Testing the activitystat hypothesis: a randomised controlled trial protocol

Background: The activitystat hypothesis proposes that when physical activity or energy expenditure is increased or decreased in one domain, there will be a compensatory change in another domain to maintain an overall, stable level of physical activity or energy expenditure. To date, there has been no experimental study primarily designed to test the activitystat hypothesis in adults. The aim of this trial is to determine the effect of two different imposed exercise loads on total daily energy expenditure and physical activity levels. Methods. This study will be a randomised, multi-arm, parallel controlled trial. Insufficiently active adults (as determined by the Active Australia survey) aged 18-60 years old will be recruited for this study (n=146). Participants must also satisfy the Sports Medicine Australia Pre-Exercise Screening System and must weigh less than 150 kg. Participants will be randomly assigned to one of three groups using a computer-generated allocation sequence. Participants in the Moderate exercise group will receive an additional 150 minutes of moderate to vigorous physical activity per week for six weeks, and those in the Extensive exercise group will receive an additional 300 minutes of moderate to vigorous physical activity per week for six weeks. Exercise targets will be accumulated through both group and individual exercise sessions monitored by heart rate telemetry. Control participants will not be given any instructions regarding lifestyle. The primary outcome measures are activity energy expenditure (doubly labeled water) and physical activity (accelerometry). Secondary measures will include resting metabolic rate via indirect calorimetry, use of time, maximal oxygen consumption and several anthropometric and physiological measures. Outcome measures will be conducted at baseline (zero weeks), mid- and end-intervention (three and six weeks) with three (12 weeks) and six month (24 week) follow-up. All assessors will be blinded to group allocation. Discussion. This protocol has been specifically designed to test the activitystat hypothesis while taking into account the key conceptual and methodological considerations of testing a biologically regulated homeostatic feedback loop. Results of this study will be an important addition to the growing literature and debate concerning the possible existence of an activitystat. Trial registration. Australian New Zealand Clinical Trials Registry ACTRN12610000248066

New reagents for the metal-free one-pot alpha-functionalisation of carbonyl compounds

This poster describes the scope and features of some new methods for the metal-free α-functionalisation of carbonyl compds. (Figure 1). A new family of reagents 1 based on an N-alkyl hydroxylamine skeleton are shown to react with both aldehydes and cyclic and acyclic ketones to generate α-functionalised products under mild conditions and in good yield. Reactions proceed in one practical step in the presence of both air and moisture, and are tolerant of a wide variety of functional groups. Addnl., in the case of non-sym. substrates the reaction proceeds with excellent regioselectivity. The reagents presented can be used to effect the first direct conversion of carbonyl compds. to α-oxy carbamates, carbonates and tosylates amongst others, and offer a valuable new technique for the synthetic chemist's toolbox. [on SciFinder(R)

A simple and versatile method to determine the enantiomeric purity of Diels-Alder adducts

The detn. of the enantiomeric purity of Diels-Alder adducts derived from cyclopentadiene and electron-deficient dienophiles is conveniently achieved by HPLC anal. on their 2,4-dinitrophenylhydrazine derivs. formed in one pot directly from the cycloaddn. reaction

A simple method for the α-oxygenation of aldehydes

A mild, efficient and general method for the chemospecific α-oxygenation of aldehydes is described. Treatment of a series of aldehydes with N-tert-butyl-O-benzoyl hydroxylamine hydrochloride gives the corresponding α-oxygenated carbonyl via a proposed pericyclic rearrangement process

The direct formation of α-carbamates from carbonyl compounds

A simple one-pot method for the direct introduction of carbamates α to carbonyl groups that proceeds at room temp. in the presence of both moisture and air was developed. Treatment of aldehydes and both cyclic and acyclic ketones with N-methyl-O-carbamoyl hydroxylamine hydrochlorides provides the α-functionalized products in 50-88% isolated yield. The transformation is tolerant of a range of functional groups within the substrate and is also effective for the introduction of a variety of oxycarbamoyl groups

A new chiral diol derived from tetralone for the complexation of Lewis acids

A new approach to the rational design of Lewis acids based on face-face π-π interactions is described. The synthesis of two novel diols (-)(1R,3R)-2,2-dimethyl-1,2,3,4-tetrahydronaphthalene-1,3-diol (I) and (-)(1S,3R)-trans-2,2-dimethyl-1,2,3,4-tetrahydronaphthalene-1-3-diol (II) is reported in six and five steps resp. starting from α-tetralone. Complexation of (-)(1R,3R)-2,2-dimethyl-1,2,3,4-tetrahydronaphthalene-1,3-diol to phenylboronic acid shows the interplanar distance between the boron atom and the arom. ring to be 3.05 A, which is ideal for the proposed interactions. [on SciFinder(R)

The direct introduction of carbonates α to carbonyl groups

The first method for the direct formation of α-oxycarbonates from both aldehydes and ketones is described. N-Methyl-O-alkoxyformate hydroxylamine hydrochloride reagents can be prepd. in two high-yielding steps from N-Boc-N-methylhydroxylamine and were found to be bench stable. These were reacted with a variety of carbonyl compds. to give the corresponding α-functionalized products in 48-98% isolated yield via a proposed [3,3]-sigmatropic rearrangement