Hydrolytic kinetic resolution of terminal mono- and bis-epoxides in the synthesis of insect pheromones: routes to (-)-(R)- and (+)-(S)-10-methyldodecyl acetate, (-)-(R)-10-methyl-2-tridecanone, (-)-(R)-(Z)-undec-6-en-2-ol (Nostrenol), (-)-(1R,7R)-1,7-dime

Hydrolytic kinetic resolution (HKR) of functionalised epoxides using (salen)Co(OAc) complexes provides enantiomerically enriched epoxides and diols, which have been transformed into important insect sex pheromones. In this general approach, (-)-(R)- and (+)-(S)-10-methyldodecyl acetates from the smaller tea tortrix moth were obtained, as was (-)-(R)-10-methyltridecan-2-one from the southern corn rootworm. The (S)-epoxide obtained from undec-1-en-6-yne was transformed to (-)-(R)-(Z)-undec-6-en-2-ol (Nostrenol) from ant-lions. HKR of appropriate bisepoxides was also investigated, and transformations of the resulting bisepoxides and epoxydiols provided (-)-(1R,7R)-1,7-dimethylnonylpropanoate from corn rootworms, (-)-(6R,12R)-6,12-dimethylpentadecan-2-one from the female banded cucumber beetle, and (-)-(2S,11S)-2,11-diacetoxytridecane and (+)-(2S,12S)-2,12-diacetoxytridecane from female pea-midges. (C) 2002 Elsevier Science Ltd. All rights reserved.

Are transitions in human gait determined by mechanical, kinetic or energetic factors?

It is currently unclear whether it is the need to maintain metabolic efficiency, the need to keep skeletal loading below critical force levels, or simple mechanical factors that drive the walk-to-run (W R) and run-to-walk (R-W) transitions in human gait. Eighteen adults (9 males and 9 females) locomoted on an instrumented treadmill using their preferred gait. Each completed 2 ascending (W-R) and 2 descending (R-W) series of trials under three levels of loading (0%, 15% and 30% body weight). For each trial, participants locomoted for 60 s at each of 9 different speeds -4 speeds both above and below their preferred transition speed (PTS) plus their PTS. Evidence was sought for critical levels of key kinetic (maximum vertical force, impulse, first peak force, time to first peak force and maximum loading rate), energetic (oxygen consumption, transport cost) and mechanical variables (limb lengths, strength) predictive of the gait transition. Analyses suggested the kinetic variables of time to first peak force and loading rate as the most likely determinants of the W-R and R-W transitions. (C) 2003 Elsevier Science B.V. All rights reserved.

Improving attitude-behavior correspondence through exposure to normative support from a salient ingroup

Two experiments were conducted to test predictions derived from social identity/self-categorization theory concerning the role of group norms in attitude-behavior consistency. In Experiment 1, 160 students who could be classified as having a more or less certain target attitude were exposed to attitude congruent versus incongruent normative support from a relevant reference group (own university) under conditions of low versus high group salience. Experiment 2 was very similar in design and methodology (N=180), but a different correlate of attitude accessibility was used (an experimental manipulation of repeated expression), the target attitude was changed, and the reference group was gender. Across the 2 experiments there was consistent support for the hypothesis that participants would behave more in accordance with their attitudes when they received normative support for, rather than opposition to, their original attitude from a relevant reference group (i.e., their ingroup, not an outgroup). There was slightly weaker support for the second hypothesis that this effect would be stronger under high-than low-salience conditions. The third hypothesis (see Fazio, 1986), that attitude certainty and repeated expression of the attitude would strengthen attitude-behavior consistency, was well supported, as was the expectation that accessibility effects would be independent of reference group norm effects on attitude-behavior consistency.

Predictors of cheating behavior at a university: A lesson from the psychology of work

The present study investigated students' behavior across academic departments to establish how personality, demographic, educational, attitudinal, and climate (both psychological and departmental) predicted self-reported cheating behavior at a university, Participants were 107 students from a variety of academic disciplines, The results explain 50.5% of the variability in self-reported cheating behavior in terms of demographic (male, school education qualifications), departmental climate, and individual differences (Lie and Neuroticism scales), We concluded that an expanded theoretical perspective (utilizing a wide range of person and situation variables) explained more variability than would otherwise be explained from any single perspective, and that findings from the literature of integrity at work generalize to educational settings. Finally, we discuss the limitations and implications of this research.

Rumors and stable-cause attribution in prediction and behavior

Two stock-market simulation experiments investigated the notion that rumors that invoke stable-cause attributions spawn illusory associations and less regressive predictions and behavior. In Study 1, illusory perceptions of association and stable causation (rumors caused price changes on the day after they appeared) existed despite rigorous conditions of nonassociation (price changes were unrelated to rumors). Predictions (recent price trends will continue) and trading behavior (departures from a strong buy-low-sell-high strategy) were both anti-regressive. In Study 2, stability of attribution was manipulated via a computerized tutorial. Participants taught to view price-changes as caused by stable forces predicted less regressively and departed more from buy-low-sell-high trading patterns than those taught to perceive changes as caused by unstable forces. Results inform a social cognitive and decision theoretic understanding of rumor by integrating it with causal attribution, covariation detection, and prediction theory. (C) 2002 Elsevier Science (USA). All rights reserved.

Behavior of argon gas release from manganese oxide minerals as revealed by Ar-40/Ar-39 laser incremental heating analysis

Manganese oxides in association with paleo-weathering may provide significant insights into the multiple factors affecting the formation and evolution of weathering profiles, such as temperature, precipitation, and biodiversity. Laser probe step-heating analysis of supergene hollandite and cryptomelane samples collected from central Queensland, Australia, yield well-defined plateaus and consistent isochron ages, confirming the feasibility, dating very-fined supergene manganese oxides by Ar-40/(39) Ar technique. Two distinct structural sites hosting Ar isotopes can be identified in light of their degassing behaviors obtained by incremental heating analyses. The first site, releasing its gas fraction at the laser power 0.2-0.4 W, yields primarily Ar-40(atm), Ar-38(atm), and Ar-36(atm), (atmospheric Ar isotopes). The second sites yield predominantly Ar-40* (radiogenic Ar-40), Ar-39(K), and Ar-38(K) (nucleogenic components), at similar to0.5-1.0 W. There is no significant Ar gas released at the laser power higher than 1.0 W, indicating the breakdown of the tunnel sites hosting the radiogenic and nucleogenic components. The excellent match between the degassing behaviors of Ar-40*, Ar-39(K), and Ar-38(K) suggests that these isotopes occupy the same crystallographic sites and that Ar-39(K) loss from the tunnel site by recoil during neutron irradiation and/or bake-out procedure preceding isotopic analysis does not occur. Present investigation supports that neither the overwhelming atmospheric Ar-40 nor the very-fined nature of the supergene manganese oxides poses problems in extracting meaningful weathering geo-chronological information by analyzing supergene manganese oxides minerals.

Simulation of the influence of rate- and state-dependent friction on the macroscopic behavior of complex fault zones with the lattice solid model

In order to understand the earthquake nucleation process, we need to understand the effective frictional behavior of faults with complex geometry and fault gouge zones. One important aspect of this is the interaction between the friction law governing the behavior of the fault on the microscopic level and the resulting macroscopic behavior of the fault zone. Numerical simulations offer a possibility to investigate the behavior of faults on many different scales and thus provide a means to gain insight into fault zone dynamics on scales which are not accessible to laboratory experiments. Numerical experiments have been performed to investigate the influence of the geometric configuration of faults with a rate- and state-dependent friction at the particle contacts on the effective frictional behavior of these faults. The numerical experiments are designed to be similar to laboratory experiments by DIETERICH and KILGORE (1994) in which a slide-hold-slide cycle was performed between two blocks of material and the resulting peak friction was plotted vs. holding time. Simulations with a flat fault without a fault gouge have been performed to verify the implementation. These have shown close agreement with comparable laboratory experiments. The simulations performed with a fault containing fault gouge have demonstrated a strong dependence of the critical slip distance D-c on the roughness of the fault surfaces and are in qualitative agreement with laboratory experiments.

Play Preferences and Behavior of Preschool Children with Autistic Spectrum Disorder in the Clinical Environment

The play of children with autistic spectrum disorder (ASD) is a valuable medium for assessment and intervention, and its analysis has the potential to aid diagnosis. This study investigated spontaneous play behavior and play object preferences for 24 preschool children with ASD in a typical occupational therapy clinical environment. Play behavior was rated and choice of play object noted at 10-second intervals from a 15-minute video recording of unstructured play. Statistical analyses indicated that play behavior was consistent with descriptions in the literature. In addition, the children demonstrated clear preferences for play objects in the form of popular characters (e.g., Thomas the Tank Engine) and those with sensorimotor properties. We propose that the inclusion of preferred play objects in a clinical environment may increase intrinsic motivation to play, and thereby enhance assessment and intervention.

Kinetic parameters associated with self-heating of New Zealand coals under adiabatic conditions

Adiabatic self-heating tests were carried out on five New Zealand coal samples ranging in rank from lignite to high-volatile bituminous. Kinetic parameters of oxidation were obtained front the self-heating curves assuming Arrhenius behaviour. The activation energy E (kJ mol(-1)) and the pre-exponential factor A (s(-1)) were determined in the temperature range of 70-140 degreesC. The activation energy exhibited a definite rank relationship with a minimum E of 55 kJ mol(-1) occurring at a Suggate rank of similar to6.2 corresponding to subbituminous C. Either side of this rank there was a noticeable increase in the activation energy indicating lower reactivity of the coal. A similar rank trend was also observed in the R-70 self-heating rate index values that were taken from the initial portion of the self-heating curve front 40 to 70 degreesC. From these results it is clear that the adiabatic method is capable of providing reliable kinetic parameters of coal oxidation.

Quadriceps activation in closed and in open kinetic chain exercise

Purpose: For treatment of various knee disorders, muscles are trained in open or closed kinetic chain tasks. Coordination between the heads of the quadriceps muscle is important for stability and optimal joint loading for both the tibiofemoral and the patellofemoral joint. The aim of this study was to examine whether the quadriceps femoris muscles are activated differently in open versus closed kinetic chain tasks. Methods: Ten healthy men and women (mean age 28.5 +/- 0.7) extended the knees isometrically in open and closed kinetic chain tasks in a reaction time paradigm using moderate force. Surface electromyography (EMG) recordings were made from four different parts of the quadriceps muscle. The onset and amplitude of EMG and force data were measured. Results: In closed chain knee extension, the onset of EMG activity of the four different muscle portions of the quadriceps was more simultaneous than in the open chain. In open chain, rectus femoris (RF) had the earliest EMG onset while vastus medialis obliquus was activated last (7 +/- 13 ms after RF EMG onset) and with smaller amplitude (40 +/- 30% of maximal voluntary contraction (MVC)) than in closed chain (46 +/- 43% MVC). Conclusions: Exercise in closed kinetic chain promotes more balanced initial quadriceps activation than does exercise in open kinetic chain. This may be of importance in designing training programs aimed toward control of the patellofemoral joint.

Physical activity and sedentary behavior: A population-based study of barriers, enjoyment, and preference

The associations of physical activity and sedentary behavior with barriers, enjoyment, and preferences were examined in a population-based mail survey of 1,332 adults. Respondents reporting high enjoyment and preference for physical activity were more likely to report high levels of activity. Those reporting cost, the weather, and personal barriers to physical activity were less likely to be physically active. Preference for sedentary behavior was associated with the decreased likelihood of being physically active, and the weather as a barrier to physical activity was associated with the increased likelihood of sedentary behavior. These constructs can be used to examine individual and environmental influences on physical activity and sedentary behavior in specific populations and could inform the development of targeted interventions.

A kinetic study of the thermally initiated free radical reactions of styrene with octanedithiol as a model for the reactions of multifunctional thiols with divinylbenzene

The kinetics of chain reactions of octanedithiol with styrene, thermally initiated with TX29B50 (a 50:50 wt% solution of TX29 diperoxy initiator in a phthalate plasticizer), have been studied over a range of initiator concentrations, a range of mixture formulations and a range of temperatures. This system has been investigated as a model system for the reactions of polyfunctional thiols with divinyl benzene. The reactions have been shown to follow first-order kinetics for both the thiol and the ene species and to be characterized by a dependence on the initiator concentration to the power of one half. The kinetic rate parameters have been shown to adhere to Arrhenius behaviour. A kinetic model for the chain reactions for this system has been proposed. (C) 2003 Society of Chemical Industry.

Injury related risk behavior - a study of Australian skydivers

Risk taking behaviour has been identified as an important host-related determinant of injury in young adults. The aim of this study is to clarify the relationship between the two key elements of risk taking behaviour - ie, risk assessment and risk acceptance - in participants of a high risk sporting activity. Skydivers registered with the Australian Parachute Federation were sampled at several jump meetings held at three 'drop-zones' in North Eastern Australia. A cross sectional survey of 215 skydivers ascertained each subject's risk assessment of each of nine hypothetical sky diving scenes and whether or not they would jump in the described conditions. Variables which independently predicted an individual's risk assessment were age group (p < 0.05), gender (p < 0.05) and scene details (p < 0.001). Risk assessment was found to be a statistically significant predictor of the decision to jump, with a 22% decrease in the odds of jumping with every unit increase in risk assessment (OR = 0.78: 95% Cl; 0.76, 0.80). Gender was also found to be a statistically significant predictor of the decision to jump, with males being 19% more likely to jump than females, after controlling for age, experience, currency and risk assessment (OR = 1.19: 95% CI; 1.04, 1.38). The importance of these results is that, by quantifying the relationship between two key elements of risk taking behaviour and several important host factor determinants, they facilitate more informed discussion about the possible role of risk taking behaviour in the causation of injury.