A concise approach to the polycyclic scaffold of frondosin D

Frondosins A−E, 1−5 (Figure 1), are a family of related marine sesquiterpenoids first isolated in their dextro-rotatory form from the sponge Dysidea frondosa.(1a) Additionally, levo-rotatory frondosins A and D were isolated from an unidentified Eurospongia species.(1b) Frondosins A−E are compounds of interest due to their promising interleukin-8 (IL-8) affinity and protein kinase C inhibition.(1a) IL-8 antagonists are of particular interest in view of their antiinflammatory,(2a) anti-HIV,(1b, 2b) and antitumor(2c-2f) properties. To date, frondosins A, B, and C have been synthesized.(3) Notwithstanding these successes, the frondosins have proved quite a formidable synthetic challenge, and as of yet, there has been no synthesis of frondosin D or E. In this report, we describe our approaches to the molecular scaffold of frondosins D. This work has culminated in a very effective means of producing the trimethylbicyclo[5.4.0]undecane ring system common to all frondosins (shown in bold, Figure 1).

Distress, coping and posttraumatic growth in refugees from Burma

Refugees flee their countries of origin due to supreme hardship and threat to life; frequently bearing witness to mass atrocity. This research is embedded in a salutogenic paradigm which emphasises strength and adjustment. Twenty-five refugees from Burma who were newly arrived in Australia were interviewed and transcripts were analysed using an Interpretive Phenomenological Analytic (IPA) approach. In addition to themes of distress, data revealed an extraordinary adaptive capacity and highlighted strengths, both individually and collectively. Specific adaptive strategies included religiousness, and a sense of duty to family, community and country. Findings have implications for policy and practice that aim to support refugees and asylum seekers.

Production and isolation of ligated metal(IV)-oxo ions by tandem mass spectrometry

High valent metal(IV)-oxo species, \[M(=O)(Melm)(n)(OAc)](+) (M = Mn-Ni, MeIm = 1-methylimidazole, n = 1-2), which are relevant to biology and oxidative catalysis, were produced and isolated in gas-phase reactions of the metal(II) precursor ions \[M(MeIm)(n)(OAc)](+) (M = Mn-Zn, n = 1-3) with ozone. The precursor ions \[M(MeIm)(OAc)](+) and \[M(MeIm)(2)(OAc)](+) were generated via collision-induced dissociation of the corresponding \[M(MeIm)(3)(OAc)](+) ion. The dependence of ozone reactivity on metal and coordination number is discussed. Copyright (C) 2010 John Wiley & Sons, Ltd.

A detailed investigation of nominally 2-D radical-farming scramjet combustion

This paper reports on an investigation of the flow/chemistry coupling inside a nominally two-dimensional inlet-fuelled scramjet configuration. The experiments were conducted at a freestream Mach number of 7.3 and a total flow enthalpy of 4.3MJ/kg corresponding to a Mach 9.7 flight condition. The phenomenon of radical-farming has been studied in detail using two-dimensional OH* chemiluminescence imaging and emission spectroscopy. High signal levels of excited OH (OH*) were detected behind the first shock reflections inside the combustion chamber upstream of any measurable pressure rise from combustion, which occurred towards the rear of the combustor. The production of OH in the first hot pocket initiates the ignition process and then accelerates the combustion process in the next downstream hot pocket. This was confirmed by numerical simulations of premixed hydrogen/air flow through the scramjet. Chemical kinetics analyses reveal that the ignition process is governed by the interaction between various reaction groups leading to a chainbranching explosion for low mean temperature and pressure combustion flowfields.

High-level expression of Rhodotorula gracilis d-amino acid oxidase in Pichia pastoris

By combining gene design and heterologous over-expression of Rhodotorula gracilis D-amino acid oxidase (RgDAO) in Pichia pastoris, enzyme production was enhanced by one order of magnitude compared to literature benchmarks, giving 350 kUnits/l of fed-batch bioreactor culture with a productivity of 3.1 kUnits/l h. P. pastoris cells permeabilized by freeze-drying and incubation in 2-propanol (10% v/v) produce a highly active (1.6 kUnits/g dry matter) and stable oxidase preparation. Critical bottlenecks in the development of an RgDAO catalyst for industrial applications have been eliminated.

Stepwise engineering of a Pichia pastoris D-amino acid oxidase whole cell catalyst

Trigonopsis variabilis D-amino acid oxidase (TvDAO) is a well characterized enzyme used for cephalosporin C conversion on industrial scale. However, the demands on the enzyme with respect to activity, operational stability and costs also vary with the field of application. Processes that use the soluble enzyme suffer from fast inactivation of TvDAO while immobilized oxidase preparations raise issues related to expensive carriers and catalyst efficiency. Therefore, oxidase preparations that are more robust and active than those currently available would enable a much broader range of economically viable applications of this enzyme in fine chemical syntheses. A multi-step engineering approach was chosen here to develop a robust and highly active Pichia pastoris TvDAO whole-cell biocatalyst. As compared to the native T. variabilis host, a more than seven-fold enhancement of the intracellular level of oxidase activity was achieved in P. pastoris through expression optimization by codon redesign as well as efficient subcellular targeting of the enzyme to peroxisomes. Multi copy integration further doubled expression and the specific activity of the whole cell catalyst. From a multicopy production strain, about 1.3 x 103 U/g wet cell weight (wcw) were derived by standard induction conditions feeding pure methanol. A fed-batch cultivation protocol using a mixture of methanol and glycerol in the induction phase attenuated the apparent toxicity of the recombinant oxidase to yield final biomass concentrations in the bioreactor of >or= 200 g/L compared to only 117 g/L using the standard methanol feed. Permeabilization of P. pastoris using 10% isopropanol yielded a whole-cell enzyme preparation that showed 49% of the total available intracellular oxidase activity and was notably stabilized (by three times compared to a widely used TvDAO expressing Escherichia coli strain) under conditions of D-methionine conversion using vigorous aeration. Stepwise optimization using a multi-level engineering approach has delivered a new P. pastoris whole cell TvDAO biocatalyst showing substantially enhanced specific activity and stability under operational conditions as compared to previously reported preparations of the enzyme. The production of the oxidase through fed-batch bioreactor culture and subsequent cell permeabilization is high-yielding and efficient. Therefore this P. pastoris catalyst has been evaluated for industrial purposes.

Why trust the head? Key practices for transformational school leaders to build a purposeful relationship of trust

Trust is widely recognized as one of the key qualities that a successful leader needs to bring about change within his/her organization. Literature has also shown that trust plays a pivotal role in effective school leadership. However, little research has been undertaken to identify specific actions of a transformational school leader enabling him/her to develop purposeful relationships of trust with his/her staff and Chair of the school’s governing body. Using a theoretical framework of transformational leadership in the context of the independent schooling sector in Australia, a multicase study of four highly trusted, transformational school leaders revealed 10 key trust building practices in the Head–staff dyad and three practices in the Head–Chair dyad. These practices were independent of the leader’s personal attributes. The study also revealed an inextricable link between trust and transformational leadership.

What aspects of demographic, personality, attitudes, and perceptions of law enforcement influence self-reported likelihood of drink driving?

The aim of the current study was to examine the associations between a number of individual factors (demographic factors (age and gender), personality factors, risk-taking propensity, attitudes towards drink driving, and perceived legitimacy of drink driving enforcement) and how they influence the self-reported likelihood of drink driving. The second aim of this study was to examine the potential of attitudes mediating the relationship between risk-taking and self-reported likelihood of drink driving. In total, 293 Queensland drivers volunteered to participate in an online survey that assessed their self-reported likelihood to drink drive in the next month, demographics, traffic-related demographics, personality factors, risk-taking propensity, attitudes towards drink driving, and perceived legitimacy of drink driving enforcement. An ordered logistic regression analysis was utilised to evaluate the first aim of the study; at the first step the demographic variables were entered; at step two the personality and risk-taking were entered; at the third step, the attitudes and perceptions of legitimacy variables were entered. Being a younger driver and having a high risk-taking propensity were related to self-reported likelihood of drink driving. However, when the attitudes variable was entered, these individual factors were no longer significant; with attitudes being the most important predictor of self-reported drink driving likelihood. A significant mediation model was found with the second aim of the study, such that attitudes mediated the relationship between risk-taking and self-reported likelihood of drink driving. Considerable effort and resources are utilised by traffic authorities to reducing drink driving on the Australian road network. Notwithstanding these efforts, some participants still had some positive attitudes towards drink driving and reported that they were likely to drink drive in the future. These findings suggest that more work is needed to address attitudes regarding the dangerousness of drink driving.

Adolescent pedometer protocols : examining reactivity, tampering and participants' perceptions

The aim of this study was to investigate adolescents' potential reactivity and tampering while wearing pedometers by comparing different monitoring protocols to accelerometer output. The sample included adolescents (N=123, age range=14-15 years) from three secondary schools in New South Wales, Australia. Schools were randomised to one of the three pedometer monitoring protocols: (i) daily sealed (DS) pedometer group, (ii) unsealed (US) pedometer group or (iii) weekly sealed (WS) pedometer group. Participants wore pedometers (Yamax Digi-Walker CW700, Yamax Corporation, Kumamoto City, Japan) and accelerometers (Actigraph GT3X+, Pensacola, USA) simultaneously for seven days. Repeated measures analysis of variance was used to examine potential reactivity. Bivariate correlations between step counts and accelerometer output were calculated to explore potential tampering. The correlation between accelerometer output and pedometer steps/day was strongest among participants in the WS group (r=0.82, P <= 0.001), compared to the US (r=0.63, P <= 0.001) and DS (r=0.16, P=0.324) groups. The DS (P <= 0.001) and US (P=0.003), but not the WS (P=0.891), groups showed evidence of reactivity. The results suggest that reactivity and tampering does occur in adolescents and contrary to existing research, pedometer monitoring protocols may influence participant behaviour.

Losing sleep : examining the cascading effects of supervisors' experience of injustice on subordinates' psychological health

In this paper, we identify two types of injustice as antecedents of abusive supervision and ultimately of subordinate psychological distress and insomnia. We examine distributive justice (an individual's evaluation of their input to output ratio compared to relevant others) and interactional injustice (the quality of interpersonal treatment received when procedures are implemented). Using a sample of Filipinos in a variety of occupations, we identify two types of injustice experienced by supervisors as stressors that provoke them to display abusive supervision to their subordinates. We examine two consequences of abusive supervision - subordinate psychological distress and insomnia. In addition, we identify two moderators of these relationships, namely, supervisor distress and subordinate self-esteem. We collected survey data from multiple sources including subordinates, their supervisors, and their partners. Data were obtained from 175 matched supervisor-subordinate dyads over a 6-month period, with subordinates' partners providing ratings of insomnia. Results of structural equation modelling analyses provided support for an indirect effects model in which supervisors' experience of unfair treatment cascades down the organization, resulting in subordinate psychological distress and, ultimately in their insomnia. In addition, results partially supported the proposed moderated relationships in the cascading model. © 2010 Taylor & Francis.

The collision induced loss of carbon monoxide from deprotonated benzyl benzoate in the gas phase. An anionic 1,2-Wittig type rearrangement

The ion PhCO2--CHPh, upon collision activation, undergoes competitive losses of CO and CO2 of which the former process produces the base peak of the spectrum. Product ion and substituent effect (Hammett) studies indicate that PhCO2--CHPh cyclises to a deprotonated hydroxydiphenyloxirane which ring opens to PhCOCH(O-)Ph. This anion then undergoes an anionic 1,2-Wittig type rearrangement {through [PhCO- (PhCHO)]} to form Ph2CHO- and CO. The mechanism of the 1,2-rearrangement has been probed by an ab initio study [at MP4(SDTQ)/6-31++G(d,p) level] of the model system HCOCH2O- →; MeO- + CO The analogous system RCO2--CHPh (R = alkyl) similarly loses CO, and the migratory aptitudes of the alkyl R groups in this reaction are Bu′ > Me > Et ∼Pri). This trend correlates with the order of anion basicities (i.e. the order of ΔG○acid values of RH), supporting the operation of an anion migration process. The loss of CO2 from PhCO2--CHPh yields Ph2CH- as the anionic product: several mechanistic scenarios are possible, one of which involves an initial ipso nucleophilic substitution.

Using objective physical activity measures with youth : How many days of monitoring are needed?

Purpose The purpose of this study was to establish the minimal number of days of monitoring required for accelerometers to assess usual physical activity in children. Methods A total of 381 students (189 M, 192 F) wore a CSA 7164 uniaxial accelerometer for seven consecutive days. To examine age-related trends students were grouped as follows: Group I: grades 1-3 (N = 92); Group II: grades 4-6 (N = 98); Group III: grades 7-9 (N = 97); Group IV: grades 10-12 (N = 94). Average daily time spent in moderate-to-vigorous physical activity (MVPA) was calculated from minute-by-minute activity counts using the regression equation developed by Freedson et al. (1997). Results Compared with adolescents in grades 7 to 12, children in grades 1 to 6 exhibited less day-to-day variability in MVPA behavior. Spearman-Brown analysts indicated that between 4 and 5 d of monitoring would be necessary to a achieve a reliability of 0.80 in children, and between 8 and 9 d of monitoring would be necessary to achieve a reliability of 0.80 in adolescents. Within all grade levels, the 7-d monitoring protocol produced acceptable estimates of daily participation in MVPA (R = 0.76 (0.71-0.81) to 0.87 (0.84-0.90)). Compared with weekdays, children exhibited significantly higher levels of MVPA on weekends, whereas adolescents exhibited significantly lower levels of MVPA on weekends. Principal components analysis revealed two distinct time components for MVPA during the day for children (early morning, rest of the day), and three distinct time components for MVPA during the day for adolescents (morning, afternoon, early evening). Conclusions These results indicate that a 7-d monitoring protocol provides reliable estimates of usual physical activity behavior in children and adolescents and accounts for potentially important differences in weekend versus weekday activity behavior as well as differences in activity patterns within a given day.

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.