Asymmetric induction in Diels-Alder reactions of o-quinodimethanes

Asymmetric inductive effects have been measured on the Diels-Alder reaction of dimethyl fumarate with o-quinodimethane bearing a chiral α-alkoxy group. The chiral substituents used were 1-phenylethoxy, 2-(1-phenyl)propoxy, 1-(2-phenyl)propoxy, 2-(4-phenyl)-butoxy and 1-cyclohexylethoxy. The greatest asymmetric induction was found with the first of these chiral substituents (47% ee). A π-stacking effect, previously suggested as the rationale for asymmetric induction in a similar system, is shown to be inconsistent with the results from this study.     

New source of dense, cryogenic positron plasmas

We have developed a new method, based on the ballistic transfer of preaccumulated plasmas, to obtain large and dense positron plasmas in a cryogenic environment. The method involves transferring plasmas emanating from a region with a low magnetic field (0.14 T) and relatively high pressure (10(-9) mbar) into a 15 K Penning-Malmberg trap immersed in a 3 T magnetic field with a base pressure better than 10(-13) mbar. The achieved positron accumulation rate in the high field cryogenic trap is more than one and a half orders of magnitude higher than the previous most efficient UHV compatible scheme. Subsequent stacking resulted in a plasma containing more than 1.2 x 10(9) positrons, which is a factor 4 higher than previously reported. Using a rotating wall electric field, plasmas containing about 20 x 10(6) positrons were compressed to a density of 2.6 x 10(10) cm(-3). This is a factor of 6 improvement over earlier measurements.     

Optical trirefringence in photonic crystal waveguides

We demonstrate that 2D photonic crystals can possess optical trirefringence in which there are six field orientations for which linear incident light is not perturbed on reflection or transmission. Such a property is rigorously forbidden in homogeneous nonmagnetic dielectrics which can possess only optical birefringence. We experimentally demonstrate this phenomena in silicon-based mesostructures formed from photonic crystal waveguides embedded in a Fabry-Perot cavity. Multirefringence is controlled by the presence of submicron dielectric patterning and is well explained by an exact scattering matrix theory.     

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.     

An Accurate In Vitro Model of the E. coli Envelope

Gram‐negative bacteria are an increasingly serious source of antibiotic‐resistant infections, partly owing to their characteristic protective envelope. This complex, 20 nm thick barrier includes a highly impermeable, asymmetric bilayer outer membrane (OM), which plays a pivotal role in resisting antibacterial chemotherapy. Nevertheless, the OM molecular structure and its dynamics are poorly understood because the structure is difficult to recreate or study in vitro. The successful formation and characterization of a fully asymmetric model envelope using Langmuir–Blodgett and Langmuir–Schaefer methods is now reported. Neutron reflectivity and isotopic labeling confirmed the expected structure and asymmetry and showed that experiments with antibacterial proteins reproduced published in vivo behavior. By closely recreating natural OM behavior, this model provides a much needed robust system for antibiotic development.     

TIRF microscopy as a screening method for non-specific binding on surfaces

We report a method for studying nanoparticle-biosensor surface interactions based on total internal reflection fluorescence (TIRF) microscopy. We demonstrate that this simple technique allows for high throughput screening of non-specific adsorption (NSA) of nanoparticles on surfaces of different chemical composition. Binding events between fluorescent nanoparticles and functionalized Zeonor? surfaces are observed in real-time, giving a measure of the attractive or repulsive properties of the surface and the kinetics of the interaction. Three types of coatings have been studied: one containing a polymerized aminosilane network with terminal -NH(2) groups, a second film with a high density of -COOH surface groups and the third with sterically restraining branched poly(ethylene)glycol (PEG) functionality. TIRF microscopy revealed that the NSA of nanoparticles with negative surface charge on such modified coatings decreased in the following order -NH(2)>-branched PEG>-COOH. The surface specificity of the technique also allows discrimination of the degree of NSA of the same surface at different pH.     

The production oflow energy positrons and positronium

A summary is given of the techniques of positron and positronium production which may be of relevance to the production of antihydrogen atoms at low kinetic energies. Topics covered include positron beams from radioactive isotopes and via pair production at electron accelerators, methods for trapping and accumulating positrons and prospects for the use of slow positrons to create antihydrogen at CERN.     

o-quinodimethanes from 3,6-dihydrobenzo[b]-1,2-oxathiin-2-oxides

A two step synthesis of 3,6-dihydrobenzo[b]-1,2-oxathiin-2-oxide 5a from o-tolual-dehyde via the photochemically produced 1-hydroxy-1,3-dihydrobenzo[b]thiophene-2,2-dioxide is described. Analogous syntheses of 3 and 6 substituted derivatives of the benzosultines 5 have also been carried out. The feasibility of using these benzosultines as o-quinodimethane precursors has been tested by thermalizing the phenyl sultine 5c in refluxing cyclohexane in the presence of dimethyl fumarate, dimethyl maleate and methyl crotonate to form cycloadducts, stereospecifically and in good yield. The stereochemistry of addition of maleate appears to be exclusively “exo” in conflict with earlier studies on Diels-Alder reactions of α-aryl-o-quino-dimethanes.