A Ring Contraction Strategy toward a Diastereoselective Total Synthesis of (+)-Bakkenolide A

A diastereoselective route to (+)-bakkenolide A is presented from the readily available optically active Wieland-Miescher ketone. This novel synthesis of this sesquiterpene lactone features the following as key stereoselective transformations: (i) the ring contraction reaction of a octalone mediated by thallium(III) nitrate (TTN); (ii) a hydrogenation to create the cis-fused junction; and (iii) the formation of the C7 quaternary center through an enolate intermediate. Furthermore, during this work, the absolute configuration of a trinorsesquiterpene isolated from Senecio Humillimus was assigned.

Ring Contraction of 1,2-Dihydronaphthalenes Promoted by Thallium(III) in Acetonitrile: A Diastereoselective Approach to Indanes

trans-1,3-Disubstituted indanes are conveniently accessed by a stereoselective ring contraction of 1,2-dihydronaphthalenes upon treatment with thallium(III) nitrate (TTN) in acetonitrile. Under these conditions, the oxidative rearrangement of either di- or trisubstituted double bonds is possible.

A Diastereoselective Total Synthesis of trans-Trikentrin A: A Ring Contraction Approach

A new route to obtain the polyalkylated indole (+/-)-trans-trikentrin A was developed. The synthesis of this natural alkaloid features a thallium(III)mediated ring contraction reaction to obtain the trans-1,3-disubstituted five-membered ring in a diastereoselective manner. Thallium(III) is chemoselective in this rearrangement, reacting with the olefin without oxidation of the indole moiety. Other key transformations are the Bartoli`s reaction to construct the heterocyclic ring and a Heck coupling to add the carbons atom that will originate the nonaromatic cycle.

On theory multiple contraction

The one which is considered the standard model of theory change was presented in [AGM85] and is known as the AGM model. In particular, that paper introduced the class of partial meet contractions. In subsequent works several alternative constructive models for that same class of functions were presented, e.g.: safe/kernel contractions ([AM85, Han94]), system of spheres-based contractions ([Gro88]) and epistemic entrenchment-based contractions ([G ar88, GM88]). Besides, several generalizations of such model were investigated. In that regard we emphasise the presentation of models which accounted for contractions by sets of sentences rather than only by a single sentence, i.e. multiple contractions. However, until now, only two of the above mentioned models have been generalized in the sense of addressing the case of contractions by sets of sentences: The partial meet multiple contractions were presented in [Han89, FH94], while the kernel multiple contractions were introduced in [FSS03]. In this thesis we propose two new constructive models of multiple contraction functions, namely the system of spheres-based and the epistemic entrenchment-based multiple contractions which generalize the models of system of spheres-based and of epistemic entrenchment-based contractions, respectively, to the case of contractions (of theories) by sets of sentences. Furthermore, analogously to what is the case in what concerns the corresponding classes of contraction functions by one single sentence, those two classes are identical and constitute a subclass of the class of partial meet multiple contractions. Additionally, and as the rst step of the procedure that is here followed to obtain an adequate de nition for the system of spheres-based multiple contractions, we present a possible worlds semantics for the partial meet multiple contractions analogous to the one proposed in [Gro88] for the partial meet contractions (by one single sentence). Finally, we present yet an axiomatic characterization for the new class(es) of multiple contraction functions that are here introduced.

Measurement of gastric contraction activity in dogs by means of AC biosusceptometry

The mechanical nature of gastric contraction activity (GCA) plays an important role in gastrointestinal motility. The aim of this study was to detect GCA in anaesthetized dogs, using simultaneously the techniques of AC biosusceptometry (ACB) and manometry, analysing the characteristics of frequency and amplitude (motility index) of GCA, modified by drugs such as prostigmine and N-butyl-scopolamine. The ACB method is based on a differential transformer of magnetic flux and the magnetic tracer works as a changeable external nucleus. This magnetic tracer causes a modification in the magnetic flux, which is detected by the coils. The results obtained from the ACB showed a performance comparable to the manometry in measuring the modifications in the frequency and amplitude of the GCA. We concluded that this ACB technique, non-invasive and free of ionizing radiation, is an option for evaluating GCA and can be employed in future clinical studies.

The ACB technique: a biomagentic tool for monitoring gastrointestinal contraction directly from smooth muscle in dogs

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Validation of ACB in vitro and in vivo as a biomagnetic method for measuring stomach contraction

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

ACUTE EFFECT of STATIC STRETCHING on RATE of FORCE DEVELOPMENT and MAXIMAL VOLUNTARY CONTRACTION IN OLDER WOMEN

Gurjao, ALD, Goncalves, R, de Moura, RF, and Gobbi, S. Acute effect of static stretching on rate of force development and maximal voluntary contraction in older women. J Strength Cond Res 23(7): 2149-2154, 2009-The purpose of this study was to investigate, in older women, the acute effect of static stretching (SS) on both muscle activation and force output. Twenty-three older women (64.6 +/- 7.1 yr) participated in the study. The maximal voluntary contraction (MVC), rate of force development (RFD) (50, 100, 150, and 200 ms relative to onset of muscular contraction), and peak RFD (PRFD) (the steepest slope of the curve during the first 200 ms) were tested under 2 randomly separate conditions: SS and control (C). Electromyographic (EMG) activity of the vastus medialis (VM), vastus lateralis (VL), and biceps femoris (BF) muscles also was assessed. The MVC was significantly lower (p < 0.05) in the 3 trials of SS when compared with the C condition (control: 925.0 +/- 50.9 N; trial 1 : 854.3 +/- 55.3 N; trial 2 : 863.1 +/- 52.2 N; and trial 3 : 877.5 +/- 49.9 N). PRFD showed a significant decrease only for the first 2 trials of SS when compared with the C condition (control: 2672.3 +/- 259.1 N/s; trial 1 : 2296.6 +/- 300.7 N/s; and trial 2 : 2197.9 +/- 246.3 N/s). However, no difference was found for RFD (50, 100, 150, and 200 ms relative to onset of muscular contraction). The EMG activity for VM, VL, and BF was not significantly different between the C and SS conditions. In conclusion, the older women's capacity to produce muscular force decreased after their performance of SS exercises. The mechanisms responsible for this effect do not appear to be related to muscle activation. Thus, if flexibility is to be trained, it is recommended that SS does not occur just before the performance of activities that require high levels of muscular force.

THE RATE of FORCE DEVELOPMENT OBTAINED AT EARLY CONTRACTION PHASE IS NOT INFLUENCED BY ACTIVE STATIC STRETCHING

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)