Contribution of Motivational Climates and Social Competence in Physical Education on Overall Physical Activity: A Self-Determination Theory Approach with a Creative Physical Education Twist.

Using a cross-sectional study design, we tested a structural equation model of hypothesized relationships among a group of variables: motivational climate in physical education (PE), students' social competence in PE, out of-school physical activity (PA) motivation, PA intention and their moderate-to-vigorous PA (MVPA). Based on the self-reports of 363 fourth to sixth grade elementary school students (172 girls, 191 boys), the model revealed that the task-involving motivational climate in PE was linked to higher MVPA via cooperation in PE, and also via extrinsic motivation and PA intention. Ego-involving motivational climate was related to higher extrinsic motivation and amotivation, further to higher PA intention and, finally, to higher MVPA. Task-involving motivational climate was positively linked to students' social competence markers of cooperation and empathy, and negatively to disruptiveness. Ego-involving motivational climate was positively related to disruptiveness and impulsivity, the markers of low social competence. The study showed that the motivational climate and co-operational aspect of social competence both played significant roles in students' PA motivation, PA intention and MVPA. A pedagogical model that brings the learning of social competence relevant skills to the fore is creative physical education (CPE). Analysis of CPE is provided which highlights teaching behaviors which contribute to the students' MVPA through motivational climates, co-operation, PA motivation and PA intention.

FiD: a software for ab initio structural identification of product ions from tandem mass spectrometric data.

We present FiD (Fragment iDentificator), a software tool for the structural identification of product ions produced with tandem mass spectrometric measurement of low molecular weight organic compounds. Tandem mass spectrometry (MS/MS) has proven to be an indispensable tool in modern, cell-wide metabolomics and fluxomics studies. In such studies, the structural information of the MS(n) product ions is usually needed in the downstream analysis of the measurement data. The manual identification of the structures of MS(n) product ions is, however, a nontrivial task requiring expertise, and calls for computer assistance. Commercial software tools, such as Mass Frontier and ACD/MS Fragmenter, rely on fragmentation rule databases for the identification of MS(n) product ions. FiD, on the other hand, conducts a combinatorial search over all possible fragmentation paths and outputs a ranked list of alternative structures. This gives the user an advantage in situations where the MS/MS data of compounds with less well-known fragmentation mechanisms are processed. FiD software implements two fragmentation models, the single-step model that ignores intermediate fragmentation states and the multi-step model, which allows for complex fragmentation pathways. The software works for MS/MS data produced both in positive- and negative-ion modes. The software has an easy-to-use graphical interface with built-in visualization capabilities for structures of product ions and fragmentation pathways. In our experiments involving amino acids and sugar-phosphates, often found, e.g., in the central carbon metabolism of yeasts, FiD software correctly predicted the structures of product ions on average in 85% of the cases. The FiD software is free for academic use and is available for download from www.cs.helsinki.fi/group/sysfys/software/fragid.

Comparison of partial filling MEKC analyses of steroids with use of ESI-MS and UV spectrophotometry.

Until now, partial filling micellar EKC-ESI-MS (PF-MEKC-ESI-MS) has seldom been applied for human biomolecules. In this study, determination of three electrically neutral endogenous steroid hormones, namely androstenedione, testosterone, and epitestosterone, by PF-MEKC-ESI-MS was investigated. Since ESI-MS and ESI-MS/MS behaviors of testosterone and epitestosterone proved to be nearly identical, efficient separation of the two compounds was required to obtain reliable identification. The chemical conditions as well as the instrumental parameters affecting the PF-MEKC-ESI-MS analysis were researched. In optimal conditions, ESI-MS showed excellent selectivity, and all the steroids could be identified using SIM. LODs were 0.75-5 microg/mL. The results obtained by PF-MEKC-ESI-MS were compared with those obtained by corresponding PF-MEKC-UV. PF-MEKC-UV provided better resolution, repeatability, and more than ten-fold higher sensitivity, in terms of LODs, than PF-MEKC-ESI-MS. The reasons for this were carefully examined. In comparison with PF-MEKC-UV, PF-MEKC-ESI-MS suffered from greater band broadening owing to the sheath-liquid interface. Resolution was also decreased owing to the elevated capillary temperature. Finally, we discovered that in the analysis of electrically neutral compounds, in-capillary sample concentration by micellar sweeping could be more efficiently utilized in PF-MEKC-UV than in PF-MEKC-ESI-MS.

Central carbon metabolism of Saccharomyces cerevisiae in anaerobic, oxygen-limited and fully aerobic steady-state conditions and following a shift to anaerobic conditions.

Saccharomyces cerevisiae CEN.PK113-1A was grown in glucose-limited chemostat culture with 0%, 0.5%, 1.0%, 2.8% or 20.9% O2 in the inlet gas (D=0.10 h(-1), pH 5, 30 degrees C) to determine the effects of oxygen on 17 metabolites and 69 genes related to central carbon metabolism. The concentrations of tricarboxylic acid cycle (TCA) metabolites and all glycolytic metabolites except 2-phosphoglycerate+3-phosphoglycerate and phosphoenolpyruvate were higher in anaerobic than in fully aerobic conditions. Provision of only 0.5-1% O2 reduced the concentrations of most metabolites, as compared with anaerobic conditions. Transcription of most genes analyzed was reduced in 0%, 0.5% or 1.0% O2 relative to cells grown in 2.8% or 20.9% O2. Ethanol production was observed with 2.8% or less O2. After steady-state analysis in defined oxygen concentrations, the conditions were switched from aerobic to anaerobic. Metabolite and transcript levels were monitored for up to 96 h after the transition, and this showed that more than 30 h was required for the cells to fully adapt to anaerobiosis. Levels of metabolites of upper glycolysis and the TCA cycle increased following the transition to anaerobic conditions, whereas those of metabolites of lower glycolysis generally decreased. Gene regulation was more complex, with some genes showing transient upregulation or downregulation during the adaptation to anaerobic conditions.

Analysis of anabolic steroids by partial filling micellar electrokinetic capillary chromatography and electrospray mass spectrometry.

A partial filling micellar electrokinetic capillary chromatography (PF-MEKC) separation of six anabolic androgenic steroids (androstenedione, metandienone, fluoxymesterone, methyltestosterone, 17-epimetandienone and testosterone) is introduced. The method utilises a mixed micellar solution consisting of sodium dodecyl sulphate (SDS) and sodium taurocholate. The analytes are detected with a photodiode array detector at 247 nm wavelength. Methyltestosterone is used as internal standard. The detection limits were 39 microg/L for androstenedione, 40 microg/L for testosterone, 45 microg/L for fluoxymesterone, 45-90 microg/L for 17-epimetandienone, 59 microg/L for methyltestosterone and 90 microg/L for metandienone. Linear correlation between concentration (0.1-5.0 mg/L) and detector response was obtained with r2 of 0.994 for fluoxymesterone, 0.998 for 17-epimetandienone and 0.999 for androstenedione, metandienone and testosterone. In addition, ionisation of the investigated compounds in electrospray mass spectrometry (ESI-MS) was studied in positive ion mode. The most intense signal (100%) was the protonated molecular ion [M + H]+, except for 17-epimetandienone, which gave its strongest signal at m/z corresponding to [M - H2O + H]+. Finally, separation and identification of fluoxymesterone, androstenedione and testosterone by PF-MEKC-ESI-MS is described. This is the first use of PF-MEKC and PF-MEKC-ESI-MS assays for anabolic androgenic steroids.

Isolation and identification of oligomeric procyanidins from Crataegus leaves and flowers.

Oligomeric procyanidins were isolated from the leaves and flowers of hawthorn (Crataegus laevigata). A trimer, epicatechin-(4 beta-->8)-epicatechin-(4 beta-->6)-epicatechin, and a pentamer consisting of (-)-epicatechin units linked through C-4 beta/C-8 bonds have been isolated from hawthorn for the first time, in addition to known procyanidins including dimers B-2, B-4 and B-5, trimers C-1 and epicatechin-(4 beta-->6)-epicatechin-(4 beta-->8)-epicatechin, and tetramer D-1. A fraction containing a hexamer was also found.

Computing positional isotopomer distributions from tandem mass spectrometric data.

The isotopomer distributions of metabolites are invaluable pieces of information in the computation of the flux distribution in a metabolic network. We describe the use of tandem mass spectrometry with the daughter ion scanning technique in the discovery of positional isotopomer distributions (PID). This technique increases the possibilities of mass spectrometry since given the same fragment ions, it uncovers more information than the full scanning mode. The mathematics of the new technique is slightly more complicated than the techniques needed by full scanning mode methods. Our experiments, however, show that in practice the inadequacy of the fragmentation of amino acids in the tandem mass spectrometer does not allow uncovering the PID exactly even if the daughter ion scanning is used. The computational techniques have been implemented in a MATLAB application called PIDC (Positional Isotopomer Distribution Calculator).