TY - JOUR A1 - Pontius, N. A1 - Kachel, T. A1 - Schüssler-Langeheine, C. A1 - Schlotter, W. F. A1 - Beye, Martin A1 - Sorgenfrei, Nomi A1 - Chang, C. F. A1 - Föhlisch, Alexander A1 - Wurth, W. A1 - Metcalf, P. A1 - Leonov, I. A1 - Yaresko, A. A1 - Stojanovic, N. A1 - Berglund, Martin A1 - Guerassimova, N. A1 - Duesterer, S. A1 - Redlin, H. A1 - Duerr, H. A. T1 - Time-resolved resonant soft x-ray diffraction with free-electron lasers femtosecond dynamics across the Verwey transition in magnetite JF - Applied physics letters N2 - Resonant soft x-ray diffraction (RSXD) with femtosecond (fs) time resolution is a powerful tool for disentangling the interplay between different degrees of freedom in strongly correlated electron materials. It allows addressing the coupling of particular degrees of freedom upon an external selective perturbation, e. g., by an optical or infrared laser pulse. Here, we report a time-resolved RSXD experiment from the prototypical correlated electron material magnetite using soft x-ray pulses from the free-electron laser FLASH in Hamburg. We observe ultrafast melting of the charge-orbital order leading to the formation of a transient phase, which has not been observed in equilibrium. Y1 - 2011 U6 - https://doi.org/10.1063/1.3584855 SN - 0003-6951 VL - 98 IS - 18 PB - American Institute of Physics CY - Melville ER - TY - JOUR A1 - Herzschuh, Ulrike A1 - Ni, Jian A1 - Birks, H. John B. A1 - Böhner, Jürgen T1 - Driving forces of mid-Holocene vegetation shifts on the upper Tibetan Plateau, with emphasis on changes in atmospheric CO2 concentrations JF - Quaternary science reviews : the international multidisciplinary research and review journal N2 - Numerous pollen records across the upper Tibetan Plateau indicate that in the early part of the mid-Holocene, Kobresia-rich high-alpine meadows invaded areas formerly dominated by alpine steppe vegetation rich in Artemisia. We examine climate, land-use, and CO2 concentration changes as potential drivers for this marked vegetation change. The climatic implications of these vegetational shifts are explored by applying a newly developed pollen-based moisture-balance transfer-function to fossil pollen spectra from Koucha Lake on the north-eastern Tibetan Plateau (34.0 degrees N; 97.2 degrees E; 4540 m a.s.l.) and Xuguo Lake on the central Tibetan Plateau (31.97 degrees N; 90.3 degrees E; 4595 m a.s.l.), both located in the meadow-steppe transition zone. Reconstructed moisture-balances were markedly reduced (by similar to 150-180 mm) during the early mid-Holocene compared to the late-Holocene. These findings contradict most other records from the Indian monsoonal realm and also most non-pollen records from the Tibetan Plateau that indicate a rather wet early- and mid-Holocene. The extent and timing of anthropogenic land-use involving grazing by large herbivores on the upper Tibetan Plateau and its possible impacts on high-alpine vegetation are still mostly unknown due to the lack of relevant archaeological evidence. Arguments against a mainly anthropogenic origin of Kobresia high-alpine meadows are the discovery of the widespread expansion of obviously 'natural' Kobresia meadows on the south-eastern Tibetan Plateau during the Lateglacial period indicating the natural origin of this vegetation type and the lack of any concurrence between modern human-driven vegetation shifts and the mid-Holocene compositional changes. Vegetation types are known to respond to atmospheric CO2 concentration changes, at least on glacial-interglacial scales. This assumption is confirmed by our sensitivity study where we model Tibetan vegetation at different CO2 concentrations of 375 (present-day), 260 (early Holocene), and 650 ppm (future scenario) using the BIOME4 global vegetation model. Previous experimental studies confirm that vegetation growing on dry and high sites is particularly sensitive to CO2 changes. Here we propose that the replacement of drought-resistant alpine steppes (that are well adapted to low CO2 concentrations) by mesic Kobresia meadows can, at least, be partly interpreted as a response to the increase of CO2 concentration since 7000 years ago due to fertilization and water-saving effects. Our hypothesis is corroborated by former CO2 fertilization experiments performed on various dry grasslands and by the strong recent expansion of high-alpine meadows documented by remote sensing studies in response to recent CO2 increases. KW - Tibetan Plateau KW - Pollen KW - Holocene KW - Transfer function KW - Kobresia meadow KW - Atmospheric CO2 concentration Y1 - 2011 U6 - https://doi.org/10.1016/j.quascirev.2011.03.007 SN - 0277-3791 VL - 30 IS - 15-16 SP - 1907 EP - 1917 PB - Elsevier CY - Oxford ER - TY - JOUR A1 - Bagnich, Sergey A. A1 - Unger, Th. A1 - Jaiser, Frank A1 - Neher, Dieter A1 - Thesen, M. W. A1 - Krüger, H. T1 - Efficient green electrophosphorescence based on ambipolar nonconjugated polymers evaluation of transport and emission properties JF - Journal of applied physics N2 - New materials for polymer organic light-emitting diodes based on a polymer matrix doped with phosphorescent dyes are presented. The matrix system is based on a polystyrene backbone bearing either electron or hole transporting units at the 4-position of each repeat unit. Random copolymers and polymer blend systems of the homopolymers are prepared, both with 62 wt.% electron transporting and 38 wt.% hole transporting moieties. Adding a green electrophosphorescent dye to the polymer matrix leads to efficient electroluminescence with a maximum current efficiency of 35 cd/A and a maximum external quantum efficiency of up to 10%. The mobilities of electrons and holes in the dye-doped copolymer, as measured by transient electroluminescence, are around 5 x 10(-5) and 5 x 10(-6) cm(2)/Vs, respectively, while the blend of the two homopolymers exhibits slightly lower mobilities of both types of carriers. Despite the pronounced imbalance of charge transport, the device performance is almost entirely limited by the phosphorescence efficiency of the dye, implying balanced flow of holes and electrons into the active region. Also, devices made with either the copolymer or the blend yielded very similar device efficiencies, despite the noticeable difference in electron and hole mobility. It is proposed that electrons are efficiently blocked at the interlayer and that the so-formed space charge assists the balanced injection of holes. Y1 - 2011 U6 - https://doi.org/10.1063/1.3618681 SN - 0021-8979 SN - 1089-7550 VL - 110 IS - 3 PB - American Institute of Physics CY - Melville ER - TY - JOUR A1 - Shayduk, Roman A1 - Navirian, Hengameh A1 - Leitenberger, Wolfram A1 - Goldshteyn, Jevgenij A1 - Vrejoiu, Ionela A1 - Weinelt, Martin A1 - Gaal, Peter A1 - Herzog, Marc A1 - von Korff Schmising, Clemens A1 - Bargheer, Matias T1 - Nanoscale heat transport studied by high-resolution time-resolved x-ray diffraction JF - New journal of physics : the open-access journal for physics N2 - We report on synchrotron-based high-repetition rate ultrafast x-ray diffraction (UXRD) experiments monitoring the transport of heat from an epitaxial La(0.7)Sr(0.3)MnO(3)/SrTiO(3) superlattice (SL) into the substrate on timescales from 100 ps to 4 mu s. Transient thermal lattice expansion was determined with an accuracy of 10(-7), corresponding to a sensitivity to temperature changes down to 0.01 K. We follow the heat flow within the SL and into the substrate after the impulsive laser heating leads to a small temperature rise of Delta T = 6 K. The transient lattice temperature can be simulated very well using the bulk heat conductivities. This contradicts the interpretation of previous UXRD measurements, which predicted a long-lasting expansion of SrRuO(3) for more than 200 ps. The disagreement could be resolved by assuming that the heat conductivity changes in the first hundred picoseconds. Y1 - 2011 U6 - https://doi.org/10.1088/1367-2630/13/9/093032 SN - 1367-2630 VL - 13 IS - 11 PB - IOP Publ. Ltd. CY - Bristol ER - TY - JOUR A1 - Hundertmark, Michaela A1 - Dimova, Rumiana A1 - Lengefeld, Jan A1 - Seckler, Robert A1 - Hincha, Dirk K. T1 - The intrinsically disordered late embryogenesis abundant protein LEA18 from Arabidopsis thaliana modulates membrane stability through binding and folding. N2 - Intrinsically disordered proteins (IDPs) constitute a substantial part of cellular proteomes. Late embryogenesis abundant (LEA) proteins are mostly predicted to be IDPs associated with dehydration tolerance in many plant, animal and bacterial species. Their functions, however, are largely unexplored and also their structure and interactions with potential target molecules have only recently been experimentally investigated in a small number of proteins. Here, we report on the structure and interactions with membranes of the Pfam LEA_1 protein LEA18 from the higher plant Arabidopsis thaliana. This functionally uncharacterized positively charged protein specifically aggregated and destabilized negatively charged liposomes. Isothermal titration calorimetry showed binding of the protein to both charged and uncharged membranes. LEA18 alone was largely unstructured in solution. While uncharged membranes had no influence on the secondary structure of LEA18, the protein partially folded into ;-sheet structure in the presence of negatively charged liposomes. These data suggest that LEA18 does not function as a membrane stabilizing protein, as suggested for other LEA proteins. Instead, a possible function of LEA18 could be the composition-dependent modulation of membrane stability, e.g., during signaling or vesicle-mediated transport. Research Highlights Y1 - 2011 SN - 0006-3002 ER - TY - JOUR A1 - Jeltsch, Florian A1 - Moloney, Kirk A. A1 - Schwager, Monika A1 - Körner, Katrin A1 - Blaum, Niels T1 - Consequences of correlations between habitat modifications and negative impact of climate change for regional species survival JF - Agriculture, ecosystems & environment : an international journal for scientific research on the relationship of agriculture and food production to the biosphere N2 - While several empirical and theoretical studies have clearly shown the negative effects of climate or landscape changes on population and species survival only few of them addressed combined and correlated consequences of these key environmental drivers. This also includes positive landscape changes such as active habitat management and restoration to buffer the negative effects of deteriorating climatic conditions. In this study, we apply a conceptual spatial modelling approach based on functional types to explore the effects of both positive and negative correlations between changes in habitat and climate conditions on the survival of spatially structured populations. We test the effect of different climate and landscape change scenarios on four different functional types that represent a broad spectrum of species characterised by their landscape level carrying capacity, the local population turnover rates at the patch level (K-strategies vs. r-strategies) and dispersal characterstics. As expected, simulation results show that correlated landscape and climatic changes can accelerate (in case of habitat loss or degradation) or slow down (in case of habitat gain or improvement) regional species extinction. However, the strength of the combined changes depends on local turnover at the patch level, the overall landscape capacity of the species, and its specific dispersal characteristics. Under all scenarios of correlated changes in habitat and climate conditions we found the highest sensitivity for functional types representing species with a low landscape capacity but a high population growth rate and a strong density regulation causing a high turnover at the local patch level. The relative importance of habitat loss or habitat degradation, in combination with climate deterioration, differed among the functional types. However, an increase in regional capacity revealed a similar response pattern: For all types, habitat improvement led to higher survival times than habitat gain, i.e. the establishment of new habitat patches. This suggests that improving local habitat quality at a regional scale is a more promising conservation strategy under climate change than implementing new habitat patches. This conceptual modelling study provides a general framework to better understand and support the management of populations prone to complex environmental changes. KW - Functional types KW - Spatially explicit modelling KW - Dynamic landscapes KW - Species conservation KW - Habitat fragmentation KW - Habitat management Y1 - 2011 U6 - https://doi.org/10.1016/j.agee.2010.12.019 SN - 0167-8809 VL - 145 IS - 1 SP - 49 EP - 58 PB - Elsevier CY - Amsterdam ER - TY - JOUR A1 - Blaum, Niels A1 - Mosner, Eva A1 - Schwager, Monika A1 - Jeltsch, Florian T1 - How functional is functional?Ecological groupings in terrestrial animal ecology - towards an animal functional type approach JF - Biodiversity and conservation N2 - Understanding mechanisms to predict changes in plant and animal communities is a key challenge in ecology. The need to transfer knowledge gained from single species to a more generalized approach has led to the development of categorization systems where species' similarities in life strategies and traits are classified into ecological groups (EGs) like functional groups/types or guilds. While approaches in plant ecology undergo a steady improvement and refinement of methodologies, progression in animal ecology is lagging behind. With this review, we aim to initiate a further development of functional classification systems in animal ecology, comparable to recent developments in plant ecology. We here (i) give an overview of terms and definitions of EGs in animal ecology, (ii) discuss existing classification systems, methods and application areas of EGs (focusing on terrestrial vertebrates), and (iii) provide a "roadmap towards an animal functional type approach" for improving the application of EGs and classifications in animal ecology. We found that an animal functional type approach requires: (i) the identification of core traits describing species' dependency on their habitat and life history traits, (ii) an optimization of trait selection by clustering traits into hierarchies, (iii) the assessment of "soft traits" as substitute for hardly measurable traits, e.g. body size for dispersal ability, and (iv) testing of delineated groups for validation including experiments. KW - Ecological classification KW - Functional type KW - Guild KW - Functional trait KW - Trait selection KW - Effect group KW - Response group KW - Environmental relationships Y1 - 2011 U6 - https://doi.org/10.1007/s10531-011-9995-1 SN - 0960-3115 VL - 20 IS - 11 SP - 2333 EP - 2345 PB - Springer CY - Dordrecht ER - TY - JOUR A1 - Wasiolka, Bernd A1 - Blaum, Niels T1 - Comparing biodiversity between protected savanna and adjacent non-protected farmland in the southern Kalahari JF - Journal of arid environments N2 - In this study we investigated the effect of different land use options (wildlife versus livestock) on species richness of plants and reptiles in the protected Kgalagadi Transfrontier Park (KTP) versus adjacent non-protected farmland within the same savanna habitat type (Aoub dune veld) in the southern Kalahari, South Africa. Our results show that both plant and reptile species richness as well as plant cover and reptile abundance was significantly higher in the protected KTP than in the non-protected farmland. The higher proportion of shrub but lower proportions of perennial grass cover, herb cover, and herb species richness in the farmland can be explained by higher stocking rates and the differences in feeding behaviour between native wild ungulates (e.g. Antidorcas marsupialis, Oryx gazella) and livestock (mainly sheep). The reptile's prey availability and microhabitats (perennial grass tussocks and rodent burrows) for thermoregulation and protection against predators were significantly lower in the farmland. To conclude, our results clearly show that long term effects of different land use options (wildlife in protected KTP versus extensive livestock production in the non-protected farmland) even within the same habitat type have led to significant changes in vegetation composition, availability of microhabitat structures and in the reptile community. KW - Kgalagadi Transfrontier Park KW - Rangeland KW - Degradation KW - Species richness KW - Conservation KW - Reptile Y1 - 2011 U6 - https://doi.org/10.1016/j.jaridenv.2011.04.011 SN - 0140-1963 VL - 75 IS - 9 SP - 836 EP - 841 PB - Elsevier CY - London ER - TY - JOUR A1 - Csuetoertoeki, Renata A1 - Szatmari, Istvan A1 - Koch, Andreas A1 - Heydenreich, Matthias A1 - Kleinpeter, Erich A1 - Fueloep, Ferenc T1 - Synthesis and conformational analysis of new naphth[1,2-e][1,3]oxazino[3,4-c]quinazoline derivatives JF - Tetrahedron N2 - A new highly functionalized aminonaphthol derivative, 1-(amino(2-aminophenyl)methyl)-2-naphthol (4), was synthesized by the reaction of 2-naphthol, 2-nitrobenzaldehyde and tert-butyl carbamate or benzyl carbamate, followed by reduction and/or removal of the protecting group. The aminonaphthol derivative thus obtained was converted in ring-closure reactions with formaldehyde. benzaldehyde and/or phosgene to the corresponding naphth[1,2-e][1,3]oxazino[3,4-c]quinazoline derivatives. The conformational analysis of some derivatives by NMR spectroscopy and accompanying molecular modelling are also reported. KW - Naphthoxazinoquinazolines KW - NMR KW - Conformational analysis KW - DFT calculations KW - Hammett-Brown plots Y1 - 2011 U6 - https://doi.org/10.1016/j.tet.2011.08.074 SN - 0040-4020 VL - 67 IS - 44 SP - 8564 EP - 8571 PB - Elsevier CY - Oxford ER - TY - JOUR A1 - Kramer, Markus A1 - Kleinpeter, Erich T1 - A conformational study of N-acetyl glucosamine derivatives utilizing residual dipolar couplings JF - Journal of magnetic resonance N2 - The conformational analyses of six non-rigid N-acetyl glucosamine (NAG) derivatives employing residual dipolar couplings (RDCs) and NOEs together with molecular dynamics (MD) simulations are presented. Due to internal dynamics we had to consider different conformer ratios existing in solution. The good quality of the correlation between theoretically and experimentally obtained RDCs show the correctness of the calculated conformers even if the ratios derived from the MD simulations do not exactly meet the experimental data. If possible, the results were compared to former published data and commented. KW - NMR KW - Residual dipolar couplings KW - Molecular dynamics KW - N-acetyl glucosamine derivatives KW - Carbohydrates Y1 - 2011 U6 - https://doi.org/10.1016/j.jmr.2011.06.029 SN - 1090-7807 VL - 212 IS - 1 SP - 174 EP - 185 PB - Elsevier CY - San Diego ER - TY - GEN A1 - Kramer, Markus A1 - Kleinpeter, Erich T1 - A conformational study of N-acetyl glucosamine derivatives utilizing residual dipolar couplings (vol 212, pg 174, 2011) T2 - Journal of magnetic resonance Y1 - 2011 U6 - https://doi.org/10.1016/j.jmr.2011.09.017 SN - 1090-7807 VL - 213 IS - 1 SP - 210 EP - 211 PB - Elsevier CY - San Diego ER - TY - JOUR A1 - Carlsohn, Anja A1 - Cassel, Michael A1 - Linne, Karsten A1 - Mayer, Frank T1 - How much is too much? - a case report of nutritional supplement use of a high-performance athlete JF - The British journal of nutrition : an international journal devoted to the science of human and animal nutrition N2 - Although dietary nutrient intake is often adequate, nutritional supplement use is common among elite athletes. However, high-dose supplements or the use of multiple supplements may exceed the recommended daily allowance (RDA) of particular nutrients or even result in a daily intake above tolerable upper limits (UL). The present case report presents nutritional intake data and supplement use of a highly trained male swimmer competing at international level. Habitual energy and micronutrient intake were analysed by 3 d dietary reports. Supplement use and dosage were assessed, and total amount of nutrient supply was calculated. Micronutrient intake was evaluated based on RDA and UL as presented by the European Scientific Committee on Food, and maximum permitted levels in supplements (MPL) are given. The athlete's diet provided adequate micronutrient content well above RDA except for vitamin D. Simultaneous use of ten different supplements was reported, resulting in excess intake above tolerable UL for folate, vitamin E and Zn. Additionally, daily supplement dosage was considerably above MPL for nine micronutrients consumed as artificial products. Risks and possible side effects of exceeding UL by the athlete are discussed. Athletes with high energy intake may be at risk of exceeding UL of particular nutrients if multiple supplements are added. Therefore, dietary counselling of athletes should include assessment of habitual diet and nutritional supplement intake. Educating athletes to balance their diets instead of taking supplements might be prudent to prevent health risks that may occur with long-term excess nutrient intake. KW - Dietary supplements KW - Tolerable upper limits KW - Elite athletes KW - Vitamins KW - Minerals Y1 - 2011 U6 - https://doi.org/10.1017/S0007114510005556 SN - 0007-1145 VL - 105 IS - 12 SP - 1724 EP - 1728 PB - Cambridge Univ. Press CY - Cambridge ER - TY - JOUR A1 - Marsat, Jean-Noel A1 - Heydenreich, Matthias A1 - Kleinpeter, Erich A1 - Berlepsch, Hans V. A1 - Boettcher, Christoph A1 - Laschewsky, André T1 - Self-Assembly into multicompartment micelles and selective solubilization by Hydrophilic-Lipophilic-Fluorophilic block copolymers JF - Macromolecules : a publication of the American Chemical Society N2 - Amphiphilic linear ternary block copolymers (ABC) were synthesized in three consecutive steps by the reversible addition fragmentation chain transfer (RAFT) method. Using oligo(ethylene oxide) monomethyl ether acrylate, benzyl acrylate, and 1H,1H-perfluorobutyl acrylate monomers, the triblock copolymers consist of a hydrophilic (A), a lipophilic (B), and a fluorophilic (C) block. The block sequence of the triphilic copolymers was varied systematically to provide all possible variations: ABC, ACB, and BAC. All blocks have glass transition temperatures below 0 degrees C. Self-assembly into spherical micellar aggregates was observed in aqueous solution, where hydrophobic cores undergo local phase separation into various ultrastructures as shown by cryogenic transmission electron microscopy (cryo-TEM). Selective solubilization of substantial quantities of hydrocarbon and fluorocarbon low molar mass compounds by the lipophilic and fluorophilic block, respectively, is demonstrated. Y1 - 2011 U6 - https://doi.org/10.1021/ma200032j SN - 0024-9297 VL - 44 IS - 7 SP - 2092 EP - 2105 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Pihlaja, Kalevi A1 - Sinkkonen, Jari A1 - Stajer, Geza A1 - Koch, Andreas A1 - Kleinpeter, Erich T1 - 1-Oxo-1,3-dithiolanes - synthesis and stereochemistry JF - Magnetic resonance in chemistry N2 - 1-Oxo-1,3-dithiolane (4) and its cis- and trans-2-methyl (5,6), -4-methyl (7,8) and -5-methyl (9,10) derivatives were prepared by oxidizing the corresponding 1,3-dithiolanes (1-3) with NaIO(4) in water. The oxides were purified and their isomers separated using thin layer chromatography. The structural characterization was carried out with (1)H and (13)C NMR spectroscopy and molecular modelling. The sulfoxides 4-6 and 8-10 attain two S(1) type envelopes (sometimes slightly distorted) the S=O(ax) envelope greatly dominating. Cis-4-methyl-1-oxo-1,3-dithiolane is a special case exhibiting both two closely related S=O(ax) (30 and 27%) as well as S=O(eq) (21 and 22%) forms [S(1) and C(4) envelopes, respectively]. The relative energies of these conformations, the values of (1)H-(1)H coupling constants and (1)H and (13)C chemical shifts were estimated by computational methods and they support well the conclusions based on the experimental data. KW - NMR KW - (1)H NMR KW - (13)C NMR KW - sulfur heterocycles KW - conformational analysis KW - computational chemistry Y1 - 2011 U6 - https://doi.org/10.1002/mrc.2764 SN - 0749-1581 VL - 49 IS - 7 SP - 443 EP - 449 PB - Wiley-Blackwell CY - Malden ER - TY - JOUR A1 - Mayer, Frank A1 - Scharhag-Rosenberger, Friederike A1 - Carlsohn, Anja A1 - Cassel, Michael A1 - Müller, Steffen A1 - Scharhag, Jürgen T1 - The intensity and effects of strength training in the elderly JF - Deutsches Ärzteblatt international : a weekly online journal of clinical medicine and public health N2 - Background: The elderly need strength training more and more as they grow older to stay mobile for their everyday activities. The goal of training is to reduce the loss of muscle mass and the resulting loss of motor function. The dose-response relationship of training intensity to training effect has not yet been fully elucidated. Methods: PubMed was selectively searched for articles that appeared in the past 5 years about the effects and dose-response relationship of strength training in the elderly. Results: Strength training in the elderly (> 60 years) increases muscle strength by increasing muscle mass, and by improving the recruitment of motor units, and increasing their firing rate. Muscle mass can be increased through training at an intensity corresponding to 60% to 85% of the individual maximum voluntary strength. Improving the rate of force development requires training at a higher intensity (above 85%), in the elderly just as in younger persons. It is now recommended that healthy old people should train 3 or 4 times weekly for the best results; persons with poor performance at the outset can achieve improvement even with less frequent training. Side effects are rare. Conclusion: Progressive strength training in the elderly is efficient, even with higher intensities, to reduce sarcopenia, and to retain motor function. Y1 - 2011 U6 - https://doi.org/10.3238/arztebl.2011.0359 SN - 1866-0452 VL - 108 IS - 21 SP - 359 EP - U30 PB - Dt. Ärzte-Verl. CY - Cologne ER - TY - JOUR A1 - Kleinpeter, Erich A1 - Koch, Andreas T1 - The anisotropic effect of functional groups in H-1 NMR spectra is the molecular response property of spatial NICS-the frozen conformational equilibria of 9-arylfluorenes JF - Tetrahedron N2 - Rotation about the single bond adjoining the aryl and fluorene moieties in 9-arylfluorenes can be frozen out on the NMR timescale if methyl groups are located at either one or both of the ortho positions of the aryl substituent. In the ground-state of these rotamers, the planes of the aryl and fluorene moieties are perpendicular to each other and the methyl substituents are consequently positioned either above the fluorene moiety or in-plane with it; thus, the methyl protons are either shielded or deshielded, respectively, due to the ring current effect of the fluorene moiety. This anisotropic effect on the H-1 chemical shifts of the methyl protons has been quantified on the basis of through-space NMR shieldings (TSNMRS) and subsequently Delta delta(calcd) compared with the experimentally observed chemical shift differences, Delta delta(exp). In this context, the experimental anisotropic effects of functional groups in the H-1 NMR have proven to quantitatively be the molecular response property of theoretical spatial nucleus independent chemical shieldings (NICS). Differences between Delta delta(calcd) and Delta delta(exp) were, for the first time, also quantified as arising from steric compression. KW - Through-space NMR shieldings (TSNMRS) KW - Spatial NICS KW - Anisotropic effect KW - Iso-chemical-shielding surfaces (ICSS) KW - 9-Arylfluorenes Y1 - 2011 U6 - https://doi.org/10.1016/j.tet.2011.06.005 SN - 0040-4020 VL - 67 IS - 32 SP - 5740 EP - 5743 PB - Elsevier CY - Oxford ER - TY - JOUR A1 - Shainyan, Bagrat A. A1 - Suslova, Elena N. A1 - Kleinpeter, Erich T1 - Conformational analysis of N-phenyl- and N-trifyl-4,4-dimethyl-4-silathiane 1-sulfimides JF - Journal of physical organic chemistry N2 - N-Substituted 4,4-dimethyl-4-silathiane 1-sulfimides Me2Si(sic)S=NSO2R [R- Ph (1), CF3 (2)] were studied experimentally by variable temperature dynamic NMR spectroscopy. Low temperature 13 C NMR spectra of the two compounds revealed the frozen ring inversion process and approximately equal content of the axial and equatorial conformers. Calculations of the 4-silathiane derivatives 1, 2 and the model compound [R Me (3)] as well as their carbon analogs, the similarly N-substituted (sic)S=NSO2R thiane 1-sulfimides [R = Ph (4), CF3 (5), Me (6)] at the DFT/B3LYP/6-311G(d, p) level in the gas phase and in chloroform solution using the PCM model at the same level of theory showed a strong dependence of the relative stability of the conformer on the solvent. The electronegative trifluoromethyl group increases the relative stability of the axial conformer. KW - 4-silathianes KW - conformational analysis KW - dynamic NMR KW - quantum chemical calculations KW - sulfimides Y1 - 2011 U6 - https://doi.org/10.1002/poc.1811 SN - 0894-3230 VL - 24 IS - 8 SP - 698 EP - 704 PB - Wiley-Blackwell CY - Malden ER - TY - JOUR A1 - Carlsohn, Anja A1 - Scharhag-Rosenberger, Friederike A1 - Cassel, Michael A1 - Weber, Josefine A1 - Guzman, Annette de Guzman A1 - Mayer, Frank T1 - Physical activity levels to estimate the energy requirement of adolescent athletes JF - Pediatric exercise science N2 - Adequate energy intake in adolescent athletes is considered important. Total energy expenditure (TEE) can be calculated from resting energy expenditure (REE) and physical activity level (PAL). However, validated PAL recommendations are available for adult athletes only. Purpose was to comprise physical activity data in adolescent athletes and to establish PAL recommendations for this population. In 64 competitive athletes (15.3 +/- 1.5yr, 20.5 +/- 2.0kg/m(2)) and 14 controls (15.1 +/- 1.1yr, 21 +/- 2.1kg/m(2)) TEE was calculated using 7-day activity protocols validated against doubly-labeled water. REE was estimated by Schofield-HW equation, and PAL was calculated as TEE:REE. Observed PAL in adolescent athletes (1.90 +/- 0.35) did not differ compared with controls (1.84 +/- 0.32, p = .582) and was lower than recommended for adult athletes by the WHO. In conclusion, applicability of PAL values recommended for adult athletes to estimate energy requirements in adolescent athletes must be questioned. Instead, a PAL range of 1.75-2.05 is suggested. Y1 - 2011 SN - 0899-8493 VL - 23 IS - 2 SP - 261 EP - 269 PB - Human Kinetics Publ. CY - Champaign ER - 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 -