The advantage of knowing where to listen

This study examined the role of focused attention along the spatial (azimuthal) dimension in a highly uncertain multitalker listening situation. The task of the listener was to identify key words from a target talker in the presence of two other talkers simultaneously uttering similar sentences. When the listener had no a priori knowledge about target location, or which of the three sentences was the target sentence, performance was relatively poor-near the value expected simply from choosing to focus attention on only one of the three locations. When the target sentence was cued before the trial, but location was uncertain, performance improved significantly relative to the uncued case. When spatial location information was provided before the trial, performance improved significantly for both cued and uncued conditions. If the location of the target was certain, proportion correct identification performance was higher than 0.9 independent of whether the target was cued beforehand. In contrast to studies in which known versus unknown spatial locations were compared for relatively simple stimuli and tasks, the results of the current experiments suggest that the focus of attention along the spatial dimension can play a very significant role in solving the "cocktail party" problem.     

Direct magnitude estimation and interval scaling of pleasantness and severity in dysphonic and normal speakers

The purpose of this study was to determine the validity of voice pleasantness and overall voice severity ratings of dysphonic and normal speakers using direct magnitude estimation (DME) and equal-appearing interval (EAI) auditory-perceptual scaling procedures. Twelve naive listeners perceptually evaluated voice pleasantness and severity from connected speech samples produced by 24 adult dysphonic speakers and 6 normal adult speakers. A statistical comparison of the two auditory-perceptual scales yielded a linear relationship representative of a metathetic continuum for voice pleasantness. A statistical relationship that is consistent with a prothetic continuum was revealed for ratings of voice severity. These data provide support for the use of either DME or EAI scales when making auditory-perceptual judgments of pleasantness, but only DME scales when judging overall voice severity for dysphonic speakers. These results suggest further psychophysical study of perceptual dimensions of voice and speech must be undertaken in order to avoid the inappropriate and invalid use of EAI scales used in the auditory-perceptual evaluation of the normal and dysphonic voice.     

On Thermodynamic Consistency of Turbulent Closures

The problem of the implementation of the second law of thermodynamics for the determination of the thermodynamic consistency of solutions determined by turbulent closures is considered for incompressible fluids. The possibility of the application of the methods of thermodynamics to constraining constitutive laws describing turbulent flow features, but not material behaviour, is discussed. It is shown that the ordinary realizability conditions requiring non-negative values of the averaged squared fluctuations are necessary and sufficient conditions determining the thermodynamic consistency of a process governed by a closure model. Because turbulent closures are not universal, using the second law of thermodynamics to constrain them can impose unnecessary restrictions on the models, when the turbulent entropy is considered as a constitutive quantity. The notion and validity of different forms of the turbulent entropy is discussed. It is found that the form of the turbulent entropy originating from the analogy between the turbulent kinetic energy and absolute temperature contradicts the principle of irreversibility. In a particular case of small temperature fluctuations, the second law yields correct constraints, if the turbulent entropy is assumed not to be a constitutive quantity, but a variable governed by an evolution equation of special form generated by the balance equation for internal energy. Received 14 October 2000 and accepted 30 May 2001     

Phase IIb randomized trial of adjunct immunotherapy in patients with first-diagnosed tuberculosis,relapsed and multi-drug-resistant (MDR) TB

Placebo-controlled, randomized, phase 2b trial was conducted in 34 adults comprising 18 first-diagnosed (52.9%), 6 relapsed (17.6%), and 10 MDR-TB (29.4%) cases to investigate the safety and efficacy of an oral immune adjunct (V5). The immunotherapy (N = 24) and placebo (N = 10) arms received once-daily tablet of V5 or placebo for one month in addition to conventional anti-TB therapy (ATT) administered under directly observed therapy (DOT).     

A general solution method for an anti-plane shear crack dynamically accelerating along a bimaterial interface

We develop a general solution method for a dynamically accelerating crack under anti-plane shear conditions along the interface between two different homogeneous isotropic elastic materials. The crack is initially at rest, and after loading is applied the crack-tip speed which may accelerate up to the shear wave speed of the more compliant material. The analysis includes an exact, closed-form expression for the stress intensity factor for an arbitrary time-dependent crack-face traction, as well as expressions for computing the crack-face displacements and the stress in front of the crack. We also present some numerical examples for fixed loads and for loads moving with the crack tip, using a stress intensity factor fracture criterion, in order to examine the predicted effect of material mismatch on interfacial fracture.     

Theory of incremental motion in a body with initial elasto-plastic deformation

A theory of incremental deformation is developed for a body with initial stress and strain, valid for elastic and plastic pre-deformation. The superimposed motion is assumed hyperelastic. We present the constitutive equation, relating a measure of incremental stress to incremental strain, and the momentum equations referred to the prestrained initial configuration of the body. The latter is linearized with respect to the displacement field of the superimposed motion. For general nonlinear pre-deformation the constitutive theory of an anisotropic body may be based on the assumed strain energy that is an isotropic function of the Green strain tensor and a number of material directors of unit length. For bodies with elastoplastic prestrain and prestress, an elastic constitutive relation that depends on the plastic pre-deformation and the deformation from a relaxed state is postulated. Imposing the requirements of invariance with respect to rotations of the plastic pre-deformation and using the objectivity rule, we show that the constitutive function of stress must be an isotropic function of its arguments. This leads to a new theory of acoustoelasticity for an elasto-plastically prestrained material with anisotropic natural state by incorporating materially fixed unit directors as independent variables in the constitutive equations.

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Zusammenfassung Es wird eine Theorie der inkrementellen Deformation für einen Körper mit Vorspannung und Vorverformung entwickelt, welche sowohl für elastische wie plastische Vorverformung Gültigkeit hat. Die überlagerte Bewegung wird als hyperelastisch angenommen. Wir leiten die Materialgleichung her, welche eine inkrementelle Spannung mit einer inkrementellen Verzerrung verknüpft und geben die Impulsgleichung in einer auf die anfängliche Verformung bezogenen Konfiguration. Diese Impulsgleichung wird bezüglich des überlagerten Verschiebungsfeldes linearisiert. Für eine allgemeine nichtlineare Vorverformung kann die Materialtheorie eines anisotropen Körpers auf der Basis einer postulierten Verzerrungsenergie gegründet werden, welche eine isotrope Funktion des Greenschen Verzerrungstensors und einer Zahl materieller Direktoren mit Länge 1 darstellt. Für elasto-plastisch vorgespannte und vorverformte Körper wird eine elastische Materialgleichung postuliert, die von der plastischen Vorverformung sowie der Deformation aus einer relaxierten Konfiguration abhängt. Es wird gezeigt, daß die Materialgleichung für den Spannungstensor eine isotrope Funktion ihrer Argumente sein muß, wenn man als übergeordnetes Prinzip das Objektivitätsprinzip fordert und Invarianz des Spannungsfunktionals gegenüber Rotationen der plastischen Vordeformation verlangt. Durch Einführen von materiellen Direktoren der Einheitslänge als unabhängige Konstitutivvariablen erhält man hieraus eine neue Theorie der Akusteolastizität für elasto-plastisch vorverformte Materialien mit anisotropen natürlichen Referenzzuständen.

     

Spectroscopic studies on a ‘turn-on’ fluorescent sensor for transition metals with selective ‘turn-off’ for mercury(II) ions

Spectroscopic studies on a dansyl-based fluorescent sensor N-(4-aminophenyl)-5-(dimethylamino)naphthalene-1-sulphonamide (1) and its interactions with transition metals are reported. The sensor's absorption and emission spectra exhibited different profiles at different polarities and pH values. Enhanced fluorescence was observed in the presence of chromium(III) ions in methanol, while the emission was quenched significantly in the presence of mercury(II) ions both in methanol and aqueous solution. The binding constants of 1 to chromium(III) in methanol and to mercury(II) ions in methanol and aqueous solution were calculated.     

Comparative study of the nature of chemical bonding of corrugated graphene on Ru(0001) and Rh(111) by electronic structure calculations

Recently, atomic resolved scanning tunneling microscopy investigations revealed that, depending on the substrate (Ni(111), Ru(0001), Ir(111), Pt(111), Rh(111)), graphene overlayer might present regular corrugation patterns, with periodically repeated units of a few nanometers. Variations of the interactions at the interface and the modulation of the local electronic properties are associated with the exact atomic arrangement of the carbon pairs with respect to the metal atoms of the substrate. Better understanding of the atomic structure and of the chemical bonding between graphene and the underlying transition metal is motivated by the fundamental scientific relevance of such systems, but it is also crucial in the perspective of possible applications. With the present work, we propose model systems for the two interfaces showing the most pronounced corrugation patterns, i.e. graphene/Ru(0001) and graphene/Rh(111). Our goal is to understand the nature of the interactions by means of electronic structure calculations based on Density Functional Theory. Our simulations qualitatively reproduce very well experimental results such as the STM topographies and the electrostatic potential maps, and quantitatively provide the closest agreement that has been published so far. The detailed analysis of the electronic structure at the interface highlights similarities and differences by changing the supporting transition metal. Our results point to a fundamental role of the hybridization between the π orbitals of graphene with the d band of the metal in determining the specific corrugation of the adsorbed monolayer. It is shown that differences in the response of the graphene electronic structure to the interaction with the metal can hinder the hybridization and lead to substantially different structures.     

Selective Endo and Exo Binding of Mono‐ and Ditopic Ligands to a Rhomboidal Diporphyrin Prism

Copper(I) can preferentially form heteroleptic complexes containing two phosphine and two nitrogen donors due to steric factors. This preference was employed to direct the self‐assembly of a porphyrin‐faced rhomboidal prism having two parallel tetrakis(4‐iminopyridyl)porphyrinatozinc(II) faces linked by eight 1,4‐bis(diphenylphosphino)benzene pillars. The coordination preferences of the Cu^I ions and geometries of the ligands come together to generate a slipped‐cofacial orientation of the porphyrinatozinc(II) faces. This orientation enables selective encapsulation of 3,3′‐bipyridine (bipy), which bridges the Zn^II ions of the parallel porphyrins, whereas 4,4′‐bipy exhibits weaker external coordination to the porphyrin faces. Reaction with 2,2′‐bipy, by contrast, results in the displacement of the tetratopic porphyrin ligand and formation of [{(2,2′‐bipy)Cu^I}₂(diphosphine)₂]. The differing strengths of interactions of bipyridine isomers with the system allows for a hierarchy to be deciphered, whereby 4,4′‐bipy may be displaced by 3,3′‐bipy, which in turn is displaced by 2,2′‐bipy.     

Fluorescence-based aluminum ion sensing using a surface-functionalized microstructured optical fiber

The first microstructured optical fiber-based sensor platform for aluminum ions using a surface-attached derivative of lumogallion (3), a known fluorescence-based indicator, has been fabricated. These fibers allow for strong evanescent field interactions with the surrounding media because of the small core size while also providing the potential for real-time and distributed measurements. The fluorescence response to aluminum ions was first demonstrated by applying the procedure to glass slides. This was achieved through the covalent attachment of the fluorophore to a polyelectrolyte-coated glass surface and then to the internal holes of a suspended-core microstructured optical fiber to give an effective aluminum sensor. Whereas the sensor platform reported is fabricated for aluminum, the approach is versatile, with applicability to the detection of other ions.