Femtosecond dynamics of secondary radiation formation from quantum well excitons

The time-resolved secondary emission of resonantly created excitons in GaAs quantum wells is studied using femtosecond up-conversion spectroscopy. The behaviour of the rise and decay of the secondary emission and reflectivity in quantum wells is strongly dependent upon the disorder at the interfaces, the exciton density and the temperature. In the case of low densities and temperatures the emission is independent of the exciton density and rises quadratically in time, in excellent agreement with recent theory for Rayleigh scattering from two-dimensional excitons subjected to disorder. These rise times are compared directly with times measured by time-integrated four-wave mixing (FWM). The comparison of the dynamics displayed in time-resolved secondary radiation and time-integrated FWM provide a clear understanding of the coherence properties of QW excitons in the first few picoseconds after excitation. High-contrast oscillations that are due to quantum beats between the heavy- and light-hole 1s-states are seen. The visibility decay at very low densities is long ps and is related to the action of potential fluctuations on the scattering of heavy-hole and light-hole excitons.     

An unusual effect of fast neutron irradiation of lanthanide /III/ chlorides

When anhydrous EuCl₃, GdCl₃, DyCl₃ or Eu₂O₃ are irradiated with fast neutrons and then dissolved in dilute hydrochloric acid, small amounts of reducing species, believed to be divalent lanthanide cations, are revealed. The amount produced increases with the thermodynamic stability of the Ln²⁺ species /Eu>Dy>Gd>/.     

Facile syntheses of surface-functionalized micelles and shell cross-linked nanoparticles

Block copolymer micelles and shell cross-linked nanoparticles (SCKs) presenting Click-reactive functional groups on their surfaces were prepared using two separate synthetic strategies, each employing functionalized initiators for the controlled radical polymerization of acrylate and styrenic monomers to afford amphiphilic block copolymers bearing an alkynyl or azido group at the α-terminus. The first route for the synthesis of the azide-functionalized nanostructures was achieved via sequential nitroxide-mediated radical polymerization (NMP) of tert-butyl acrylate and styrene, originating from a benzylic chloride-functionalized initiator, followed by deprotection of the acrylic acids, supramolecular assembly of the block copolymer in water and conversion of the benzylic chloride to a benzylic azide. In contrast, the second strategy utilized an alkynyl-functionalized reversible addition fragmentation transfer (RAFT) agent directly for the RAFT-based sequential polymerization of tetrahydropyran acrylate and styrene, followed by selective cleavage of the tetrahydropyran esters to give the α-alkynyl-functionalized block copolymers. These Click-functionalized polymers, with the functionality located at the hydrophilic polymer termini, were then self-assembled using a mixed-micelle methodology to afford surface-functionalized “Clickable” micelles in aqueous solutions. The optimum degree of incorporation of the Click-functionalized polymers was investigated and determined to be ca. 25%, which allowed for the synthesis of well-defined surface-functionalized nanoparticles after cross-linking selectively throughout the shell layer using established amidation chemistry. Functionalization of the chain ends was shown to be an efficient process under standard Click conditions and the resulting functional groups revealed a more “solution-like” environment when compared to the functional group randomly inserted into the hydrophilic shell layer. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5203–5217, 2006     

Practical syntheses of [1,3,5]‐triazine dendritic molecules on solid supports

A practical and divergent synthesis of supported [1,3,5]‐triazine dendritic molecules on Wang resin, PEGA resin, SynPhase? Lanterns, and silica gel is described. The alkylamine linkers used allow derivatization with functionality for both synthetic (e.g., supported reagent and scavenger activity) and chemical biology applications. The use of supported intermediates allows differentiation of symmetric linkers without the need for protecting group chemistry. The synthetic route uses inexpensive, readily available starting materials in a straightforward and scaleable strategy. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2248–2259, 2006     

Gold ultra-microelectrode arrays: application to the steady-state voltammetry of hydroxide ion in aqueous solution.

Gold ultra-microelectrode arrays are used to explore the electrochemical oxidation of hydroxide ions and are shown to be analytical useful. Two types of ultra-microelectrode arrays are used; the first consist of 256 individual electrodes of 5 microm in radius, 170 of which are electrochemically active in a cubic arrangement which are separated from their nearest neighbour by a distance of 100 microm. The second array compromises 2597 electrodes of 2.5 microm in radius and of which 1550 of which are electrochemically active in a hexagonal arrangement separated by the nearest neighbour by 55 microm. Well defined voltammetric waves are found with peak currents proportional to the concentration of hydroxide ions in the range 50 microM to 1 mM. Detection limits of 20 microM using the 170 ultra-microelectrode and 10 microM with the 1550 ultra-microelectrode array are shown to be possible but with a higher sensitivity of 4 mA M(-1) observed using the 1550 ultra-microelectrode array compared to 1.2 mA M(-1) with the 170 ultra-microelectrode array.     

The preparation and properties of low molar mass liquid crystals possessing lateral alkyl chains

The first twelve members of three new mesogenic homologous series have been characterized, each of which are composed of molecules possessing lateral alkyl chains. The n-alkyl 2,5-bis-(4-n-hexyloxy-benzoyloxy)-benzoates are purely nematic whereas both nematic and smectic behaviour is observed for the 4-cyano-4'-biphenylyl 3'-n-alkyloxybenzoates and the 4-cyano-4'-biphenylyl 3',4'-n-alkyloxybenzoates. The transitional properties of these series are similar to those of the analogous conventional mesogens and hence, can be rationalized without making any special assumptions concerning the conformational distribution of the lateral alkyl chain.     

Studies toward the synthesis of pinnatoxins: the spiroimine fragment

An enantioselective approach to the spiroimine fragment of pinnatoxins is described. The strategy is based on a recently developed diastereoselective Ireland-Claisen rearrangement to establish the challenging congested quaternary and tertiary stereocenters within the cyclohexene ring.     

Sub-megabar Mössbauer studies using diamond anvil cells

The development and the use of the diamond anvil cell for Mössbauer Spectroscopy (MS) to pressures nearing 100 GPa are discussed. Three types of cells and their typical performance are given. Pressure calibration, hydrostatic media, gasketing, collimation, -ray absorption, and sample size for MS are reviewed. New MS results showing hysteresis in the room temperature high pressure transition in iron and showing the rapid rise ofT _N in NiI₂ with pressure are presented.