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The syn and anti isomers of cis,cis-tricyclo[5.3.0.0(2.6)]dec-3-ene derivatives have been synthesized and their (1)H and (13)C NMR spectra unequivocally analyzed. Both their structures and their (1)H and (13)C NMR chemical shifts were calculated by DFT, the latter two calculations employing the GIAO perturbation method. Additionally, calculated NMR shielding values were partitioned into Lewis and non-Lewis contributions from the bonds and lone pairs involved in the molecules by accompanying NBO and NCS analyses. The differences between the syn and anti isomers were evaluated with respect to steric and spatial hyperconjugation interactions.
The proportion of the axial conformer increases in the ax reversible arrow eq equilibrium of cyclohexyl acetates (RCOOC(6)H(11), R reversible arrow Me, Et, iPr, tBu, CH(2)Cl, CHCl(2), CO(3). CH(2)Br, CHBr(2), CBr(3)) with the increasing size of the acyloxy substitution. The nature of this unexpected steric substituent effect, which is opposite to general stereochemical concepts, was studied by means of ab kiln MO method, accompanied by NBO and isodesmic calculations. NBO parameters seem to be good descriptors for quantitative prediction of the experimental Delta G degrees value of the title conformational equilibrium. The origin and propagation of the substituent effect of the polar substitutions (CH(2)Cl, CHCl(2), CCl(3), CH(2)Br, CHBr(2), CBr(3)) differ, however, from those of the pure alkyl (Me, Et, iPr, tBu) substitutions. The Delta G degrees value of the polar derivatives depends on the qC8 charges, on the occupation of the sigma(center dot)(C1-07) orbital and on the hyperconjugative pi(center dot)(c=O) -> sigma(center dot)(C10-X) and sigma(center dot)(C10-X) -> pi(center dot)(c=O) interactions. The substituent sensitivity of these NBC parameters for the two conformers differ to the effect that the ax reversible arrow eq equilibrium is shifted to the left side with increasing electron withdrawing character of the acyloxy group. The Delta G degrees values of the alkyl derivatives are interpreted in terms of the calculated dipole moments. The destabilization in the non-polar medium (the experimental Delta G degrees values used were measured in CD(2)Cl(2)) due to the enhanced dipolar character is more prominent in the case of the equatorial alkyl conformers. As the consequence, the ax reversible arrow eq equilibrium is shifted to the left despite the increasing size of the R group when going from Me to tBu substitution.
Isokinetic dynamometry is a standard technique for strength testing and training. Nevertheless reliability and validity is limited due to inertia effects, especially for high velocities. Therefore in a first methodological approach the purpose was to evaluate a new isokinetic measurement mode including inertia compensation compared to a classic isokinetic measurement mode for single and multijoint movements at different velocities.
Isokinetic maximum strength measurements were carried out in 26 healthy active subjects. Tests were performed using classic isokinetic and new isokinetic mode in random order. Maximum torque/force, maximum movement velocity and time for acceleration were calculated. For inter-instrument agreement Bland and Altman analysis, systematic and random error was quantified. Differences between both methods were assessed (ANOVA alpha = 0.05).
Bland and Altman analysis showed the highest agreement between the two modes for strength and velocity measurements (bias: < +/- 1.1%; LOA: < 14.2%) in knee flexion/extension at slow isokinetic velocity (60 degrees/s). Least agreement (range: bias: -67.6% +/- 119.0%; LOA: 53.4% 69.3%) was observed for shoulder/arm test at high isokinetic velocity (360 degrees/s). The Isokin(new) mode showed higher maximum movement velocities (p < 0.05).
For low isokinetic velocities the new mode agrees with the classic mode. Especially at high isokinetic velocities the new isokinetic mode shows relevant benefits coupled with a possible trade-off with the force/torque measurement. In conclusion, this study offers for the first time a comparison between the 'classical' and inertia-compensated isokinetic dynamometers indicating the advantages and disadvantages associated with each individual approach, particularly as they relate to medium or high velocities in testing and training.
Since the legend of the ancient Marathon run, the risk of endurance exercise-induced cardiovascular damage or sudden cardiac death is discussed. In recent studies, the exercise-induced increases in cardiac biomarkers in endurance athletes as well as acute alterations in cardiac function and cardiovascular abnormalities have been reported. As elevations of the cardiac biomarkers troponin and BM) have been observed frequently for the vast majority of athletes after Marathon runs or strenuous exercise bouts followed by a decrease within a short period, a physiological reaction rather than a pathologicial cause is presumed. Also a transient decrease of cardiac function demonstrated by newer echocardiographic techniques (tissue Doppler or speckle tracking imaging, 3D echocardiography) after strenuous exercise often termed "cardiac fatigue" should not be considered necessarily as pathologic, as cardiac function also depends on hemodynamic load and heart rate. Furthermore, exercise-induced changes in cardiac function did not correlate with exercise-induced increases in cardiac biomarkers in most studies. The functional cardiac alterations can also be detected by magnetic resonance imaging (MRI) after Marathon runs. However, no signs of acute or chronic myocardial damage have been demonstrated in MRI studies in cardiovascular healthy athletes after running a Marathon, although especially in older athletes undetected cardiovascular diseases such as coronary artery disease or myocardial necrosis or fibrosis can be present. hi conclusion, according to recent studies. there seems to be a lack of evidence to support endurance exercise-induced cardiac damage in the healthy heart which is adapted tostrenous exercise by regular endurance training. Nevertheless, as running a Marathon results in a high cardiac load, a sufficient endurance training period as well as a preparticipation or regular medical screening to exclude relevant congenital or aquired cardiovascular diseases is recommended from a sports cardiology perspective to exclude relevant congenital or acquired cardiovascular diseases
Background: Athletes may differ in their resting metabolic rate (RMR) from the general population. However, to estimate the RMR in athletes, prediction equations that have not been validated in athletes are often used. The purpose of this study was therefore to verify the applicability of commonly used RMR predictions for use in athletes. Methods: The RMR was measured by indirect calorimetry in 17 highly trained rowers and canoeists of the German national teams (BMI 24 +/- 2 kg/m(2), fat-free mass 69 +/- 15 kg). In addition, the RMR was predicted using Cunningham (CUN) and Harris-Benedict (HB) equations. A two-way repeated measures ANOVA was calculated to test for differences between predicted and measured RMR (alpha = 0.05). The root mean square percentage error (RMSPE) was calculated and the Bland-Altman procedure was used to quantify the bias for each prediction. Results: Prediction equations significantly underestimated the RMR in males (p < 0.001). The RMSPE was calculated to be 18.4% (CUN) and 20.9% (HB) in the entire group. The bias was 133 kcal/24 h for CUN and 202 kcal/24 h for HB. Conclusions: Predictions significantly underestimate the RMR in male heavyweight endurance athletes but not in females. In athletes with a high fat-free mass, prediction equations might therefore not be applicable to estimate energy requirements. Instead, measurement of the resting energy expenditure or specific prediction equations might be needed for the individual heavyweight athlete.
The spatial magnetic properties (through space NMR shieldings-TSNMRS) of metal complexes (with ligands such as acetylacetone, 3-hydroxy-pyran(4) one) and "metallobenzenes" have been calculated by the GIAO perturbation method and visualized as Iso-Chemical-Shielding Surfaces (ICSS) of various sizes and directions. The TSNMRS values, thus obtained, can be successfully employed to quantify and visualize partial aromaticity of the metallocyclic ring by comparison with the spatial magnetic properties of the corresponding non-complexed ligands in comparable structural and electronic situations, and benzene, respectively. Because anisotropy/ring current effects in H-1 NMR spectra proved to be the molecular response property of TSNMRS, the results obtained concerning partial "chelatoaromaticity" are experimentally ensured.
The inversion of the flexible five-membered ring in tetrahydrodicyclopentadiene (TH-DCPD) derivatives remains fast on the NMR timescale even at 103 K. Since the intramolecular exchange process could not be sufficiently slowed for spectroscopic evaluation, the conformational equilibrium is thus inaccessible by dynamic NMR. Fortunately, the spatial magnetic properties of the aryl and carbonyl groups attached to the DCPD skeleton can be employed in order to evaluate the conformational state of the system. In this context, the anisotropic effects of the functional groups in the H-1 NMR spectra prove to be the molecular response property of spatial nucleus independent chemical shifts (NICS).