Design and Asymmetric Synthesis of beta-Strand Peptidomimetics

We describe the asymmetric synthesis of non-peptidic compounds that feature rigid backbone conformations and present various side-chain functions. The key step in the synthesis of these compounds is the C-acylation of an appropriate ketone with a suitably protected aspartic acid derivative. The resulting dipeptide modules may be connected to form tetrapeptide mimics. Specifically is described the mimicry of a four-residue segment of CD4, the cellular receptor of HIV-1. The design was based on molecular modeling and the X-ray crystal structures of CD4 and intended to present the most important side chains and backbone elements of the Phe43-Lys46 segment.     

Photochemical Reactions of Alkyl Phenylglyoxylates(1)

Three new photoproducts, ethyl O-benzoyl mandelate (5a), ethyl O-acetylmandelate (6a), and biphenyl triketone (7a) are isolated and identified in the reactions of ethyl phenylglyoxylate (1a) in benzene. Quantum yields and initial rate constants of product formation are shown to be concentration dependent. For the formation of carbonyl product 3 at lower starting material concentrations (<0.01 M), quantum yields greater than 1 are observed. Variations in the quantum yields as a function of reaction time are due to the accumulation of alpha-hydroxyphenyl ketene (D). The relative reactivities of triplet excited states of phenylglyoxylates 1 and phenyl ketones are compared. A mechanism involving both intramolecular gamma-H abstraction and intermolecular H abstraction, which leads to radical chain reaction, is proposed. Rate constants for intramolecular gamma-H abstraction (k(N)) and intermolecular H abstraction (k(I)) of methyl phenylglyoxylate (1d) are measured.     

R-matrix methods for studying nuclear effects in μCF

Properties ofR-matrix theory that are useful for studying muon-catalyzed fusion reactions are reviewed, and applications to the dt system are discussed, using both improved adiabatic and non-adiabatic (variational) wave functions. We give complex eigenvalues and - sticking fractions for the (L, v)=(0,0) and (0, 1) states of dt using variational Hamiltonian matrix elements that have been properly symmetrized by means of the Block operator. Expressions for the fusion rate and - sticking fraction are developed from a time-dependent theory that uses the complex-energy states corresponding to the poles of the systemS-matrix. These are shown to reduce with the appropriate approximations to the expressions and values commonly used. Additional nuclear effects on these quantities can easily be studied within the framework developed, but they are not expected to be large.     

A five-channel grating spectrometer for millimeter-waves

A five-channel grating spectrometer for use in millimeter wave band (25100GHz) is described with its design theory of optical path, and measured results of insertion loss and resolving power.