer simulations in explicit water and salt on a model TWJ and use free energy calculations to quantify the role of ionic character and strength on stability. We find that enthalpic stabilization of the first and second hydration shells by Mg2+ accounts for 1/3 and all of the free energy gain in 50% and pure MgCl2 solutions, respectively. The more distorted DNA molecule is actually destabilized in pure MgCl2 compared to pure NaCl. Notably, the first shell, interfacial waters have very low translational and rotational entropy (i.e., mobility) compared to the bulk, an entropic loss that is overcompensated by increased enthalpy from additional electrostatic interactions with Mg2+. In contrast, the second hydration shell has anomalously high entropy as it is trapped between an immobile and bulklike layer. The nonmonotonic entropic signature and long-range perturbations of the hydration shells to Mg2+ may have implications in the molecular recognition of these motifs. For example, we find that low salt stabilizes the parallel configuration of the three-way junction, whereas at normal salt we find antiparallel configurations deduced from the NMR. We use the 2PT analysis to follow the thermodynamics of this transition and find that the free energy barrier is dominated by entropic effects that result from the decreased surface area of the antiparallel form which has a smaller number of low entropy waters in the first monolayer.

How Does the Spacer Length of Cationic Gemini Lipids Influence the Lipoplex Formation with Plasmid DNA? Physicochemical and Biochemical Characterizations and their Relevance in Gene Therapy

Lipoplexes formed by the pEGFP-C3 plasmid DNA (pDNA) and lipid mixtures containing cationic gemini surfactant of the 1,2-bis(hexadecyl dimethyl ammonium) Acmes family referred to as C16CnC16, where n = 2 3, 5, or 12, and the zwitterionic helper lipid, 1,2-dioleoyl-sn-glycero-3-phosphatidylethanolamine (DOPE) have been studied from a wide variety of physical, chemical, and biological standpoints. The study has been carried out using several experimental methods, such as zeta potential, gel electrophoresis, small-angle X-ray scattering (SAXS), cryo-TEM, gene transfection, cell viability/cytotoxicity, and confocal fluorescence microscopy. As reported recently in a communication (J. Am. Chem. Soc. 2011, 133, 18014), the detailed physicochemical and biological studies confirm that, in the presence of the studied series lipid mixtures, plasmid DNA is compacted with a large number of its associated Na+ counterions. This in turn yields a much lower effective negative charge, q(pDNA)(-), a value that has been experimentally obtained for each mixed lipid mixture. Consequently, the cationic lipid (CL) complexes prepared with pDNA and CL/DOPE mixtures to be used in gene transfection require significantly less amount of CL than the one estimated assuming a value of q(DNA)(-) = -2. This drives to a considerably lower cytotoxicity of the gene vector. Depending on the CL molar composition, alpha, of the lipid mixture, and the effective charge ratio of the lipoplex, rho(eff), the reported SAXS data indicate the presence of two or three structures in the same lipoplex, one in the DOPE-rich region, other in the CL-rich region, and another one present at any CL composition. Cryo-TEM and SAXS studies with C16CnC16/DOPE-pDNA lipoplexes indicate that pDNA is localized between the mixed lipid bilayers of lamellar structures within a monolayer of similar to 2 nm. This is consistent with a highly compacted supercoiled pDNA conformation compared with that of linear DNA. Transfection studies were carried out with HEK293T, HeLa, CHO, U343, and H460 cells. The alpha and rho(eff) values for each lipid mixture were optimized on HEK293T cells for transfection, and using these values, the remaining cells were also transfected in absence (-FBS-FBS) and presence (-FBS+FBS) of serum. The transfection efficiency was higher with the CLs of shorter gemini spacers (n = 2 or 3). Each formulation expressed GFP on pDNA transfection and confocal fluorescence microscopy corroborated the results. C16C2C16/DOPE mixtures were the most efficient toward transfection among all the lipid mixtures and, in presence of serum, even better than the Lipofectamine2000, a commercial transfecting agent Each lipid combination was safe and did not show any significant levels of toxicity. Probably, the presence of two coexisting lamellar structures in lipoplexes synergizes the transfection efficiency of the lipid mixtures which are plentiful in the lipoplexes formed by CLs with short spacer (n = 2, 3) than those with the long spacer (n = 5, 12).

Layer-dependent resonant Raman scattering of a few layer MoS2

We report resonant Raman scattering of MoS2 layers comprising of single, bi, four and seven layers, showing a strong dependence on the layer thickness. Indirect band gap MoS2 in bulk becomes a direct band gap semiconductor in the monolayer form. New Raman modes are seen in the spectra of single- and few-layer MoS2 samples which are absent in the bulk. The Raman mode at similar to 230 cm(-1) appears for two, four and seven layers. This mode has been attributed to the longitudinal acoustic phonon branch at the M point (LA(M)) of the Brillouin zone. The mode at similar to 179 cm(-1) shows asymmetric character for a few-layer sample. The asymmetry is explained by the dispersion of the LA(M) branch along the G-M direction. The most intense spectral region near 455 cm(-1) shows a layer-dependent variation of peak positions and relative intensities. The high energy region between 510 and 645 cm(-1) is marked by the appearance of prominent new Raman bands, varying in intensity with layer numbers. Resonant Raman spectroscopy thus serves as a promising non invasive technique to accurately estimate the thickness of MoS2 layers down to a few atoms thick. Copyright (C) 2012 John Wiley & Sons, Ltd.

Self-Adapting Peripherally Heterofunctionalized Hyperbranched Polymers: Formation of Janus and Tripodal Structures

A peripherally clickable hyperbranched polyester carrying numerous propargyl terminal groups was prepared by a simple melt transesterification polycondensation of a suitably designed AB(2) monomer; this clickable hyperscaffold was then transformed into a variety of different derivatives by using the Cu-catalyzed azide-yne click reaction. Functionalization of the periphery with equimolar quantities of mutually immiscible segments, such as hydrocarbon, fluorocarbon, and PEG, yielded frustrated molecular systems that readapt and form structures wherein the immiscible segments appear to self-segregate to generate either Janus structures (when two immiscible segments are present) or tripodal structures (when three immiscible segments are present). Evidence for such self-segregation was obtained from a variety of studies, such as differential scanning calorimetry, Langmuir isotherms, AFM imaging, and small-angle X-ray scattering measurements. Crystallization of one or more of the peripheral segments reinforced this self-segregation; the weight-fraction-normalized enthalpies of melting associated with the different domains revealed a competition between the segments to optimize their crystalline organization. When one or more of the segments are amorphous, the remaining segments crystallize more effectively and consequently exhibit a higher melting enthalpy. AFM images of monolayers, transferred from the Langmuir trough, revealed that the thickness matches the expected values; furthermore, contact angle measurements clearly demonstrated that the monolayer films are fairly hydrophobic, and in the case of the tripodal hybramers, the presence of domains of hydrocarbon and fluorocarbon appears to impart nanoscale chemical heterogeneity that is reflected in the strong hysteresis in the advancing and receding contact angles.