Application of direct analysis in real time to the study of chemical vapor generation mechanisms: identification of intermediate hydrolysis products of amine-boranes

Analytical and Bioanalytical Chemistry - In order to elucidate controversial results emerging in chemical vapor generation (CVG) for trace element determination, we conducted a series of...     

Effects of partial crack–face contact for the bending of thin shell structures

The physical occurrence that crack surfaces are in contact at the compressive edges when a flat or a shell is subjected to a bending load has been recognized. This article presents a theoretical analysis of crack–face contact effect on the stress intensity factor of various shell structures such as spherical shell, cylindrical shell containing an axial crack, cylindrical shell containing a circumferential crack and shell with two non-zero curvatures, under a bending load. The formulation of the problem is based on the shear deformation theory, incorporating crack–face contact by introducing distributed force at the compressive edge. Material orthotropy is concerned in this analysis. Three-dimensional finite element analysis (FEA) is conduced to compare with the theoretical solution. It is found that due to curvature effect crack–face contact behavior in shells differs from that in flat plates, in that partial contact of crack surfaces may occur in shells, depending on the shell curvature and the nature of the bending load. Crack–face contact has significant influence on the stress intensity factor and it increases the membrane component but decreases the bending component.     

Attosecond streak camera

An electron generated by x-ray photoionization can be deflected by a strong laser field. Its energy and angular distribution depends on the phase of the laser field at the time of ionization. This phase dependence can be used to measure the duration and chirp of single sub100-attosecond x-ray pulses.     

Organic/inorganic supramolecular channel frameworks containing a photosensitive azobenzene molecule as an included guest

Two independent channel frameworks are occupied by photoactive E-azobenzene in an unprecedented one-dimensional zigzag motif and thus form virtual three-dimensional supramolecular host-guest networks.     

The effect of the breakdown of the Born-Oppenheimer approximation on the rotation-vibration Hamiltonian of a triatomic molecule

The rotation-vibration-electronic Hamiltonian of a triatomic molecule has been derived in a manner similar to that used by J. T. Hougen, P. R. Bunker, and J. W. C. Johns [J. Mol. Spectrosc.34, 136 (1970)] in deriving the rotation-vibration Hamiltonian. An effective rotation-vibration Hamiltonian for the ground electronic state has been obtained from this, by using the perturbation technique of P. R. Bunker and R. E. Moss [Mol. Phys.33, 417 (1977)], in order to account for the effect of the breakdown of the Born-Oppenheimer approximation to second order. The same form of effective rotation-vibration Hamiltonian, in which the breakdown of the Born-Oppenheimer approximation is allowed for, will be obtained for any molecule. This Hamiltonian contains effective moments of inertia (these involve rotation g-factor corrections) and effective nuclear masses (likely to be close to the atomic masses). Following the procedure of A. R. Hoy and P. R. Bunker [J. Mol. Spectrosc.74, 1 (1979)] the effective rotation-bending Hamiltonian is derived from the effective rotation-vibration Hamiltonian, and this could be used to fit the rotation-bending energy levels.     

Performance predictions in solid oxide fuel cells

The results of numerical calculations performed for planar solid oxide fuel cells are presented. Two different approaches are developed: (i) A detail numerical method and (ii) a presumed flow method. In the first approach, a commercial computational fluid dynamics code is employed, and user-defined-functions are developed to account for electro-chemical considerations. In the second approach, where the momentum equations do not require to be solved, an in-house code is developed and used to perform calculations. In both cases the following coupled physicochemical phenomena are modelled; heat and mass transfer, electrochemistry and electric potential. The polarisation curve is generally accepted as an important performance measure of the fuel cell. Performance predictions for this characteristic made by the two different approaches are compared. Results show voltage losses due activation, Ohmic resistance, and mass transfer in a typical solid oxide fuel cell, over a range of current density values. The results for the detailed numerical method are discussed in some detail with regard to the influence of different parameters on the overall performance of the device.     

13C Hyperfine interactions in CD3C60 and the distribution of unpaired spin on the C60 cage

¹³C hyperfine interactions obtained for CD₃C₆₀ are compared with previous data for MuC₆₀ and used to map the unpaired spin distribution on the C₆₀ surface of these radicals with the help of semi-empirical and density functional calculations. It is concluded that the unpaired spin is predominantly located on seven atoms near the point of attachment of the substituent.     

Torsion-rotation far-infrared spectrum of O-18 methanol

High-resolution Fourier transform spectra have been recorded from 15–470 cm^–1 for the far-infrared trosion-rotation band of O-18 methanol in the vibrational ground state. So far, 57 subbands have been assigned in the 15–220 cm^–1 region for a wide range of rotational and torsional states, and their J-independent origins have been determined to an estimated accuracy of ±0.01 cm^–1. The observed origins were found to deviate in many cases by several tenths of a cm^–1 from the values calculated with the previous molecular parameters. Together with 4 known microwave origins, the new data have been fitted to a model torsion-rotation Hamiltonian in order to refine the set ofb-type molecular constants for the ground state. With the new parameter set, the experimental subband origins are reproduced with an rms error of ±0.02 cm^–1, representing a substantial improvement over the earlier situation. The spectroscopic results have also been of great assistance with our assignments of optically-pumped FIR laser emission in CH₃ ¹⁸OH, in providing FIR data for checking the identification of the IR-pump/FIR-laser transition systems through combination loop relations.     

Measures for assessing architectural speech security (privacy) of closed offices and meeting rooms

Objective measures were investigated as predictors of the speech security of closed offices and rooms. A new signal-to-noise type measure is shown to be a superior indicator for security than existing measures such as the Articulation Index, the Speech Intelligibility Index, the ratio of the loudness of speech to that of noise, and the A-weighted level difference of speech and noise. This new measure is a weighted sum of clipped one-third-octave-band signal-to-noise ratios; various weightings and clipping levels are explored. Listening tests had 19 subjects rate the audibility and intelligibility of 500 English sentences, filtered to simulate transmission through various wall constructions, and presented along with background noise. The results of the tests indicate that the new measure is highly correlated with sentence intelligibility scores and also with three security thresholds: the threshold of intelligibility (below which speech is unintelligible), the threshold of cadence (below which the cadence of speech is inaudible), and the threshold of audibility (below which speech is inaudible). The ratio of the loudness of speech to that of noise, and simple A-weighted level differences are both shown to be well correlated with these latter two thresholds (cadence and audibility), but not well correlated with intelligibility.     

Distribution and modification of sorption sites in amphiphilic calixarene-based solid lipid nanoparticles from hyperpolarized 129Xe NMR spectroscopy

The site distribution and accessibility in amphiphilic calixarenes-based solid lipid nanoparticles were determined as a function of lipid chain length using in situ 129Xe NMR spectroscopy with flowing hyperpolarized Xe gas. The study illustrates that host cavities in as-prepared materials are increasingly occluded by the lipid chain for compounds with chain lengths from C6 to C12 and are almost completely occluded for C14 and C16 chain lengths. Host cavities present at the surface of the particles are still accessible to small atoms (xenon) and organic molecules (methylene chloride, etc). The Xe spectra show that the accessible void space can be increased remarkably by exposure of the particle surface to suitably sized guest molecules that appear to displace the occluding hydrocarbon chains from the host cavities by competitive adsorption. This postsynthesis treatment thus modifies the state of self-assembly and improves sorption capability. The HP Xe NMR approach presented is suitable for small samples (a few milligrams) of SLNs, likely also for other biomaterials such as vesicles, model membranes, etc.