Non-protein amino acids in peptide design

An overview of the use of non-protein amino acids in the design of conformationally well-defined peptides, based on work from the author’s laboratory, is discussed. The crystal structures of several designed oligopeptides illustrate the useα-aminoisobutyric acid (Aib) in the construction of helices, D-amino acids in the design of helix termination segments and^DPro-Xxx segments for nucleating ofβ-hairpin structures.β- andγ-amino acid residues have been used to expand the range of designed polypeptide structures. Dedicated to Professor C N R Rao on his 70th birthday     

Microwave-accelerated conjugate addition of aldehydes to α,β-unsaturated ketones

Aldehydes undergo smooth conjugate addition to α,β-unsaturated ketones in the presence of 5-(2-hydroxyethyl)-1,3-thiazolium halides and DBU adsorbed onto the surface of basic alumina under microwave irradiation and solvent-free conditions to afford 1,4-diketones in enhanced yields and reduced reaction times compared to conventional methods.     

Addition of Bromotrichloromethane and Tetrachloromethane to cis-Cyclooctene,Cyclohexene, and Norbornadiene in the Presence of Palladium(II) Complexes

Addition of bromotrichloromethane and tetrachloromethane to alkenes in the presence of palladium(II) complexes begins with single-electron transfer from the palladium atom to polyhalomethane molecule, followed by fragmentation of the radical anion thus formed and generation of trichloromethyl radical. Halogen transfer to a carbon-centered radical arising from addition of trichloromethyl radical at the double bond occurs both from the polyhalomethane molecule and from halide palladium complex.     

Synthesis and Structure of Mixed Phosphonium-iodonium Ylide

A mixed phosphonium-iodonium ylide, phenyliodoniumethoxycarbonylmethylenetriphenylphosphorane borofluoride, was synthesized. Its structure was established by means of X-ray diffraction analysis. Temperature dependence of ¹H, ¹³C, and ³¹P spectra of the ylide synthesized was investigated. A dynamic equilibrium between Z and E-isomers was observed.     

Three-dimensional structure of Saccharomyces cerevisiae inorganic pyrophosphatase complexed with cobalt and phosphate ions

Crystals of Saccharomyces cerevisiae inorganic pyrophosphatase suitable for X-ray diffraction study were grown by cocrystallization of the enzyme with cobalt chloride and imidodiphosphate. Saccharomyces cerevisiae is a metal-dependent enzyme which catalyzes hydrolysis of inorganic pyrophosphate to orthophosphate. The three-dimensional structure of this enzyme was solved by the molecular-replacement method and refined at 1.8 Å resolution to an R factor of 19.5%. Cobalt and phosphate ions were revealed in the active centers of both identical subunits (A and B) of the pyrophosphatase molecule. In subunit B, a water molecule was found between two cobalt ions. It is believed that this water molecule acts as an attacking nucleophile in the enzymatic cleavage of the pyrophosphate bond. It was demonstrated that cobalt ions and a phosphate group occupy only part of the potential binding sites (two chemically identical and crystallographically independent subunits have different binding sites). The arrangement of ligands and the structure of the nucleophile-binding site are discussed in relation to the mechanism of action of the enzyme and the nature of the metal activator.     

Retardation characteristics and birefringence of a multiple-order crystalline quartz plate

A crystalline quartz plate of thickness 1.070 mm is calibrated between 370 and 794 nm. Throughout this spectral interval, the retardance varied by 32π and the plate introduced quarterwave retardance 16 times at different wavelengths. The birefringence (n_e−n_o) of crystalline quartz was calculated as a single quantity and varied from 0.00971 at 370 nm to 0.00891 at 794 nm. All measurements were carried out at 23°C.     

Performance of a CW pumped Nd:YVO4 amplifier with kHz pulses

Until recently, simple and reliable high repetition-rate laser sources with nanosecond pulses much shorter than from conventional A-O Q-switch lasers were not available. However over the past 2 years we have developed such lasers based on proprietary fast E-O switching technology, which allows designs delivering 1 ns pulses and subnanosecond jitter for good synchronisation. The technology provides pulses with multi-kW peak power and repetition-rates to >100 kHz.Most recently, the performance of these short pulse lasers has been developed further by implementing oscillator/amplifier (master oscillator and power amplifier, MOPA) technology which increases the output to >1 W average power. Here we report on a simple model that has been used to predict the performance of the CW pumped Nd:YVO₄ amplifier used in the MOPA laser. The model is based on the well-known expressions for the saturated gain applying to laser pulses, but more usually applied to pulse-excited amplifiers. The model is shown to allow a good interpretation of the amplifier behaviour for kHz pulses and to be a useful tool for predicting the performance of the MOPA laser.     

Photoinduced intramolecular electron-transfer reactions in carbazole-fullerene and phenothiazine-fullerene linked compounds in benzene and benzonitrile as studied by fluorescence, transient absorption, time-resolved EPR, and magnetic field effects

Photoinduced intramolecular electron-transfer reactions in carbazole (Cz)-fullerene (C₆₀) (Cz(8)C₆₀) and phenothiazine (Ph)-C₆₀ (Ph(n)C₆₀ (n=8, 10, 12)) linked compounds have been investigated in benzene and benzonitrile by fluorescence, transient absorption, and time-resolved electron paramagnetic resonance measurements, and by magnetic field effects on the decay rate constants of the photogenerated biradicals. In benzonitrile, photoinduced intramolecular electron transfer from Cz to the singlet excited state of C₆₀ (¹C₆₀ ^*) occurred in Cz(8)C₆₀, but not to the triplet excited state (³C₆₀ ^*), while the intramolecular electron-transfer to both¹C₆₀ ^* and³C₆₀ ^* occurred in Ph(n)C₆₀ (n=8, 10, 12). In benzene, on the other hand, no electron transfer to both¹C₆₀ ^* and³C₆₀ ^* took place in all linked compounds. These results were interpreted in terms of the different Gibbs free energy changes in the two solvents.     

Composite polymeric electrolytes based on PMMA-LiCF3SO3-SiO2

Preliminary results on the mechanical, optical and electrical properties of composite gel electrolytes (CGEs) with fumed silica (SiO₂) as a filler added to gel polymeric electrolyte (GPE) based on PMMA, LiCF₃SO₃ and PC are presented in this paper. Added fumed silica is seen to enhance the mechanical properties of the GPE without changing the conductivity significantly. The high ionic conductivity (×10⁻³ S/cm), high transmission in the visible region and nominal variance of conductivity and viscosity over a wide temperature window show that these CGEs are potential electrolytes for electrochromic windows (ECWs).