Single enatiomer free-radical chemistry - Lewis acid-mediated reductions of racemic halides using chiral non-racemic stannanes

Additions of one to two equivalents of Lewis acids that include magnesium salts to free-radical reduction reactions involving ester functionalized radicals and (1R,2S,5R)-menthyldiphenyltin hydride 4, bis((1R,2S,5R)-menthyl)phenyltin hydride 5, tris((1R,2S,5R)-menthyl)tin hydride 6, bis((1R,2S,5R)-menthyl)-[8-(N,N-dimethylamino)naphthyl]tin hydride 12, bis((1R,2S,5R)-menthyl)-[1-((S)-N,N-dimethylaminoethyl)phenyl]tin hydride 13 or 3α-dimethylstannyl-5α-cholestane 14 result in remarkable enantioselectivities. Examples include (S)-naproxen ethyl ester 16, produced in 74% yield and greater than 99% ee at −78°C from the bromide and 5 in the presence of MgBr₂, and ethyl (R)-N-trifluoroacetyl-_D-phenylglycinate 18, obtained in 78% yield and 99% ee under identical conditions. Kinetic and computational studies provide insight into the origins of these observations.

Performance of murray cod, Maccullochella peelii peelii (Mitchell) in response to different feeding schedules

The Australian freshwater fish Murray cod, Maccullochella peelii peelii (Mitchell) is gaining popularity as a suitable species for intensive culture, particularly in closed systems. The aim of this study was to evaluate the performance of Murray cod in response to different feeding schedules. Growth, survival, food conversion and a range of other related parameters including carcass proximate composition were evaluated for fish in five feed management regimes. The feeding regimes used in the experiment were hand fed to satiation twice daily (SAT), a pre-determined ration of 1.2% of the body weight day−1 which was hand fed twice daily (HFR), and belt fed through the day only (B/D), belt fed through the night only (B/N) and belt fed for 24 h (B/DN). Each of the five feeding regimes was randomly allocated to three tanks (triplicates). All of the feeding regimes used a commercially prepared diet formulated specifically for Murray cod, containing ≈50% protein and ≈16% lipid. The experiment was conducted for 84 days. Specific growth rate ranged from 0.89±0.01 to 1.07±0.04% day−1. Food conversion ratio (FCR) ranged from 1.09±0.02 to 0.92±0.03. The fastest growth and greatest final body weight were observed in the SAT treatment; however, the highest FCR, visceral fat index (VFI %) and hepatosomatic index (HSI %) were also observed in this treatment. Significant differences were found in specific growth rate and final mean weight between fish in the B/D and SAT treatments. B/N and B/DN feeding regimes appeared to result in the most favourable fish performance.

Asymptomatic hypoechoic regions on patellar tendon ultrasound : a 4-year clinical and ultrasound followup of 46 tendons

Patellar tendon ultrasound appearance is commonly used in clinical practice to diagnose patellar tendinopathy and guide management. Using a longitudinal study design we examined whether or not the presence of a hypoechoic ultrasonographic lesion in an asymptomatic patellar tendon conferred a risk for developing jumper's knee compared with a tendon that was ultrasonographically normal. Ultrasonographic, symptomatic and anthropometric assessment was completed at baseline and followup. Magnetic resonance imaging was performed on four tendons that resolved ultrasonographically in the study period. Forty-six patellar tendons were followed over 47±11.8 months. Eighteen tendons were hypoechoic at baseline and 28 were ultrasonographically normal. Five tendons resolved ultrasonographically in the study period. Magnetic resonance imaging in four of these tendons was normal. Seven normal patellar tendons at baseline developed a hypoechoic area but only two became symptomatic. Analysis of ultrasonography at baseline and clinical outcome with Fisher's exact test shows there is no association between baseline ultrasound changes and symptoms at followup. In this study there is no statistically significant relationship between ultrasonographic patellar tendon abnormalities and clinical outcome in elite male athletes. Management of jumper's knee should not be solely based on ultrasonographic appearance; clinical assessment remains the cornerstone of appropriate management.

Net energy analysis of solar and conventional domestic hot water systems in Melbourne, Australia

It is commonly assumed that solar hot water systems save energy and reduce greenhouse gas emissions. Very rarely has the life-cycle energy requirements of solar hot water systems been analysed, including their embodied energy. The extent to which solar hot water systems save energy compared to conventional systems in Melbourne, Australia, is shown through a comparative net energy analysis. The solar systems provided a net energy saving compared to the conventional systems after 0.5 to 2 years, for electricity and gas systems respectively.

Purification and membrane reconstitution of catalytically active Menkes copper-transporting P-type ATPase (MNK; ATP7A)

The MNK (Menkes disease protein; ATP7A) is a major copper- transporting P-type ATPase involved in the delivery of copper to cuproenzymes in the secretory pathway and the efflux of excess copper from extrahepatic tissues. Mutations in the MNK (ATP7A) gene result in Menkes disease, a fatal neurodegenerative copper deficiency disorder. Currently, detailed biochemical and biophysical analyses of MNK to better understand its mechanisms of copper transport are not possible due to the lack of purified MNK in an active form. To address this issue, we expressed human MNK with an N-terminal Glu-Glu tag in Sf9 [Spodoptera frugiperda (fall armyworm) 9] insect cells and purified it by antibody affinity chromatography followed by size-exclusion chromatography in the presence of the non-ionic detergent DDM (n-dodecyl b-D-maltopyranoside). Formation of the classical vanadate-sensitive phosphoenzyme by purified MNK was activated by Cu(I) [EC50=0.7 µM; h (Hill coefficient) was 4.6]. Furthermore, we report the first measurement of Cu(I)-dependent ATPase activity of MNK (K0.5=0.6 µM; h=5.0). The purified MNK demonstrated active ATP-dependent vectorial 64Cu transport when reconstituted into soya-bean asolectin liposomes. Together, these data demonstrated that Cu(I) interacts with MNK in a co-operative manner and with high affinity in the sub-micromolar range. The present study provides the first biochemical characterization of a purified full-length mammalian copper-transporting P-type ATPase associated with a human disease.

Australian telecommuting : management communication strategies

This paper reports findings on the significance of management communication strategies to telecommuting, based on a survey of telecommuters at IBM Australia. With increased adoption of telecommuting, many strategies have been proffered to ensure that telecommuters have appreciable levels of job satisfaction. Low levels of job satisfaction can lead to unduly rapid employee turnover that is detrimental to business operation. The objective of this paper is to ascertain the perceptions of telecommuters at IBM Australia on a number of telecommuting practice measures, and to suggest how job satisfaction can be improved and maintained at high levels by giving greater attention to particular communication management strategies in Australia. Although the management communication strategies proffered in the literature appear to apply generally, this study concludes that a few aspects are distinctively applicable to the Australian environment. Those aspects should be specifically noted by those interested in benefiting from telecommuting practice.

Thermal evaluation of a low cost wood burner

Small-scale producers of dried products in rural areas of developing countries must often rely on sun drying to dry their crops, but this can be unreliable and produce an inferior product. There is therefore a need for simple and inexpensive combustion devices that can be fabricated and used locally. A wood burner has been constructed from a "200 litre" steel drum and has then been evaluated experimentally. The thermal efficiency of the burner was found to be 31% in two trials. An energy balance, calculated for three trials, was within + 16%. Approximately one third of the energy available in the wood was lost in the flue gases, either as sensible heat or unburned volatile gases. Excess combustion air through the burner was calculated and measured to be approximately 400% of the stoichiometric requirements. A significant amount of energy was required to heat the thermal mass surrounding the burner, indicating that a lightweight insulated structure would be more suitable in most circumstances.

Optimal range-difference-based localization considering geometrical constraints

This paper proposes a new type of algorithm aimed at finding the traditional maximum-likelihood (TML) estimate of the position of a target given time-difference-of-arrival (TDOA) information, contaminated by noise. The novelty lies in the fact that a performance index, akin to but not identical with that in maximum likelihood (ML), is a minimized subject to a number of constraints, which flow from geometric constraints inherent in the underlying problem. The minimization is in a higher dimensional space than for TML, and has the advantage that the algorithm can be very straightforwardly and systematically initialized. Simulation evidence shows that failure to converge to a solution of the localization problem near the true value is less likely to occur with this new algorithm than with TML. This makes it attractive to use in adverse geometric situations.

Can sand slugs in rivers deliver conservation benefits? The biodiversity value of tributary junction plug wetlands in the Glenelg River, Australia

Restoration works are carried out to alleviate human impacts and improve habitats within ecosystems. However, human impacts may also create new (anthropogenic) habitat for species to exploit.A dilemma arises when proposed restoration works would remove anthropogenic habitat and the assemblages it supports. Sediment input into the Glenelg River has formed tributary junction plug wetlands at confluences. Sand slug removal is proposed as part of river rehabilitation, but would also drain plug wetlands. We sampled four plug wetland, four river run and three river pool sites to determine whether plug wetlands influence water quality and add to the biodiversity of macroinvertebrates in the Glenelg River.Water quality and macroinvertebrate diversity were similar in plug wetlands, river runs and river pools.Assemblages were distinct among all sites, regardless of type, so there was no characteristic ‘plug-wetland fauna’. Therefore, although removal of plug wetlands would not cause a dramatic loss of invertebrate biodiversity, it would destroy anthropogenic habitat that supports a similar range of species to natural habitats in a river subject to multiple degrading processes. Gains from rehabilitation should be weighed against the value of anthropogenic habitat and the extent of similar habitat lost elsewhere in the ecosystem.

Fish assemblage response to rehabilitation of a sand-slugged lowland river

The impact of excessive sediment supply on river channels has been  described in many areas of the world. Sediment deposition disturbance alters habitat  structure by decreasing channel depth, changing substrate composition and burying woody debris. River rehabilitation is occurring worldwide, but information is scant on fish assemblage responses to rehabilitation in sedimentdisturbed lowland rivers. Sediment removal and large woody debris (LWD) replacement  were used to experimentally rehabilitate habitat along a 1500m stretch of the Glenelg River in western Victoria, Australia. Using an asymmetrical before-after control-impact (BACI) design, fish were captured before and after the reach was rehabilitated, from two control reaches and from a ‘higher quality’ reference reach. After two years post-rehabilitation monitoring, the fish assemblage at the rehabilitated reach did not differ from control reaches. Temporal changes in taxa richness and the abundance of Philypnodon grandiceps, Nannoperca spp. and three angling taxa occurred after rehabilitation (winter 2003) compared with the before period (winter 2002), but these effects did not differ between rehabilitated and control locations. Highest taxa richness and abundances occurred at the reference location. High salinity coincided with the timing of rehabilitation works, associated with low river discharges due to drought. The negative effects of other large-scale disturbances may have impaired the effectiveness of reachscale rehabilitation or the effects of rehabilitation may take longer than two years to develop in a lowland river subjected to multiple environmental disturbances.

Histological assessment of intermediate - and long-term creatine monohydrate supplementation in mice and rats

Creatine monohydrate (CrM) supplementation appears to be relatively safe based on data from short-term and intermediate-term human studies and results from several therapeutic trials. The purpose of the current study was to characterize pathological changes after intermediate-term and long-term CrM supplementation in mice [healthy control and SOD1 (G93A) transgenic] and rats (prednisolone and nonprednisolone treated). Histological assessment (18-20 organs/tissues) was performed on G93A mice after 159 days, and in Sprague-Dawley rats after 365 days, of CrM supplementation (2% wt/wt) compared with control feed. Liver histology was also evaluated in CD-1 mice after 300 days of low-dose CrM supplementation (0.025 and 0.05 g · kg^-1 · day^-1) and in Sprague-Dawley rats after 52 days of CrM supplementation (2% wt/wt) with and without prednisolone. Areas of hepatitis were observed in the livers of the CrM-supplemented G93A mice (P < 0.05), with no significant inflammatory lesions in any of the other 18-20 tissues/organs that were evaluated. The CD-1 mice also showed significant hepatic inflammatory lesions (P < 0.05), yet there was no negative effect of CrM on liver histology in the Sprague-Dawley rats after intermediate-term or long-term supplementation nor was inflammation seen in any other tissues/organs (P = not significant). Dietary CrM supplementation can induce inflammatory changes in the liver of mice, but not rats. The observed inflammatory changes in the murine liver must be considered in the evaluation of hepatic metabolism in CrM-supplemented mice. Species differences must be considered in the evaluation of toxicological and physiological studies.

Mechanochemical synthesis and characterization of GaN nanocrystals

A solid-state displacement reaction of Ga₂O₃ with Mg₃N₂ has been used to synthesize GaN nanocrystals by mechanochemical processing. X-ray diffraction, transmission electron microscopy (TEM) and selected area electron diffraction (SAED) measurements indicated that the nanocrystals had a hexagonal structure and sizes ranging from 4 to 20thinspnm. Optical absorption and transmission measurement showed the bandgap of the nanocrystals was consistent with that of bulk GaN samples (3.43thinspeV). This study  demonstrates that mechanochemical processing has significant potential for the synthesis of GaN nanocrystals in a simple and efficient way.

Background paper : "Aid effectiveness and selectivity : integrating multiple objectives into aid allocation"

Research on development aid has largely focused on the effectiveness of these transfers in promoting growth or on their allocation among developing countries. Rarely if ever did these research areas intersect, in that studies seeking to explain observed or prescribe optimal inter-country aid allocations did not take into account effectiveness issues and vice versa. Collier and Dollar (C-D, 2002), in a move broadly consistent with the IDA’s long-standing approach to its country allocation system, changed this state of affairs with their “aid selectivity” approach to inter-country aid allocation. C-D, building on the empirical work of Burnside and Dollar (B-D, 1997, 2000), which concluded that the effectiveness of aid in promoting growth depended on the policy regimes of recipient countries, derived “poverty efficient” inter-recipient aid allocations. According to the prescriptive C-D selectivity approach, optimal aid allocation favours countries with high levels of poverty, low per capita incomes and sound policy regimes. Such allocations are considered poverty efficient by maximising the number of people pulled out of poverty. Countries with unsound policies regimes receive less aid in the C-D selectivity approach as these regimes lessen aid’s impact on growth and thus poverty reduction.