Efficient and practical Ag-catalyzed cycloadditions between arylimines and the Danishefsky diene

An efficient Ag-catalyzed method for asymmetric addition of the Danishefsky diene to various aryl imines to afford cycloadducts in > or =89% ee and > or =85% isolated yield is reported. Reactions are effected with 0.1-1 mol % catalyst (4 degrees C), and the chiral ligand is readily prepared from commercially available materials, including the inexpensive i-Leu. These catalytic asymmetric cycloadditions can be carried out without the use of solvent or with undistilled THF in air. A first generation supported chiral catalyst that effectively promotes the cycloaddition reaction and can be recycled (five cycles) is described.     

Electronic and vibrational second-order nonlinear optical properties of protein secondary structural motifs

A perturbation theory approach was developed for predicting the vibrational and electronic second-order nonlinear optical (NLO) polarizabilities of materials and macromolecules comprised of many coupled chromophores, with an emphasis on common protein secondary structural motifs. The polarization-dependent NLO properties of electronic and vibrational transitions in assemblies of amide chromophores comprising the polypeptide backbones of proteins were found to be accurately recovered in quantum chemical calculations by treating the coupling between adjacent oscillators perturbatively. A novel diagrammatic approach was developed to provide an intuitive visual means of interpreting the results of the perturbation theory calculations. Using this approach, the chiral and achiral polarization-dependent electronic SHG, isotropic SFG, and vibrational SFG nonlinear optical activities of protein structures were predicted and interpreted within the context of simple orientational models.     

Polymers for catalytic cation radical chemistry

Cation radical polymers which have cation radical functions at up to 5% of the poly(styrene) monomer sites have been prepared, and their effectiveness in catalyzing the cation radical Diels-Alder reaction is demonstrated.     

Bimetric general relativity and cosmology

A modification of the general relativity theory is proposed (bimetric general relativity) in which, in addition to the usual metric tensorg _v describing the space-time geometry and gravitation, there exists also a background metric tensor _v The latter describes the space-time of the universe if no matter were present and is taken to correspond to a space-time of constant curvature with positive spatial curvature (k=1). Field equations are obtained, and these agree with the Einstein equations for systems that are small compared to the size of the universe, such as the solar system. Energy considerations lead to a generalized form of the De Donder condition. One can set up simple isotropic closed models of the universe which first contract and then expand without going through a singular state. It is suggested that the maximum density of the universe was of the order ofc ^{5 –1} G ^–210⁹³ g/cm³. The expansion from such a high-density state is similar to that from the singular state (big bang) of the general relativity models. In the case of the dust-filled model one can fit the parameters to present cosmological data. Using the radiation-filled model to describe the early history of the universe, one can account for the cosmic abundance of helium and other light elements in the same way as in ordinary general relativity.     

Preparation and photoelectron spectrum of the glycine molecular anion: assignment to a dipole-bound electron species with a high-dipole moment, non-zwitterionic form of the neutral core

We report the gas-phase preparation of negatively charged glycine as well as the Gly(H(2)O)(1,2) (-) complexes by entrainment of the neutral precursor into an ionized supersonic expansion tuned to optimize the (H(2)O)(n) (-)Ar(m) clusters. The photoelectron spectrum of Gly(-) displays the signature of a dipole-bound species, with sufficient vibrational fine structure to characterize the core neutral as a higher energy, non-zwitterionic isomer of the amino acid.     

Weyl's geometry and physics

It is proposed to remove the difficulty of nonitegrability of length in the Weyl geometry by modifying the law of parallel displacement and using standard vectors. The field equations are derived from a variational principle slightly different from that of Dirac and involving a parameter . For =0 one has the electromagnetic field. For <0 there is a vector meson field. This could be the electromagnetic field with finite-mass photons, or it could be a meson field providing the missing mass of the universe. In cosmological models the two natural gauges are the Einstein gauge and the cosmic gauge. With the latter the universe has a fixed size, but the sizes of small systems decrease with time and their masses and energies increase, thus producing the Hubble effect. The field of a particle in this gauge is investigated, and it leads to an interesting solution of the Einstein equations that raises a question about the Schwarzschild solution.     

Efficiency enhancement of high power vacuum BWO's using nonuniformslow wave structures

The Sinus-6, a high-power relativistic repetitively-pulsed electron beam accelerator, is used to drive various slow wave structures in a BWO configuration in vacuum. Peak output power of about 550 MW at 9.45 GHz was radiated in an 8-ns pulse. We describe experiments which study the relative efficiencies of microwave generation from a two-stage nonuniform amplitude slow wave structure and its variations without an initial stage. Experimental results are compared with 2.5 D particle-in-cell computer simulations. Our results suggest that prebunching the electron beam in the initial section of the nonuniform BWO results in increased microwave generation efficiency, Furthermore, simulations reveal that, in addition to the backward propagating surface harmonic of the TM₀₁ mode, backward and forward propagating volume harmonics with phase velocity twice that of the surface harmonic play an important role in high-power microwave generation and radiation     

Passive mode-locking by use of waveguide arrays

A novel mode-locking technique is presented in which the intensity-dependent spatial coupling dynamics of a waveguide array is used to achieve temporal mode-locking in a passive optical fiber laser. By use of the discrete, nearest-neighbor spatial coupling of the waveguide array, low-intensity light can be transferred to the neighboring waveguides and ejected (attenuated) from the laser cavity. In contrast, higher-intensity light is self-focused in the waveguide and remains largely unaffected. Numerical studies of this pulse shaping mechanism (intensity discrimination) show that using current waveguide arrays and standard optical fiber technology produces stable and robust mode-locked soliton-like pulses.