Nanotube growth during annealing of mechanically milled Boron

Boron powder, finely ground in a tungsten carbide ball mill in an ammonia atmosphere, has been annealed at 1200 °C in flowing nitrogen to produce small quantities of cylindrical BN nanotubes, both as isolated individuals and grouped into ropes. Thick-walled conical BN tubes are abundant in specimens annealed for longer times, and their growth was catalysed once WC debris was converted into W metal particles. Some catalytic effect of small W nanoparticles could be necessary for nanotube formation, though no tip particles have been imaged here. Given the low temperature of mechanical milling and annealing, BN growth must involve surface diffusion and solid-state reconfiguration. It could be possible to engineer desirable physical and chemical properties by exploiting the variation in cylindrical versus conical BN structures as a function of annealing time. Received: 19 December 2001 / Accepted: 3 April 2002 / Published online: 19 July 2002 RID="*" ID="*"Corresponding author. Fax: +61-2/6125-8253, E-mail: john.fitzgerald@anu.edu.au     

The role of aqueous interfaces in the cell

The cell is rich with biopolymeric surfaces. Yet, the role of these surfaces and attendant surface-water interfaces has received little attention among biologists, most of whom consider water as a neutral carrier. This review aims to begin bridging the gap between biology and interface science-to show that a surface-oriented approach has power to bring fresh insights into an otherwise impenetrably complex maze. In this approach the cell is treated as a polymer gel. If the cell is a gel, then a logical approach to the understanding of cell function is through an understanding of gel function. Great strides have been made recently in understanding the principles of polymer-gel dynamics, and particularly the role of the polymer-water interface. It has become clear that a central mechanism in biology is the phase-transition-a major structural change prompted by a subtle change of environment. Phase-transitions are capable of doing work and such work could be responsible for much of the work of the cell. Here, we pursue this approach. We set up a polymer-gel-based foundation for cell behavior, and explore the extent to which this foundation explains how the cell achieves its everyday tasks.     

Chelate bis(imino)pyridine cobalt complexes: synthesis, reduction, and evidence for the generation of ethene polymerization catalysts by Li+ cation activation

Treatment of the bis(iminobenzyl)pyridine chelate Schiff-base ligand 8 (ligPh) with FeCl2 or CoCl2 yielded the corresponding (ligPh)MCl2 complexes 9 (Fe) and 10 (Co). The reaction of 10 with methyllithium or "butadiene-magnesium" resulted in reduction to give the corresponding (ligPh)Co(I)Cl product 11. Similarly, the bis(aryliminoethyl)pyridine ligand (ligMe) was reacted with CoCl2 to yield (ligMe)CoCl2 (12). Reduction to (ligMe)CoCl (13) was effected by treatment with "butadiene-magnesium". Complex 13 reacted with Li[B(C6F5)4] in toluene followed by treatment with pyridine to yield [(ligMe)Co+-pyridine] (15). The reaction of the Co(II) complexes 10 or 12 with ca. 3 molar equiv of methyllithium gave the cobalt(I) complexes 16 and 17, respectively. Treatment of the (ligMe)CoCH3 (17) with Li[B(C6F5)4] gave a low activity ethene polymerization catalyst. Likewise, complex 16 produced polyethylene (activity = 33 g(PE) mmol(cat)(-1) h(-1) bar(-1) at room temperature) upon treatment with a stoichiometric amount of Li[B(C6F5)4]. A third ligand (lig(OMe)) was synthesized featuring methoxy groups in the ligand backbone (22). Coordination to FeCl2 and CoCl2 yielded the desired compounds 23 and 24. Reaction with MeLi gave (ligOMe)CoMe (25/26). Treatment of 25/26 with excess B(C6F5)3 gave the eta6-arene cation complex 27, where one Co-N linkage was cleaved. Activation of 25/26 with Li[B(C6F5)4] again gave a catalytically active species.     

A chromium catalyst for the polymerization of ethylene as a homogeneous model for the phillips catalyst

A structurally characterized cationic chromium(III) alkyl featuring a bulky nacnac ligand catalyzes the polymerization of ethylene as well as the copolymerization of ethylene with alpha-olefins. This well-characterized homogeneous catalyst constitutes a structural as well as functional model of the widely used heterogeneous Phillips olefin polymerization catalyst.     

Medial surface dynamics of an in vivo canine vocal fold during phonation

Quantitative measurement of the medial surface dynamics of the vocal folds is important for understanding how sound is generated within the larynx. Building upon previous excised hemilarynx studies, the present study extended the hemilarynx methodology to the in vivo canine larynx. Through use of an in vivo model, the medial surface dynamics of the vocal fold were examined as a function of active thyroarytenoid muscle contraction. Data were collected using high-speed digital imaging at a sampling frequency of 2000 Hz, and a spatial resolution of 1024 x 1024 pixels. Chest-like and fry-like vibrations were observed, but could not be distinguished based on the input stimulation current to the recurrent laryngeal nerve. The subglottal pressure did distinguish the registers, as did an estimate of the thyroarytenoid muscle activity. Upon quantification of the three-dimensional motion, the method of Empirical Eigenfunctions was used to extract the underlying modes of vibration, and to investigate mechanisms of sustained oscillation. Results were compared with previous findings from excised larynx experiments and theoretical models.     

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.     

Informational masking for simultaneous nonspeech stimuli: psychometric functions for fixed and randomly mixed maskers

Sensitivity d' and response bias beta were measured as a function of target level for the detection of a 1000-Hz tone in multitone maskers using a one interval, two-alternative forced-choice (1I-2AFC) paradigm. Ten such maskers, each with eight randomly selected components in the region 200-5000 Hz, with 800-1250 Hz excluded to form a protected zone, were presented under two conditions: the fixed condition, in which the same eight-component masker is used throughout an experimental run, and the random condition, in which an eight-component masker is chosen randomly trial-to-trial from the given set of ten such maskers. Differences between the results obtained with these two conditions help characterize the listener's susceptibility to informational masking (IM). The d' results show great intersubject variability, but can be reasonably well fit by simple energy-detector models in which internal noise and filter bandwidth are used as fitting parameters. In contrast, the beta results are not well fit by these models. In addition to presentation of new data and its relation to energy-detector models, this paper provides comments on a variety of issues, problems, and research needs in the IM area.     

Breaking of balanced and unbalanced equatorial waves

A clear-cut signature of a wave-breaking event is irreversible modification of the mean flow. In this paper, we provide examples of different breaking mechanisms and show that breaking scenario of equatorial waves in the beta-plane shallow water model is determined by the degree of balance between the zonal component of the Coriolis force and the pressure gradient. Our analysis is based on a specially designed numerical method which guarantees two essential conditions to simulate nonlinear equatorial waves: (i) the scheme converges toward weak solutions including shocks and (ii) preserves the steadiness of balanced stationary solutions. This allows for accurate diagnostics of Lagrangian invariants of motion such as passive tracer density or potential vorticity. For unbalanced waves, the lack of balance leads to shock formation in finite time. In shock fronts, the variation of the dissipation rate induces a nonadvective potential vorticity flux and violates the local potential vorticity conservation valid for smooth solutions. This dissipative breaking mechanism is generic for unbalanced waves and is associated with enhanced mixing. For long, balanced (Rossby) waves, breaking consists in appearance of recirculation regions. It results in the formation of propagating patterns, the equatorial modons, which trap fluid particles. Such breaking occurs during the propagation of Rossby wave packets with positive geopotential anomaly and is strengthened by decreasing fluid depth. The modons are robust and collide quasielastically with Kelvin waves.     

Modular synthesis of cyclic peptidomimetics inspired by gamma-turns

[reaction: see text] A series of peptidomimetics based on a gamma-turn motif were synthesized using a modular approach, in which N-protected piperidones were reacted with a selection of 2-hydroxyalkyl azides derived from common l-amino acids. Hydrolysis of the initially formed iminium ethers afforded the targeted series of substituted 1,4-diazepin-5-ones.