Direct evidence for base-mediated decomposition of alkyl hydroperoxides (ROOH) in the gas phase

Alkyl hydroperoxides (ROOH) are attributed a key role in the biochemical oxidation of lipids during oxidative stress.1 In this chemistry ROOH compounds, where the R groups are unsaturated fatty acids, are viewed as transient ntermediates which are readily degraded, due to the lability of the RO-OH bond, to yield potentially genotoxic aldehydes and ketones.2 Generally, the decomposition of alkyl hydroperoxides is thought to be mediated by radical abstraction or electron transfer processes usually involving enzymes, transition metals, or recently, Vitamin C.3 In this paper we present the first unambiguous experimental and computational evidence for base-mediated heterolytic decomposition of simple alkyl hydroperoxides by the mechanism outlined in Scheme 1.

Direct observation of the gas phase reaction of the cyclohexyl radical with dioxygen using a distonic radical ion approach

Alkylperoxyl radicals are intermediates in the oxidation Of hydrocarbons. The reactive nature of these intermediates, however, has made therin elusive to direct observation and isolation. We have employed ion trap mass spectrometry to synthesize and characterize 4-carboxylatocyclohexyl radical anions ((center dot)C(6)H(10)-CO(2)(-)) and observe their reactivity in the presence of dioxygen. The resulting reaction is facile (k = 1.8 x 10(-10) cm(3) molecule(-1) s(-1) or 30% of calculated collision rate) and results in (i) the addition Of O(2) to form stabilized 4-carboxylatocyclohexylperoxyl radical anions ((center dot)OO-C(6)H(10)-CO(2)(-)), providing the first direct observation of a cyclohexylperoxyl radical, and (ii) elimination of HO(2)(center dot) and HO(center dot) radicals consistent with recent laser-induced fluorescence studies of the reaction of neutral cyclohexyl radicals with O(2). Electronic structure calculations at the B3LYP/6-31+G(d) level of theory reveal viable pathways for the observed reactions showing that formation of the peroxyl radical is exothermic by 37 kcal mol(-1) with subsequent transition states its low as -6.6 kcal mol(-1) (formation of HO(2)(center dot)) and -9.1 kcal mol(-1) (formation of HO(center dot)) with respect to the entrance channel. The combined computational and experimental data Suggest that the structures of the reaction products correspond to cyclohexenes and epoxides from HO(2)(center dot) and HO(center dot) loss, respectively, while alternative pathways leading to cyclohexanone or ring-opened isomers ate not observed, Activation of the charged peroxyl radical (center dot)OO-C(6)H(10)-CO(2)(-) by collision induced disassociation also results in the loss Of HO(2)(center dot) and HO(center dot) radicals confirming that these products are directly connected to the peroxyl radical intermediate.

Trait and behavioural motor control is associated with resistance to overconsumption

While overall obesity rates are rising, a minority of individuals appear to resist overconsumption and remain lean in spite of an ‘obesogenic’ environment. Studying the factors hypothesised to underpin behaviours associated with resistance to overconsumption may inform weight management strategies in an adverse environment. Trait (BIS-11) and behavioural (response inhibition, GoStop) self control were assessed in the laboratory. Snack food consumption was measured covertly via a sham taste test. Lack of motor control was positively correlated (r = .32, p <. 05) and successful response inhibition was negatively correlated (r = −.35, p <. 05) with snack food intake. Low motor control was also associated with further food intake when satiated (r = .39, p < .01). These relationships were independent of self-reported palatability and perceived reward value of the food. Motor control may be an important factor implicated in ‘mindless’ eating in an environment abundant in palatable, energy-dense snack foods.

Calibration and validation of wearable monitors

Background Wearable monitors are increasingly being used to objectively monitor physical activity in research studies within the field of exercise science. Calibration and validation of these devices are vital to obtaining accurate data. This article is aimed primarily at the physical activity measurement specialist, although the end user who is conducting studies with these devices also may benefit from knowing about this topic. Best Practices Initially, wearable physical activity monitors should undergo unit calibration to ensure interinstrument reliability. The next step is to simultaneously collect both raw signal data (e.g., acceleration) from the wearable monitors and rates of energy expenditure, so that algorithms can be developed to convert the direct signals into energy expenditure. This process should use multiple wearable monitors and a large and diverse subject group and should include a wide range of physical activities commonly performed in daily life (from sedentary to vigorous). Future Directions New methods of calibration now use "pattern recognition" approaches to train the algorithms on various activities, and they provide estimates of energy expenditure that are much better than those previously available with the single-regression approach. Once a method of predicting energy expenditure has been established, the next step is to examine its predictive accuracy by cross-validating it in other populations. In this article, we attempt to summarize the best practices for calibration and validation of wearable physical activity monitors. Finally, we conclude with some ideas for future research ideas that will move the field of physical activity measurement forward.

Calibration and comparison of accelerometer cut points in preschool children

Objective The present study aimed to develop accelerometer cut points to classify physical activities (PA) by intensity in preschoolers and to investigate discrepancies in PA levels when applying various accelerometer cut points. Methods To calibrate the accelerometer, 18 preschoolers (5.8 +/- 0.4 years) performed eleven structured activities and one free play session while wearing a GT1M ActiGraph accelerometer using 15 s epochs. The structured activities were chosen based on the direct observation system Children's Activity Rating Scale (CARS) while the criterion measure of PA intensity during free play was provided using a second-by-second observation protocol (modified CARS). Receiver Operating Characteristic (ROC) curve analyses were used to determine the accelerometer cut points. To examine the classification differences, accelerometer data of four consecutive days from 114 preschoolers (5.5 +/- 0.3 years) were classified by intensity according to previously published and the newly developed accelerometer cut points. Differences in predicted PA levels were evaluated using repeated measures ANOVA and Chi Square test. Results Cut points were identified at 373 counts/15 s for light (sensitivity: 86%; specificity: 91%; Area under ROC curve: 0.95), 585 counts/15 s for moderate (87%; 82%; 0.91) and 881 counts/15 s for vigorous PA (88%; 91%; 0.94). Further, applying various accelerometer cut points to the same data resulted in statistically and biologically significant differences in PA. Conclusions Accelerometer cut points were developed with good discriminatory power for differentiating between PA levels in preschoolers and the choice of accelerometer cut points can result in large discrepancies.

A dual inverter-based supercapacitor direct integration scheme for wind energy conversion systems

Interfacing converters used in connecting energy storage systems like supercapacitors and battery banks to wind power systems introduce additional cost and power losses. This paper therefore presents a direct integration scheme for supercapacitors used in mitigating short-term power fluctuations in wind power systems. This scheme uses a dual inverter topology for both grid connection and interfacing a supercapacitor bank. The main inverter of the dual inverter system is powered by the rectified output of a wind turbine-coupled permanent-magnet synchronous generator. The auxiliary inverter is directly connected to the supercapacitor bank. With this approach, an interfacing converter is not required, and there are no associated costs and power losses incurred. The operation of the proposed system is discussed in detail. Simulation and experimental results are presented to verify the efficacy of the proposed system in suppressing short-term wind power fluctuations.

Modeling and sensorless direct torque and flux control of a dual-airgap axial flux permanent-magnet machine with field-weakening operation

This paper presents the modeling and motion-sensorless direct torque and flux control of a novel dual-airgap axial-flux permanent-magnet machine optimized for use in flywheel energy storage system (FESS) applications. Independent closed-loop torque and stator flux regulation are performed in the stator flux ( x-y) reference frame via two PI controllers. This facilitates fast torque dynamics, which is critical as far as energy charging/discharging in the FESS is concerned. As FESS applications demand high-speed operation, a new field-weakening algorithm is proposed in this paper. Flux weakening is achieved autonomously once the y-axis voltage exceeds the available inverter voltage. An inherently speed sensorless stator flux observer immune to stator resistance variations and dc-offset effects is also proposed for accurate flux and speed estimation. The proposed observer eliminates the rotary encoder, which in turn reduces the overall weight and cost of the system while improving its reliability. The effectiveness of the proposed control scheme has been verified by simulations and experiments on a machine prototype.

Diode-clamped three-level inverter-based battery/supercapacitor direct integration scheme for renewable energy systems

This paper describes a diode-clamped three-level inverter-based battery/supercapacitor direct integration scheme for renewable energy systems. The study is carried out for three different cases. In the first case, one of the two dc-link capacitors of the inverter is replaced by a battery bank and the other by a supercapacitor bank. In the second case, dc-link capacitors are replaced by two battery banks. In the third case, ordinary dc-link capacitors are replaced by two supercapacitor banks. The first system is supposed to mitigate both long-term and short-term power fluctuations while the last two systems are intended for smoothening long-term and short-term power fluctuations, respectively. These topologies eliminate the need for interfacing dc-dc converters and thus considerably improve the overall system efficiency. The major issue in aforementioned systems is the unavoidable imbalance in dc-link voltages. An analysis on the effects of unbalance and a space vector modulation method, which can produce undistorted current even in the presence of such unbalances, are presented in this paper. Furthermore, small vector selection-based power sharing and state of charge balancing techniques are proposed. Experimental results, obtained from a laboratory prototype, are presented to verify the efficacy of the proposed modulation and control techniques.

Direct integration of battery energy storage systems in distributed power generation

In this paper, a wind energy conversion system interfaced to the grid using a dual inverter is proposed. One of the two inverters in the dual inverter is connected to the rectified output of the wind generator while the other is directly connected to a battery energy storage system (BESS). This approach eliminates the need for an additional dc-dc converter and thus reduces power losses, cost, and complexity. The main issue with this scheme is uncorrelated dynamic changes in dc-link voltages that results in unevenly distributed space vectors. A detailed analysis on the effects of these variations is presented in this paper. Furthermore, a modified modulation technique is proposed to produce undistorted currents even in the presence of unevenly distributed and dynamically changing space vectors. An analysis on the battery charging/discharging process and maximum power point tracking of the wind turbine generator is also presented. Simulation and experimental results are presented to verify the efficacy of the proposed modulation technique and battery charging/discharging process.

Practice and procedure - Motor Accident Insurance Act 1994 s45 - duty of claimant to cooperate with insurer

In Suncorp Metway Insurance Limited v Brown [2004] QCA 325 the Queensland Court of Appeal considered the extent of the duty of cooperation imposed on a claimant under s45 of the Motor Accident Insurance Act 1994 (Qld). The issue is an important one because it affects virtually all claims made under the Act.

Mandatory offers under the Motor Accident Insurance Act 1994 - with interest please!

In Windon v Edwards [2005] QDC 029 Robin QC DCJ considered the cost consequence of mandatory final offers under the Motor Accident Insurance Act 1994 (Qld)

Practice and Procedures - Motor Accident Insurance Act 1994 ss 39 and 57

In Bermingham v Priest [2002] QSC 057 jones J considered the position of persons seeking to claim damages where the Motor Accident Insurance Act 1994 applies prior to its amendment by the Motor Accident Insurance Amendment Act 2000, and where proceedings are brought close to expiration of the statutory limitation period.

Motor Accident Insurance Act 1994 - obligation to disclose

In Turpin v Allianz Australia Insurance Ltd (unreported, Supreme Court of Queensland, S5216 of 2001), Mullins J, 17.10.2001) the plaintiff applied for a declaration that the respondent disclose pursuant to s47 of the Motor Accident Insurance Act 1994 copies of three statements referred to in a loss assessor's investigation report as "attached". The issue involved determination of whether the statements must be disclosed under s48(2) even though protected by legal professional privilege. The Court applied the decision of the Queensland Court of Appeal in James v Workcover Queensland.

Personal injury in motor accident in NSW - procedural requirements under Motor Accidents Insurance Act 1988 (NSW)

In Hooper v Robinson [2002] QDC 080 (District Court of Queensland, D 4841 of 2001, McGill DCJ, 19.4.2002) McGill DCJ considered the application of the decision in John Pfeiffer Pty Ltd v Rogerson [2000] 203 CLR 503 to notice requirements such as in s42 of NSW Motor Accident Insurance Act 1988 and concluded such provisions are now substantive.

Motor Accident Insurance Act 1994 - whether vehicle in question a vehicle "for which registration is required"

In Gideona v Nominal Defendant [2005] QCA 261, the Queensland Court of Appeal reconsidered the question of what is the material time for determining whether registration of a motor vehicle is required. The Court declined to follow the decision in Kelly v Alford [1988] 1 Qd R 404; deciding that the material time was the time when the accident occurred.