Palladium mediated spiroketal synthesis: application to pheromone synthesis

Stereospecific Stille coupling reactions of 2-metallo-dihydropyrans with Z-vinyl iodo alcohols and subsequent cyclisation provides rapid access to 1,7-dioxaspiro[5.5]undecane family of spiroketals.     

Electrospray mass spectrometry of neuac oligomers associated with the c fragment of the tetanus toxin

The Clostridial neurotoxins, botulinum and tetanus, gain entry into motor neurons by binding to the sialic or N-acetylneuraminic acid (NeuAc) residues of gangliosides and specific protein receptors attached to the cell's surface. While the C-fragment of tetanus toxin (TetC) has been identified to be the ganglioside binding domain, remarkably little is known about how this domain discriminates between the structural features of different gangliosides. We have used electrospray ionization mass spectrometry (ESI-MS) to examine the formation of complexes between TetC and carbohydrates containing NeuAc groups to determine how NeuAc residues contribute to ganglioside binding. ESI-MS was used to obtain an estimate of the dissociation constants (KD values) for TetC binding to a number of related NeuAc-containing carbohydrates (sialyllactose and disialyllactose), as well as six (NeuAc)n oligomers (n = 1-6). KD values were found to range between approximately 10-35 microM. The strength of the interactions between the C fragment and (NeuAc)n are consistent with the topography of the targeting domain of tetanus toxin and the nature of its carbohydrate binding sites. These results suggest that the targeting domain of tetanus toxin contains two binding sites that can accommodate NeuAc (or a dimer) and that NeuAc may play an important role in ganglioside binding and molecular recognition, a process critical for normal cell function and one frequently exploited by toxins, bacteria, and viruses to facilitate their entrance into cells.     

Exact Fourier expansion in cylindrical coordinates for the three-dimensional Helmholtz Green function

A new method is presented for Fourier decomposition of the Helmholtz Green function in cylindrical coordinates, which is equivalent to obtaining the solution of the Helmholtz equation for a general ring source. The Fourier coefficients of the Green function are split into their half advanced + half retarded and half advanced–half retarded components, and closed form solutions for these components are then obtained in terms of a Horn function and a Kampé de Fériet function respectively. Series solutions for the Fourier coefficients are given in terms of associated Legendre functions, Bessel and Hankel functions and a hypergeometric function. These series are derived either from the closed form 2-dimensional hypergeometric solutions or from an integral representation, or from both. A simple closed form far-field solution for the general Fourier coefficient is derived from the Hankel series. Numerical calculations comparing different methods of calculating the Fourier coefficients are presented. Fourth order ordinary differential equations for the Fourier coefficients are also given and discussed briefly.     

Characterization of partially transesterified poly(beta-hydroxyalkanoate)s using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) was used for the characterization of a partially transesterified poly(beta-hydroxyalkanoate), PHA, polymer produced by the bacterial strain Alcaligenes eutrophus using saponified vegetable oils as the sole carbon sources. The transesterification was carried out separately under acidic and basic conditions to obtain PHA oligomers weighing less than 10 kDa. The intact oligomers were detected in their cationized [M + Na](+) and [M + K](+) forms by MALDI-TOFMS. A composition analysis, using the MALDI-TOF spectra, indicate that the oligomers obtained via acid catalysis were terminated with a methyl 3-hydroxybutyrate end group, and those obtained by base catalysis had a methyl crotonate (olefinic) termination. In addition to HB (hydroxy butyrate), the oligomers were found to contain a small percentage of HV (hydroxy valerate). This was independently confirmed using gas chromatography/mass spectrometry (GC/MS). In comparison, the analysis of a commercial PHA polymer, transesterified under identical conditions, only showed the presence of HB, i.e. a pure PHB homopolymer. Copyright 1999 John Wiley & Sons, Ltd.     

The antipode construction for sphere packings

Summary. A construction for sphere packings is introduced that is parallel to the “anticode” construction for codes. This provides a simple way to view Vardy’s recent 20-dimensional sphere packing, and also produces packings in dimensions 22, 44–47 that are denser than any previously known. Oblatum 18-VII-1994 & 7-XII-1994     

Nanotube growth during annealing of mechanically milled Boron

Boron powder, finely ground in a tungsten carbide ball mill in an ammonia atmosphere, has been annealed at 1200 °C in flowing nitrogen to produce small quantities of cylindrical BN nanotubes, both as isolated individuals and grouped into ropes. Thick-walled conical BN tubes are abundant in specimens annealed for longer times, and their growth was catalysed once WC debris was converted into W metal particles. Some catalytic effect of small W nanoparticles could be necessary for nanotube formation, though no tip particles have been imaged here. Given the low temperature of mechanical milling and annealing, BN growth must involve surface diffusion and solid-state reconfiguration. It could be possible to engineer desirable physical and chemical properties by exploiting the variation in cylindrical versus conical BN structures as a function of annealing time. Received: 19 December 2001 / Accepted: 3 April 2002 / Published online: 19 July 2002 RID="*" ID="*"Corresponding author. Fax: +61-2/6125-8253, E-mail: john.fitzgerald@anu.edu.au     

Reagent Selector: using Synthon Analysis to visualize reagent properties and assist in combinatorial library design

Reagent Selector is an intranet-based tool that aids in the selection of reagents for use in combinatorial library construction. The user selects an appropriate reagent group as a query, for example, primary amines, and further refines it on the basis of various physicochemical properties, resulting in a list of potential reagents. The results of this selection process are, in turn, converted into synthons: the fragments or R-groups that are to be incorporated into the combinatorial library. The Synthon Analysis interface graphically depicts the chemical properties for each synthon as a function of the topological bond distance from the scaffold attachment point. Displayed in this fashion, the user is able to visualize the property space for the universe of synthons as well as that of the synthons selected. Ultimately, the reagent list that embodies the selected synthons is made available to the user for reagent procurement. Application of the approach to a sample reagent list for a G-protein coupled receptor targeted library is described.