New chiral phosphine-phosphite ligands in the enantioselective palladium-catalyzed allylic alkylation

A series of chiral phosphine-phosphite ligands 1-6 have been synthesized and used in the enantioselective palladium-catalyzed reaction of rac-1,3-diphenyl-2-propenyl acetate with dimethyl malonate as nucleophile. Ligands 1a, 2, 3, 5a, 6a, and 6b have been synthesized starting from racemic tert-butylphenylphosphinoborane. The use of dynamically resolved Li phosphide (-)-sparteine provided the optically pure ligands. Crystals of the allylpalladium (6a) complex were obtained, suitable for X-ray crystal structure determination. The X-ray crystal structure of the allylpalladium (6a) complex revealed a longer palladium-carbon bond distance trans to the phosphine moiety indicating that the attack of the nucleophile takes place at the carbon trans to the phosphine moiety. This was confirmed by the fact that the phosphine moiety did not affect the enantioselectivity directly. Under mild reaction conditions, enantioselectivities up to 83% were obtained (25 degrees C) with ligand 1e. Systematic variation of the ligand bridge and the phosphite moiety showed that the configuration of the product is controlled by the atropisomerism of the biphenyl substituent at the phosphite moiety. The conformation of the biphenyl group, in turn, is controlled by the substituent at the chiral carbon in the bridge. Ligands with large bite angles yielded higher enantioselectivities.     

Aminosulf(ox)ides as ligands for Iridium(I)-catalyzed asymmetric transfer hydrogenation

A new class of efficient catalysts was developed for the asymmetric transfer hydrogenation of unsymmetrical ketones. A series of chiral N,S-chelates (6-22) was synthesized to serve as ligands in the iridium(I)-catalyzed reduction of ketones. Both formic acid and 2-propanol proved to be suitable as hydrogen donors. Sulfoxidation of an (R)-cysteine-based aminosulfide provided a diastereomeric ligand family containing a chiral sulfur atom. The two chiral centers of these ligands showed a clear effect of chiral cooperativity. In addition, aminosulfides containing two asymmetric carbon atoms in the backbone were synthesized. Both the sulfoxide-containing beta-amino alcohols and the aminosulfides derived from 1,2-disubstituted amino alcohols gave rise to high reaction rates and moderate to excellent enantioselectivities in the reduction of various ketones. The enantioselective outcome of the reaction was favorably affected by selecting the most appropriate hydrogen donor. Enantioselectivities of up to 97% were reached in the reduction of aryl-alkyl ketones.     

Novel search for heavy nu mixing from the beta+ decay of 38mK confined in an atom trap

A new technique, full neutrino momentum reconstruction, is used to set limits on the admixture of heavy neutrinos into the electron neutrino. We measure coincidences between nuclear recoils and positrons from the beta decay of trapped radioactive atoms and deduce the neutrino momentum. A search for peaks in the reconstructed recoil time-of-flight spectrum as a function of positron energy is performed. The admixture upper limits range from 4 x 10(-3) to 2 x 10(-2) and are the best direct limits for neutrinos (as opposed to antineutrinos) for the mass region of 0.7 to 3.5 MeV.     

Chemical oxidation of endohedral metallofullerenes: identification and separation of distinct classes

Chemical oxidation is useful for solubilizing and separating endohedral metallofullerenes, as demonstrated here by a separation of three categories of Gd@C2n species and by the solubilization of Tm@C60+ and Tm@C70+ for the first time.     

Gapless color superconductivity

We present the dispersion relations for quasiparticle excitations about the color-flavor locked ground state of QCD at high baryon density. In the presence of condensates which pair light and strange quarks there need not be an energy gap in the quasiparticle spectrum. This raises the possibility of gapless color superconductivity, with a Meissner effect but no minimum excitation energy. Analysis within a toy model suggests that gapless color superconductivity may occur only as a metastable phase.     

The effects of selective consonant amplification on sentence recognition in noise by hearing-impaired listeners

Weak consonants (e.g., stops) are more susceptible to noise than vowels, owing partially to their lower intensity. This raises the question whether hearing-impaired (HI) listeners are able to perceive (and utilize effectively) the high-frequency cues present in consonants. To answer this question, HI listeners were presented with clean (noise absent) weak consonants in otherwise noise-corrupted sentences. Results indicated that HI listeners received significant benefit in intelligibility (4 dB decrease in speech reception threshold) when they had access to clean consonant information. At extremely low signal-to-noise ratio (SNR) levels, however, HI listeners received only 64% of the benefit obtained by normal-hearing listeners. This lack of equitable benefit was investigated in Experiment 2 by testing the hypothesis that the high-frequency cues present in consonants were not audible to HI listeners. This was tested by selectively amplifying the noisy consonants while leaving the noisy sonorant sounds (e.g., vowels) unaltered. Listening tests indicated small (～10%), but statistically significant, improvements in intelligibility at low SNR conditions when the consonants were amplified in the high-frequency region. Selective consonant amplification provided reliable low-frequency acoustic landmarks that in turn facilitated a better lexical segmentation of the speech stream and contributed to the small improvement in intelligibility.     

Beta–neutrino correlation experiments on laser trapped 38mK, 37K

Laser trapping and cooling techniques are now being applied to the study of nuclear β-decay at several labs. A magneto-optical trap (MOT) provides a localized source of atoms suspended in space, so the low-energy recoiling nuclei can freely escape and be detected in coincidence with the β. This allows reconstruction of the neutrino momentum, and the deduction of the β-v correlation in a more direct fashion than previously possible. In addition, the nuclei can be polarized by atomic techniques, opening a new class of spin correlation measurements to test the degree to which parity is maximally violated in the weak interaction. Our present experiment has detected several hundred thousand recoil-β⁺ coincidences from the 0⁺ → 0⁺ pure Fermi decay of ^38mK, produced at the on-line isotope separators TISOL and ISAC at TRIUMF. Our goal is to set constraints on non-Standard Model scalar bosons competitive with high-energy colliders and more conventional β-v correlation experiments. This revised version was published online in August 2006 with corrections to the Cover Date.     

Ensembles of engineered cardiac tissues for physiological and pharmacological study: heart on a chip

Traditionally, muscle physiology experiments require multiple tissue samples to obtain morphometric, electrophysiological, and contractility data. Furthermore, these experiments are commonly completed one at a time on cover slips of single cells, isotropic monolayers, or in isolated muscle strips. In all of these cases, variability of the samples hinders quantitative comparisons among experimental groups. Here, we report the design of a "heart on a chip" that exploits muscular thin film technology--biohybrid constructs of an engineered, anisotropic ventricular myocardium on an elastomeric thin film--to measure contractility, combined with a quantification of action potential propagation, and cytoskeletal architecture in multiple tissues in the same experiment. We report techniques for real-time data collection and analysis during pharmacological intervention. The chip is an efficient means of measuring structure-function relationships in constructs that replicate the hierarchical tissue architectures of laminar cardiac muscle.