Poisson's effects in electrical field flow fractionation

Recent and earlier models of electrical field flow fractionation (ELFFF) have assumed that the electric field within the fluid domain is governed by Laplace's equation. This assumption results in a linear potential and a spatially constant field across the channel and is generally true for very dilute systems and relatively high effective potentials. Experimental studies show, however, that the effective potential within the channel may be less than 1% of the applied potential; this is apparently due to double layer formation and charge buildup at the poles. In such cases, local analyte concentrations can, nonetheless, be orders of magnitude higher than the bulk mean and the local potential small, both of which can lead to a nonlinear spatial distribution of the field strength. In such cases Poisson's equation must be used rather than Laplace's equation. Steady-state ELFFF simulations were performed using a Poisson's equation-based model. The domain in which Laplace's equation is valid was identified and the effects of concentration and effective field strength on device performance were explored.     

Reproducible SERRS from structured gold surfaces

Metallic substrates with ordered spherical cavities have been shown to be very effective for surface-enhanced Raman scattering (SERS) and can be fabricated reproducibly using electrodeposition. The sensitivity of detection is increased by several orders of magnitude by using surface-enhanced resonance Raman scattering (SERRS). In this report we demonstrate SERRS for the first time on electrodeposited gold films templated with colloidal spheres and demonstrate the reproducibility of the response. We also obtain a direct comparison between SERRS and SERS by choosing two dyes, Cy5 and Cy3, which are similar in structure but differ in their excitation maxima, such that one is resonant and the other non-resonant with our laser excitation. As expected, the resonant enhancement is found to be of the order of 10(3) over and above that for SERS. The net SERRS enhancements are shown to be of the order of 10(9). We also find that the resonant enhancement profile of the different peaks for the chromophore follows the plasmonic resonance absorption spectrum obtained for the structured surface.     

Synthesis of lariat organochalcogenoethers based on azacalix[3]arenes for the potentiometric detection of [UO2] ions

The syntheses of organochalcogen-supported azacalix[3]arenes are described in a one-pot manner in satisfactory yields. A remarkably selective potentiometric response was accomplished for uranyl ions over a variety of other metal ions, including alkali (Na⁺, K⁺), alkaline-earth (Mg²⁺, Ca²⁺, Ba²⁺), transition and heavy metal ions (Co²⁺, Ni²⁺, Cu²⁺, Ag⁺, Fe³⁺, Zn²⁺, Cd²⁺ and Pb²⁺) using an ion-selective electrode based on compound 3 incorporated into a polymeric (PVC) membrane.     

SERS at structured palladium and platinum surfaces

Palladium and platinum are important catalytic metals, and it would be highly advantageous to be able to use surface enhanced Raman spectroscopy (SERS) to study reactive species and intermediates on their surfaces. In this paper we describe the use of templated electrodeposition through colloidal templates to produce thin (<1 microm) films of palladium and platinum containing close packed hexagonal arrays of uniform sphere segment voids. We show that, even though these films are not rough, when the appropriate film thickness and sphere diameter are employed these surfaces give stable, reproducible surface enhancements for Raman scattering from molecules adsorbed at the metal surface. We report SERS spectra for benzenethiol adsorbed on the structured palladium and platinum surfaces of different thicknesses and void diameters and show that, for 633 nm radiation, enhancements of 1800 and 550 can be obtained for palladium and platinum, respectively.     

Thermal C2-C6 cyclization of enyne-allenes. Experimental evidence for a stepwise mechanism and for an unusual thermal silyl shift

Enyne-allenes 4a-c bearing various cyclopropyl systems as radical clock reporter groups at the allene terminus have been synthesized and subjected to thermal C2-C6 cyclization. The ratio of ene versus formal Diels-Alder products could be rationalized on the basis of steric effects. Only the thermolysis of 4c, equipped with the fast diphenylcyclopropylcarbinyl radical clock, afforded a 1,3-butadienyl benzofulvene clearly formed via cyclopropyl ring opening. This finding provides unambiguous evidence for a stepwise mechanism of the C2-C6 cyclization making it possible to suggest a lifetime for the intermediate diradical of >1x10(-10) s (at 170 degrees C). An interesting corollary was the isolation of an unexpected silyl shift product in the thermolysis of all three enyne-allenes that allows explanation of the loss of the TIPS group in some of the Diels-Alder products. For a full understanding of the mechanism, silyl and hydrogen shift processes were interrogated using DFT.     

Adaptive finite element analysis of structures under transient dynamic loading using modal superposition

In this paper, the error estimation and adaptive strategy developed for the linear elastodynamic problem under transient dynamic loading based on the Z–Z criterion is utilized for 2D and plate bending problems. An automatic mesh generator based on “growth meshing” is utilized effectively for adaptive mesh refinement. Optimal meshes are obtained iteratively corresponding to the prescribed domain discretization error limit and for a chosen number of basis modes satisfying modal truncation errors. Numerous examples show the effectiveness of the integrated approach in achieving the target accuracy in finite element transient dynamic analysis.     

Wei Hua’s four-parameter potential: Comments and computation of molecular constants αe and εeXe

The value of adjustable parameterC in the four-parameter potentialU(r) =D _e [(1 - exp[-b(r -r _e)])/(1 -C exp[-b(r -r _e)])]² has been expressed in terms of molecular parameters and its significance has been brought out. The potential so constructed, withC derived from the molecular parameters, has been applied to ten electronic states in addition to the states studied by Wei Hua. Average mean deviation for these 25 states has been found to be 3.47 as compared to 6.93, 6.95 and 9.72 obtained from Levine, Varshni and Morse potentials, respectively. Also Dunham’s method has been used to express rotation-vibration interaction constant (α_e) and anharmonicity constant (ω_ex_e) in terms ofC and other molecular constants. These relations have been employed to determine these quantities for 37 electronic states. For α_e, the average mean deviation is 7.2% compared to 19.7% for Lippincott’s potential which is known to be the best to predict these values. Average mean deviation for (ω_ex_e) turns out to be 17.4% which is almost the same as found from Lippincott’s potential function.     

Linear and Nonlinear Stability Analysis of a Horton–Rogers–Lapwood Problem with an Internal Heat Source and Brinkman Effects

The effect of internal heat source on convection in a layer of fluid in a porous medium was analyzed using linear and nonlinear analysis, and boundaries are assumed to be stress-free and isothermal. Normal mode technique is used for linear analysis, and energy method is used for nonlinear stability analysis. The presence of heat generation leads to the possibility of the existence of a subcritical instability. Effects of increase of Darcy–Brinkman number and internal heat parameter on critical Rayleigh numbers were analyzed numerically using Chebyshev pseudospectral method.     

Complex Classical Mechanics of a QES Potential

We study a combined parity (P) and time reversal (T) invariant non-Hermitian quasi-exactly solvable (QES) potential, which exhibits PT phase transition, in the complex plane classically to demonstrate different quantum effects. The particle with real energy makes closed orbits around one of the periodic wells of the complex potential depending on the initial condition. However interestingly the particle escapes to an open orbits even with real energy if it is placed beyond a certain distance from the center of the well. On the other hand when the particle energy is complex the trajectory is open and the particle tunnels back and forth between two wells which are separated by a classically forbidden path. The tunneling time is calculated for different pair of wells and is shown to vary inversely with the imaginary component of energy. Our study reveals that spontaneous PT symmetry breaking does not affect the qualitative features of the particle trajectories in the analogous complex classical model.     

A nonlinear stability analysis for rotating magnetized ferrofluid heated from below saturating a porous medium

A nonlinear (energy) stability analysis is performed for a rotating magnetized ferrofluid layer heated from below saturating a porous medium, in the stress-free boundary case. By introducing a generalized energy functional, a rigorous nonlinear stability result for a thermoconvective rotating magnetized ferrofluid is derived. The mathematical emphasis is on how to control the nonlinear terms caused by magnetic body force. It is found that the nonlinear critical stability magnetic thermal Rayleigh number does not coincide with that of linear instability analysis, and thus indicates that the subcritical instabilities are possible. However, it is noted that, in case of non-ferrofluid, global nonlinear stability Rayleigh number is exactly the same as that for linear instability. For lower values of magnetic parameters, this coincidence is immediately lost. The effect of magnetic parameter, M ₃, medium permeability, D _a , and rotation, , on subcritical instability region has also been analyzed. It is shown that with the increase of magnetic parameter, M ₃, and Darcy number, D _a , the subcritical instability region between the two theories decreases quickly while with the increase of Taylor number, , the subcritical region expands. We also demonstrate coupling between the buoyancy and magnetic forces in the presence of rotation in nonlinear energy stability analysis as well as in linear instability analysis.