Dendron-protected Au nanoparticles--effect of dendritic structure on chemical stability

A series of gold nanoparticles stabilised by 'Newkome-type' dendritic branching has been synthesised and fully characterised. In particular, the properties and behaviour of these hybrid materials are compared with those of a previously reported set of nanoparticles stabilised by dendrons constructed using l-lysine building blocks. The rates of cyanide-induced nanoparticle decomposition were determined, and it was found that the rate of decomposition increased on the introduction of dendritic branching. Furthermore, 'Newkome-type' dendrons were significantly more effective at protecting the encapsulated gold nanoparticle than the l-lysine based dendrons. It is proposed that this observation can be explained on the basis of more effective packing and surface coverage by the 'Newkome-type' dendrons. Importantly, this study therefore demonstrates that the organic chemical structure of dendritic ligands plays a crucial role in controlling the reactivity of self-assembled hybrid nanostructures.     

Isotope ratio monitoring gas chromatography/Mass spectrometry of D/H by high temperature conversion isotope ratio mass spectrometry

Of all the elements, hydrogen has the largest naturally occurring variations in the ratio of its stable isotopes (D/H). It is for this reason that there has been a strong desire to add hydrogen to the list of elements amenable to isotope ratio monitoring gas chromatography/mass spectrometry (irm-GC/MS). In irm-GC/MS the sample is entrained in helium as the carrier gas, which is also ionized and separated in the isotope ratio mass spectrometer (IRMS). Because of the low abundance of deuterium in nature, precise and accurate on-line monitoring of D/H ratios with an IRMS requires that low energy helium ions be kept out of the m/z 3 collector, which requires the use of an energy filter. A clean mass 3 (HD(+.)) signal which is independent of a large helium load in the electron impact ion source is essential in order to reach the sensitivity required for D/H analysis of capillary GC peaks. A new IRMS system, the DELTA(plus)XL(trade mark), has been designed for high precision, high accuracy measurements of transient signals of hydrogen gas. It incorporates a retardation lens integrated into the m/z 3 Faraday cup collector. Following GC separation, the hydrogen bound in organic compounds must be quantitatively converted into H(2) gas prior to analysis in the IRMS. Quantitative conversion is achieved by high temperature conversion (TC) at temperatures >1400 degrees C. Measurements of D/H ratios of individual organic compounds in complicated natural mixtures can now be made to a precision of 2 per thousand (delta notation) or, better, with typical sample amounts of approximately 200 ng per compound. Initial applications have focused on compounds of interest to petroleum research (biomarkers and natural gas components), food and flavor control (vanillin and ethanol), and metabolic studies (fatty acids and steroids). Copyright 1999 John Wiley & Sons, Ltd.     

Synthesis of Acetophenone Azine

Conditions for preparing acetophenone azine via the oxidative dimerization of acetophenone imine anion are investigated.     

Oxidation of Alcohols by Bromine on Alumina

Bromine adsorbed on neutral alumina is an effective reagent for the oxidation of secondary alcohols to ketones.     

Self-assembled monolayers of alkanethiolates on palladium are good etch resists

This paper describes microcontact printing (muCP) of long-chain alkanethiolates on palladium, followed by solution-phase etching with an iron(III)-based etchant, to make patterned structures. The commonly used soft-lithographic procedure for fabricating microstructures-muCP of SAMs on gold-has three shortcomings: a significant surface density of pinhole defects, substantial edge roughness, and incompatibility with processes used in CMOS fabrication. Microcontact printing on palladium gives fewer defects and smaller edge roughness than on gold, and is compatible with CMOS. The mechanism by which etch-resistant patterns are formed is different for palladium and gold. The Pd/S interfacial layer formed by the reaction of palladium films with sulfur-containing compounds provides good resistance to etches independently of the barrier to access the surface provided by the film of (CH2)n groups in the long-chain SAMs. This barrier is the basis of the etch resistance of SAMs on gold, but only supplements the etch resistance of the sulfur-containing interfacial layer on palladium. Characterization of the SAM formed from hexadecanethiol on palladium is described.     

Chromatographic,spectroscopic, topographic,and X-ray crystallographic studies of the solid solution formed by racemic 3-carboxy-2,2,5,5-tetramethyl-1-pyrrolidinyloxy (3-carboxy-proxyl)

The solid solution formed by the title compound, C₉H₁₆NO₃, has been examined by a variety of techniques and shown to be an equi-molecular mixture of the two enantiomers. Refinement of the disordered structure was based on the orthorhombic space groupPnma witha=8.023(2),b=10.030(3), andc=12.352(2)Å, finalR=0.055. The oxygens of the carboxyl group are disordered and both enantiomers can occupy the same, rather than alternate, crystallographic sites. Results from studies involving IR, GC-MS, and chiral chromatography are also presented. In addition we report on the use of synchrotron X-ray topography to investigate strain in crystals of the solid solution.     

Anomalous loss in depressed-cladding and W-fibres

Anomolous spikes in the loss spectrum of practical depressed-cladding fibres with a finite cladding and absorbing jacket can be explained in terms of a combination of three effects — the excitation conditions, the absorption behaviour of core and cladding modes, and the slight variation in the fibre diameter along its length.     

An efficient synthesis of oosporein

Fungal metabolite oosporein was prepared in four steps and 24% overall yield starting from 2,5-dimethoxytoluene. It was demonstrated that treatment of phoenicin with pyrrolidine and copper(II) acetate led to oosporein, whereas similar treatment of the isomeric ‘isophoenicin’ produced a benzofuran diquinone. No chromatography was required during any step of the synthesis.     

Generation of spatial solitons using non-linear guided modes

We investigate how two-dimensional spatial optical solitons can be generated in a non-linear Kerr medium using the non-linear guided modes of a weakly-guiding slab waveguide with a linear core and a non-linear cladding as the source of excitation. Symmetric, antisymmetric and asymmetric non-linear modes are considered, from which we determine the parameters of single solitons, oscillating two-soliton bound states, and two repelling solitons, respectively. Both the beam propagation method and inverse scattering transform are used.