Low-divergence operation of a long-pulse excimer laser using a SBS phase-conjugate cavity

The use of an optical cavity containing a stimulated Brillouin scattering (SBS) phase-conjugate reflector to control the spatial and spectral output of a long pulse (>100 ns) X-ray preionized XeCl laser is reported. The divergence of the 3×4 cm² output beam has been improved by a factor of 20 to <150 rad. The temporal form of the output depends on the acoustic decay times of the liquid and gaseous SBS media used. Four-wave mixing via gain saturation has been observed within the discharge volume, leading to depolarisation of the output beam.     

Double diastereoselective [3,3]-sigmatropic aza-Claisen rearrangements

Asymmetric [3,3]-sigmatropic aza-Claisen rearrangement of the (Z)-N-allyl-N,O-silylketene aminal of (3S,4E,alphaR)-1-benzyloxy-3-(N-propionyl-N-alpha-methylbenzylamino)hex-4-ene furnishes (2S,3R,4E,alphaR)-N-alpha-methylbenzyl-2,3-dimethyl-7-benzyloxyhept-4-enamide in > 92% d.e.; rearrangement of the diastereomeric (3R,4E,alphaR)-(Z)-N,O-silylketene aminal proceeds with low diastereoselectivity.     

Conformational and receptor-binding properties of the insect neuropeptide proctolin and its analogues

Summary Proctolin (Arg-Tyr-Leu-Pro-Thr) was the first insect neuropeptide to be chemically characterised. It plays an essential role in insect neurophysiology and is involved in muscular contraction and neuromodulation. Elements of secondary structure in solution have been studied by comparing data obtained from NMR and molecular dynamics simulations. Different secondary structural requirements are associated with agonist and antagonist activities. A favoured conformation of proctolin has an inverse -turn, comprising an intramolecular hydrogen bond near the C-terminal end between Thr NH and Leu CO. Antagonists have a more compact structure resembling a paperclip loop, containing an intramolecular hydrogen bond between Tyr NH and Pro CO, possibly stabilised by a salt bridge between the N- and C-terminal groups. A cyclic analogue retains antagonist activity and resembles a -bulge loop, also comprising intramolecular hydrogen bonds between Tyr NH and Pro CO and Thr CO. These models may offer feasible starting points for designing novel compounds with proctolinergic activity.     

Selective fluorination of 1-hydroxyisoquinolines using Selectfluor™

The highly regioselective fluorination of 1-hydroxyisoquinoline is described using Selectfluor™ (F-TEDA-BF₄) under a variety of conditions.