Metabolomic analysis characterizes tissue specific indomethacin-induced metabolic perturbations of rats

In this study, the promising metabolomic approach integrating with ingenuity pathway analysis (IPA) was applied to characterize the tissue specific metabolic perturbation of rats that was induced by indomethacin. The selective pattern recognition analyses were applied to analyze global metabolic profiling of urine of rats treated by indomethacin at an acute dosage of reference that has been proven to induce tissue disorders in rats, evaluated throughout the time-course of -24-72 h. The results preliminarily revealed that modifications of amino acid metabolism, fatty acid metabolism and energetically associated metabolic pathways accounted for metabolic perturbation of the rats that was induced by indomethacin. Furthermore, IPA was applied to deeply analyze the biomarkers and their relations with the metabolic perturbations evidenced by pattern recognition analyses. Specific biochemical functions affected by indomethacin suggested that there is an important correlation of its effects in kidney and liver metabolism, based on the determined metabolites and their pathway-based analysis. The IPA correlation of the three major biomarkers, identified as creatinine, prostaglandin E2 and guanosine, suggested that the administration of indomethacin induced certain levels of toxicity in the kidneys and liver. The changes in the levels of biomarker metabolites allowed the phenotypical determination of the metabolic perturbations induced by indomethacin in a time-dependent manner.     

J-aggregation of a sulfonated amphiphilic porphyrin at the air-water interface as a function of pH

π-A isotherms, ellipsometric measurements, Brewster angle microscopy (BAM) and reflection spectroscopy have been utilized to characterize the films of an amphiphilic porphyrin ((OD)(3)TPPS(3)) at the air-water interface as a function of pH. This porphyrin forms stable mono-molecular layers at such interfaces, and exhibits different J-aggregation as a function of pH. The J-aggregation of (OD)(3)TPPS(3) on neutral pH subphases is notable considering that the nitrogen atoms at the central macrocycle have a pK(a)≈4.9. The type of aggregates at neutral pH is like those detected at pH<4, because the central porphyrin ring is already protonated. However at basic pH the aggregation happens without protonation of the central ring but can be instead controlled by application of the surface pressure. At the air-water interface, (OD)(3)TPPS(3) shows two bands, a red component and a blue component, which have characteristics of non-degenerate linear oscillators being perpendicularly polarized between each other. The spectral behavior observed on subphases at different pHs is qualitatively interpreted by means of exciton coupling theory, assuming that the degenerate transitions attributed to the Soret band are split. Additionally, highly oriented molecular films of these J-aggregates were deposited onto transparent quartz slides.     

Using multiple short-end injections to develop fast electrophoretic separations--applications in iodide analysis

The aim of this study was to develop a fast CE separation method by using multiple short-end injections in a capillary coated with quaternary ammonium chitosan (HACC), in order to determine the iodide content of pharmaceutical formulations. The BGE was composed of 20 mM tris(hydroxymethyl)aminomethane and 11 mM hydrochloric acid, at pH 8. The internal standard used was thiocyanate. Separations were performed in a fused silica capillary (32 cm total length, 8.5 cm effective length and 50 μm i.d.) coated with HACC and direct UV detection at 220 nm. EOF was modified by flushing the capillary with polymeric solution, resulting in a semi-permanent coating of controlled and stable EOF. The EOF was anodic at pH 8. Different strategies, using single and multiple injection short-end configurations, were studied to develop a CE method that resulted in a maximum number of iodide samples analyzed per hour: one plug and flush (Sflush) 35 samples/h, one plug without flush (SWflush) 76 samples/h, four plugs and flush (Mflush) 61 samples/h, and four plugs without flush (MWflush) 80 samples/h. Using the multiple injection configuration, it was possible to inject up to four plugs using spacer electrolytes with good separation efficiency and selectivity. The voltage application time needed to separate the eight peaks (iodide and thiocyanate) with MWflush was only 12s. The method was validated and samples were analyzed using MWflush. Good linearity (R(2)>0.999); a limit of detection 0.4 mg L(-1); intermediate precision better than 3.8% (peak area) and recovery in the range of 99-102% were obtained.     

Liquid-vapor interfacial properties of vibrating square well chains

Liquid-vapor interfacial properties of square well chains are calculated. Surface tension, orthobaric densities, and vapor pressures are reported. Spinodal decomposition with a discontinuous molecular dynamics simulation program is used to obtain the results which are compared to previously published data for orthobaric densities and vapor pressures. In order to analyze the effect of the chain stiffness results for near tangent and overlapping linear chains as well as angled chains are obtained. Properties are calculated for linear chains of 2, 4, and 8 spheres for intramolecular distances of 0.97, 0.6, and 0.4 as well as for angled chains of 4 and 8 spheres and intramolecular distances of 0.4. The complete series of fully flexible near tangent square well chains is also studied (chains of 2, 4, 8, 12, and 16 particles with intramolecular distances of 0.97). The corresponding states principle applies to most of the systems considered. Critical properties values are reported as obtained from orthobaric densities, surface tensions, and vapor pressures. For the near tangent chains the critical temperatures increase with chain length but the rate of increment tends to zero for the longest chains considered. When the stiffness of the chain increases (intramolecular distance from 1 , 0.6, and 0.4) this saturation effect is either not present or reverses itself. The surface tension increases with the length of the chain while the width of the interface decreases.     

Molecular association of heteronuclear vibrating square-well dumbbells in liquid-vapor phase equilibrium

Molecular aggregates are formed by heteronuclear vibrating square-well dumbbells. In a recent article [G. A. Chapela and J. Alejandre, J. Chem. Phys., 132(10), 104704 (2010)], it is shown that heteronuclear vibrating square-well dumbbells with a diameter ratio between particles of 1/2 and interacting potential ratio of 4 form micelles of different sizes and shapes which manifest themselves in both the liquid and vapor phases, up to and above the critical point. This means that micellization and phase separation are present simultaneously in this simple model. These systems present a maximum in the critical temperature when plotted against the potential well depth of the second particle ε(2). In the same publication, it was speculated that the formation of micelles was responsible for the appearance of the maximum. A thorough study on this phenomena is presented here and it is found that there is a threshold on the size of the second particle and its corresponding depth of interaction potential, where the micelles are formed. If the diameter and well depth of the second particle are small enough for the first and deep enough for the second, micelles are formed. For σ(2)/σ(1) between 0.25 and 0.65 and ε(2)/ε(1) larger than 5.7, micelles are formed up to and above the critical temperature. Outside these ranges micelles appear only at temperatures lower than the critical point. There is a strong temperature dependence on the formation and persistence of the aggregates. For the deepest wells and large enough second particles, a gel interconnected aggregate is obtained. In this work, the micelles are formed at temperatures as low as the triple point and as high as the critical point and, in some cases, persist well above it. The presence of these maxima in critical temperatures T(c) when plotted against ε(2) as follows. At lower values of ε(2), an increase of T(c) is obtained as is expected by the increase of the attractive volume as indicated by the principle of corresponding states. As ε(2) increases further, the formation of molecular aggregates produce a saturation effect of the deepening of the potential well by encapsulating the particles of the second kind inside the micelles, so the resulting T(c) represents a new poly disperse system of molecular aggregates and not the original heteronuclear vibrating square-well dumbbells. The surface tension is also analyzed for these systems, and it is shown that decreases with increasing attraction due to the formation of molecular aggregates.     

Relativistic effects on the nuclear magnetic resonance shielding of FX (X = F, Cl, Br, I, and At) molecular systems

We present ab inito full four-component and spin-free calculations of the NMR shielding parameter, σ, in the FX (X = F, Cl, Br, I and At) molecular systems. A different expression that overcomes the traditional non-relativistic (NR) approximation used to calculate the relationship between spin-rotation constants and the paramagnetic terms of σ(p) are given. Large deviations from NR results are obtained for σ(X; X = I and At) and for σ(F; FAt). σ(∥)(p)(I; FI) is zero within the NR approach but -447.4 parts per million from our calculations. The electronic origin of relativistic corrections are analyzed. All passive SO contributions are obtained as a difference between full four-component calculations and spin-free ones. Considering relativistic effects on the anisotropy, we obtain a deviation of 10% for I and 25% for At. σ(∥)(SO)(X) is always negative and σ(∥)(SF)(X) is always positive; the passive SO becomes larger than the SF one for X = Br, I, and At. Both σ(∥)(SO)(X) and σ(⊥)(SO)(X) have a functional dependence such as a Z(X)(b) being the exponent 3.5 and 3.65, respectively. The passive SO contribution to the anisotropy has a similar functional dependence with an exponent of 3.60, meaning that its perpendicular component is larger than its corresponding parallel component.     

Determining concentration depth profiles in fluorinated networks by means of electric force microscopy

By means of electric force microscopy, composition depth profiles were measured with nanometric resolution for a series of fluorinated networks. By mapping the dielectric permittivity along a line going from the surface to the bulk, we were able to experimentally access to the fluorine concentration profile. Obtained data show composition gradient lengths ranging from 30 nm to 80 nm in the near surface area for samples containing from 0.5 to 5 wt. % F, respectively. In contrast, no gradients of concentration were detected in bulk. This method has several advantages over other techniques because it allows profiling directly on a sectional cut of the sample. By combining the obtained results with x-ray photoelectron spectroscopy measurements, we were also able to quantify F/C ratio as a function of depth with nanoscale resolution.     

Long-range-corrected hybrids using a range-separated Perdew-Burke-Ernzerhof functional and random phase approximation correlation

We build on methods combining a short-range density functional approximation with a long-range random phase approximation [B. G. Janesko, T. M. Henderson, and G. E. Scuseria, J. Chem. Phys. 130, 081105 (2009)] or second-order screened exchange [J. Paier et al., J. Chem. Phys. 132, 094103 (2010)] by replacing the range-separated local density approximation functional with a range-separated generalized gradient approximation functional in the short range. We present benchmark results that show a marked improvement in the thermodynamic tests over the previous local density approximation-based methods while retaining those methods' excellent performance in van der Waals interactions.     

Liquid-crystalline hybrid materials based on [60]fullerene and bent-core structures

What a core-ker! By the appropriate combination of promesogenic bent-core structures and the C(60) unit, lamellar polar liquid-crystal phases were induced. The supramolecular organization of the functional fullerene-based assemblies, the temperature range of the soft phase, the stabilization of the mesophase-like order at room temperature, and the molecular switching under an electric field can be tuned, depending on the molecular structure.     

Leading-Order Dynamics of Gravity-Driven Flows in?Free-Standing Soap Films

We derive the leading-order equations that govern the dynamics of the flow in a falling, free-standing soap film. Starting with the incompressible Navier?CStokes equations, we carry out an asymptotic analysis using parameters that correspond to a common experimental setup. We account for the effects of inertia, surface elasticity, pressure, viscous stresses, gravity, and air drag. We find that the dynamics of the flow is dominated by the effects of inertia, surface elasticity, gravity, and air drag. We solve the leading-order equations to compute the steady-state profiles of velocity, thickness, and pressure in an experiment in which the film is in the Marangoni elasticity regime. The computational results, which include a Marangoni shock, are in good accord with the experimental measurements.