Investigating ionic effects applied to water based organocatalysed aldol reactions

Saturated aqueous solutions of various common salts were examined for their effect on aqueous aldol reactions catalysted by a highly active C₂-symmetric diprolinamide organocatalyst developed in our laboratory. With respect to the aldol reaction between cyclohexanone and 4-nitrobenzaldehyde, deionised water was always a superior medium to salt solutions though some correlation to increasing anion size and depression in enantiomeric excess could be observed. Additionally, the complete inhibition of catalyst activity observed when employing tap water could be alleviated by the inclusion of ethylenediaminetetraacetate (EDTA) into the aqueous media prior to reaction initiation. Extension of these reaction conditions demonstrated that these ionic effects vary on a case-to-case basis depending on the ketone/aldehyde combination.

Emotional reactions to real-world events in social networks

A convergence of emotions among people in social networks is potentially resulted by the occurrence of an unprecedented event in real world. E.g., a majority of bloggers would react angrily at the September 11 terrorist attacks. Based on this observation, we introduce a sentiment index, computed from the current mood tags in a collection of blog posts utilizing an affective lexicon, potentially revealing subtle events discussed in the blogosphere. We then develop a method for extracting events based on this index and its distribution. Our second contribution is establishment of a new bursty structure in text streams termed a sentiment burst. We employ a stochastic model to detect bursty periods of moods and the events associated. Our results on a dataset of more than 12 million mood-tagged blog posts over a 4-year period have shown that our sentiment-based bursty events are indeed meaningful, in several ways.

Leaving the professional tennis circuit : exploratory study of experiences and reactions from elite female athletes

In 2002, Tennis Australia commissioned a report into the experiences of elite female past players on leaving the professional tennis circuit. Australian players who were in the top 800 of the Women’s Tennis Association (WTA) end of year rankings and who had left the professional circuit within the previous 15 years were asked by mail to respond to a questionnaire. The questionnaire asked players to describe their feelings about leaving the tour during the time leading up to leaving the tour to two years after retirement. The main findings of the study suggested that those who planned to leave the tour found the transition process easy, whereas those who did not plan to leave the tour found the process difficult. Most players (66%) did not regret leaving the tour, and, although the remaining players responded that they regretted leaving, none attempted a comeback. Tennis Australia has implemented strategies to assist current players on the professional tour based on the results of this study.

Direct asymmetric aldol reactions in water catalysed by a highly active C2-Symmetrical bisprolinamide organocatalyst

A novel C2-symmetrical bisprolinamide organocatalyst was synthesised and used to facilitate asymmetric direct aldol reactions in a water emulsion. Reactions were performed at room temperature with very low catalyst loadings (12.5 mol%) without the required use of additives, co-catalysts or extended reaction times (24 h). This catalyst system was then used with a variety of aldehyde substrates showing good reaction generality for benzaldehydes with cyclohexanone (dr range 77/23 to >99/1, anti/syn; ee range 33% to >99%) and moderate scope with cyclopentanone (dr range 45/55 to 76/24, anti/syn; ee range 14% to 68%). Ultra-low catalysts loadings (0.1 and 0.05 mol%) were also investigated demonstrating catalyst turnover numbers in the order of 1000.

Reactions of Nb2 and Nb3 with CO, D2, N2, and O2 : reconciling experimental kinetics with density functional theory-calculated reaction profiles

 Calculated energy profiles for the reactions of neutral Nb₂ and Nb₃ metal clusters with CO, D₂, N₂, and O₂ are presented. In each reaction path, both a physisorption energy minimum, where the reactant remains intact, and a chemisorption energy minimum, where the reactant has dissociated, are calculated and linked by saddle points. We calculate branching ratios for the forward (dissociative) and reverse reactions which we compare with the experimental kinetic data. It is found that a combination of average thermal energies and barrier heights leads to wide variation in branching ratios which compares favourably to previously determined experimental reaction rates.

Insight into reactions and interface between boron nitride nanotube and aluminium

Nature and mechanism of interfacial reactions between boron nitride nanotubes (BNNTs) and aluminum matrix at high temperature (650 °C) are studied using high-resolution transmission electron microscopy (HRTEM). This study analyzes the feasibility of the use of BNNTs as reinforcement in aluminum matrix composites for structural application, for which interface plays a critical role. Thermodynamic comparison of aluminum (Al)-BNNT with analogous Al-carbon nanotube (Al-CNT) system reveals lesser amount of reaction in the former. Experimental observation also reveals thin (~7 nm) reaction-product formation at Al-BNNT interface even after 120 min of exposure at 650 °C. The spatial distribution of the reaction-product species at the interface is governed by the competitive diffusion of N, Al, and B. Morphology of the reaction products are influenced by their orientation relationship with BNNT walls. A theoretical prediction on Al-BNNT interface in macroscale composite suggests the formation of strong bond between the matrix and reinforcement phase.

Mechanisms linking affective reactions to competition-related and competition-extraneous concerns in male martial artists

The main aim of this study was to examine affective linkages between competition-related and competition-extraneous concern domains. A secondary purpose was to establish the contributions of pre-competition affects to post-competition performance appraisals, independent of pre-competition performance expectations. Thirty-nine highly skilled male martial artists were assessed at five random times a day for a week and 1 h before a major competition on affective states and sources of concern. They also reported their performance expectations and post-competition performance appraisals. Affective states triggered by competition-related and competition-extraneous concerns persisted in time. Carry-over effects were stronger after reports of competition-related concerns, emphasizing the subjective importance of the competitive event. Although positive (enjoyment and surprise) and negative (sadness and guilt) affective spill-over was observed from competition-extraneous to competition-related concerns, the reverse held true only for disgust. These findings may be due to the athletes' ability to regulate affective reactions within a sporting setting, in particular. Spill-over from competition-extraneous to competition-related concerns is indicative of a lesser degree of control over work/study and family life. Given that average weekly negative affects and anger/disgust were independent predictors of post-competition performance appraisals, the phenomenon of spill-over and other affective linkage mechanisms in sport warrant further investigation.

Incidence, clinical spectrum, diagnostic features, treatment and predictors of paradoxical reactions during antibiotic treatment of Mycobacterium ulcerans infections

Background: Paradoxical reactions from antibiotic treatment of Mycobacterium ulcerans have recently been recognized. Data is lacking regarding their incidence, clinical and diagnostic features, treatment, outcomes and risk factors in an Australian population.

Methods: Data was collected prospectively on all confirmed cases of M. ulcerans infection managed at Barwon Health Services, Australia, from 1/1/1998-31/12/2011. Paradoxical reactions were defined on clinical and histological criteria and cases were determined by retrospectively reviewing the clinical history and histology of excised lesions. A Poisson regression model was used to examine associations with paradoxical reactions.

Results: Thirty-two of 156 (21%) patients developed paradoxical reactions a median 39 days (IQR 20-73 days) from antibiotic initiation. Forty-two paradoxical episodes occurred with 26 (81%) patients experiencing one and 6 (19%) multiple episodes. Thirty-two (76%) episodes occurred during antibiotic treatment and 10 (24%) episodes occurred a median 37 days after antibiotic treatment. The reaction site involved the original lesion (wound) in 23 (55%), was separate to but within 3 cm of the original lesion (local) in 11 (26%) and was more than 3 cm from the original lesion (distant) in 8 (19%) episodes. Mycobacterial cultures were negative in 33/33 (100%) paradoxical episodes. Post-February 2009 treatment involved more cases with no antibiotic modifications (12/15 compared with 11/27, OR 5.82, 95% CI 1.12-34.07, p = 0.02) and no further surgery (9/15 compared with 2/27, OR 18.75, 95% CI 2.62-172.73, p < 0.001). Six severe cases received prednisone with marked clinical improvement. On multivariable analysis, age ≥ 60 years (RR 2.84, 95% CI 1.12-7.17, p = 0.03), an oedematous lesion (RR 3.44, 95% CI 1.11-10.70, p=0.03) and use of amikacin in the initial antibiotic regimen (RR 6.33, 95% CI 2.09-19.18, p < 0.01) were associated with an increased incidence of paradoxical reactions.

Conclusions: Paradoxical reactions occur frequently during or after antibiotic treatment of M. ulcerans infections in an Australian population and may be increased in older adults, oedematous disease forms, and in those treated with amikacin. Recognition of paradoxical reactions led to changes in management with less surgery, fewer antibiotic modifications and use of prednisolone for severe reactions.