Pd nanoparticles prepared by “controlled colloidal synthesis” in solid/liquid interfacial layer on silica. I. Particle size regulation by reduction time

Controlled colloidal synthesis (CCS) was developed to prepare monodisperse palladium particles in the nano-scale range on suspended SiO₂ particles in an ethanol–toluene mixture. On colloidal SiO₂ an about 1 nm thick ethanol-rich adsorption layer was produced in adsorption equilibrium with the liquid mixture. Ethanol served as a reducing agent for the Pd(II) ions diffusing from a toluene-rich liquid solution into the interfacial layer. The low reduction rate ensures the dominancy of particle growth over the nucleation of palladium during the reduction process after the initial nucleation. The relation between the reduction time and the particle size produced was studied. XRF, XPS, TEM, CO chemisorption, and benzene hydrogenation as catalytic test were employed to characterize the samples prepared using different reduction time.     

Nanosphere Lithography as a Versatile Method to Generate Surface‐Imprinted Polymer Films for Selective Protein Recognition

A versatile approach based on nanosphere lithography is proposed to generate surface‐imprinted polymers for selective protein recognition. A layer of 750 nm diameter latex bead‐protein conjugate is deposited onto the surface of gold‐coated quartz crystals followed by the electrosynthesis of a poly(3,4‐ethylenedioxythiophene)/poly(styrenesulfonate) (PEDOT/PSS) film with thicknesses on the order of the bead radius. The removal of the polymer bead‐protein conjugates, facilitated by using a cleavable protein‐nanosphere linkage is shown to result in 2D arrays of periodic complementary size cavities. Here it is demonstrated by nanogravimetric measurements that the imprinting proceeds further at molecular level and the protein (avidin) coating of the beads generates selective recognition sites for avidin on the surface of the PEDOT/PSS film. The binding capacity of such surface‐imprinted polymer films is ca. 6.5 times higher than that of films imprinted with unmodified beads. They also exhibit excellent selectivity against analogues of avidin, i.e., extravidin, streptavidin, and neutravidin, the latter being in fact undetectable. This methodology, if coupled with properly oriented conjugation of the macromolecular template to the nanoparticles, offers the possibility of site‐directed imprinting.     

TESTING EQUALITY OF MEANS WHEN THE OBSERVATIONS ARE FROM FUNCTIONAL TIME SERIES

There are numerous examples of functional data in areas ranging from earth science to finance where the problem of interest is to compare several functional populations. In many instances, the observations are obtained consecutively in time, and thus, the classical assumption of independence within each population may not be valid. In this article, we derive a new, asymptotically justified method to test the hypothesis that the mean curves of multiple functional populations are the same. The test statistic is constructed from the coefficient vectors obtained by projecting the functional observations into a finite dimensional space. Asymptotics are established when the observations are considered to be from stationary functional time series. Although the limit results hold for projections into arbitrary finite dimensional spaces, we show that higher power is achieved by projecting onto the principle components of empirical covariance operators that diverge under the alternative. Our method is further illustrated by a simulation study as well as an application to electricity demand data.     

Capillary electrochromatography of proteins on an anion-exchanger column

Capillary electrochromatography (CEC) of proteins was carried out using 50-microm-i.d. fused-silica capillaries packed with 5-microm silica beads having strong anion-exchanger functions attached to hydrophilic spacers at the chromatographic surface. The siliceous microspheres and the capillary innerwall were treated first with a heterobifunctional silanizing agent and reacted subsequently with a vinyl monomer containing quaternary ammonium groups to form a "tentacular" anion exchanger. A mixture of bovine carbonic anhydrase, alpha-lactalbumin, soybean trypsin inhibitor, and ovalbumin was separated using CEC by isocratic elution in the codirectional mode with aqueous phosphate buffer, pH 7.0, containing sodium chloride. The retention mechanism of isocratic CEC for proteins on the anion-exchanger column was illustrated by the results of a study on the effect of salt concentration on the separation. The potential of CEC for protein separation with high resolution was also demonstrated by electrochromatograms of conalbumin and hemoglobin variants. The results shed light on the mechanism of protein separation by isocratic CEC, which is believed to be a combination of chromatographic retention by electrostatic interactions and electrophoretic migration. Assuming that the contributions of the two mechanisms to the overall migration velocity are additive, an electrochromatographic resolution equation was derived and compared to the resolution equation in HPLC to reveal the constituents responsible for the enhancement of resolution by CEC with respect to that in HPLC. The advantage of CEC was also examined by comparing peak capacities in CEC on an, isocratic platform with peak capacities obtained with isocratic and gradient elution HPLC.     

Imaging polarimetry of the fogbow: polarization characteristics of white rainbows measured in the high Arctic

The knowledge on the optics of fogbows is scarce, and their polarization characteristics have never been measured to our knowledge. To fill this gap we measured the polarization features of 16 fogbows during the Beringia 2005 Arctic polar research expedition by imaging polarimetry in the red, green and blue spectral ranges. We present here the first polarization patterns of the fogbow. In the patterns of the degree of linear polarization p, fogbows and their supernumerary bows are best visible in the red spectral range due to the least dilution of fogbow light by light scattered in air. In the patterns of the angle of polarization α fogbows are practically not discernible because their α-pattern is the same as that of the sky: the direction of polarization is perpendicular to the plane of scattering and is parallel to the arc of the bow, independently of the wavelength. Fogbows and their supernumeraries were best seen in the patterns of the polarized radiance. In these patterns the angular distance δ between the peaks of the primary and the first supernumerary and the angular width σ of the primary bow were determined along different radii from the center of the bow. δ ranged between 6.08° and 13.41°, while σ changed from 5.25° to 19.47°. Certain fogbows were relatively homogeneous, meaning small variations of δ and σ along their bows. Other fogbows were heterogeneous, possessing quite variable δ- and σ-values along their bows. This variability could be a consequence of the characteristics of the high Arctic with open waters within the ice shield resulting in the spatiotemporal change of the droplet size within the fog.     

Experimental and theoretical study of skylight polarization transmitted through Snell's window of a flat water surface

The celestial polarization pattern may be scrambled by refraction at the air-water interface. This polarization pattern was examined in shallow waters with a submersible polarimeter, and it was calculated by using land measurements ('semiempirical predictions') and models of the skylight polarization. Semiempirically predicted and measured e-vector orientations were significantly similar. Conversely, predicted percent polarization was correlated but lower than measurements. Percent polarization depended on wavelength, where at high sun altitudes maximal percent polarization generally appeared in the UV and red spectral regions. The wavelength dependency of polarization may lead to differential spectral sensitivity in polarization-sensitive animals according to time and type of activity.     

Tuneable Piezoresistance of Graphene-Based 2D:2D Nanocomposite Networks

Piezoresistive nanocomposites are an important class of materials that allow the production of very sensitive strain sensors. Herein, a new class of piezoresistive nanocomposites prepared by mixing different types of 2D nanosheets is explored. In this way, three distinct types of nanocomposite are produced by mixing conducting and insulating nanosheets (graphene, Gr and boron nitride, BN), conducting and semiconducting nanosheets (graphene and tungsten diselenide, WSe₂ or tungsten disulfide, WS₂) as well as mixing two different types of conducting nanosheets (graphene and silver, Ag). For each nanocomposite type, a different dependence of composite conductivity on filler volume fraction is observed although all behaviors can be fully described by percolation theory. In addition, each composite type shows different piezoresistive properties. Interestingly, while the conductor insulator composites show the standard monotonic relationship between gauge factor and conductivity, both conductor:semi-conductor and conductor:conductor composites show very unusual behavior, in each case displaying a peak engage factor at the percolation threshold. In each case, percolation theory is used to develop simple equations for gauge factor as a function of both volume fraction and conductivity that fully describes all experimental data. This work expands the understanding of piezoresistive nanocomposites and provides a platform for the engineering of high-performance strain sensors.     

A review of reliable numerical models for three‐dimensional linear parabolic problems

The preservation of characteristic qualitative properties of different phenomena is a more and more important requirement in the construction of reliable numerical models. For phenomena that can be mathematically described by linear partial differential equations of parabolic type (such as the heat conduction, the diffusion, the pricing of options, etc.), the most important qualitative properties are: the maximum–minimum principle, the non‐negativity preservation and the maximum norm contractivity. In this paper, we analyse the discrete analogues of the above properties for finite difference and finite element models, and we give a systematic overview of conditions that guarantee the required properties a priori. We have chosen the heat conduction process to illustrate the main concepts, but engineers and scientists involved in scientific computing can easily reformulate the results for other problems too. Copyright © 2006 John Wiley & Sons, Ltd.     

Selective enrichment of low-abundance peptides in complex mixtures by elution-modified displacement chromatography and their identification by electrospray ionization mass spectrometry

Trace components were selectively enriched and detected in the tryptic digest of recombinant human growth hormone using elution-modified displacement chromatography, a hybrid technique combining features of elution and displacement chromatography. Based on the retention behavior of sample components in the elution mode, rapid and selective trace enrichment and high-resolution separation was achieved in a single step by utilizing appropriate combinations of an eluent such as aqueous acetonitrile with the displacer. Mass spectral and chromatographic analysis of displacement zones revealed up to 400-fold enhancement of the concentration of some low-abundance sample components. Potential application of this technique in proteomics to augment the sensitivity of LC-MS and 2-D gel electrophoretic approaches for the detection of biologically important low-abundance species is discussed.