TY - JOUR A1 - Kleinpeter, Erich A1 - Laemmermann, Anica A1 - Kühn, Heiner T1 - Synthesis and NMR spectra of the syn and anti isomers of substituted cyclobutanes-evidence for steric and spatial hyperconjugative interactions JF - Tetrahedron N2 - 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. KW - Conformational analysis KW - cis,cis-Tricyclo[5.3.0.0(2,6)]dec-3-enes KW - NMR KW - DFT calculation KW - NBO/NCS analysis Y1 - 2011 U6 - https://doi.org/10.1016/j.tet.2011.02.012 SN - 0040-4020 VL - 67 IS - 14 SP - 2596 EP - 2604 PB - Elsevier CY - Oxford ER - TY - JOUR A1 - Neuvonen, Kari A1 - Neuvonen, Helmi A1 - Koch, Andreas A1 - Kleinpeter, Erich T1 - NBO analysis of polar and steric effect using the axial-equatorial equilibrium of cyclohexyl acetates as a probe JF - Computational and theoretical chemistry N2 - 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. KW - Substituent effects KW - Ab initio MO computations KW - Conformational equilibria KW - Cyclohexyl esters KW - NBO analysis Y1 - 2011 U6 - https://doi.org/10.1016/j.comptc.2010.12.033 SN - 2210-271X VL - 964 IS - 1-3 SP - 234 EP - 242 PB - Elsevier CY - Amsterdam ER - TY - JOUR A1 - Müller, Steffen A1 - Mayer, Patrizia A1 - Baur, Heiner A1 - Mayer, Frank T1 - Higher velocities in isokinetic dynamometry a pilot study of new test mode with active compensation of inertia JF - Isokinetics and exercise science : official journal of the European Isokinetic Society N2 - 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. KW - Strength testing KW - concentric KW - validity KW - trunk KW - knee KW - shoulder Y1 - 2011 U6 - https://doi.org/10.3233/IES-2011-0398 SN - 0959-3020 VL - 19 IS - 2 SP - 63 EP - 70 PB - IOS Press CY - Amsterdam ER - TY - JOUR A1 - Scharhag, Jürgen A1 - Knebel, F. A1 - Mayer, Frank A1 - Kindermann, Wilfried T1 - Does marathon running damage the heart? - an update JF - Deutsche Zeitschrift für Sportmedizin : offizielles Organ der Deutschen Gesellschaft für Sportmedizin und Prävention (Deutscher Sportärztebund) e.V. (DGSP) und Weiterbildungsorgan der Österreichischen Gesellschaft für Sportmedizin und Prävention N2 - 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 KW - Marathon KW - cardiac biomarkers KW - endurance exercise KW - athlete's heart KW - cardiac fatigue Y1 - 2011 SN - 0344-5925 VL - 62 IS - 9 SP - 293 EP - 298 PB - WWF-Verl.-Ges. CY - Greven ER - TY - JOUR A1 - Carlsohn, Anja A1 - Scharhag-Rosenberger, Friederike A1 - Cassel, Michael A1 - Mayer, Frank T1 - Resting metabolic rate in elite rowers and canoeists difference between indirect calorimetry and prediction JF - Annals of nutrition & metabolism : journal of nutrition, metabolic diseases and dietetics ; an official journal of International Union of Nutritional Sciences (IUNS) N2 - 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. KW - Energy requirement KW - Calorimetry KW - Fat-free mass KW - Nutritional counseling KW - Athletes Y1 - 2011 U6 - https://doi.org/10.1159/000330119 SN - 0250-6807 VL - 58 IS - 3 SP - 239 EP - 244 PB - Karger CY - Basel ER - TY - JOUR A1 - Kleinpeter, Erich A1 - Koch, Andreas T1 - Chelatoaromaticity-existing: yes or no? An answer given by spatial magnetic properties (through space NMR shieldings-TSNMRS) JF - Physical chemistry, chemical physics : a journal of European Chemical Societies N2 - 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. Y1 - 2011 U6 - https://doi.org/10.1039/c1cp21942a SN - 1463-9076 SN - 1463-9084 VL - 13 IS - 46 SP - 20593 EP - 20601 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Kleinpeter, Erich A1 - Laemmermann, Anica A1 - Kühn, Heiner T1 - The anisotropic effect of functional groups in H-1 NMR spectra is the molecular response property of spatial nucleus independent chemical shifts (NICS)-Conformational equilibria of exo/endo tetrahydrodicyclopentadiene derivatives JF - Organic & biomolecular chemistry : an international journal of synthetic, physical and biomolecular organic chemistry N2 - 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). Y1 - 2011 U6 - https://doi.org/10.1039/c0ob00356e SN - 1477-0520 VL - 9 IS - 4 SP - 1098 EP - 1111 PB - Royal Society of Chemistry CY - Cambridge ER -