Highly diastereoselective catalytic Meerwein-Ponndorf-Verley reductions

[reaction: see text] Very practical synthesis of ephedrine analogues in high yields and enantiopurity was realized by a highly diastereoselective Meerwein-Ponndorf-Verley (MPV) reduction of protected alpha-amino aromatic ketones using catalytic aluminum isopropoxide. The high anti selectivity resulted from the chelation of the nitrogen anion to the aluminum. In contrast, high syn selectivity was obtained with alpha-alkoxy ketones and other compounds via Felkin-Ahn control.     

Preparation and characterization of a suite of ephedra-containing standard reference materials

The National Institute of Standards and Technology, the U.S. Food and Drug Administration, Center for Drug Evaluation and Research and Center for Food Safety and Applied Nutrition, and the National Institutes of Health, Office of Dietary Supplements, are collaborating to produce a series of Standard Reference Materials (SRMs) for dietary supplements. A suite of ephedra materials is the first in the series, and this paper describes the acquisition, preparation, and value assignment of these materials: SRMs 3240 Ephedra sinica Stapf Aerial Parts, 3241 E. sinica Stapf Native Extract, 3242 E. sinica Stapf Commercial Extract, 3243 Ephedra-Containing Solid Oral Dosage Form, and 3244 Ephedra-Containing Protein Powder. Values are assigned for ephedrine alkaloids and toxic elements in all 5 materials. Values are assigned for other analytes (e.g., caffeine, nutrient elements, proximates, etc.) in some of the materials, as appropriate. Materials in this suite of SRMs are intended for use as primary control materials when values are assigned to in-house (secondary) control materials and for validation of analytical methods for the measurement of alkaloids, toxic elements, and, in the case of SRM 3244, nutrients in similar materials.     

A confocal set‐up for micro‐XRF and XAFS experiments using diamond‐anvil cells

A confocal set‐up is presented that improves micro‐XRF and XAFS experiments with high‐pressure diamond‐anvil cells (DACs). In this experiment a probing volume is defined by the focus of the incoming synchrotron radiation beam and that of a polycapillary X‐ray half‐lens with a very long working distance, which is placed in front of the fluorescence detector. This set‐up enhances the quality of the fluorescence and XAFS spectra, and thus the sensitivity for detecting elements at low concentrations. It efficiently suppresses signal from outside the sample chamber, which stems from elastic and inelastic scattering of the incoming beam by the diamond anvils as well as from excitation of fluorescence from the body of the DAC.     

A new synthetic approach to functionalize pyrimido[4,5-<Emphasis Type="Italic">b</Emphasis>]quinoline-2,4(1<Emphasis Type="Italic">H</Emphasis>,3<Emphasis Type="Italic">H</Emphasis>)-diones via a three-component one-pot reaction

Functionalized pyrimido[4,5-b]quinoline-2,4 (1H,3H)-diones were synthesized by a three-component one-pot reaction involving barbituric acid, aldehydes, and anilines. The use of commercially available anilines allowed the facile syntheses of pyrimido[4,5-b]quinolinediones substituted in all the positions on the benzene ring with electron donor or electron withdrawing groups. This straightforward method circumvents the preparation of unstable substituted 2-aminobenzaldehydes that limits the scope of previously described syntheses. Furthermore, access to the 5-substituted derivatives is now also possible starting from aliphatic or aromatic aldehydes. Our strategy and methodology offer significant and practical improvements over other methodologies.     

Differential activation of the lateral premotor cortex during action observation

Background  

Action observation leads to neural activation of the human premotor cortex. This study examined how the level of motor expertise (expert vs. novice) in ballroom dancing and the visual viewpoint (internal vs. external viewpoint) influence this activation within different parts of this area of the brain.     

Steroid receptor expression in the fish inner earvaries with sex,social status,and reproductive state

Background  

Gonadal and stress-related steroid hormones are known to influence auditory function across vertebrates but the cellular and molecular mechanisms responsible for steroid-mediated auditory plasticity at the level of the inner ear remain unknown. The presence of steroid receptors in the ear suggests a direct pathway for hormones to act on the peripheral auditory system, but little is known about which receptors are expressed in the ear or whether their expression levels change with internal physiological state or external social cues. We used qRT-PCR to measure mRNA expression levels of multiple steroid receptor subtypes (estrogen receptors: ERα, ERβa, ERβb; androgen receptors: ARα, ARβ; corticosteroid receptors: GR2, GR1a/b, MR) and aromatase in the main hearing organ of the inner ear (saccule) in the highly social African cichlid fish Astatotilapia burtoni, and tested whether these receptor levels were correlated with circulating steroid concentrations.     

Self‐Aligned Micropatterns of Bifunctional Polymer Surfaces with Independent Chemical and Topographical Contrast

Bifunctional surfaces are micropatterned using a self‐aligned, dual‐purpose lithographic mask and pairs of conformally deposited iCVD polymers. A first layer is deposited, then physically masked and etched in oxygen plasma. A second layer is deposited with the mask still in place. Lift‐off reveals the micropatterned surface. The thicknesses of the two layers are independently controlled so that the resultant surface displays both chemical and topographical contrast. The patterning scheme is independent of the polymers used and order of deposition. We use this scheme to create surfaces that spatially confine microcondensation, as well as chemical functionality. We also demonstrate microwells whose depth can be altered in response to a water stimulus.

     

Recovery of distortion-product otoacoustic emissions after a 2-kHz monaural sound-exposure in humans: effects on fine structures

A better understanding of the vulnerability of the fine structures of distortion-product otoacoustic emissions (DPOAEs) after acoustic overexposure may improve the knowledge about DPOAE generation, cochlear damage, and lead to more efficient diagnostic tools. It is studied whether the DPOAE fine structures of 16 normal-hearing human subjects are systematically affected after a moderate monaural sound-exposure of 10 min to a 2-kHz tone normalized to an exposure level L(EX,8h) of 80 dBA. DPOAEs were measured before and in the following 70 min after the exposure. The experimental protocol allowed measurements with high time and frequency resolution in a 1/3-octave band centered at 3 kHz. On average, DPOAE levels were reduced approximately 5 dB in the entire measured frequency-range. Statistically significant differences in pre- and post-exposure DPOAE levels were observed up to 70 min after the end of the sound exposure. The results show that the effects on fine structures are highly individual and no systematic change was observed.     

Measurement of hard X-ray coherence in the presence of a rotating random-phase-screen diffuser

A suitably large coherence area is important in coherent X-ray optics, when using techniques such as interferometry or phase contrast imaging (PCI). The work done by Suzuki using a prism interferometer to measure X-ray coherence at 12.4 keV [1] is here extended to consider the use of a diffuser at the bio-medical imaging energy of 25 keV. In order to achieve a broader, more even X-ray field and eliminate speckle, a spinning piece of paper may be used as a rotating random-phase screen to diffuse the hard X-ray beam, but this will concomitantly decrease the magnitude of the complex degree of second-order coherence. We also study the effect of source size and source-to-sample distance on coherence, where imaging area and required flux must be considered. Coherence measurements at the 20XU beamline at the SPring-8 synchrotron are compared to results from wave-optical computer modelling. These show that while the diffuser will decrease the magnitude of the complex degree of coherence, further free-space propagation will lessen this effect. In the design of an experiment, the collimating slit size and use of a diffuser must therefore be balanced with distance from the source, in order to maximise coherence while maintaining the desired field of view and exposure time.     

Reconstruction algorithms applied to in-line Gabor digital holographic microscopy

This paper investigates the application of Fresnel based numerical algorithms for the reconstruction of Gabor in-line holograms. We focus on the two most widely used Fresnel approximation algorithms, the direct method and the angular spectrum method. Both algorithms involve calculating a Fresnel integral, but they accomplish it in fundamentally different ways. The algorithms perform differently for different physical parameters such as distance, CCD pixel size, and so on. We investigate the constraints for the algorithms when applied to in-line Gabor digital holographic microscopy. We show why the algorithms fail in some instances and how to alter them in order to obtain useful images of the microscopic specimen. We verify the altered algorithms using an optically captured digital hologram.