Microwave-assisted, solid-phase synthesis of a chiral 1,2,3,4-tetrahydro-quinoline library

The synergy of a solution-phase preparation of scaffolds with a solid-phase combinatorial synthesis let to develop an efficient route to a small library of chiral, highly functionalized tetrahydroisoquinolines. Both loading on the Merrifield resin and the key acid-catalyzed Pictet-Spengler condensation were efficiently promoted by microwave irradiation. The library was designed such that up to five points of diversity would be potentially introduced, making the strategy in principle suitable for generation of a large number of compounds.     

Microbead chemical switches: an approach to detection of reactive organophosphate chemical warfare agent vapors

In this article, we describe the preparation and application of microbeads that exhibit a "turn on" fluorescence response within seconds of exposure to diethyl chlorophosphate (DCP) vapor. This sensing approach is modeled after the mechanism for acetylcholinesterase enzyme activity inhibition and uses a specific and irreversible reaction between phosphoryl halides and a fluorescent indicator. The microbeads are fabricated by adsorbing fluoresceinamine (FLA) onto carboxylate-functionalized polymer microbeads coated with poly(2-vinylpyridine) (PVP). When the microbeads are subjected to DCP vapor, the conversion of FLA into a phosphoramide causes a rapid and intense fluorescence increase. The PVP layer provides a high density of proton-accepting pyridine nitrogen sites that neutralize the HCl released during the reaction, thereby maintaining high product fluorescence, even after vapor exposure. No significant response is observed when the microbeads are subjected to other nerve agent simulants, a mustard gas simulant, and volatile organics. The size, sensitivity, and subsecond response of these microbeads make them suitable for nerve agent vapor detection and inclusion into microbead sensor arrays.     

Environmentally induced quantum dynamical phase transition in the spin swapping operation

Quantum information processing relies on coherent quantum dynamics for a precise control of its basic operations. A swapping gate in a two-spin system exchanges the degenerate states |(up arrow, down arrow)> and |(down arrow, up arrow)>. In NMR, this is achieved turning on and off the spin-spin interaction b=DeltaE that splits the energy levels and induces an oscillation with a natural frequency DeltaE/Planck's. Interaction of strength Planck's/tau(SE), with an environment of neighboring spins, degrades this oscillation within a decoherence time scale tau(phi). While the experimental frequency omega and decoherence time tau(phi) were expected to be roughly proportional to b/Planck's and tau(SE), respectively, we present here experiments that show drastic deviations in both omega and tau(phi). By solving the many spin dynamics, we prove that the swapping regime is restricted to DeltaEtau(SE) similar or greater than Planck's. Beyond a critical interaction with the environment the swapping freezes and the decoherence rate drops as 1/tau(phi) proportional to (b/Planck's)2tau(SE). The transition between quantum dynamical phases occurs when omega proportional to sqrt (b/Planck's)2-(k/tau(SE)2 becomes imaginary, resembling an overdamped classical oscillator. Here, 0< or =k2< or =1 depends only on the anisotropy of the system-environment interaction, being 0 for isotropic and 1 for XY interactions. This critical onset of a phase dominated by the quantum Zeno effect opens up new opportunities for controlling quantum dynamics.     

Nilfactors of ℝ m and configurations in sets of positive upper density in ℝ m

We use ergodic theoretic tools to solve a classical problem in geometric Ramsey theory. LetE be a measurable subset of ℝ ^m , with . LetV = {0,v ₁,...,v _k} ⊂ ℝ^m. We show that fort large enough, we can find an isometric copy oftV arbitrarily close toE. This is a generalization of a theorem of Furstenberg, Katznelson and Weiss [FuKaW] showing a similar property form=k=2.