Parabolic equation solution of seismo-acoustics problems involving variations in bathymetry and sediment thickness

Recent improvements in the parabolic equation method are combined to extend this approach to a larger class of seismo-acoustics problems. The variable rotated parabolic equation [J. Acoust. Soc. Am. 120, 3534-3538 (2006)] handles a sloping fluid-solid interface at the ocean bottom. The single-scattering solution [J. Acoust. Soc. Am. 121, 808-813 (2007)] handles range dependence within elastic sediment layers. When these methods are implemented together, the parabolic equation method can be applied to problems involving variations in bathymetry and the thickness of sediment layers. The accuracy of the approach is demonstrated by comparing with finite-element solutions. The approach is applied to a complex scenario in a realistic environment.     

Vocal learning in Budgerigars (Melopsittacus undulatus): effects of an acoustic reference on vocal matching

Budgerigars were trained to produce specific vocalizations (calls) using operant conditioning and food reinforcement. The bird's call was compared to a digital representation of the call stored in a computer to determine a match. Once birds were responding at a high level of precision, we measured the effect of several manipulations upon the accuracy and the intensity of call production. Also, by differentially reinforcing other aspects of vocal behavior, budgerigars were trained to produce a call that matched another bird's contact call and to alter the latency of their vocal response. Both the accuracy of vocal matching and the intensity level of vocal production increased significantly when the bird could hear the template immediately before each trial. Moreover, manipulating the delay between the presentation of an acoustic reference and the onset of vocal production did not significantly affect either vocal intensity or matching accuracy. Interestingly, the vocalizations learned and reinforced in these operant experiments were only occasionally used in more natural communicative situations, such as when birds called back and forth to one another in their home cages.     

The relationship between precursor level and the temporal effect

Previous studies have suggested that temporal effects in masking may be consistent with a decrease in cochlear gain. One paradigm used to show this is to measure the level of a long-duration masker required to just mask a short-duration tone that occurs near masker onset. The temporal effect is revealed when the signal is detected at a lower signal-to-noise ratio following preceding stimulation (either an extension of the masker or a separate precursor). The present study examined whether this effect depends on precursor level. The signal was a 10-ms, 4-kHz tone. The masker was 200 ms. A fixed-level precursor had the same frequency characteristics as the masker, and was 205 ms. The masker and precursor had either no notch or a wide notch about the signal frequency. For a given precursor level, the growth of masker level with signal level was determined. These data were used to estimate input-output functions. The results are consistent with a graded decrease in gain at the signal frequency when there is no notch in the masker and precursor, and a graded decrease in suppression when there is a large notch. These results could be consistent with the action of the medial olivocochlear reflex.     

Evaluation of Different Interstimulus Rinse Protocols on Smoke Attribute Perception in Wildfire-Affected Wines

Wildfires produce smoke that can carry organic compounds to a vineyard, which are then absorbed by the grape berry and result in wines with elevated levels of smoke-related phenols. These phenols have been found to have a large impact on the flavor of wines, being the cause of a smokey flavor with a lasting ashy aftertaste. When evaluating the sensory profile of these wines, there is an observed problem due to the lasting nature of these undesirable attributes and potential flavor carryover between samples. Through the use of standard and temporal attribute check-all-that-apply, this research desires to better understand the impact of smoke on the sensorial profiles of wines with various levels of smoke phenols (high, moderate, and low). Additionally, through the employment of different interstimulus protocols, the effectiveness of rinses on diminishing the smoke flavor in wines and optimal time separation were investigated. It was determined that a 1 g/L pectin rinse in between samples with a 120 s separation is optimal to ensure the removal of smoke attribute perception. This work also indicated the need to look deeper at the effects of the in-mouth hydrolysis of glyconjugate phenols that impact overall smoke flavor.     

Evaluating a direct swabbing method for screening pesticides on fruit and vegetable surfaces using direct analysis in real time (DART) coupled to an Exactive benchtop orbitrap mass spectrometer

Rapid screening of pesticides present on the surfaces of fruits and vegetables has been facilitated by using a Direct Analysis in Real Time (DART(?)) open air surface desorption ionization source coupled to an Exactive(?) high-resolution accurate mass benchtop orbitrap mass spectrometer. The use of cotton and polyester cleaning swabs to collect and retain pesticides for subsequent open air desorption ionization is demonstrated by sampling the surface of various produce to which solutions of pesticides have been applied at levels 10 and 100 times below the tolerance levels established by the United States Environmental Protection Agency (US EPA). Samples analyzed include cherry tomatoes, oranges, peaches and carrots each chosen for their surface characteristics which include: smooth, pitted, fuzzy, and rough respectively. Results from the direct analysis of fungicides on store-bought oranges are also described. In all cases, the swabs were introduced directly into the heated ionizing gas of the DART source resulting in production of protonated pesticide molecules within seconds of sampling. Operation of the orbitrap mass spectrometer at 25,000 full-width half maximum resolution was sufficient to generate high-quality accurate mass data. Stable external mass calibration eliminated the need for addition of standards typically required for mass calibration, thus allowing multiple analyses to be completed without instrument recalibration.     

Deciphering the activation sequence of ferrociphenol anticancer drug candidates

The complete oxidation sequence of a model for ferrociphenols, a new class of anticancer drug candidate, is reported. Cyclic voltammetry was used to monitor the formation of oxidation intermediates on different timescales, thereby allowing the electrochemical characterization of both the short-lived and stable species obtained from the successive electron-transfer and deprotonation steps. The electrochemical preparation of the ferrocenium intermediate enabled a stepwise voltammetric determination of the stable oxidation compounds obtained upon addition of a base as well as the electron stoichiometry observed for the overall oxidation process. A mechanism has been established from the electrochemical data, which involves a base-promoted intramolecular electron transfer between the phenol and the ferrocenium cation. The resulting species is further oxidized then deprotonated to yield a stable quinone methide. To further characterize the transient species successively formed during the two-electron oxidation of the ferrociphenol to its quinone methide, EPR was used to monitor the fate of the paramagnetic species generated upon addition of imidazole to the electrogenerated ferrocenium. The study revealed the passage from an iron-centered to a carbon-centered radical, which is then oxidized to yield the quinone methide, namely, the species that interacts with proteins and so forth under biological conditions.     

Hydrotris(triazolyl)borate complexes as functional models for Cu nitrite reductase: the electronic influence of distal nitrogens

Hydrotris(triazolyl)borate (Ttz) ligands form CuNO(x) (x = 2, 3) complexes for structural and functional models of copper nitrite reductase. These complexes have distinct properties relative to complexes of hydrotris(pyrazolyl)borate (Tp) and neutral tridentate N-donor ligands. The electron paramagnetic resonance spectra of five-coordinate copper complexes show rare nitrogen superhyperfine couplings with the Ttz ligand, indicating strong σ donation. The copper(I) nitrite complex [PPN](+)[(Ttz(tBu,Me))Cu(I)NO(2)](-) has been synthesized and characterized and allows for the stoichiometric reduction of NO(2)(-) to NO with H(+) addition. Anionic Cu(I) nitrite complexes are unusual and are stabilized here for the first time because Ttz is a good π acceptor.     

Histamine determination in human urine using sub-2 μm C18 column with fluorescence and mass spectrometric detection

A fast, sensitive, and selective method for the determination of histamine in human urine samples by ultrahigh pressure liquid chromatography (LC) with fluorescence and mass spectrometry (MS) detection is investigated. A fluorescent reagent, 4-(1-pyrene) butyric acid N-hydroxysuccinimide ester was conjugated to the primary and secondary amino moieties of histamine. The structure of dipyrene-labeled histamine in human urine was determined by quadrupole time-of-flight MS with electospray ionization interface. The determination of the dipyrene derivative of histamine in urine samples was achieved within 3.9 min on an ultrahigh pressure LC Eclipse Zorbax XDB-C(18) column with 1.8 μm particle diameter. In this work, histamine separation was achieved significantly faster (3.9 min) with improved detection limit (signal-to-noise = 3) of 0.04 nM than 19.5 min with a detection limit of 0.183 nM as reported in a previous method.     

Fine tuning Nesterov’s steepest descent algorithm for differentiable convex programming

We modify the first order algorithm for convex programming described by Nesterov in his book (in Introductory lectures on convex optimization. A basic course. Kluwer, Boston, 2004). In his algorithms, Nesterov makes explicit use of a Lipschitz constant L for the function gradient, which is either assumed known (Nesterov in Introductory lectures on convex optimization. A basic course. Kluwer, Boston, 2004), or is estimated by an adaptive procedure (Nesterov 2007). We eliminate the use of L at the cost of an extra imprecise line search, and obtain an algorithm which keeps the optimal complexity properties and also inherit the global convergence properties of the steepest descent method for general continuously differentiable optimization. Besides this, we develop an adaptive procedure for estimating a strong convexity constant for the function. Numerical tests for a limited set of toy problems show an improvement in performance when compared with the original Nesterov’s algorithms.