Transition‐State Stabilization by a Secondary Substrate–Ligand Interaction: A New Design Principle for Highly Efficient Transition‐Metal Catalysis

A library of monodentate phosphane ligands, each bearing a guanidine receptor unit for carboxylates, was designed. Screening of the library gave some excellent catalysts for regioselective hydroformylation of β,γ‐unsaturated carboxylic acids. A terminal alkene, but‐3‐enoic acid, was hydroformylated with a linear/branched (l/b) regioselectivity up to 41. An internal alkene, pent‐3‐enoic acid was hydroformylated with regioselectivity up to 18:1. Further substrate selectivity (e.g., acid vs. methyl ester) and reaction site selectivity (monofunctionalization of 2‐vinylhept‐2‐enoic acid) were also achieved. Exploration of the structure–activity relationship and a practical and theoretical mechanistic study gave us an insight into the nature of the supramolecular guanidinium–carboxylate interaction within the catalytic system. This allowed us to identify a selective transition‐state stabilization by a secondary substrate–ligand interaction as the basis for catalyst activity and selectivity.     

Evaluation of comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry for the diagnosis of inherited metabolic disorders using an automated data processing strategy

Organic acidurias are a large group of inherited metabolic disorders (IMDs), commonly diagnosed by GC-MS analysis of organic acids in urine after acidic extraction and trimethylsilylation. In this study, a GC×GC-ToF-MS method has been optimized for the analysis of pathological metabolites in urine. An automated data processing strategy based on the use of mass spectra and GC retention times for the target search and quantification of pathological metabolites has been developed. Using this procedure, each unknown sample is automatically examined for the presence of markers of several diseases at the same time. The method has been applied for the analysis of 6 challenging proficiency testing samples from patients with IMDs (thymidine phosphorylase deficiency, mevalonic aciduria, hawkinsinuria, aromatic l-amino acid decarboxylase deficiency, propionic acidemia and medium-chain acyl-CoA dehydrogenase deficiency). Using the GC×GC-ToF-MS method, we were able to determine complete sets of markers for all the IMDs. The quality of the mass spectral matches for the pathological markers was higher than 800 (out of 1000).     

Auditory evoked potentials in two short-finned pilot whales (Globicephala macrorhynchus)

The hearing sensitivities of two short-finned pilot whales (Globicephala macrorhynchus) were investigated by measuring auditory evoked potentials generated in response to clicks and sinusoidal amplitude modulated (SAM) tones. The first whale tested, an adult female, was a long-time resident at SeaWorld San Diego with a known health history. Click-evoked responses in this animal were similar to those measured in other echolocating odontocetes. Auditory thresholds were comparable to dolphins of similar age determined with similar evoked potential methods. The region of best sensitivity was near 40 kHz and the upper limit of functional hearing was between 80 and 100 kHz. The second whale tested, a juvenile male, was recently stranded and deemed non-releasable. Click-evoked potentials were not detected in this animal and testing with SAM tones suggested severe hearing loss above 10 kHz.     

Vocal tract changes caused by phonation into a tube: a case study using computer tomography and finite-element modeling

Phonation into a glass tube is a voice training and therapy method that leads to beneficial effects in voice production. It has not been known, however, what changes occur in the vocal tract during and after the phonation into a tube. This pilot study examined the vocal tract shape in a female subject before, during, and after phonation into a tube using computer tomography (CT). Three-dimensional finite-element models (FEMs) of the vocal tract were derived from the CT images and used to study changes in vocal tract input impedance. When phonating on vowel [a:] the data showed tightened velopharyngeal closure and enlarged cross-sectional areas of the oropharyngeal and oral cavities during and after the tube-phonation. FEM calculations revealed an increased input inertance of the vocal tract and an increased acoustic energy radiated out of the vocal tract after the tube-phonation. The results indicate that the phonation into a tube causes changes in the vocal tract which remain also when the tube is removed. These effects may help improving voice production in patients and voice professionals.     

Zero Temperature Limits of Gibbs Equilibrium States for Countable Markov Shifts

We prove that, given a uniformly locally constant potential f on a countable state Markov shift and suitable conditions which guarantee the existence of the equilibrium states μ _tf for all t, the measures μ _tf converge in the weak star topology as t tends to infinity.     

Local dimming algorithm and color gamut calibration for RGB LED backlight LCD display

A 32 in RGB LED backlight unit is developed. A local dimming algorithm is designed for the backlight, and grid-noise artifacts in the LC driving signal are successfully removed with consideration of the backlight distribution to provide identical intensity from each LED block. The 32 in RGB LED backlight LCD display has achieved a static display contrast of over 20000:1 and an average power reduction of 30%. We have also obtained the color gamut transformation matrix for transferring a cold cathode fluorescent lamp BLU LCD display gamut system to our RGB LED BLU LCD display gamut system, and extended the color saturation by suppositional color expansion method. As a result, the color has been accurately reproduced in RGB LED BLU LCD display with more richness and more saturation.     

Motion of micrometer sized spherical particles exposed to a transient radial flow: attraction, repulsion, and rotation

It is now accepted that the physical forces in ultrasonic cleaning are due to strongly pulsating bubbles driven by the sound field. Here we have a detailed look at bubble induced cleaning flow by analyzing the transport of an individual particle near an expanding and collapsing bubble. The induced particulate transport is compared with a force balance model. We find two important properties of the flow which explain why bubbles are effectively cleaning: During bubble expansion a strong shear layer loosens the particle from the surface through particle spinning and secondly an unsteady boundary layer generates an attractive force, thus collecting the contamination in the bubble's close proximity.     

Cavity induced shift and narrowing of the positronium Lyman-α transition

We report experiments in which the line shape of the Lyman-alpha (1S-2P) transition was measured for positronium (Ps) atoms both inside and outside a porous silica target. The energy interval ΔE for confined atoms was observed to be larger than that of free Ps by 1.26±0.06 meV. A configuration interaction calculation yields results that are consistent with our ～5 nm sample, and suggests that ΔE decreases dramatically for larger cavity diameters. The linewidth of the transition, (0.066±0.004) nm (FWHM), is about half of what one would expect for free Ps at room temperature due to the Dicke line narrowing effect of confinement. Such measurements can be used to determine void sizes in porous films and Ps dynamics therein, and elimination of the Doppler spread of atoms in a porous film could be useful for the efficient excitation of a Ps gas.     

Laser excitation of positronium in the Paschen-Back regime

Zeeman mixing of singlet and triplet 2P states of positronium (Ps) atoms, followed by decay back to the ground state, can effectively turn a long-lived triplet atom into a short-lived singlet state, which would seem to preclude laser cooling of Ps in a magnetic field. Here we report experiments which show that, in fact, because of the large splitting of the n=2 states in a high magnetic field (the Paschen-Back regime), the amount of such mixing diminishes approximately exponentially with an increasing magnetic field >0.01 T and is essentially eliminated above ～2 T. Thus, laser cooling of Ps should be feasible at high fields, which will facilitate the production of a Ps Bose-Einstein condensate.     

Improvement of <Emphasis Type="Italic">n</Emphasis>-ZnO/<Emphasis Type="Italic">p</Emphasis>-Si photodiodes by embedding of silver nanoparticles

The photo-current of n-ZnO/p-Si heterojunction photodiodes was improved by embedding Ag nanoparticles in the interface (ZnO/nano-P_Ag/p-Si), and the ratio between photo- and dark-current increased by about three orders more than that of a n-ZnO/p-Si specimen. The improvement in the photo-current resulted from the light scattering of embedded Ag nanoparticles. The I–V curve of n-ZnO/p-Si degraded after thermal treatment (A-ZnO/p-Si) because the silicon robbed the oxygen from ZnO to form amorphous silicon dioxide and left an oxygen vacancy. Notably, the properties of ZnO/nano-P_Ag/p-Si were better in the time-dependent photoresponse under 10 V bias. Ag nanoparticles (15–20 nm) scattered the UV light randomly and increased the probability for the absorption of ZnO to enhance the properties of the photodiode.