A facile and efficient direct aldol addition of simple thioesters

[reaction: see text] Simple thioesters undergo direct aldol addition to aldehydes in the presence of MgBr(2).OEt(2) and i-Pr(2)NEt using untreated, reagent-grade CH(2)Cl(2) under atmospheric conditions. The reactions proceed extremely rapidly and in excellent yield.     

Audition in sciaenid fishes with different swim bladder-inner ear configurations

We investigated how morphological differences in the auditory periphery of teleost fishes may relate to hearing capabilities. Two species of western Atlantic sciaenids were examined: weakfish (Cynoscion regalis, Block and Schneider) and spot (Leiostomus xanthurus, Lacepede). These species differ in the anatomical relationship between the swim bladder and the inner ear. In weakfish, the swim bladder has a pair of anterior horns that terminate close to the ear, while there are no extensions of the swim bladder in spot. Thus, the swim bladder in spot terminates at a greater distance from the ear when compared to weakfish. With the use of the auditory brainstem response technique, Cynoscion regalis were found to detect frequencies up to 2000 Hz, while Leiostomus xanthurus detected up to 700 Hz. There were, however, no significant interspecific differences in auditory sensitivity for stimuli between 200 and 700 Hz. These data support the hypothesis that the swim bladder can potentially expand the frequency range of detection.     

Spectrophotometric determination and computational evaluation of the rates of hydrolysis of 9-amino-substituted acridines

Aminoacridines have a long history in the drug and dye industries and display a wide range of biological and physical properties. Despite the historical relevance of 9-aminoacridines, there have been few studies investigating their stability. 9-Aminoacridines are known to hydrolyze at the C9-N15 bond, yielding acridones. In this study, the pH-dependent hydrolysis rates of a series of 9-substituted aminoacridines are investigated. In addition, ground-state physical properties of the compounds are determined using ab initio quantum mechanics calculations to gain insight into the forces that drive hydrolysis. An analysis of the bond orders, bond dissociation energies, and conformational energies show that the rate of hydrolysis depends on two main factors: delocalization across the C9-N15 bond and steric effects. The computational results are applied to explain the change in experimental rates of hydrolysis going from primary to secondary and to tertiary substituted 9-aminoacridines. In the case of tertiary substituted amines, the calculations indicate the C9-N15 bond is forced into a more gauche-like conformation, greatly diminishing delocalization (as shown by reductions in bond orders and bond energy), which leads to rapid hydrolysis. A model of intramolecular hydrogen bonding is also presented, which explains the increased rate of hydrolysis observed for highly substituted compounds under acidic conditions.     

Directing energy flow through quantum dots: towards nanoscale sensing

Nanoscale sensors can be created when an expected energetic pathway is created and then that pathway is either initiated or disrupted by a specific binding event. Constructing the sensor on the nanoscale could lead to greater sensitivity and lower limits of detection. To this end, quantum dots (QDs) can be considered prime candidates for the active components. Relative to organic chromophores, QDs have tunable spectral properties, show less susceptibility to photobleaching, have similar brightness, and have been shown to display electro-optical properties. In this review, we discuss recent articles that incorporate QDs into directed energy flow systems, some with the goal of building new and more powerful sensors and others that could lead to more powerful sensors. Figure     

Probing the quantum state of a guided atom laser pulse

We describe bichromatic superradiant pump-probe spectroscopy as a tomographic probe of the Wigner function of a dispersing particle beam. We employed this technique to characterize the quantum state of an ultracold atomic beam, derived from a 87Rb Bose-Einstein condensate, as it propagated in a 2.5 mm diameter circular waveguide. Our measurements place an upper bound on the longitudinal phase space area occupied by the 3 x 10(5) atom beam of 9(1)Planck's constant and a lower bound on the coherence length of L>or=13(1) microm. These results are consistent with full quantum degeneracy after multiple orbits around the waveguide.     

Effect of sparse basis selection on ultrasonic signal representation

Recently, adaptive sparse representations of ultrasonic signals have been utilized to improve the performance of scanning acoustic microscopy (SAM), a common nondestructive tool for failure analysis of microelectronic packages. The adaptive sparse representation of an ultrasonic signal is generated by decomposing it in a learned overcomplete dictionary using a sparse basis selection algorithm. Detection and location of ultrasonic echoes are then performed on the basis of the resulting redundant representation. This paper investigates the effect of sparse basis selection algorithms on ultrasonic signal representation. The overcomplete independent component analysis, focal underdetermined system solver (FOCUSS), and sparse Bayesian learning algorithms are examined. Numerical simulations are performed to quantitatively analyze the efficiency of ultrasonic signal representations. Experiments with ultrasonic A-scans acquired from flip-chip packages are also carried out in the study. The efficiency of ultrasonic signal representations are evaluated in terms of the different criteria that can be used to measure its performance for different SAM applications, such as waveform estimation, echo detection, echo location and C-scan imaging. The results show that the FOCUSS algorithm performs best overall.     

Heterodyne mixing of laser fields for temporal gating of high-order harmonic generation

The concept of heterodyne mixing of laser fields is theoretically applied to the process of high-harmonic generation to enhance and modulate the kinetic energy of the active electron on subcycle time scales. A very small amount of intensity in the heterodyne field creates a significant modification of the electron kinetic energy, due to its amplification by the strong fundamental field in the kinetic-energy term, in which the heterodyne mixing occurs. Quantum calculations are carried out to verify the predictions of the classical results, demonstrating very good qualitative and quantitative agreement. Applications of the heterodyne-mixing concept are the extension of the harmonic cutoff to higher photon energies and the temporal gating of attosecond pulse production.     

Field-free three-dimensional alignment of polyatomic molecules

We experimentally demonstrate field-free, three-dimensional alignment (FF3DA) of polyatomic asymmetric top molecules. We achieve FF3DA in sulfur dioxide gas using two time-delayed, orthogonally polarized, nonresonant, femtosecond laser pulses. Our method avoids the use of rotational revivals and is therefore more robust to temperature. The alignment is probed using time-delayed coincidence Coulomb explosion imaging. FF3DA will be important for all molecular imaging, dynamics, or spectroscopy experiments for which random alignment leads to a loss of information.     

Inline ultrasonic rheometry by pulsed Doppler

This will be a discussion of the non-invasive determination of the viscosity of a non-Newtonian fluid in laminar pipe flow over the range of shear rates present in the pipe. The procedure used requires knowledge of the flow profile in and the pressure drop along a long straight run of pipe. The profile is determined by using a pulsed ultrasonic Doppler velocimeter. This approach is ideal for making non-invasive, real-time measurements for monitoring and control. Rheograms of a shear thinning gel will be presented. The operating parameters and limitations of the Doppler-based instrument will be discussed. The most significant limitation is velocity gradient broadening of the Doppler spectra near the walls of the pipe. This limitation can be significant for strongly shear thinning fluids (depending also on the ratio of beam to pipe diameter and the transducer's insertion angle).