Investigation of ion transfer across the micro-water/nitrobenzene interface facilitated by a fullerene derivative

A functionalized fullerene derivative containing a monoaza-18-crown-6 moiety was investigated by facilitated ion (such as Li+, Na+, K+, NH4+, Mg2+, and Ca2+) transfer across the micro-water/nitrobenzene interface supported at the tip of a micropipet. The current responses were detected by cyclic voltammetry and Osteryoung square wave voltammetry, which demonstrated that the facilitated ion transfer does occur by an interfacial complexation-dissociation process. The diffusion coefficient of this compound in nitrobenzene was approximately (5.90 +/- 0.04) x 10(-7) cm(2) s(-1), which is 1 order of magnitude less than other common ionophores due to the large size of the molecule. The selectivity of this molecule toward the metal ions followed the sequence Na+ > Li+ > K+ > NH4+ > Ca2+ similar to Mg2+. In addition, this compound was also easy to form film at the water/nitrobenzene interface to inhibit the simple ion transfer of tetramethylammonium ion. However, the adsorption of this ionophore has less influence on the facilitated metal ion transfer.

Sintering of nanopowders of amorphous silicon nitride under ultrahigh pressure

Nanopowders of amorphous silicon nitride were densified and sintered without additives under ultrahigh pressure (1.0-5.0 GPa) between room temperature and 1600 degrees C. The powders had a mean diameter of 18 nm and contained similar to 5.0 wt% oxygen that came from air-exposure oxidation, Sintering results at different temperatures were characterized in terms of sintering density, hardness, phase structure, and grain size. It was observed that the nanopowders can be pressed to a high density (87%) even at room temperature under the high pressure. Bulk Si3N4 amorphous and crystalline ceramics (relative density: 95-98%) were obtained at temperatures slightly below the onset of crystallization (1000-1100 degrees C and above 1420 degrees C, respectively. Rapid grain growth occurred during the crystallization leading to a grain size (>160 nm) almost 1 order of magnitude greater than the starting particulate diameters, With the rise of sintering temperature, a final density was reached between 1350 and 1420 degrees C, which seemed to be independent of the pressure applied (1.0-5.0 GPa), The densification temperature observed under the high pressure is lower by 580 degrees C than that by hot isostatic pressing sintering, suggesting a significantly enhanced low-temperature sintering of the nanopowders under a high external pressure.

Gas and water vapor transport through a series of novel poly(aryl ether sulfone) membranes

The permeation behavior of water vapor, H-2, CO2, O-2, N-2, and CH4 gases in a series of novel poly(aryl ether sulfone)s has been examined over a temperature range of 30-100 degreesC. These polymers include four alkyl-substituted cardo poly(aryl ether sulfone)s and four intermolecular interaction enhanced poly(aryl ether sulfone)s. Their water vapor and gas transport properties were compared to the unmodified cardo poly(aryl ether sulfone) (PES-C). It was found that the bulky alkyl substituents on the phenylene rings were advantageous for gas permeability, while the intermolecular hydrogen bonds and ionic bonds resulted in a considerable increase in gas permselectivity. The causes of the trend were interpreted according to free volume, interchain distance, and glass transition temperature, together with the respective contribution of gas solubility and diffusivity to the overall permeability. Of interest was the observation that IMPES-L, which simultaneously bears bulky isopropyl substituent and pendant carboxylic groups, displayed 377% higher O-2 permeability and 5.3% higher O-2/N-2 permselectivity than PES-C. Furthermore, sodium salt form PES-Na+ and potassium salt form PES-K+ exhibited water vapor permeability twice as high as PES-C and H2O/N-2 selectivity in 10(5) order of magnitude.

Structure and order of the discotic compound 2,3,6,7,10,11-hexakispentyloxytriphenylene as revealed by diffraction and molecular simulation studies

The aggregate structure of the discotic compound 2,3,6,7,10,11-hexakispentyloxytriphenylene (HPT) was studied both for the crystalline state and the liquid crystalline state by using electron crystallography and a molecular simulation approach. In the crystalline state, HPT was found to adopt an orthorhombic P-2212 space group with cell parameters a = 36.73 Angstrom, b = 27.99 Angstrom and c = 4.91 Angstrom. Molecular packing calculations were conducted to elucidate the molecular conformation and mutual orientational characteristics in the different states. Phase transitions and relationships are discussed from a structural point of view.

Application of the Sanchez-Lacombe lattice fluid theory to the system pvme/ps and model calculations

Cloud point curves reported in the literature for five representatives of the system poly(vinyl methyl ether)/polystyrene were evaluated theoretically by means of the Sanchez-Lacombe lattice fluid theory. The measured phase separation behavior can be described within experimental error using only one adjustable parameter (quantifying the interaction between the unlike mers). The Flory-Huggins interaction parameters calculated from this theoretical description depend in good approximation linearly on composition (volume fractions) and on the inverse temperature. An evaluation of these data yields a maximum heat effect which is almost one order of magnitude less (ca. -0.25 J/cm(3)) than obtained via Hess's cycle (dissolution of the components and of the blend) from calorimetric measurements. Model calculations on the basis of the present theory demonstrate that the critical points shift to a different extent upon a certain relative change in the molar mass of the blend components. The sensitivity of the calculated phase diagrams against changes in the scaling parameter decreases in the following order: interaction energies between unlike mers, differences in the scaling temperatures, pressures and densities.

Study of Multiple Films of Copper Phthalocyanine Embedded SnO2 Ultrafine Particles

Multiple films of copper phthalocyanine derivative embedded SnO2 ultrafine particles were studied, The results indicated that there is interaction between CuPc and SnO2, and structure of CuPc is destroyed to some extent. Gas sensitivity measurements show that conductance of LB films after embedding increases about one order of magnitude, stability of gas-sensing also increases.

NMR Spectra of polyimides: Interpretation and local chain motion study

Three kinds of high-performance polyimides 1 (poly(ketone-imide) PKI), 2 (poly(ether-imide) PEI) and 3 (poly(oxy-imide) POI) were studied using nuclear magnetic resonance (NMR). The NMR spectra of the polyimides were assigned according to the comprehensive consideration of the substitution effect of different substituting groups, viz. distortionless enhancement by polarization transfer (DEPT), no nuclear Overhauser effect (NNE), analysis of relaxation time, and two-dimensional correlated spectroscopy (COSY) techniques. The structural units of these three polyimides were determined. Carbon-13 and proton relaxation times for PEI and PKI were interpreted in terms of segmental motion characterized by the sharp cutoff model of Jones and Stockmayer (JS model) and anisotropic group rotation such as phenyl group rotation and methyl group rotation. Correlation times for the main-chain motion are in the tens of picosecond range which indicates the high flexibility of polyimide chains. Correlation times for phenyl group and methyl group rotations are more than 1 order of magnitude lower and approximately 1 order of magnitude higher than that of the main chain, respectively.

Observations of Kuroshio intrusion into the South China Sea

To discuss the intrusion of the Kuroshio into the SCS, we examined the mixing between the North Pacific and South China Sea (SCS) waters based on in-situ CTD data collected in August and September 2008 and the moored ADCP data taken from mid September 2008 to early July 2009. The CTD survey included four meridional sections from 119A degrees E to 122A degrees E around the Luzon Strait, during which pressure, temperature, and salinity were measured. The CTD data show that the isopycnal surface tilted from the SCS to the North Pacific; and it was steeper in the lower layers than in the upper ones. Meanwhile, we found strong vertical mixing taken place in the areas near 121A degrees E. The Kuroshio in high temperature and salinity intruded westward through Luzon Strait. The frequency of buoyancy was one order of magnitude greater than that of the common ones in the ocean, suggesting stronger stratification in the northeastern SCS. On the other hand, the long-term ADCP data show that before late October 2008, the direction of water flow in the SCS was eastward, and from November 2008 to late February 2009, it turned northwestward in the layers shallower than 150 m, while remained unchanged in deep layers from 200 to 450 m. From March to June 2009, the direction shifted with increasing depth from northward to southward, akin to the Ekman spiral. EOF analysis of the current time series revealed dominant empirical modes: the first mode corresponded to the mean current and showed that the Kuroshio intrusion occurred in the upper layers only from late December to early March. The temporal coefficient of the first and the second mode indicated clearly a dominant signal in a quasi-seasonal cycle.

Nutrient Dynamics in the Upwelling Area of Changjiang (Yangtze River) Estuary

Nutrient dynamics and its influence on the distribution of chlorophyll-a in the upwelling area of the Changjiang (Yangtze) River estuary were investigated in the spring (May) and summer (August) of 2004. In the spring, upwelling was apparent in the region of 122 degrees 20'-123 degrees 00' E, 31 degrees 00'-32 degrees 00' N and was associated with low temperature (16-21 degrees C), high salinity (24-33 practical salinity units [psu]), and low dissolved oxygen (2.5-6.0 mg L-1) in the upper 10 m of the water column. The spring upwelling increased the mixed-layer phosphate, nitrate, and silicate concentrations to roughly 1, 15, and 15 mu mol L-1, respectively, and improved the light transparency in the euphotic zone. This improvement in phytoplankton growing conditions was followed by an increase in chlorophyll-a concentrations. The summer upwelling was weaker and occurred over a smaller geographical area (122 degrees 20'-123 degrees 00' E, 31 degrees 15'-31 degrees 50' N). Strongly influenced by turbid Changjiang diluted water (CDW), it had little impact on the upper 10 m of the water column but instead increased nutrient concentrations at greater depths. The high concentration of particulates in the CDW reduced light transmission in the upper 10 m and, hence, limited phytoplankton growth throughout the water column. Chlorophyll-a concentrations in the summer upwelling area were roughly an order of magnitude lower than in the spring. Water clarity, as influenced by the CDW, appears to be the principal factor limiting the impact of upwelling on phytoplankton biomass in this area.

Deterministic Computations Whose History Is Independent of the Order of Asynchronous Updating

Consider a network of processors (sites) in which each site x has a finite set N(x) of neighbors. There is a transition function f that for each site x computes the next state ξ(x) from the states in N(x). But these transitions (updates) are applied in arbitrary order, one or many at a time. If the state of site x at time t is η(x; t) then let us define the sequence ζ(x; 0); ζ(x; 1), ... by taking the sequence η(x; 0),η(x; 1), ... , and deleting each repetition, i.e. each element equal to the preceding one. The function f is said to have invariant histories if the sequence ζ(x; i), (while it lasts, in case it is finite) depends only on the initial configuration, not on the order of updates. This paper shows that though the invariant history property is typically undecidable, there is a useful simple sufficient condition, called commutativity: For any configuration, for any pair x; y of neighbors, if the updating would change both ξ(x) and ξ(y) then the result of updating first x and then y is the same as the result of doing this in the reverse order. This fact is derivable from known results on the confluence of term-rewriting systems but the self-contained proof given here may be justifiable.

A Two-Tiered On-Line Server-Side Bandwidth Reservation Framework for the Real-Time Delivery of Multiple Video Streams

The advent of virtualization and cloud computing technologies necessitates the development of effective mechanisms for the estimation and reservation of resources needed by content providers to deliver large numbers of video-on-demand (VOD) streams through the cloud. Unfortunately, capacity planning for the QoS-constrained delivery of a large number of VOD streams is inherently difficult as VBR encoding schemes exhibit significant bandwidth variability. In this paper, we present a novel resource management scheme to make such allocation decisions using a mixture of per-stream reservations and an aggregate reservation, shared across all streams to accommodate peak demands. The shared reservation provides capacity slack that enables statistical multiplexing of peak rates, while assuring analytically bounded frame-drop probabilities, which can be adjusted by trading off buffer space (and consequently delay) and bandwidth. Our two-tiered bandwidth allocation scheme enables the delivery of any set of streams with less bandwidth (or equivalently with higher link utilization) than state-of-the-art deterministic smoothing approaches. The algorithm underlying our proposed frame-work uses three per-stream parameters and is linear in the number of servers, making it particularly well suited for use in an on-line setting. We present results from extensive trace-driven simulations, which confirm the efficiency of our scheme especially for small buffer sizes and delay bounds, and which underscore the significant realizable bandwidth savings, typically yielding losses that are an order of magnitude or more below our analytically derived bounds.

Efficient Nearest Neighbor Classification Using a Cascade of Approximate Similarity Measures

Nearest neighbor classification using shape context can yield highly accurate results in a number of recognition problems. Unfortunately, the approach can be too slow for practical applications, and thus approximation strategies are needed to make shape context practical. This paper proposes a method for efficient and accurate nearest neighbor classification in non-Euclidean spaces, such as the space induced by the shape context measure. First, a method is introduced for constructing a Euclidean embedding that is optimized for nearest neighbor classification accuracy. Using that embedding, multiple approximations of the underlying non-Euclidean similarity measure are obtained, at different levels of accuracy and efficiency. The approximations are automatically combined to form a cascade classifier, which applies the slower approximations only to the hardest cases. Unlike typical cascade-of-classifiers approaches, that are applied to binary classification problems, our method constructs a cascade for a multiclass problem. Experiments with a standard shape data set indicate that a two-to-three order of magnitude speed up is gained over the standard shape context classifier, with minimal losses in classification accuracy.

Quantitative analysis of the effect of derivatisation of [Ru(BPY) phen] with a quinoline moiety on the interaction with DNA

The bifunctional Ru(II) complex [Ru(BPY)2POQ-Nmet]2+ (1), in which the metallic unit is tethered by an aliphatic chain to an organic DNA binder, was designed in order to increase the affinity toward nucleic acids. The interaction of 1 with DNA was characterised from luminescence and absorption data and compared with the binding of its monofunctional metallic and organic analogues, [Ru(BPY)2(ac)phen]2+ (2) and Nmet-quinoline (3). The bifunctional complex has a binding affinity one order of magnitude higher than that of each of its separated moieties. Absorption changes induced upon addition of DNA at different pH indicate protonation of the organic sub-unit upon interaction with DNA under neutral conditions. The combination of the luminescence data under steady-state and time-resolved conditions shows that the attachment of the organic unit in 1 induces modifications of the association modes of the metallic unit, owing to the presence of the aliphatic chain which probably hinders the metallic moiety binding. The salt dependence of the binding constants was analysed in order to compare the thermodynamic parameters describing the association with DNA for each complex. This study demonstrates the interest of the derivatisation of a Ru(II) complex with an organic moiety (ia the bifunctional ligand POQ-Nmet) for the development of high affinity DNA probes or photoreactive agents.

Chondrogenesis and mineralization during in vitro culture of human mesenchymal stem cells on three-dimensional woven scaffolds.

Human mesenchymal stem cells (hMSCs) and three-dimensional (3D) woven poly(ɛ-caprolactone) (PCL) scaffolds are promising tools for skeletal tissue engineering. We hypothesized that in vitro culture duration and medium additives can individually and interactively influence the structure, composition, mechanical, and molecular properties of engineered tissues based on hMSCs and 3D poly(ɛ-caprolactone). Bone marrow hMSCs were suspended in collagen gel, seeded on scaffolds, and cultured for 1, 21, or 45 days under chondrogenic and/or osteogenic conditions. Structure, composition, biomechanics, and gene expression were analyzed. In chondrogenic medium, cartilaginous tissue formed by day 21, and hypertrophic mineralization was observed in the newly formed extracellular matrix at the interface with underlying scaffold by day 45. Glycosaminoglycan, hydroxyproline, and calcium contents, and alkaline phosphatase activity depended on culture duration and medium additives, with significant interactive effects (all p < 0.0001). The 45-day constructs exhibited mechanical properties on the order of magnitude of native articular cartilage (aggregate, Young's, and shear moduli of 0.15, 0.12, and 0.033 MPa, respectively). Gene expression was characteristic of chondrogenesis and endochondral bone formation, with sequential regulation of Sox-9, collagen type II, aggrecan, core binding factor alpha 1 (Cbfα1)/Runx2, bone sialoprotein, bone morphogenetic protein-2, and osteocalcin. In contrast, osteogenic medium produced limited osteogenesis. Long-term culture of hMSC on 3D scaffolds resulted in chondrogenesis and regional mineralization at the interface between soft, newly formed engineered cartilage, and stiffer underlying scaffold. These findings merit consideration when developing grafts for osteochondral defect repair.

Localization in systems of non-identical oscillators

A singular perturbation method is applied to a non-conservative system of two weakly coupled strongly nonlinear non-identical oscillators. For certain parameters, localized solutions exist for which the amplitude of one oscillator is an order of magnitude smaller than the other. It is shown that these solutions are described by coupled equations for the phase difference and scaled amplitudes. Three types of localized solutions are obtained as solutions to these equations which correspond to phase locking, phase drift, and phase entrainment. Quantitative results for the phases and amplitudes of the oscillators and the stability of these phenomena are expressed in terms of the parameters of the model.