Hydrogen and deuterium diffusion in non-stoichiometric spinel

High pressure/temperature annealing experiments are used to determine diffusivities of H⁺ and D⁺ in non-stoichiometric spinel, a low-pressure analogue for nominally anhydrous minerals in Earth’s mantle. Data are fitted to the following Arrhenius law: Diffusivity (m²/s)?=?4?±?1?×?10^?12 exp(?54?±?2 kJ?mol^?1/RT). At low temperatures, H⁺ and D⁺ diffusion in non-stoichiometric spinel is charge balanced by flux of O vacancies, with infrared data consistent with protonation of both octahedral and tetrahedral O–O edges in non-stoichiometric spinel, and additional fine structure due to Mg–Al mixing and/or coupling of structurally incorporated H⁺ with cation vacancies. Absence of changes in the fine structure of O–H absorption bands indicates that H⁺ can become locally coupled and uncoupled to other defects during bulk diffusion. As such, proton conductivity in spinel group minerals, arising from faster flux of uncoupled H⁺, can only be calculated from H⁺ mobility data if the extent of defect coupling is constrained.     

High electrocatalytic oxidation of folic acid at carbon paste electrode bulk modified with iron nanoparticle-decorated multiwalled carbon nanotubes and its application in food and pharmaceutical analysis

Ionics - A simple and rapid method was employed for the modification of carbon paste electrode with iron nanoparticle-decorated multiwalled carbon nanotubes (MCPE/Fe-MWCNTs). The synergistic effect...     

Observation of Optical Second Harmonic Generation in Wet-Spun Films of Na-DNA

The observation of optical second harmonic generation (SHG) from wetspun films of Na-DNA is reported. The SHG signal is stronger at a relative humidity of 92% (corresponding to the B conformation of Na-DNA) than at low humidity of -33% (corresponding to a disordered conformation of Na-DNA). The strength of the SHG signal is also dependent on the orientation of the incident laser beam polarization with respect to the DNA helical axes.     

Persistence and breakdown of Airy beams driven by an initial nonlinearity

We study the behavior of Airy beams propagating from a nonlinear medium to a linear medium. We show that an Airy beam initially driven by a self-defocusing nonlinearity experiences anomalous diffraction and can maintain its shape in subsequent propagation, but its intensity pattern and acceleration cannot persist when driven by a self-focusing nonlinearity. The unusual behavior of Airy beams is examined from their energy flow as well as the Brillouin zone spectrum of self-induced chirped photonic lattices.     

Imaging the neural circuitry and chemical control of aggressive motivation

Background  

With the advent of functional magnetic resonance imaging (fMRI) in awake animals it is possible to resolve patterns of neuronal activity across the entire brain with high spatial and temporal resolution. Synchronized changes in neuronal activity across multiple brain areas can be viewed as functional neuroanatomical circuits coordinating the thoughts, memories and emotions for particular behaviors. To this end, fMRI in conscious rats combined with 3D computational analysis was used to identifying the putative distributed neural circuit involved in aggressive motivation and how this circuit is affected by drugs that block aggressive behavior.     

Second harmonic generation with surface plasmons in alkali metals

We calculate the reflected second harmonic light from alkali metal films with the simultaneous excitation of the surface plasmon mode. The harmonic generation from a sodium film at the ruby laser frequency increases by over two orders of magnitude at the angle for surface plasmon excitation. The harmonic enhancement is closely related to the surface plasmon density and exhibits a strong dependence on the angle of incidence, film thickness, and the linear optical constants of the metal film.     

Rigidified Macrocyclic Phosphoramides a New Family of Preorganized Ligands

Abstract

Macrocyclic molecules capable of selective recognition of ionic or neutral guests are of considerable current interest. The design and synthesis of host molecules that contain phosphorus have been developed recently. Typically, the model compound A is modified to the more rigid molecule B which can exist as two exo/endo isomers. B represents a new family of preorganized ligands that can involve the phosphorus group during complexation of various guests. The exo/endo isomerisni was investigated by NMR studies. The complexing properties of B were studied by NMR and extraction method with alkaline and ammonium cations. The complexation constants mainly depend on the molecular geometry and the size of the cavity. The highest Ka constants are obtained with the endo isomer where the P=O bond is directed toward the center of the macrocycle. Complex formation and detailed stereochemical data for A and B will be presented.     

Monomeric and Dimeric (Aminomethylidene)phosphines and -Arsines

Abstract

In (dimethylaminomethylidene)phosphines (1) [1] and -arsines (2) the internal rotation of the dimethylamino group is hindered by a barrier of 50 to 55 kJmol^?1? analogous to the corresponding amidines. In order to evaluate the influence of this conjugative effect upon the P=C and (P)-C-N bond lengths, single crystal x-ray structure determinations of 1a and 2a have been carried out. For comparison, the cyclic (aminomethylidene)phosphine 1H-1,3-benzazaphosphole 5 [2] as well as the dimeric compounds 3a, 3b, and 3c [3] have been analyzed, too, while the arsenic derivative 6 was studied by others [4]. The diarsetanes 4 could not yet be isolated. The structural results indicate the E=C bonds in 1a, 2a, 5, and 6 to be scarcely elongated, the (E)-C-N bonds, however, to be shortened considerably with respect to the dimers.