Laser-launched flyer plate and confined laser ablation for shock wave loading: validation and applications.

We present validation and some applications of two laser-driven shock wave loading techniques: laser-launched flyer plate and confined laser ablation. We characterize the flyer plate during flight and the dynamically loaded target with temporally and spatially resolved diagnostics. With transient imaging displacement interferometry, we demonstrate that the planarity (bow and tilt) of the loading induced by a spatially shaped laser pulse is within 2-7 mrad (with an average of 4+/-1 mrad), similar to that in conventional techniques including gas gun loading. Plasma heating of target is negligible, in particular, when a plasma shield is adopted. For flyer plate loading, supported shock waves can be achieved. Temporal shaping of the drive pulse in confined laser ablation allows for flexible loading, e.g., quasi-isentropic, Taylor-wave, and off-Hugoniot loading. These techniques can be utilized to investigate such dynamic responses of materials as Hugoniot elastic limit, plasticity, spall, shock roughness, equation of state, phase transition, and metallurgical characteristics of shock-recovered samples.

Three-wavelength electronic speckle pattern interferometry with the Fourier-transform method for simultaneous measurement of microstructure-scale deformations in three dimensions.

We present the simultaneous measurement of three-dimensional deformations by electronic speckle pattern interferometry using five object beams and three colors. Each color, corresponding to an orthogonal direction of displacement, is separated through dichroic filtering before being recorded by a separate CCD camera. Carrier fringes are introduced by tilting the beam path in one arm of each of the three interferometers. The measured deformation modulates these carrier fringes and is extracted using the Fourier-transform method to achieve high displacement sensitivity. The field of view is on the order of a millimeter, making the system suitable for study of microstructural deformations. We compare experimental results with calculated values to validate out-of-plane and in-plane deformation measurements and demonstrate sensitivity on the order of 10 nm.

Synthesis of phosphine containing amino acids: utilization of peptide synthesis in ligand design.

Combinatorial chemistry has recently burst on the scene as a valuable tool for the discovery of new drug candidates. The ability to synthesize hundreds of compounds for screening is a useful complement to rational drug design. There are many similarities between the design of new therapeutic agents and the development of new asymmetric ligands, the most important of which is the limitation of a rational design strategy. For this reason a program was begun that would allow the use of combinatorial technology in the development of new ligands for transition metal catalyzed asymmetric reactions. Because of the large number of catalytic reactions they are involved in the system was based around phosphine ligands. This paper reports the synthesis of phosphine derivatives of alanine, proline, and the aromatic amino acids tyrosine and hydroxyphenylglycine. Examples of the use of these amino acids in the synthesis of peptides possessing helical and beta-turn secondary structures are presented. Metal complexes of these peptide-based ligands are used in hydrogenation and alkylation reactions.

Catalysis with phosphine-containing amino acids in various "turn" motifs.

We have been actively involved in the development of parallel approaches for the discovery of phosphine ligands. Our approach has been based on the incorporation of phosphine-containing amino acids into peptide sequences that are designed to have stable secondary structures. We have examined helical and turn secondary structures and have reported that alkylation of cyclopentenyl acetate with dimethylmalonate can be catalyzed in high enantiomeric excess (ee) with a beta-turn-based ligand. The importance of the peptide secondary structure was demonstrated through the synthesis of a series of peptide ligands where the nature of the turn-forming residues was probed. Additionally, other turn-forming units and a variety of different phosphine-containing amino acids have been examined for their ability to control the selectivity of the allylation reaction. This paper reports the results obtained through the examination of different turn motifs as well as different phosphine substitutions on the "best" turn sequence, Pps-Pro-d-Xxx-Pps.

High asymmetric induction with beta-turn-derived palladium phosphine complexes.

[reaction: see text] Work toward the development of a bisphosphine ligand system for the palladium-catalyzed addition to cyclic allyl acetates is reported. A parallel approach using phosphine-containing amino acids in conjunction with natural amino acids was used to develop a selective ligand system. The ligand system was examined while attached to the polymer support as well as in solution. Selectivites with the difficult substrate 3-acetoxycyclopentene of up to 95% ee are reported.