Diterpene Chemistry—VI : SeO2/H2O2 oxidations of exocyclic olefins

Unlike endocyclic olefins the major product from the SeO₂/H₂O₂ oxidation of exocyclic olefins is the same allylic alcohol as from the uncatalysed oxidation. Minor products derived from epoxide intermediates were investigated. The use of SeO₂ as an allylic oxidant for olefins has been extensively investigated, the functionality of the product being to a degree solvent dependent. Although the earlier mechanism of Guillemonat² is incorrect, his rules for the prediction of the position of oxidation still remain valid. A survey by Tratchenburg³ of the current position in SeO₂ oxidation postulates allylic oxidation as proceeding through the intermediacy of an oxaselenocyclobutane to a selenite ester which is solvated by competitive unimolecular (S_N1) and bimolecular (S_N2′) processes (Scheme 1).     

Photothermal ionization fourier transform spectroscopy of shallow donor states in III–V semiconductors

The technique of photothermal ionization Fourir transform spectroscopy of shallow donors is very useful for the detection and identification of residual impurity species in very high purity compound semiconductors, especially GaAs. However, the use of this technique in less pure or intentionally doped samples has resulted many incorrect impurity identifications. In this paper we show how the photothermal ionization spectra change with impurity concentration, thickness, and magnetic field, and present a model of the dielectric response of shallow impurity states which explains many of the previously anomalous results.     

Effects of level and frequency on the audibility of partials in inharmonic complex tones

The effect of level and frequency on the audibility of partials was measured for complex tones with partials uniformly spaced on an equivalent rectangular bandwidth (ERB(N)) number scale. On each trial, subjects heard a sinusoidal "probe" followed by a complex tone. The probe was mistuned downwards or upwards (at random) by 4.5% from the frequency of one randomly selected partial in the complex. The subject indicated whether the probe was higher or lower in frequency than the nearest partial in the complex. The frequencies were roved from trial to trial, keeping frequency ratios fixed. In experiment 1, the level per partial, L, was 40 or 70 dB SPL and the mean frequency of the central partial, f(c), was 1201 Hz. Scores for the highest and lowest partials in the complexes were generally high for all spacings. Scores for the inner partials were close to chance at 0.75-ERB(N) spacing, and improved as the spacing was increased up to 2 ERB(N). For intermediate spacings, performance was better for the lower level used. In experiment 2, L was 70 dB SPL and f(c) was 3544 Hz. Performance worsened markedly for partial frequencies above 3544 Hz, consistent with a role of phase locking.     

Reciprocal Relativity of Noninertial Frames and the Quaplectic Group

The frame associated with a classical point particle is generally noninertial. The point particle may have a nonzero velocity and force with respect to an absolute inertial rest frame. In time–position–energy–momentum-space {t, q, p, e}, the group of transformations between these frames leaves invariant the symplectic metric and the classical line element ds² = d t². Special relativity transforms between inertial frames for which the rate of change of momentum is negligible and eliminates the absolute rest frame by making velocities relative but still requires the absolute inertial frame. The Lorentz group leaves invariant the symplectic metric and the line elements and . General relativity for particles under only the influence of gravity avoids the issue of noninertial frames as all particles follow geodesics and hence have locally inertial frames. For other forces, the question of the absolute inertial frame remains.) Born conjectured that the line element should be generalized to the pseudo-orthogonal metric . The group leaving this metrics and the symplectic metric invariant is the pseudo-unitary group of transformations between noninertial frames. We show that these transformations also eliminate the need for an absolute inertial frame by making forces relative and bounded by b and so embodies a relativity that is shape reciprocal in the sense of Born. The inhomogeneous version of this group is naturally the semidirect product of the pseudo-unitary group with the nonabelian Heisenberg group. This is the quaplectic group.     

Microfabricated quadrupole ion trap for mass spectrometer applications

An array of miniaturized cylindrical quadrupole ion traps, with a radius of 20 microm, is fabricated using silicon micromachining using phosphorus doped polysilicon and silicon dioxide for the purpose of creating a mass spectrometer on a chip. We have operated the array for mass-selective ion ejection and mass analysis using Xe ions at a pressure of 10(-4). The scaling rules for the ion trap in relation to operating pressure, voltage, and frequency are examined.     

Cavity ring-down spectroscopy of the torsional motions of 1,4-bis(phenylethynyl)benzene

The torsional motions of jet-cooled 1,4-bis(phenylethynyl)benzene (BPEB), a prototype molecular wire, were studied using cavity ring-down spectroscopy in the first UV absorption band (316-321 nm). The torsional spectrum of 1,4-bis(phenylethynyl)-2,3,5,6-tetradeuteriobenzene was also recorded in the gas phase. Both spectra were successfully simulated using simple cosine potentials to describe the torsional motions. The ground-state barrier to rotation was estimated to be 220-235 cm(-1), which is similar to that of diphenylacetylene (tolane). Complementary DFT calculations were found to overestimate the torsional barrier.     

A method for automatic identification of water and fat images from a symmetrically sampled dual-echo Dixon technique

Sampling water and fat signals symmetrically (i.e., at 0° and 180° relative phase angles) in a dual-echo Dixon technique offers high intrinsic tolerance to phase fluctuations in postprocessing and maximum signal-to-noise performance for the separated water and fat images. However, identification of which image is water and which image is fat after their separation is not possible based on the phase information alone. In this work, we proposed a semiempirical automatic image identification method that is based on the intrinsic asymmetry between the water and fat chemical shift spectra. Specifically, the approximately bimodal feature of the fat spectra and the observation that most in vivo tissues are either predominantly water or predominantly fat are used to construct a spectrum-based algorithm. Additional refinement is accomplished by considering the spatial distribution of the tissues that may have a coexistence of water and fat. The final improved algorithm was tested on a total of 131 three-dimensional patient datasets collected from different scanners and found to yield correct water and fat identification in all datasets.     

A single-machine scheduling problem with maintenance activities to minimize makespan

We study a single-machine scheduling problem with periodic maintenance activity under two maintenance stratagems. Although the scheduling problem with single or periodic maintenance and nonresumable jobs has been well studied, most of past studies considered only one maintenance stratagem. This research deals with a single-machine scheduling problem where the machine should be stopped for maintenance after a fixed periodic interval (T) or after a fixed number of jobs (K) have been processed. The objective is to minimize the makespan for the addressed problem. A two-stage binary integer programming (BIP) model is provided for driving the optimal solution up to 350-job instances. For the large-sized problems, two efficient heuristics are provided for the different combinations of T and K. Computational results show that the proposed algorithm Best-Fit-Butterfly (BBF) performs well because the total average percentage error is below 1%. Once the constraint of the maximum number of jobs (K) processed in the machine’s available time interval (T) is equal or larger than half of jobs, the heuristic Best-Fit-Decreasing (DBF) is strongly recommended.     

Circulant partial Hadamard matrices

A question arising in stream cypher cryptanalysis is reframed and generalized in the setting of Hadamard matrices as follows: For given n, what is the maximum value of k   for which there exists a k×n$k\times n$(±1)$(\pm 1)$-matrix A   such that AA^T=n_Ik$A{A}^{\mathsf{T}}=n{I}_k$, with each row after the first obtained by a cyclic shift of its predecessor by one position? For obvious reasons we call such matrices circulant partial Hadamard matrices. Further, what is the maximum value of k subject to the condition that the row sums are equal to r?