New stereoselective routes to macrocyclic ligands

Reaction of bis(ethane-1,2-diamine)copper(II) with acetaldehyde and nitromethane in methanol leads, stereoselectively, to the new macrocyclic complex (trans-5(R),7(R),12(S),14(S))-tetramethyl-6,13-dinitro-1,4,8,11-tetraazacyclotetradecane)copper(II) perchlorate alpha-[CuL1](ClO4)(2) in good yield. Reduction of the nitro groups affords the hexaamine (L-2), which was crystallized as [H4L2](ClO4)(4) . 2H(2)O and characterized by an X-ray crystal structure study (monoclinic P2(1)/n, a = 9.763(2) Angstrom, b = 12.1988(7) Angstrom, c = 13.036(2) Angstrom, beta = 105.668(7)degrees, Z = 2) and complexed with Cu-II to produce the complex beta-[Cu(H2L2)](ClO4)(4) . 2H(2)O, which has also been characterized by X-ray crystallography (monoclinic P2(1)/n, a = 9.717(4) Angstrom, b = 12.174(2) Angstrom, c = 13.036(5) Angstrom, beta = 106.51(2)degrees, Z = 2). Reaction of alpha-[CuL1](2+) with either basic hydrogen peroxide or dilute nitrous acid leads to mild reduction of the nitro groups to afford the ketoxime L-3 as its N-based isomeric Cu-II complexes, trans-I [CuL3](ClO4)(2) and trans-II [Cu(L-3)Cl]Cl . 7H(2)O, the latter of which has been characterized structurally: triclinic, <P(1)over bar> a = 10.8441(5) Angstrom, b = 11.6632(9) Angstrom, c = 11.8723(9) Angstrom, alpha = 113.634(7)degrees, beta = 95.744(5), gamma = 94.851(5)degrees Z = 2. Variations in the configurations of the coordinated amines in [CuL1](2+), [CuL2](2+), and [CuL3](2+) have a profound effect on the spectroscopy and electrochemistry of their complexes.

Metal-directed synthesis routes to a 16-membered tetraazamacrocycle with two pendant primary amine groups

The reaction of the bis(propane-1,3-diamine)copper(II) ion with paraformaldehyde and nitroethane in dry methanol under basic conditions produces a macrocyclic product, (cis-3,11-dimethyl-3,11-dinitro-1,5,9,13-tetraazacyclohexadecane)copper(II) perchlorate, in low yield, compared with the good yield obtained in the parallel chemistry possible even under aqueous conditions using palladium(II) as a template. The palladium complex was reduced with zinc amalgam in dilute aqueous acid to yield the metal-free 16-membered macrocyclic hexaamine, in this case re-complexed and characterised by an X-ray crystal structure as the (cis-3,11-dimethyl-1,5,9,13-tetraazacyclohexadecane-3,11-diamine)copper(II) perchlorate. The copper ion is found in a tetragonally elongated and trigonally-distorted octahedral environment, with all six of the ligand nitrogens coordinated, the two primary amine pendant groups occupying cis sites. (C) 2000 Elsevier Science S.A. All rights reserved.

Transitions between routes of benzodiazepine administration among heroin users in Sydney

A sample of 312 heroin users were interviewed regarding their benzodiazepine use. The majority (94%) had used benzodiazepines, 72% in the 6 months prior to interview. Benzodiazepine injecting was common, with 28% of the sample having injected these drugs, 13% in the 6 months preceding interview. Current benzodiazepine injectors showed greater polydrug use, injection-related HIV risk-taking behaviour, criminal involvement, psychological distress and injection-related health problems, as well as poorer general health, and an increased risk of having overdosed than other users of benzodiazepines. Of those subjects who had injected benzodiazepines, 55% were no longer current benzodiazepine injectors. Concern for general health emerged as the most common reason for having made a transition away from injecting, and for being likely to make such a transition.

Hydrolytic kinetic resolution of terminal mono- and bis-epoxides in the synthesis of insect pheromones: routes to (-)-(R)- and (+)-(S)-10-methyldodecyl acetate, (-)-(R)-10-methyl-2-tridecanone, (-)-(R)-(Z)-undec-6-en-2-ol (Nostrenol), (-)-(1R,7R)-1,7-dime

Hydrolytic kinetic resolution (HKR) of functionalised epoxides using (salen)Co(OAc) complexes provides enantiomerically enriched epoxides and diols, which have been transformed into important insect sex pheromones. In this general approach, (-)-(R)- and (+)-(S)-10-methyldodecyl acetates from the smaller tea tortrix moth were obtained, as was (-)-(R)-10-methyltridecan-2-one from the southern corn rootworm. The (S)-epoxide obtained from undec-1-en-6-yne was transformed to (-)-(R)-(Z)-undec-6-en-2-ol (Nostrenol) from ant-lions. HKR of appropriate bisepoxides was also investigated, and transformations of the resulting bisepoxides and epoxydiols provided (-)-(1R,7R)-1,7-dimethylnonylpropanoate from corn rootworms, (-)-(6R,12R)-6,12-dimethylpentadecan-2-one from the female banded cucumber beetle, and (-)-(2S,11S)-2,11-diacetoxytridecane and (+)-(2S,12S)-2,12-diacetoxytridecane from female pea-midges. (C) 2002 Elsevier Science Ltd. All rights reserved.

Investigating direct routes to an advanced intermediate for the synthesis of C-20 diterpene alkaloids

Rapid access to the ABCE ring system of the C-20 diterpene alkaloids was achieved by silver (I) promoted intramolecular Friedel-Crafts arylation of a functional group specific 5-bromo-3-azabicyclo[3.3.1]nonane derivative. (c) 2005 Elsevier Ltd. All rights reserved.

Effect of different preparation routes on the structure and properties of rigid polyurethane-layered silicate nanocomposites

To identify the effect of reactive preparation on the structure and properties of rigid polyurethane (PU)layered silicate nanocomposite, a range of nanocomposites were prepared by combining the various precursors in different sequences. The morphology of the samples was characterized by XRD and TEM. Tensile properties and dynamic mechanical thermal properties were measured. The reactions between the layered silicates and PU precursors were monitored via FTIR to gain an understanding of the participation of nanofiller in the polymerization reaction, and the impact of this on system stoichiometry. The XRD and TEM results provided evidence that morphology can differ significantly if different synthesis methods are used. However, the mechanical properties are dominated by the stoichiometry imbalance induced by the addition of the layered silicates. (c) 2006 Wiley Periodicals, Inc.

Performance of some unbound roadbase materials from Queensland = Performance de certains matériaux granulaires de base du Queensland

This paper summarises recent investigations into characterisation and performance of unbound roadbase materials carried out by Main Roads, Queensland (QDMR), on road projects across the state. Performance based tests such as the Repeated Load Triaxial (RLT) and the Wheel Tracker (WT) are the primary tools which are increasingly used by QDMR to overcome the limitations of simple specification type tests. This paper shows the inadequacy of current specification tests to rank material performance. The performance based tests show that the properties of the coarse aggregate alone are inadequate for sound performance; enable the contribution to mechanical behaviour by plastic fines with high matric suction to be assessed,- further, and facilitates ranking of material behaviour. Simple shakedown analyses undertaken yield similar material rankings. Finally, some materials from the performance based characterisation are compared with Falling Weight Deflectometer (FWD) in-service pavement performance data.

Mucosal immunisation with papillomavirus virus-like particles elicits systemic and mucosal immunity in mice

It has been shown previously that recombinant virus-like particles (VLPs) of papillomavirus can induce VLP-specific humoral and cellular immune responses following parenteral administration. To test whether mucosal administration of bovine papillomavirus type 1 (BPV1) VLPs could produce mucosal as well as systemic immune responses to VLPs, 50 mu g chimeric BPV1 VLPs containing an HPV16 E7 CTL epitope (BPVL1/E7 VLP) was administered intranasally to mice. After two immunisations, L1-specific serum IgG and IgA were observed. L1-specific IgG and IgA were also found in respiratory and vaginal secretions. Both serum and mucosal antibody inhibited papillomavirus VLP-induced agglutination of RBC, indicating that the antibody induced by mucosal immunisation may recognize conformational determinants associated with virus neutralisation. For comparison, VLPs were given intramuscularly, and systemic and mucosal immune responses were generally comparable following systemic or mucosal delivery. However, intranasal administration of VLP induced significantly higher local IgA response in lung, suggesting that mucosally delivered HPV VLP may be more effective for mediating local mucosal immune responses. Intranasal immunisation with HPV6b L1 VLP produced VLP-specific T proliferative responses in splenocytes, and immunisation with BPVL1 VLP containing an HPV16 E7 CTL epitope induced E7-specific CTL responses. We conclude that immunisation with papillomavirus VLPs via mucosal and intramuscular routes, without adjuvant, can elicit specific antibody at mucosal surfaces and also systemic VLP epitope specific T cell responses. These findings suggest that mucosally delivered VLPs may offer an alternative HPV VLP vaccine strategy for inducing protective humoral immunity to anogenital HPV infection, together with cell-mediated immune responses to eliminate any cells which become infected. (C) 1998 Academic Press.

Vaccines for papillomavirus infection

Vaccines to prevent PV infection, utilising PV L1 virus like particles (VLPs) to induce neutralising antibody, are in clinical trial and show all the characteristics likely to be associated with success. Results warrant global planning for the deployment of VLP vaccines within a decade, as part of a program to prevent cervical cancer. Vaccines designed to treat existing PV infection by inducing therapeutic cellular immunity targeted to PV proteins are at a much earlier stage of development. The wide choice of potential and proposed antigens, routes and mechanisms of delivery, and possible treatment regimens suggest that, to move the field forward, surrogate markers allowing comparison of the relative efficacy of different vaccine approaches are required. These should be based on reduction in load of virus infection, and need to be validated in animal models or in man. (C) 2002 Published by Elsevier Science B.V.

Targeting Antigen-loaded Liposomes to Myeloid Antigen Presenting Cells

Objective: To target antigen-loaded liposomes to myeloid APC in vivo for immunotherapy and to manipulate immune function through liposome composition. Method: Liposomes were loaded with ovalbumin, the lipophilic red fluorescent marker, DiI, with or without QuilA adjuvant then injected either i.v. or s.c. to naı¨ ve C57Bl/6 mice. Spleen, liver and draining LN were stained with MHC class II and various myeloid markers to determine the uptake of liposomes. Frozen sections of spleen and draining LN were stained with FITC-labeled mAb to determine which cells take up the liposomes. To determine the effect on OVA-specific T cell responses, liposomes were administered to Balb/c mice which received DO11.10 OVAspecific TCR transgenic T cells labelled with CFSE. Results: The DiI fluorescence was visualized in MHC class II+ macrophages and DC in draining lymph nodes after s.c. injection and in spleen and liver after i.v injection. Immunofluorescence microscopy shows liposome uptake in marginal zone macrophages and some DC in the T cell areas of the spleen after i.v. injection. Administration of ova-liposomes with or without QuilA stimulated a specific T cell response as measured by CFSE dilution. Conclusion: APC of liver, spleen and LN, and subsequent antigen presentation to T cells can be targeted for immunotherapy by the administration of liposomes encapsulating antigen and adjuvant. Varying the composition and routes of liposome administration is expected to alter the function of the targeted APC and the T cell response.

Industrial screening

Wills' Mineral Processing Technology provides practising engineers and students of mineral processing, metallurgy and mining with a review of all of the common ore-processing techniques utilized in modern processing installations. Now in its Seventh Edition, this renowned book is a standard reference for the mineral processing industry. Chapters deal with each of the major processing techniques, and coverage includes the latest technical developments in the processing of increasingly complex refractory ores, new equipment and process routes. This new edition has been prepared by the prestigious J K Minerals Research Centre of Australia, which contributes its world-class expertise and ensures that this will continue to be the book of choice for professionals and students in this field. This latest edition highlights the developments and the challenges facing the mineral processor, particularly with regard to the environmental problems posed in improving the efficiency of the existing processes and also in dealing with the waste created. The work is fully indexed and referenced.

The equilibrium penetration of monolayers. Is equilibrium really established?

In studying the penetration of water-soluble surfactants into water-insoluble monolayers the main theoretical problem is to find a relationship that would enable the amount of surfactant that has entered the monolayer to be calculated from a set of equilibrium surface pressure-area isotherms. Despite many attempts, no current theory gives satisfactory results when applied to experimental data (Langmuir 14 (1998) 2148). One possible reason is that equilibrium had not been established when the surface pressure-area curves were measured. The three experiments reported here suggest that equilibrium is extremely difficult to establish in such systems when the area is low or the surface pressure is high. The essence of these experiments is to try to reach the same final condition by two different routes. In the first route, the one nearly always used in equilibrium penetration measurements, the surfactant is injected under the expanded monolayer, which is then slowly compressed in steps, with time allowed at each step for a steady surface pressure to be attained. In the second procedure, the monolayer is first compressed to a high surface pressure and the surfactant then injected. A stepped expansion isotherm may then be observed. Surface pressure-area per monolayer molecule isotherms, reflection spectra, and slow neutron reflectivity data all show the same pattern: if the surfactant was allowed to penetrate while the monolayer was in an expanded state, it was not completely removed when the monolayer was compressed; but if the monolayer was in a highly compressed state when exposed to the surfactant little penetration took place until the film was expanded. There thus appear to be very large energy barriers to the ejection of surfactant from a compressed monolayer and to the penetration of surfactant into a compressed monolayer. Although these experiments have some limitations, it now seems likely that at least some of the penetration data used in evaluating the various thermodynamic treatments of equilibrium penetration were not equilibrium data. (C) 2001 Elsevier Science B.V. All rights reserved.

Wolbachia-mediated sperm modification is dependent on the host genotype in Drosophila

Estimates of Wolbachia density in the eggs, testes and whole flies of drosophilid hosts have been unable to predict the lack of cytoplasmic incompatibility (CI) expression in so-called mod(-) variants. Consequently, the working hypothesis has been that CI expression, although related to Wolbachia density, is also governed by unknown factors that are influenced by both host and bacterial genomes. Here, we compare the behaviour of the mod(-) over-replicating Wolbachia popcorn strain in its native Drosophila melanogaster host to the same strain transinfected into a novel host, namely Drosophila simulans. We report that (i) the popcorn strain is a close relative of other D. melanogaster infections, (ii) the mod(-) status of popcorn in D. melanogaster appears to result from its inability to colonize sperm bundles, (iii) popcorn is present in the bundles in D. simulans and induces strong CI expression, which demonstrates that the bacterial strain does not lack the genetic machinery for inducing CI and that there is host-species-specific control over Wolbachia tissue tropism, and (iv) infection of sperm bundles by the mod(-) D. simulans wCof strain indicates that there are several independent routes by which a strain can be a CI non-expressor.

Sub-structure syntheses and relative stereochemistry in the bistramide (bistratene) series of marine metabolites

The (6R*,9S*,11S*) and (22S*,23R*,27R*,31R*) stereochemistry, respectively, of the tetrahydropyranyl and spiroacetal moieties in bistramide A (1) have been established by stereoselective syntheses and high field NMR comparisons. Routes to the gamma-amino acid moiety are outlined. (C) 2002 Elsevier Science Ltd. All rights reserved.