Experimental limit on optical-photon coupling to light neutral scalar bosons

We report on the first results of a sensitive search for scalar coupling of photons to a light neutral boson in the mass range of approximately 1.0 meV (milli-electron volts) and coupling strength greater than 10(-6) GeV(-1) using optical photons. This was a photon regeneration experiment using the "light shining through a wall" technique in which laser light was passed through a strong magnetic field upstream of an optical beam dump; regenerated laser light was then searched for downstream of a second magnetic field region optically shielded from the former. Our results show no evidence for scalar coupling in this region of parameter space.     

Articulatory tradeoffs reduce acoustic variability during American English /r/ production.

The American English phoneme /r/ has long been associated with large amounts of articulatory variability during production. This paper investigates the hypothesis that the articulatory variations used by a speaker to produce /r/ in different contexts exhibit systematic tradeoffs, or articulatory trading relations, that act to maintain a relatively stable acoustic signal despite the large variations in vocal tract shape. Acoustic and articulatory recordings were collected from seven speakers producing /r/ in five phonetic contexts. For every speaker, the different articulator configurations used to produce /r/ in the different phonetic contexts showed systematic tradeoffs, as evidenced by significant correlations between the positions of transducers mounted on the tongue. Analysis of acoustic and articulatory variabilities revealed that these tradeoffs act to reduce acoustic variability, thus allowing relatively large contextual variations in vocal tract shape for /r/ without seriously degrading the primary acoustic cue. Furthermore, some subjects appeared to use completely different articulatory gestures to produce /r/ in different phonetic contexts. When viewed in light of current models of speech movement control, these results appear to favor models that utilize an acoustic or auditory target for each phoneme over models that utilize a vocal tract shape target for each phoneme.     

Revised model coefficients for vibrational relaxation in a nitrogen–oxygen gas mixture

A numerical investigation of thermal non-equilibrium flows requires species specific relaxation rates, which are often calculated using the Landau–Teller model. This model requires the determination of collision specific relaxation times, which can be computed using Millikan and White’s empirical formula. The coefficients used in this formula for each specific collision pair form a set of coefficients, which are assessed here. The focus of the investigation lies on their performance in hypersonic low-temperature (300–2,500?K) flows that occur at shock-tunnel nozzle exits or in supersonic combustion ramjets (scramjets) before combustion. Two experimental validation cases are chosen; a shock-tunnel nozzle and a sharp cone in hypersonic cross-flow experiment. A comparison of the experimentally measured vibrational temperatures at the nozzle exit against numerical data shows large discrepancies for two commonly used coefficient sets. A revised set of coefficients is proposed that greatly improves the agreement between the numerical and experimental results. Furthermore, the numerically generated shock shape over the sharp cone using the revised set of coefficients correlates well with the experimental measurements.     

Asymmetric,Stereodivergent Synthesis of (−)‐Clusianone Utilizing a Biomimetic Cationic Cyclization

We report a stereodivergent, asymmetric total synthesis of (?)‐clusianone in six steps from commercial materials. We implement a challenging cationic cyclization forging a bond between two sterically encumbered quaternary carbon atoms. Mechanistic studies point to the unique ability of formic acid to mediate the cyclization forming the clusianone framework.     

On the boundary between laboratory ‘givens’ and laboratory ‘tangibles’

From the 4-part Procedure/Observations/Data/Analysis structure of a laboratory report (generalized from Italian, Chinese and US sources), we distill a fifth flavor, the givens, whose flip side is the freedoms or tangibles of an experiment. (Stated in terms of computer science, we are trying to find inputs and outputs, but these turn out to be surprisingly vague in chemistry.) Then, in the service of a white-boxing ethos (which sounds less severe than ‘anti black-boxing’), we establish a movable boundary between givens and tangibles, with implications for ‘ontological attitudes’ and for the future of chemistry. Next, in revisiting a 2002 exchange between Schummer and Laszlo, which might be paraphrased as the chemist-as-philosopher versus chemist-as-artisan, we apply a second kind of sliding scale which seems to harmonize the discussion. Finally, on a possibly quixotic note, we look briefly at a third kind of sliding scale, now aimed squarely at ontology itself. For illustrative purposes, we adopt an atomocentric viewpoint (as distinct from atomistic), and assign it the provisional name ‘Fuzzy CH₄ Ontology’.     

The immersed boundary method for advection–electrodiffusion with implicit timestepping and local mesh refinement

We describe an immersed boundary method for problems of fluid–solute-structure interaction. The numerical scheme employs linearly implicit timestepping, allowing for the stable use of timesteps that are substantially larger than those permitted by an explicit method, and local mesh refinement, making it feasible to resolve the steep gradients associated with the space charge layers as well as the chemical potential, which is used in our formulation to control the permeability of the membrane to the (possibly charged) solute. Low Reynolds number fluid dynamics are described by the time-dependent incompressible Stokes equations, which are solved by a cell-centered approximate projection method. The dynamics of the chemical species are governed by the advection–electrodiffusion equations, and our semi-implicit treatment of these equations results in a linear system which we solve by GMRES preconditioned via a fast adaptive composite-grid (FAC) solver. Numerical examples demonstrate the capabilities of this methodology, as well as its convergence properties.     

Preparation and properties of a monomeric high-spin Mn(V)-oxo complex

Oxomanganese(V) species have been implicated in a variety of biological and synthetic processes, including their role as a key reactive center within the oxygen-evolving complex in photosynthesis. Nearly all mononuclear Mn(V)-oxo complexes have tetragonal symmetry, producing low-spin species. A new high-spin Mn(V)-oxo complex that was prepared from a well-characterized oxomanganese(III) complex having trigonal symmetry is now reported. Oxidation experiments with [FeCp(2)](+) were monitored with optical and electron paramagnetic resonance (EPR) spectroscopies and support a high-spin oxomanganese(V) complex formulation. The parallel-mode EPR spectrum has a distinctive S = 1 signal at g = 4.01 with a six-line hyperfine pattern having A(z) = 113 MHz. The presence of an oxo ligand was supported by resonance Raman spectroscopy, which revealed O-isotope-sensitive peaks at 737 and 754 cm(-1) assigned as a Fermi doublet centered at 746 cm(-1)(Δ(18)O = 31 cm(-1)). Mn Kβ X-ray emission spectra showed Kβ' and Kβ(1,3) bands at 6475.92 and 6490.50 eV, respectively, which are characteristic of a high-spin Mn(V) center.     

Bioelectrochemical signaling in green plants induced by photosensory systems

Plants generate various types of intracellular and intercellular electrical events in response to environmental stress. The generation of electrophysiological responses induced by blue and red photosensory systems was observed in soybean plants. A phototropic response is a sequence of the following four processes: reception of a directional light signal, signal transduction, transformation of the signal into a physiological response, and the production of a directional growth response. It was found that the irradiation of soybean plants at 450+/-50, 670, and 730 nm induces action potentials with duration times and amplitudes of approximately 0.3 ms and 60 mV respectively.