Hydrogen‐Bond Dynamics of C?H⋅⋅⋅O Interactions: The Chloroform⋅⋅⋅Acetone Case

Spectroscopic evidence for C? H ??? O hydrogen bonding in chloroform ??? acetone [Cl₃CH ??? O?C(CH₃)₂] mixtures was obtained from vibrational inelastic neutron scattering (INS) spectra. Comparison between the INS spectra of pure samples and their binary mixtures reveals the presence of new bands at about 82, 130 and 170 cm^?1. Assignment of the 82 cm^?1 band to the νO ??? H anti‐translational mode is considered and discussed. In addition, the βC? H mode of CHCl₃ at 1242 cm^?1 is split in the spectra of the mixtures, and the high‐wavenumber component is assigned to the hydrogen‐bonded complex. The plot of the integrated intensity of this component shows a maximum for x=0.5, in agreement with the 1:1 stoichiometry of the chloroform ??? acetone complex, with a calculated complexation constant of 0.15 dm³ mol^?1. Results also show that the complex behaves as an independent entity, that is, despite being weak, such interactions play a key role in supramolecular chemistry.     

Trends in selenium determination/speciation by hyphenated techniques based on AAS or AFS

The field of selenium speciation has been studied for decades and the growing interest in this field seems never to reach a plateau. Although powerful techniques based on mass spectrometry are nowadays used for selenium determination/speciation, few laboratories can support the high cost of such techniques. The hyphenation of chromatography to atomic absorption or atomic fluorescence spectrometry (AAS or AFS) is still a reliable and low-cost alternative for routine laboratories. In this work we present the most important parameters dealing with selenium speciation along with the latest trends in this subject, namely in the items related with sample treatment and hyphenation techniques with AAS and AFS detection.     

Varieties of Regular Pseudocomplemented de Morgan Algebras

Order - In this paper, we investigate the varieties Mn and Kn of regular pseudocomplemented de Morgan and Kleene algebras of range n, respectively. Priestley duality as it applies to...     

Neutron activation analysis of medicinal plant extracts

Instrumental neutron activation analysis was applied to the determination of the elements Br, Ca, Cl, Cs, Fe, K, La, Mg, Mn, Na, Rb and Zn in medicinal extracts obtained fromCentella asiatica, Citrus aurantium L., Achyrolcline satureoides DC, Casearia sylvestris, Solano lycocarpum, Zingiber officinale Roscoe, Solidago microglossa andStryphnondedron barbatiman plants. The elements Hg and Se were determined using radiochemical separation by means of retention of Se in HMD inorganic exchanger and solvent extraction of Hg by bismuth diethyldithiocarbamate solution. Precision and accuracy of the results were evaluated by analyzing biological reference materials. The therapeutic action of some elements found in plant extracts analyzed is briefly discussed.     

A particle swarm pattern search method for bound constrained global optimization

In this paper we develop, analyze, and test a new algorithm for the global minimization of a function subject to simple bounds without the use of derivatives. The underlying algorithm is a pattern search method, more specifically a coordinate search method, which guarantees convergence to stationary points from arbitrary starting points. In the optional search phase of pattern search we apply a particle swarm scheme to globally explore the possible nonconvexity of the objective function. Our extensive numerical experiments showed that the resulting algorithm is highly competitive with other global optimization methods also based on function values. Support for Luís N. Vicente was provided by Centro de Matemática da Universidade de Coimbra and by FCT under grant POCI/MAT/59442/2004.     

Mechanical instabilities of bubble clusters between parallel walls

We have carried out a systematic study of buckling-like mechanical instabilities in simple two- (2D) and three-dimensional (3D) symmetric foam clusters sandwiched between parallel planar walls. These instabilities occur when the wall separation w is reduced below a critical value, w^*, for which the foam surface energy E reaches its minimum, E^*. The clusters under investigation consist of either a single bubble, or of twin bubbles of fixed equal sizes (areas A in 2D or volumes V in 3D), which are either free to slide or pinned at the confining walls. We have numerically obtained w^* for both free and pinned 2D and 3D clusters. Furthermore, we have calculated the buckled configurations of 2D twin bubbles, either free or pinned, and of 3D free twin bubbles, whose energy is independent of w and equal to the minimum energy E^* of the unbuckled state. Finally, we have also predicted the critical w_t^* at which the terminal configurations under extension of 2D and 3D single and twin bubbles are realised. Experimental illustrations of these transitions under compression and extension are presented. Our results, together with others from the literature, suggest that a bubble cluster bounded by two parallel walls is stable only if the normal force it exerts on the walls is attractive, i.e., if dE/dw > 0; clusters that cause repulsion between the walls are unstable. We correlate this with the distribution of film orientations: films in a stable cluster cannot be too parallel to the confining walls; rather, their average tilt must be larger than for a random distribution of film orientations.     

Direct observation of domain-wall configurations transformed by spin currents

Direct observations of current-induced domain-wall propagation by spin-polarized scanning electron microscopy are reported. Current pulses move head-to-head as well as tail-to-tail walls in submicrometer Fe20Ni80 wires in the direction of the electron flow, and a decay of the wall velocity with the number of injected current pulses is observed. High-resolution images of the domain walls reveal that the wall spin structure is transformed from a vortex to a transverse configuration with subsequent pulse injections. The change in spin structure is directly correlated with the decay of the velocity.     

Doppler power spectrum from a Gaussian sample volume

A closed-form expression for the Doppler power spectrum due solely to the range of blood velocities passing through a Gaussian sample volume placed anywhere in a vessel under conditions of axisymmetric flow, uniform backscatter and negligible intrinsic spectral broadening has been derived. The formulation presented here allows the independent specification of the sample volume position and width, in the three dimensions, and enables simple estimations of spectral shape for pulsed wave Doppler systems. Simpler expressions were derived for the cases of symmetric sample volume projections onto the vessel cross-section and/or sample volumes centred in the vessel. Closed form expressions were derived for mean frequency and spectral width in the case of a symmetric sample volume projection centred in the vessel. The effects of sample volume size and position on the Doppler spectral width and mean frequency are shown for a range of velocity profiles.     

Stability constants of chloro-complexes of cadmium(II) in sea-water medium

Potentiometry with ion-selective electrodes and anodic stripping voltammetry were used to measure the stability constants for cadmium chloro-complexes at 20 +/- 0.1 degrees in synthetic sea-water and at an ionic strength of 0.700 (NaClO(4) + NaCl). The values of beta(ML) and beta(ML(2)) obtained by the two methods are in good agreement.     

Reactivity of muonium atoms in aqueous solution

A beam of surface muons (4.1 MeV) was used to generate thermalised muonium atoms (μ⁺e^?) in aqueous solutions. From measurements of the muonium atom relaxation time in the presence of various solutes, bimolecular rate constants were determined and compared with the corresponding reactions of the much heavier isotope, the hydrogen atom.