Connectedness percolation of elongated hard particles in an external field

A theory is presented of how orienting fields and steric interactions conspire against the formation of a percolating network of, in some sense, connected elongated colloidal particles in fluid dispersions. We find that the network that forms above a critical loading breaks up again at higher loadings due to interaction-induced enhancement of the particle alignment. Upon approach of the percolation threshold, the cluster dimensions diverge with the same critical exponent parallel and perpendicular to the field direction, implying that connectedness percolation is not in the universality class of directed percolation.     

Geometrical phase and surface plasmon focusing with azimuthal polarization

Owing to a geometric phase effect, an isosceles triangular aperture etched into thin metal film leads to constructive or destructive interference of surface plasmons excited at the two equal sides under linearly polarized illumination. Through appropriate spatial arrangement of an array of triangles, a highly confined focal spot beyond the diffraction limit can be achieved at the geometric center under azimuthally polarized excitation with field enhancement comparable to a bull's eye plasmonic lens under radially polarized illumination. Through simply rotating the orientation of each triangle aperture by 90°, the plasmonic structure defocuses the same azimuthal polarization illumination due to destructive interference caused by a geometric π-phase difference between the two sides of the triangle and between the adjacent triangles.     

Metalorganic vapor phase epitaxy and characterizations of nearly-lattice-matched AlInN alloys on GaN/sapphire templates and free-standing GaN substrates

The epitaxy optimization studies of high-quality n-type AlInN alloys with different indium contents grown on two types of substrates by metalorganic vapor phase epitaxy (MOVPE) were carried out. The effect of growth pressure and V/III molar ratio on growth rate, indium content, and surface morphology of these MOVPE-grown AlInN thin films were examined. The surface morphologies of the samples were characterized by scanning electron microscopy and atomic force microscopy. By varying the growth temperatures from 860 °C to 750 °C, the indium contents in AlInN alloys were increased from 0.37% up to 21.4% as determined by X-ray diffraction (XRD) measurements. The optimization studies on the growth conditions for achieving nearly-lattice-matched AlInN on GaN templates residing on sapphire and free-standing GaN substrates were performed, and the results were analyzed in a comparative way. Several applications of AlInN alloy for thermoelectric and light-emitting diodes are also discussed.     

Recent advances on the Discretizable Molecular Distance Geometry Problem

The Molecular Distance Geometry Problem (MDGP) consists in finding an embedding in R³${\mathbb{R}}^3$ of a nonnegatively weighted simple undirected graph with the property that the Euclidean distances between embedded adjacent vertices must be the same as the corresponding edge weights. The Discretizable Molecular Distance Geometry Problem (DMDGP) is a particular subset of the MDGP which can be solved using a discrete search occurring in continuous space; its main application is to find three-dimensional arrangements of proteins using Nuclear Magnetic Resonance (NMR) data. The model provided by the DMDGP, however, is too abstract to be directly applicable in proteomics. In the last five years our efforts have been directed towards adapting the DMDGP to be an ever closer model of the actual difficulties posed by the problem of determining protein structures from NMR data. This survey lists recent developments on DMDGP related research.     

An experimental comparison of the focused beamformer and the inverse method for the characterisation of acoustic sources in ideal and non-ideal acoustic environments

The current availability and affordability of multi-microphone array systems has awakened a strong interest in sound source location and characterisation in many fields of experimental acoustics and noise control. Although the theory behind the design of such arrays has been known for some time, the algorithms used to process the microphone signals are the subject of on-going research and development. The beamformer algorithm is well-known and relatively simple to implement. It is useful for ‘scanning’ an area to find the position of sound sources but has limited ability to characterise fully the spatial distribution of the strength of an acoustic source. The inverse method, on the other hand, requires prior information regarding the position of sources or an appropriate discretisation of the source strength distribution. The method is more difficult to implement but can yield more useful source characterisation data. This paper presents a comparison between the two methods based on experimental data. The results show that, in the presence of more than one source, the beamformer cannot yield reliable estimates of the source strength of individual sources since the output from the beamformer is shown to be dependent upon the degree of correlation between multiple sources as well as the source strengths themselves. The inverse method, on the other hand, is shown to yield reliable estimates of source strength when more than one source is present, regardless of the correlation between the sources, although the results presented here are restricted to the case of a relatively small number of sources. It is clearly demonstrated, both theoretically and through carefully controlled experiments, that either method can be used effectively under reverberant conditions through the use of measured Green functions in place of the simple geometrically-derived free-space values of the Green function. This greatly improves the possibility for the successful use of these methods in many important industrial applications.     

Retinyl palmitate polymeric nanocapsules as carriers of bioactives

Nanocapsules containing poly(d,l-lactide) shell and retinyl palmitate core have been prepared by the pre-formed polymer interfacial deposition method. Dynamic light scattering measurements yielded an average hydrodynamic diameter of ～220nm and a polydispersity index of ～0.12. Small-angle neutron scattering experiments revealed the presence of two populations of nanocapsules of core diameters ～192 and 65nm. Freeze fracture transmission electron microscopy showed a polydisperse population of nanocapsules (NC), with a poly(d,l-lactide) shell thickness between 11 and 3nm. For comparison purposes, nanoemulsions (NE, no polymer) and nanospheres (NS, polymer matrix) were also prepared. Each type of nanoparticles exhibited a different morphology (when examined by electron microscopy), in particular NC showed deformability by capillary adhesion. All three types of nanoparticles successfully encapsulated the poorly water-soluble molecules baicalein and benzophenone-3. The thermal behavior of the various nanoparticles was different to a physical mixture of its individual components. Cytotoxicity and phototoxicity assays, performed in human keratinocytes (HaCaT) and murine fibroblasts (BALB/c 3T3), showed that the NC were only cytotoxic at high concentrations. In vitro release studies of benzophenone-3, by the dialysis bag method using NC and NS, showed a sustained release; however, permeation studies using plastic surgery human abdominal skin in Franz diffusion cells showed that a higher amount of benzophenone-3 from NC penetrated into the skin, most probably due to the deformable nature of these nanoparticles.     

Assessing colloidal stability of long term MWCNT based nanofluids

This report presents an assessment on colloidal stability of functionalized multiwalled carbon nanotubes based nanofluids. To this end, an innovative technique that allows for measurement of settling velocity during centrifugation is applied. This method also enables measurements without dilution, inferring further accuracy to the experimental study. The results suggest that functionalization techniques enable the production of highly stable nanofluids. It is also found, that the colloidal stabilities of these nanofluids are characterized by hindered settling. The settling velocity decreases when the nanoparticles volume fraction rises from 0.25% to 1.50% due to the increase of interparticle interaction. Furthermore, a high aspect ratio of nanoparticles directly contributed to an increase in colloidal stability. It is expected that these results may significantly contribute to proper tailor of nanofluids engineering, ensuring a long term stable dispersion enhancing industrial application suitability.     

Synthesis of 5-fluoro- and 5-hydroxymethanoprolines via lithiation of N-BOC-methanopyrrolidines. Constrained Cγ-exo and Cγ-endo Flp and Hyp conformer mimics

Proline derivatives with a C(γ)-exo pucker typically display a high amide bond trans/cis (K(T/C)) ratio. This pucker enhances n→π* overlap of the amide oxygen and ester carbonyl carbon, which favors a trans amide bond. If there were no difference in n→π* interaction between the ring puckers, then the correlation between ring pucker and K(T/C) might be broken. To explore this possibility, proline conformations were constrained using a methylene bridge. We synthesized discrete gauche and anti 5-fluoro- and 5-hydroxy-N-acetylmethanoproline methyl esters from 3-syn and 3-anti fluoro- and hydroxymethanopyrrolidines using directed α-metalation to introduce the α-ester group. NBO calculations reveal minimal n→π* orbital interactions, so contributions from other forces might be of greater importance in determining K(T/C) for the methanoprolines. Consistent with this hypothesis, greater trans amide preferences were found in CDCl(3) for anti isomers en-MetFlp and en-MetHyp (72-78% trans) than for the syn stereoisomers ex-MetFlp and ex-MetHyp (54-67% trans). These, and other, K(T/C) results that we report here indicate how substituents on proline analogues can affect amide preferences by pathways other than ring puckering and n→π* overlap and suggest that caution should be exercised in assigning enhanced pyrrolidine C(γ)-exo ring puckering based solely on enhanced trans amide preference.     

Palladium(II)-catalyzed cycloisomerization of substituted 1,5-hexadienes: a combined experimental and computational study on an open and an interrupted hydropalladation/carbopalladation/β-hydride elimination (HCHe) catalytic cycle

The Pd(II)-catalyzed cycloisomerization of 3-alkoxycarbonyl-3-hydroxy-substituted 1,5-hexadienes has been studied experimentally and computationally. Experimentally, the reaction is characterized by a rapid room temperature formation of monomeric as well as dimeric cycloisomerization products using the commercially available precatalyst [(CH(3)CN)(4)Pd](BF(4))(2). In situ NMR measurements indicate the initial kinetic advantage of the desired cycloisomerization pathway to methylene cyclopentanes; however, double bond isomerization, elimination, and dimer formation are competitive undesired pathways. Evaluation of the obtained product structures by NMR spectroscopy and X-ray crystallography indicates that the sole determinant for the monomer/dimer ratio is the regioselectivity of the initial hydropalladation in favor of the allylic (monomer formation) or the homoallylic double bond (dimer formation). In order to account for the experimental results, we propose the coexistence of two product-forming catalytic cycles, an open, monomer generating, as well as an interrupted and redirected, dimer generating, hydropalladation/carbopalladation/β-hydride elimination (HCHe) process. Results from computational studies of the proposed competing catalytic cycles are supportive to our mechanistic hypothesis and pinpoint the pivotal importance of Pd(II)-hydroxo-chelate complexes for the reactivity-stability interplay of on- and off-pathway intermediates.