Calibration and Limits of Camera‐Based Fluorescence Correlation Spectroscopy: A Supported Lipid Bilayer Study

Camera‐based fluorescence correlation spectroscopy (FCS) approaches allow the measurement of thousands of contiguous points yielding excellent statistics and details of sample structure. Imaging total internal reflection FCS (ITIR‐FCS) provides these measurements on lipid membranes. Herein, we determine the influence of the point spread function (PSF) of the optical system, the laser power used, and the time resolution of the camera on the accuracy of diffusion coefficient and concentration measurements. We demonstrate that the PSF can be accurately determined by ITIR‐FCS and that the laser power and time resolution can be varied over a wide range with limited influence on the measurement of the diffusion coefficient whereas the concentration measurements are sensitive to changes in the measurement parameters. One advantage of ITIR‐FCS is that the measurement of the PSF has to be performed only once for a given optical setup, in contrast to confocal FCS in which calibrations have to be performed at least once per measurement day. Using optimized experimental conditions we provide diffusion coefficients for over ten different lipid membranes consisting of one, two and three constituents, measured in over 200000 individual correlation functions. Using software binning and thus the inherent advantage of ITIR‐FCS of providing multiple observation areas in a single measurement we test the FCS diffusion law and show how they can be complemented by the local information provided by the difference in cross‐correlation functions (ΔCCF). With the determination of the PSF by ITIR‐FCS and the optimization of measurement conditions ITIR‐FCS becomes a calibration‐free method. This allows us to provide measurements of absolute diffusion coefficients for bilayers with different compositions, which were stable over many different bilayer preparations over a time of at least one year, using a single PSF calibration.     

Pillared clays as efficient catalysts for cyclohexanol oxidation

Summary Iron, aluminium and mixed iron aluminium pillared clays were prepared by partial hydrolysis method and doped with 10% V and Mo. The samples were characterised by XRD, FTIR and surface area and pore volume measurements. Oxidation of cyclohexanol with hydrogen peroxide was done as probe reaction to test catalytic activity. Iron pillared systems exhibited maximum activity. The effects of various reaction variables on the reaction were studied.     

Acid base properties and catalytic activity of vanadium pentoxide supported on cerium oxide

The surface acidity and basicity of vanadium pentoxide supported on CeO₂ were determined using a set of Hammett indicators. The data have been correlated with the catalytic activity of these oxides towards liquid phase acylation of phenol.     

Photoinduced oxidation of benzhydrol over lanthana modified sol-gel titania

Lanthana modified sol-gel titania is prepared through particulate sol-gel route and the physico-chemical characterizations of the prepared systems were done using X-Ray diffration, EDX, BET surface area-pore volume measurements and TG-DTG analysis. Benzophenone was observed to be the sole product in the TiO₂ photocatalyzed oxidation of benzhydrol in oxygen purged acetonitrile. The influence of various parameters, like irradiation time, amount of catalyst, concentration of the catalyst and other factors on the photocatalytic oxidation has been investigated. The proposed mechanism envisages the involvement of a superoxide radical anion.     

Subgrid combustion modeling of 3-D premixed flames in the thin-reaction-zone regime

Large eddy simulation (LES) is used to investigate three-dimensional (3D) lean premixed turbulent methane–air flames in the thin-reaction-zone regime. In this regime, the Kolmogorov scale is smaller than the preheat zone thickness, but larger than the reaction zone thickness. Past numerical studies of similar flames were primarily direct numerical simulation either in two-dimensions or using the artificially thickened flame approach in 3D. For an LES the effect of small (unresolved) scales on the scalar field must be, modeled accurately to capture the correct flame structure. A subgrid combustion model based on the linear-eddy-mixing (LEM) model is used within an LES framework (called LEM–LES hereafter) to capture the 3D flame-structure of the highly stretched premixed flames. A finite-rate, one-step methane–air chemistry with a non-unity Lewis number formulation is used in this study. The simulated flame structure resembles flames experimentally studied in the thin-reaction-zone regime. Even though the preheat zone is broadened by the penetration of small eddies, the chemical reaction zone remains thin and localized. This feature is captured properly in the current LEM–LES approach. The flame structure and other statistics such as the flame area evolution, curvature, and strain-rate statistics computed using the LEM–LES are also in good agreement with the past DNS studies.     

Mesh quality effects on the accuracy of CFD solutions on unstructured meshes

The order of accuracy and error magnitude of node- and cell-centered schemes are examined on representative unstructured meshes and flowfield solutions for computational fluid dynamics. Specifically, we investigate the properties of inviscid and viscous flux discretizations for isotropic and highly stretched meshes using the Method of Manufactured Solutions. Grid quality effects are studied by randomly perturbing the base meshes and cataloguing the error convergence as a function of grid size. For isotropic grids, node-centered approaches produce less error than cell-centered approaches. Moreover, a corrected node-centered scheme is shown to maintain third order accuracy for the inviscid terms on arbitrary triangular meshes. In contrast, for stretched meshes, cell-centered schemes are favored, with cell-centered prismatic approaches in particular showing the lowest levels of error. In three dimensions, simple flux integrations on non-planar control volume faces lead to first-order solution errors, while second-order accuracy is recovered by triangulation of the non-planar faces.     

Characteristics of auto-ignition in a stratified iso-octane mixture with exhaust gases under homogeneous charge compression ignition conditions

Ignition and propagation of a reaction front in a counterflow system of an iso-octane/air stream mixing with an exhaust gas stream is computationally investigated to understand the fundamental characteristics of homogeneous charge compression ignition (HCCI) auto-ignition. Various mixing rates are imposed on the system and the effects of dissipation rates on auto-ignition are studied. Ignition delay and front propagation speed across the mixing layer are determined as a function of a local mixture fraction variable. The results show that mixture inhomogeneity and dissipation rate have a significant influence on ignition. Diffusive transport is found to either hamper or advance ignition depending on the initial reactivity of the mixture. Based on the relative importance of diffusion on ignition front propagation, two distinct ignition regimes are identified: the spontaneous ignition regime and the diffusion-controlled regime. The transition between these two regimes is identified using a criterion based on the ratio of the timescales of auto-ignition and diffusion. The results show that ignition in the spontaneous regime is more likely under typical HCCI operating conditions with iso-octane due to its high reactivity. The present analysis provides a means to develop an improved modelling strategy for large-scale engine simulations.     

HAADF imaging of the omega (ω) phase in a gum metal-related alloy

Nanosized precipitates have been observed in a Nb-lean gum metal-related alloy, Ti–20.0Nb–0.6Ta–1.7Zr–1.1O?at.% (Ti–31.9Nb–2.0Ta–2.7Zr–0.3O?wt.%) using probe-corrected high-resolution scanning transmission electron microscopy with a high-angle annular dark-field detector (HAADF). This characterization yields three distinct atomic motifs and STEM multislice simulations are semi-quantitatively used to verify that each motif can be attributed to the widely observed “athermal” omega phase. However, the presence of chemical ordering cannot be unambiguously ruled out in this system. Data presented here, demonstrate the complexity of interpreting HAADF images of multiphase, multicomponent alloys when complementary experimental data are unavailable.     

Identifying influential nodes in weighted networks based on evidence theory

The design of an effective ranking method to identify influential nodes is an important problem in the study of complex networks. In this paper, a new centrality measure is proposed based on the Dempster–Shafer evidence theory. The proposed measure trades off between the degree and strength of every node in a weighted network. The influences of both the degree and the strength of each node are represented by basic probability assignment (BPA). The proposed centrality measure is determined by the combination of these BPAs. Numerical examples are used to illustrate the effectiveness of the proposed method.