Intramolecular Heck reactions of aryl chlorides with alkynes

We have developed a reaction that affords the selective preparation of hexahydro-2H-pyrido[2,1-a]isoquinoline dienes, allenes, or alkenes via an intramolecular Heck cyclization of an aryl chloride with an alkyne. Tricyclic isoquinoline core structures of this nature are difficult to access by alternative methods. The unsaturated product formed can be partially controlled by choice of ligand and reaction solvent.     

Pronounced negative thermal expansion from a simple structure: cubic ScF(3)

Scandium trifluoride maintains a cubic ReO(3) type structure down to at least 10 K, although the pressure at which its cubic to rhombohedral phase transition occurs drops from >0.5 GPa at ～300 K to 0.1-0.2 GPa at 50 K. At low temperatures it shows strong negative thermal expansion (NTE) (60-110 K, α(l) ≈ -14 ppm K(-1)). On heating, its coefficient of thermal expansion (CTE) smoothly increases, leading to a room temperature CTE that is similar to that of ZrW(2)O(8) and positive thermal expansion above ～1100 K. While the cubic ReO(3) structure type is often used as a simple illustration of how negative thermal expansion can arise from the thermally induced rocking of rigid structural units, ScF(3) is the first material with this structure to provide a clear experimental illustration of this mechanism for NTE.     

Pt dendrimer nanocomposites for oxygen reduction reaction in direct methanol fuel cells

Dendrimer-encapsulated Pt nanoparticles (G4OHPt) were prepared by chemical reduction at room temperature. The G4OHPt, with average diameters of ca. 2.7 nm, were characterized by X-ray diffraction, scanning electron microscopy, and thermogravimetric analysis. Electrocatalytic behavior for oxygen reduction reaction was investigated using a rotating disk electrode configuration in an acidic medium, with and without the presence of methanol (0.01, 0.1, and 1 M). Kinetic studies showed that electrodes based on Pt nanoparticles encapsulated inside the dendrimer display a higher selectivity for ORR in the presence of methanol than electrodes based on commercial Pt black catalysts. Also, the dendritic polymer confers a protective effect on the Pt in the presence of methanol, which allows its use as a cathode in a direct methanol fuel cell operating at different temperatures. Good performance was obtained at 90 °C and 2 bar of pressure with a low platinum loading on the electrode surface.     

Engineering enzyme specificity using computational design of a defined-sequence library

Engineered biosynthetic pathways have the potential to produce high-value molecules from inexpensive feedstocks, but a key limitation is engineering enzymes with high activity and specificity for new reactions. Here, we developed a method for combining structure-based computational protein design with library-based enzyme screening, in which inter-residue correlations favored by the design are encoded into a defined-sequence library. We validated this approach by engineering a glucose 6-oxidase enzyme for use in a proposed pathway to convert D-glucose into D-glucaric acid. The most active variant, identified after only one round of diversification and screening of only 10,000 wells, is approximately 400-fold more active on glucose than is the wild-type enzyme. We anticipate that this strategy will be broadly applicable to the discovery of new enzymes for engineered biological pathways.     

Low frequency deep ocean ambient noise trend in the Northeast Pacific Ocean

Concern about effects of anthropogenic noise on marine life has stimulated new studies to establish present-day ocean noise levels and compare them to noise levels from previous times. This paper reports on the trend in low-frequency (10-400 Hz) ambient noise levels and presents measurements made using a calibrated multi-element volume array at deep ocean sites in the Northeast Pacific from 1978 to 1986. The experiments provided spectral noise levels as well as horizontal and vertical noise directionality. The data presented here provide evidence that the trend derived from 1960s data extended to around 1980, but has since continued at a lower rate.     

Autoresonant excitation of antiproton plasmas

We demonstrate controllable excitation of the center-of-mass longitudinal motion of a thermal antiproton plasma using a swept-frequency autoresonant drive. When the plasma is cold, dense, and highly collective in nature, we observe that the entire system behaves as a single-particle nonlinear oscillator, as predicted by a recent theory. In contrast, only a fraction of the antiprotons in a warm plasma can be similarly excited. Antihydrogen was produced and trapped by using this technique to drive antiprotons into a positron plasma, thereby initiating atomic recombination.     

Anisotropic ion heating and tail generation during tearing mode magnetic reconnection in a high-temperature plasma

Complementary measurements of ion energy distributions in a magnetically confined high-temperature plasma show that magnetic reconnection results in both anisotropic ion heating and the generation of suprathermal ions. The anisotropy, observed in the C(+6) impurity ions, is such that the temperature perpendicular to the magnetic field is larger than the temperature parallel to the magnetic field. The suprathermal tail appears in the majority ion distribution and is well described by a power law to energies 10 times the thermal energy. These observations may offer insight into the energization process.     

Bifurcation to 3D helical magnetic equilibrium in an axisymmetric toroidal device

We report the first direct measurement of the internal magnetic field structure associated with a 3D helical equilibrium generated spontaneously in the core of an axisymmetric toroidal plasma containment device. Magnetohydrodynamic equilibrium bifurcation occurs in a reversed-field pinch when the innermost resonant magnetic perturbation grows to a large amplitude, reaching up to 8% of the mean field strength. Magnetic topology evolution is determined by measuring the Faraday effect, revealing that, as the perturbation grows, toroidal symmetry is broken and a helical equilibrium is established.     

Diffraction enhanced imaging of soft tissues

The APS hosted a two-day workshop on Catalysis Research at the APS on September 12-13, 2005. The goal of the workshop was to evaluate current catalysis-related research at the APS and to plan future directions. The outcome of the meeting will be a report with recommendations to promote new, and support current, catalysis research at the APS. The workshop was attended by 82 participants representing industry, national laboratories, and universities.