Chemo-enzymatic synthesis of unnatural amino acids

A general chemo-enzymatic process has been developed to prepare enantiomerically pure L- and D-amino acids in high yield by deracemisation of racemic starting materials. The method has been developed from initial academic studies to be a robust, scalable industrial process. Unnatural amino acids, in high optical purity, are a rapidly growing class of intermediates required for pharmaceuticals, agrochemicals and other fine chemical applications. However, no single method has proven sufficiently adaptable to prepare these compounds generally at large scale. Our approach uses an enantioselective oxidase biocatalyst and a non-selective chemical reducing agent to effect the stereoinversion of one enantiomer and can result in an enantiomeric excess of > 99 % from a starting racemate, and product yields over 90 %. The current approach compares very favourably to resolution methods which have a maximum single pass yield of 50 %. Efficient methods have been developed to adapt the biocatalyst used in this process towards new target compounds and to optimise key factors which improve the process efficiency and offer competitive economics at scale.

Determinants of physical activity in Singaporean adolescents

Backgroun An understanding of the factors that influence physical activity behavior is an important prerequisite for the design and implementation of physical activity interventions in adolescents. To date, no studies have investigated the factors that influence physical activity participation in Singaporean adolescents. Purpose he purpose of this study was to identify the psychosocial and environmental factors that influence physical activity in a representative sample of Singaporean adolescents (N=1,814, 919 boys, 895 girls, mean age 14.4 +/- 1.1 years). Methods Participants completed the Three-Day Physical Activity Recall and a questionnaire measuring hypothesized psychosocial and environmental correlates of physical activity. Results Hierarchical regression revealed self-efficacy, enjoyment of physical activity, parental support, and participation in sport teams to be significant correlates of physical activity. Conclusion Interventions promoting physical activity in Singaporean adolescents should aim to increase self-efficacy perceptions by offering enjoyable, developmentally appropriate physical activity options that promote mastery and adopt policies that increase parental support and awareness of community physical activity programs.

The role of vascularization in 3-D tissue engineering

The role of vascularization in 3-D tissue engineering was studied. Mouse fat, angiogenic growth factors, adult human stem cells and fat tissue have been inserted and subsequent tissue growth was monitored. Human fat grafts or human lipoaspirates in SCID mouse chambers induced mouse fat generation at 6 weeks. Tissue engineering models utilizing intrinsic vascularization have major advantages including rapid and appropriate vascularization of new tissues.

DDT resistance and transformation by different microbial strains isolated from DDT-contaminated soils and compost materials

Bioremediation is a potential option to treat 1, 1, 1-trichloro-2, 2 bis (4-chlorophenyl) ethane (DDT) contaminated sites. In areas where suitable microbes are not present, the use of DDT resistant microbial inoculants may be necessary. It is vital that such inoculants do not produce recalcitrant breakdown products e.g. 1, 1-dichloro-2, 2-bis (4-chlorophenyl) ethylene (DDE). Therefore, this work aimed to screen DDT-contaminated soil and compost materials for the presence of DDT-resistant microbes for use as potential inoculants. Four compost amended soils, contaminated with different concentrations of DDT, were used to isolate DDT-resistant microbes in media containing 150 mg I -1 DDT at three temperatures (25, 37 and 55°C). In all soils, bacteria were more sensitive to DDT than actinomycetes and fungi. Bacteria isolated at 55°C from any source were the most DDT sensitive. However DDT-resistant bacterial strains showed more promise in degrading DDT than isolated fungal strains, as 1, 1-dichloro 2, 2-bis (4-chlorophenyl) ethane (DDD) was a major bacterial transformation product, while fungi tended to produce more DDE. Further studies on selected bacterial isolates found that the most promising bacterial strain (Bacillus sp. BHD-4) could remove 51% of DDT from liquid culture after 7 days growth. Of the amount transformed, 6% was found as DDD and 3% as DDE suggesting that further transformation of DDT and its metabolites occurred.

Managing Ethical Dilemmas

This chapter reviews almost a decade of research and writing undertaken by the authors into ethical dilemmas faced by leaders in a number of different operational contexts, including schools, universities and the public sector. The importance of this body of work is emphasised by one of our research participants who argued that ethical dilemmas were the 'bread and butter' of what leaders do. The chapter comprises four main sections. The first section overviews key theoretical aspects as background to the chapter, including relevant discussions about ethics and ethical decision-making. The second section synthesises the research findings from our work in the three contexts noted above, drawing out a set of learnings that contribute to better understandings of the nature, complexities and challenges of ethical dilemmas. This section is followed by a discussion of an explanatory conceptual model of ethical dilemmas that was developed initially from the literature and confirmed by our research. The model reminds us of some of the critical issues at play in ethical dilemmas, and some of the consequences and implications for organisational culture building they can generate. By way of a short scenario, the final section provides a theory-to-practice illustration of an ethical dilemma in action. A set of recommendations, drawn from the ideas of school leaders who have worked with this and similar dilemmas, is offered as a way forward to better understanding and resolution of such dilemmas so prevalent in our schools today.

In conversation with the Honourable Ian Callinan AC

When, in 1977, the Australian electorate provided a double majority to effect a change of section 72 of the Commonwealth Constitution requiring judges of the High Court of Australia to retire at the age of 70 years old, I doubt we understood the continuing capacity of these esteemed members of the judiciary. For the opportunity to sit and talk with Ian Callinan AC who, in compliance with that amendment, retired from the High Court in September 2007, I needed to wait until he returned from The Hague where he was sitting as a Judge ad hoc on the International Court of Justice. Although a native of Casino, New South Wales, Mr Callinan is regarded as a Queenslander. Indeed, he grew up in Brisbane, finished high school at Brisbane Grammar and graduated in law at The University of Queensland. Appointed in 1978 as a Queen’s Counsel, Mr Callinan enjoyed this period of his legal career and we discussed an aspect of the Christopher Skase case, which reinforced my belief that Mr Callinan is an incredibly skilful advocate. On 14 September 1998, ABC Four Corners broadcasted the views of some prominent Australians on the appointment of Mr Callinan to the High Court. In assessing the type of person Mr Callinan is, Tony Morris QC said: “Ian Callinan isn't a coward���, while former Commonwealth Attorney-General, Michael Lavarch, said: “He was regarded as an absolutely outstanding criminal lawyer within the Queensland legal profession, I mean really a top-notch advocate”. I was not interested in raising any of the controversial issues that Mr Callinan has encountered as an advocate in high profile matters. I wanted to know how he felt about his time on the High Court, what his thoughts are on the operation of the High Court, the IP cases he decided, the real life issues that he feels impact on counsel who are appearing before the High Court and the people he regarded as role models. During our conversation, Mr Callinan laughed often and when he did his eyes lit up, revealing his passion for life. He is an incredibly genuine Australian who loved his time as a barrister, enjoyed his role on the High Court, enjoys his current job as mediator, loves writing novels, has a great desire for continual improvement in the quality of legal education and legal advocacy and sees a need for change in IP law. When I asked: “So, what might the future hold for you?”, he laughed and said: “Well, at my age I don’t have a long horizon time”. I said: “Just enjoy the journey?”, to which Mr Callinan responded: “Exactly”.

Drosophila 3′ UTRs are more complex than protein-coding sequences

The 3′ UTRs of eukaryotic genes participate in a variety of post-transcriptional (and some transcriptional) regulatory interactions. Some of these interactions are well characterised, but an undetermined number remain to be discovered. While some regulatory sequences in 3′ UTRs may be conserved over long evolutionary time scales, others may have only ephemeral functional significance as regulatory profiles respond to changing selective pressures. Here we propose a sensitive segmentation methodology for investigating patterns of composition and conservation in 3′ UTRs based on comparison of closely related species. We describe encodings of pairwise and three-way alignments integrating information about conservation, GC content and transition/transversion ratios and apply the method to three closely related Drosophila species: D. melanogaster, D. simulans and D. yakuba. Incorporating multiple data types greatly increased the number of segment classes identified compared to similar methods based on conservation or GC content alone. We propose that the number of segments and number of types of segment identified by the method can be used as proxies for functional complexity. Our main finding is that the number of segments and segment classes identified in 3′ UTRs is greater than in the same length of protein-coding sequence, suggesting greater functional complexity in 3′ UTRs. There is thus a need for sustained and extensive efforts by bioinformaticians to delineate functional elements in this important genomic fraction. C code, data and results are available upon request.

Serum 25-hydroxy vitamin D concentrations are more deficient/insufficient in peritoneal dialysis than haemodialysis patients in a sunny climate

Background Research has identified associations between serum 25(OH)D and a range of clinical outcomes in chronic kidney disease and wider populations. The present study aimed to investigate vitamin D deficiency/insufficiency in dialysis patients and the relationship with vitamin D intake and sun exposure. Methods A cross-sectional study was used. Participants included 30 peritoneal dialysis (PD) (43.3% male; 56.87 ± 16.16 years) and 26 haemodialysis (HD) (80.8% male; 63.58 ± 15.09 years) patients attending a department of renal medicine. Explanatory variables were usual vitamin D intake from diet/supplements (IU day−1) and sun exposure (min day−1). Vitamin D intake, sun exposure and ethnic background were assessed by questionnaire. Weight, malnutrition status and routine biochemistry were also assessed. Data were collected during usual department visits. The main outcome measure was serum 25(OH)D (nm). Results Prevalence of inadequate/insufficient vitamin D intake differed between dialysis modality, with 31% and 43% found to be insufficient (<50 nm) and 4% and 33% found to be deficient (<25 nm) in HD and PD patients, respectively (P < 0.001). In HD patients, there was a correlation between diet and supplemental vitamin D intake and 25(OH)D (ρ = 0.84, P < 0.001) and average sun exposure and 25(OH)D (ρ = 0.50, P < 0.02). There were no associations in PD patients. The results remained significant for vitamin D intake after multiple regression, adjusting for age, gender and sun exposure. Conclusions The results highlight a strong association between vitamin D intake and 25(OH)D in HD but not PD patients, with implications for replacement recommendations. The findings indicate that, even in a sunny climate, many dialysis patients are vitamin D deficient, highlighting the need for exploration of determinants and consequences.

Adsorption of the herbicide 2,4-D on organo-palygorskite

Among the clay minerals, montmorillonite is the most extensively studied material using as adsorbents, but palygorskite and its organically modified products have been least explored for their potential use in contaminated water remediation. In this study, an Australian palygorskite was modified with cationic surfactants octadecyl trimethylammonium bromide and dioctadecyl dimethylammonium bromide at different doses. A full structural characterization of prepared organo-palygorskite by X-ray diffraction, infrared spectroscopy, surface analysis and thermogravimetric analysis was performed. The morphological changes of palygorskite before and after modification were recorded using scanning electron microscopy, which showed the surfactant molecules can attach on the surface of rod-like crystals and thus can weaken the interactions between palygorskite single crystals. Real surfactants loadings on organo-palygorskites were also calculated based on thermogravimetric analysis. 1 CEC, 2 CEC octadecyl trimethylammonium bromide modified palygorskites, 1 CEC and 2 CEC dioctadecyl dimethylammonium bromide modified palygorskites absorbed as much as 12 mg/g, 42 mg/g, 9 mg/g and 25 mg/g of 2,4- dichlorophenoxyacetic acid respectively. This study has shown a potential on organo-palygorskites for organic herbicide adsorption especially anionic ones from waste water. In addition, equilibration time effects and the Langmuir and Freundlich models fitting were also investigated in details.

Synthesis, characterization and comparative study of thiophene- benzothiadiazole based donor-acceptor-donor (D-A-D) materials

The synthesis and characterization of solution processable donor-acceptor-donor (D-A-D) based conjugated molecules with varying ratios of thiophene as donor (D) and benzothiadiazole as acceptor (A) are reported. Optical, electrochemical, thermal, morphological and organic thin film transistor (OTFT) device properties of these materials were investigated. The thermal and polarized optical microscope analysis indicates that the materials having higher D/A ratios exhibit both liquid crystalline (LC) and OTFT behavior. AFM analysis of the materials having D/A ratios of 3 and 4 (3T1B and 4T1B) show well ordered structures, resulting from strong π-π interchain interactions compared to the other molecules in this study. A XRD patterns for 3T1B and 4T1B thin films also shows high crystalline ordering. Solution processed OTFTs of 3T1B and 4T1B have shown un-optimized charge carrier mobilities of 2 × 10 -2 cm 2 V -1 s -1 and 4 × 10 -3 cm 2 V -1 s -1, respectively on bare Si/SiO 2 substrate.

Thiophene-benzothiadiazole-thiophene (D-A-D) based polymers : Effect of donor/acceptor moieties adjacent to D-A-D segment on photophysical and photovoltaic properties

New push-pull copolymers based on thiophene (donor) and benzothiadiazole (acceptor) units, poly[4,7-bis(3-dodecylthiophene-2-yl) benzothiadiazole-co- thiophene] (PT3B1) and poly[4,7-bis(3-dodecylthiophene-2-yl) benzothiadiazole-co-benzothiadiazole] (PT2B2), are designed and synthesized via Stille and Suzuki coupling routes respectively. Gel permeation chromatography shows the number average molecular weights are 31100 and 8400 g mol-1 for the two polymers, respectively. Both polymers have shown absorption throughout a wide range of the UV-vis region, from 300 to 650 nm. A significant red shift of the absorption edge is observed in thin films compared to solution of the copolymers; the optical band gap is in the range of 1.7 to 1.8 eV. Cyclic voltammetry indicates reversible oxidation and reduction processes with HOMO energy levels calculated to be in the range of 5.2 to 5.4 eV. Upon testing both materials for organic field-effect transistors (OFETs), PT3B1 showed a hole mobility of 6.1 × 10-4 cm2 V-1 s -1, while PT2B2 did not show any field effect transport. Both copolymers displayed a photovoltaic response when combined with a methanofullerene as an electron acceptor. The best performance was achieved when the copolymer PT3B1 was blended with [70]PCBM in a 1:4 ratio, exhibiting a short-circuit current of 7.27 mA cm-2, an open circuit voltage of 0.85 V, and a fill factor of 41% yielding a power conversion efficiency of 2.54% under simulated air mass (AM) 1.5 global (1.5 G) illumination conditions (100 mW cm-2). Similar devices utilizing PT2B2 in place of PT3B1 demonstrated reduced performance with a short-circuit current of 4.8 mA cm -2, an open circuit voltage of 0.73 V, and a fill factor of 30% resulting in a power conversion efficiency of roughly 1.06%.

A case study of the Iranian national railway and its absolute capacity expansion using analytical models

Identifying railway capacity is an important task that can identify "in principal" whether the network can handle an intended traffic flow, and whether there is any free capacity left for additional train services. Capacity determination techniques can also be used to identify how best to improve an existing network, and at least cost. In this article an optimization approach has been applied to a case study of the Iran national railway, in order to identify its current capacity and to optimally expand it given a variety of technical conditions. This railway is very important in Iran and will be upgraded extensively in the coming years. Hence the conclusions in this article may help in that endeavor. A sensitivity analysis is recommended to evaluate a wider range of possible scenarios. Hence more useful lower and upper bounds can be provided for the performance of the system