Soluble manganese (IV); a new chemiluminescence reagent

The oxidations of twenty five organic and inorganic species, with solublised manganese(IV), were found to elicit analytically useful chemiluminescence with detection limits (3 × S/N) for Mn(II), Fe(II), morphine and codeine of 5 × 10^–8 M, 2.5 × 10^–7 M, 7.5 × 10^–8 M and 5 × 10^–8 M, respectively. Additionally, the corrected spectra from four different analytes gave wavelengths of maximum emission in the range from 733 nm up to 740 nm suggesting that all these chemiluminescence reactions shared a common emitting species.

Gait termination : a review of experimental methods and the effects of aging and gait pathologies

The study of human gait has expanded and diversified to the extent that it is now possible to identify a substantive literature concerning a variety of gait tasks, such as gait initiation [Halliday SE, Winter DA, Frank JS, Patla AE, Prince F. The initiation of gait in young, elderly, and Parkinson's disease subjects. Gait Posture 1998;8:8–14; Mickelborough J, van der Linden ML, Tallis RC, Ennos AR. Muscle activity during gait initiation in normal elderly people. Gait Posture 2004;19:50–57], stepping over and across obstacles [Patla AE, Prentice SD, Robinson C, Newfold J. Visual control of locomotion: strategies for changing direction and for going over obstacles. J Exp Psych 1991;17:603–34; Chen, HC, Ashton-Miller JA, Alexander NB, Schultz AB. Effect of age and available response time on ability to step over an obstacle. J Gerontol 1994;49:227–33; Sparrow WA, Shinkfield AJ, Chow S, Begg RK. Gait characteristics in stepping over obstacles. Hum Mov Sci 1996;15:605–22; Begg RK, Sparrow WA, Lythgo ND. Time-domain analysis of foot–ground reaction forces in negotiating obstacles. Gait Posture 1998;7:99–109; Patla AE, Rietdyk S. Visual control of limb trajectory over obstacles during locomotion: effect of obstacle height and width. Gait Posture 1993;1:45–60] negotiating raised surfaces such as curbs and stairs [Begg RK, Sparrow WA. Gait characteristics of young and older individuals negotiating a raised surface: implications for the prevention of falls. J Gerontol Med Sci 2000;55A:147–54; Mcfayden BJ, Winter DA. An integrated biomechanical analysis of normal stair ascent and descent. J Biomech 1988;21:733–44]. In addition, increasing research interest in age-related declines in gait that might predispose individuals to falls has engendered a very extensive literature concerning ageing effects on gait. While rapid locomotor adjustments are common in the course of daily activities there has been no previous review of the findings concerning gait adaptations when walking is terminated both rapidly and unexpectedly. The aims of this review were first, to summarise the key research findings and methodological considerations from studies of termination. The second aim was to demonstrate the effects of ageing and gait pathologies on termination with respect to the regulation of step characteristics, lower-limb muscle activation patterns and foot–ground reaction forces.

Chemistry, spectroscopy and analytical applications of certain chemiluminescent reactions

Chemiluminescence, the production of light from a chemical reaction, has found widespread use in analytical chemistry. Both tris (2, 2’-bipyridyl) ruthenium (II) and acidic potassium permanganate are chemiluminescence reagents that have been employed for the determination of a diverse range of analytes. This thesis encompasses some fundamental investigations into the chemistry and spectroscopy of these chemiluminescence reactions as well as extending the scope of their analytical applications. Specifically, a simple and robust capillary electrophoresis chemiluminescence detection system for the determination of codeine, O6-methylcodeine and thebaine is described, based upon the reaction of these analytes with chemically generated tris(2,2'-bipyridyl)ruthenium(III) prepared in sulfuric acid (0.05 M). The reagent solution was contained in a glass detection cell, which also held both the capillary and the cathode. The resultant chemiluminescence was monitored directly using a photomultiplier tube mounted flush against the base of the detection cell. The methodology, which incorporated a field amplification sample introduction procedure, realised detection limits (3a baseline noise) of 5 x 10~8 M for both codeine and O6-methylcodeine and 1 x 10~7 M for thebaine. The relative standard deviations of the migration times and the peak areas for the three analytes ranged from 2.2 % up to 2.5 % and 1.9 % up to 4.6 % respectively. Following minor instrumental modifications, morphine, oripavine and pseudomorphine were determined based upon their reaction with acidic potassium permanganate in the presence of sodium polyphosphate. To ensure no migration of the permanganate anion occurred, the anode was placed at the detector end whilst the electroosmotic flow was reversed by the addition of hexadimethrine bromide (0.001% m/v) to the electrolyte. The three analytes were separated counter to the electroosmotic flow via their interaction with a-cyclodextrin. The methodology realised detection limits (3 x S/N) of 2.5 x 10~7 M for both morphine and oripavine and 5 x 10~7 M for pseudomorphine. The relative standard deviations of the migration times and the peak heights for the three analytes ranged from 0.6 % up to 0.8 % and 1.5% up to 2.1 % respectively. Further improvements were made by incorporating a co-axial sheath flow detection cell. The methodology was validated by comparing the results realised using this technique with those obtained by high performance liquid chromatography (HPLC), for the determination of both morphine and oripavine in seven industrial process liquors. A complimentary capillary electrophoresis procedure with UV-absorption detection was also developed and applied to the determination of morphine, codeine, oripavine and thebaine in nine process liquors. The results were compared with those achieved using a standard HPLC method. Although over eighty papers have appeared in the literature on the analytical applications of acidic potassium permanganate chemiluminescence, little effort has been directed towards identifying the origin of the luminescence. It was found that chemiluminescence was generated during the manganese(III), manganese(IV) and manganese(VII) oxidations of sodium borohydride, sodium dithionite, sodium sulfite and hydrazine sulfate in acidic aqueous solution. From the corrected chemiluminescence spectra, the wavelengths of maximum emission were 689 ± 5 nm and 734 ± 5 nm when the reactions were performed in sodium hexametaphosphate and sodium dihydrogenorthophosphate or orthophosphoric acid environments respectively. The corrected phosphorescence spectrum of manganese(II) sulfate in a solution of sodium hexametaphosphate at 77 K, exhibited two peaks with maxima at 688 nm and 730 nm. The chemical and spectroscopic evidence presented strongly supported the postulation that the emission was an example of solution phase chemically induced phosphorescence of manganese(II). Thereby confirming earlier predictions that the chemiluminescence from acidic potassium permanganate reactions originated from an excited manganese(II) species. Additionally, these findings have had direct analytical application in that manganese(IV) was evaluated as a new reagent for chemiluminescence detection. The oxidations of twenty five organic and inorganic species, with solublised manganese(IV), were found to elicit analytically useful chemiluminescence with detection limits (3 x S/N) for Mn(II), Fe(II), morphine and codeine of 5 x 10-8 M, 2.5 x 10-7 M, 7.5 x 10-8 M and 5 x 10-8M, respectively. The corrected emission spectra from four different analytes gave wavelengths of maximum emission in the range from 733 nm up to 740 nm indicating that these chemiluminescence reactions also shared a common emitting species, excited manganese(II). Whilst several analytical problems were addressed in this thesis and answers to certain questions regarding the fundamentals of acidic potassium permanganate chemiluminescence were proposed, there are several areas that would benefit from further research. These are outlined in the final chapter of this thesis.

Distributive justice and the Nash bargaining solution

Suppes-Sen dominance or SS-proofness (SSP) is a commonly accepted criterion of impartiality in distributive justice. Mariotti (Review of Economic Studies, 66, 733–741, 1999) characterized the Nash bargaining solution using Nash’s (Econometrica, 18, 155–162, 1950) scale invariance (SI) axiom and SSP. In this article, we introduce equity dominance (E-dominance). Using the intersection of SS-dominance and E-dominance requirements, we obtain a weaker version of SSP (WSSP). In addition, we consider α − SSP, where α measures the degree of minimum acceptable inequity aversion; α − SSP is weaker than weak Pareto optimality (WPO) when α = 1. We then show that it is still possible to characterize the Nash solution using WSSP and SI only or using α -SSP, SI, and individual rationality (IR) only for any a Î [0,1)[01). Using the union of SS-dominance and E-dominance requirements, we obtain a stronger version of SSP (SSSP). It turns out that there is no bargaining solution that satisfies SSSP and SI, but the Egalitarian solution turns out to be the unique solution satisfying SSSP.

Identification of incident fractures : the Geelong Osteoporosis Study

Background: Complete fracture ascertainment is critical for fracture cost estimates and planning for future health care facilities. Virtually complete ascertainment is possible for hip fractures because they nearly always require hospitalisation.

Aims: To validate the use of radiological reports as a resource for ascertaining fracture cases, using hip fracture as a model.

Methods: Hip fracture rates obtained from radiological reports were compared with rates obtained from hospital discharge summaries of medical records using International Classification of Diseases-9 (ICD-9) codes 820.0–820.9 and 733.1 over a three-year period.

Results: Hip fracture cases numbered 589 using radiological reports and 585 using medical records. Discharge summaries failed to identify 15 cases ascertained through radiology reports whereas 11 cases ascertained through medical records were not identified from X-ray reports. The age-specific incidence rates for radiological ascertainment were within the 95% confidence limits of the rates derived from medical records.

Conclusions: Among a population of patients generally admitted to hospital for treatment of their fracture, we were able to identify more cases from radiological reports than from medical records. Incidence rates for hip fracture were comparable using the two methods. Radiological reports provide a valuable resource for identifying incident fractures. This method of case ascertainment would be suitable for identifying both major and minor fractures in regions with self-contained health services where access to all radiological reports is possible.

Isolation and characterisation via 454 sequencing of microsatellites from the tawny frogmouth, Podargus strigoides (Class Aves, Family Podargidae)

We isolated 24 novel polymorphic microsatellite markers from the tawny frogmouth, a nocturnal bird endemic to Australia, which has successfully adapted to urban environments. Initially, 454 shotgun sequencing was used to identify 733 loci with primers designed. Of these, we trialled 30 in the target species of which all amplified a product of expected size. Subsequently, all 30 of these loci were screened for variation in 25 individuals, from a single population in Melbourne, Victoria, Australia. Twenty-eight loci were polymorphic with observed heterozygosity ranging from 0.03 to 0.96 (mean 0.58) and the number of alleles per locus ranged from 2 to 18 (average of 6.5); we confirmed that 24 loci conformed to Hardy–Weinberg expectations. The 24 loci identified here will be sufficient to unequivocally identify individuals and will be useful in understanding the reproductive ecology, population genetics and the gene flow amongst localities in urban environments where this bird thrives.

Web-based alcohol intervention for Māori university students: double-blind, multi-site randomized controlled trial

AIMS: Like many indigenous peoples, New Zealand Māori bear a heavy burden of alcohol-related harm relative to their non-indigenous compatriots, and disparities are greatest among young adults. We tested the effectiveness of web-based alcohol screening and brief intervention (e-SBI) for reducing hazardous drinking among Māori university students. DESIGN: Parallel, double-blind, multi-site, randomized controlled trial. SETTING: Seven of New Zealand's eight universities. PARTICIPANTS: In April 2010, we sent e-mail invitations to all 6697 17-24-year-old Māori students to complete a brief web questionnaire including the Alcohol Use Disorders Identification Test (AUDIT)-C, a screening tool for hazardous and harmful drinking. Those screening positive were computer randomized to: <10 minutes of web-based alcohol assessment and personalized feedback (intervention) or screening alone (control). MEASUREMENTS: We conducted a fully automated 5-month follow-up assessment with observers and participants blinded to study hypotheses, design and intervention delivery. Pre-determined primary outcomes were: (i) frequency of drinking, (ii) amount consumed per typical drinking occasion, (iii) overall volume of alcohol consumed and (iv) academic problems. FINDINGS: Of the participants, 1789 were hazardous or harmful drinkers (AUDIT-C ≥ 4) and were randomized: 850 to control, 939 to intervention. Follow-up assessments were completed by 682 controls (80%) and 733 intervention group members (78%). Relative to controls, participants receiving intervention drank less often [RR = 0.89; 95% confidence interval (CI): 0.82-0.97], less per drinking occasion (RR = 0.92; 95% CI: 0.84-1.00), less overall (RR = 0.78; 95% CI: 0.69-0.89) and had fewer academic problems (RR = 0.81; 95% CI: 0.69-0.95). CONCLUSIONS: Web-based screening and brief intervention reduced hazardous and harmful drinking among non-help-seeking Māori students in a large-scale pragmatic trial. The study has wider implications for behavioural intervention in the important but neglected area of indigenous health.

Rebound or resignation: developing a predictive model of return to subjective wellbeing set-point

Though subjective wellbeing (SWB) is generally stable and consistent over time, it can fall below its set-point in response to adverse life events. However, deviations from set-point levels are usually only temporary, as homeostatic processes operate to return SWB to its normal state. Given that income and close interpersonal relationships have been proposed as powerful external resources that are coincident with higher SWB, access to these resources may be an important predictor of whether or not a person is likely to recover their SWB following a departure from their set-point. Under the guiding framework of SWB Homeostasis Theory, this study considers whether access to a higher income and a committed partner can predict whether people who score lower than normal for SWB at baseline will return to normal set-point levels of SWB (rebound) or remain below the normal range (resigned) at follow-up. Participants were 733 people (53.3 % female) from the Australian Unity Longitudinal Wellbeing Study who ranged in age from 20 to 92 years (M = 59.65 years; SD = 13.15). Logistic regression analyses revealed that participants’ demographic characteristics were poor predictors of whether they rebounded or resigned. Consistent with homeostasis theory, the extent of departure from the proposed normal SWB set-point at baseline was significantly associated with rebound or resignation at time 2. These findings have implications for the way that SWB measures can be used in professional practice to identify people who are particularly vulnerable to depression and to guide the provision of appropriate and effective therapeutic interventions.