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Michalik-Onichimowska, Aleksandra ; Kern, Simon ; Riedel, Jens ; Panne, Ulrich ; King, Rudibert ; Maiwald, Michael
Driven mostly by the search for chemical syntheses under biocompatible conditions, so called "click" chemistry rapidly became a growing field of research. The resulting simple one-pot reactions are so far only scarcely accompanied by an adequate optimization via comparably straightforward and robust analysis techniques possessing short set-up times. Here, we report on a fast and reliable calibration-free online NMR monitoring approach for technical mixtures. It combines a versatile fluidic system, continuous-flow measurement of H-1 spectra with a time interval of 20 s per spectrum, and a robust, fully automated algorithm to interpret the obtained data. As a proof-of-concept, the thiol-ene coupling between N-boc cysteine methyl ester and ally] alcohol was conducted in a variety of non-deuterated solvents while its time-resolved behaviour was characterized with step tracer experiments. Overlapping signals in online spectra during thiol-ene coupling could be deconvoluted with a spectral model using indirect hard modeling and were subsequently converted to either molar ratios (using a calibration free approach) or absolute concentrations (using 1-point calibration). For various solvents the kinetic constant k for pseudo-first order reaction was estimated to be 3.9 h(-1) at 25 degrees C. The obtained results were compared with direct integration of non-overlapping signals and showed good agreement with the implemented mass balance. (C) 2017 Elsevier Inc. All rights reserved.
Lazuras, Lambros ; Barkoukis, Vassilis ; Loukovitis, Andreas ; Brand, Ralf ; Hudson, Andy ; Mallia, Luca ; Michaelides, Michalis ; Muzi, Milena ; Petroczi, Andrea ; Zelli, Arnaldo
Doping use in recreational sports is an emerging issue that has received limited attention so far in the psychological literature. The present study assessed the lifetime prevalence of controlled performance and appearance enhancing substances ( PAES), and used behavioral reasoning theory to identify the reasons for using and for avoiding using controlled PAES in young exercisers across five European countries, in the context of the "SAFE YOU" Project. Participants were 915 young amateur athletes and exercisers (M = 21.62; SD = 2.62) from Cyprus, Germany, Greece, Italy, and UK who completed an anonymous questionnaire that included measures of self-reported use of controlled PAES, as well as reasons for using and not using controlled PAES. The results of the descriptive analyses demonstrated that almost one out five exercisers in the sample had a previous experience with controlled PAES. Higher prevalence rates were found in Greece and Cyprus and lower in Italy. The most frequently reported reasons for using controlled PAES included achieving the desired results faster; pushing the self to the (physical) limits; and recovering faster after exercise/training. Furthermore, the most frequently reported reasons for not using controlled PAES involved worry about any possible adverse health effects; not feeling the need for using them; and wanting to see what can be achieved naturally without using any controlled PAES. The findings of the present study indicate that the use of controlled PAES is fast becoming a crisis in amateur sports and exercise settings and highlight the need for preventive action and concerted anti-doping education efforts.
Vishnevetskaya, Natalya S. ; Hildebrand, Viet ; Niebuur, Bart-Jan ; Grillo, Isabelle ; Filippov, Sergey K. ; Laschewsky, Andre ; Müller-Buschbaum, Peter ; Papadakis, Christine M.
Hildebrand, Viet ; Heydenreich, Matthias ; Laschewsky, Andre ; Moeller, Heiko M. ; Müller-Buschbaum, Peter ; Papadakis, Christine M. ; Schanzenbach, Dirk ; Wischerhoff, Erik
Several series of presumed dual thermo-responsive diblock copolymers consisting of one non-ionic and one zwitterionic block were synthesized via consecutive reversible addition-fragmentation chain transfer (RAFT) polymerization. For all copolymers, poly(N-isopropylmethacrylamide) was chosen as non-ionic block that shows a coil-to-globule collapse transition of the lower critical solution temperature (LCST) type. In contrast, the chemical structure of zwitterionic blocks, which all belonged to the class of poly(sulfobetaine methacrylate)s, was varied broadly, in order to tune their coil-to-globule collapse transition of the upper critical solution temperature (UCST) type. All polymers were labeled with a solvatochromic fluorescent end-group. The dual thermo-responsive behavior and the resulting multifarious temperature-dependent self-assembly in aqueous solution were mapped by temperature resolved turbidimetry, H-1 NMR spectroscopy, dynamic light scattering (DLS), and fluorescence spectroscopy. Depending on the relative positions between the UCST-type and LCST-type transition temperatures, as well as on the width of the window in-between, all the four possible modes of stimulus induced micellization can be realized. This includes classical induced micellization due to a transition from a double hydrophilic, or respectively, from a double hydrophobic to an amphiphilic state, as well as "schizophrenic" behavior, where the core- and shell-forming blocks are inverted. The exchange of the roles of the hydrophilic and hydrophobic block in the amphiphilic states is possible through a homogeneous intermediate state or a heterogeneous one. (C) 2017 Elsevier Ltd. All rights reserved.
Chen, Zupeng ; Savateev, Aleksandr ; Pronkin, Sergey ; Papaefthimiou, Vasiliki ; Wolff, Christian Michael ; Willinger, Marc Georg ; Willinger, Elena ; Neher, Dieter ; Antonietti, Markus ; Dontsova, Dariya
Cost-efficient, visible-light-driven hydrogen production from water is an attractive potential source of clean, sustainable fuel. Here, it is shown that thermal solid state reactions of traditional carbon nitride precursors (cyanamide, melamine) with NaCl, KCl, or CsCl are a cheap and straightforward way to prepare poly(heptazine imide) alkali metal salts, whose thermodynamic stability decreases upon the increase of the metal atom size. The chemical structure of the prepared salts is confirmed by the results of X-ray photoelectron and infrared spectroscopies, powder X-ray diffraction and electron microscopy studies, and, in the case of sodium poly(heptazine imide), additionally by atomic pair distribution function analysis and 2D powder X-ray diffraction pattern simulations. In contrast, reactions with LiCl yield thermodynamically stable poly(triazine imides). Owing to the metastability and high structural order, the obtained heptazine imide salts are found to be highly active photo-catalysts in Rhodamine B and 4-chlorophenol degradation, and Pt-assisted sacrificial water reduction reactions under visible light irradiation. The measured hydrogen evolution rates are up to four times higher than those provided by a benchmark photocatalyst, mesoporous graphitic carbon nitride. Moreover, the products are able to photocatalytically reduce water with considerable reaction rates, even when glycerol is used as a sacrificial hole scavenger.
100 Jahre Roter Oktober
(2017)
Tofelde, Stefanie ; Schildgen, Taylor F. ; Savi, Sara ; Pingel, Heiko ; Wickert, Andrew D. ; Bookhagen, Bodo ; Wittmann, Hella ; Alonso, Ricardo N. ; Cottle, John ; Strecker, Manfred
Fluvial fill terraces in intermontane basins are valuable geomorphic archives that can record tectonically and/or climatically driven changes of the Earth-surface process system. However, often the preservation of fill terrace sequences is incomplete and/or they may form far away from their source areas, complicating the identification of causal links between forcing mechanisms and landscape response, especially over multi-millennial timescales. The intermontane Toro Basin in the southern Central Andes exhibits at least five generations of fluvial terraces that have been sculpted into several-hundred-meter-thick Quaternary valley-fill conglomerates. New surface-exposure dating using nine cosmogenic Be-10 depth profiles reveals the successive abandonment of these terraces with a 100 kyr cyclicity between 75 +/- 7 and 487 +/- 34 ka. Depositional ages of the conglomerates, determined by four Al-26/Be-10 burial samples and U-Pb zircon ages of three intercalated volcanic ash beds, range from 18 +/- 141 to 936 +/- 170 ka, indicating that there were multiple cut-and-fill episodes. Although the initial onset of aggradation at similar to 1 Ma and the overall net incision since ca. 500 ka can be linked to tectonic processes at the narrow basin outlet, the superimposed 100 kyr cycles of aggradation and incision are best explained by eccentricity-driven climate change. Within these cycles, the onset of river incision can be correlated with global cold periods and enhanced humid phases recorded in paleoclimate archives on the adjacent Bolivian Altiplano, whereas deposition occurred mainly during more arid phases on the Altiplano and global interglacial periods. We suggest that enhanced runoff during global cold phases - due to increased regional precipitation rates, reduced evapotranspiration, or both - resulted in an increased sediment-transport capacity in the Toro Basin, which outweighed any possible increases in upstream sediment supply and thus triggered incision. Compared with two nearby basins that record precessional (21-kyr) and long-eccentricity (400-kyr) forcing within sedimentary and geomorphic archives, the recorded cyclicity scales with the square of the drainage basin length. (C) 2017 Elsevier B.V. All rights reserved.
Direct current systems employing a kinematic surveying strategy allow to analyze the electrical resistivity of the subsurface for large areas (i.e., several hectares). Typical applications are found in precision agriculture, archaeological prospecting and soil sciences. With the typical survey setting, the collected data sets are often characterized by a rather high level of noise and a rather coarse lateral sampling compared to data acquired with fixed electrodes. We therefore present an efficient one-dimensional inversion approach in which we put special attention on modeling the effects of noise. We apply this method to data recorded with a five-offset equatorial dipole-dipole system employing rolling electrodes. By performing several synthetic tests with realistic noise levels, we found that the considered five-configuration soundings allow for a reliable imaging of two-layer cases in the uppermost two meters of the subsurface, where the subsurface can be assumed to follow a horizontally layered geometry within 3 m around the system. By analyzing the corresponding sensitivity functions, we also show that the equatorial dipole-dipole array is relatively well suited for a 1D inversion approach compared to standard in-line electrode arrays. To illustrate this aspect, we show that our method can provide results similar to those obtained with a 2D Wenner imaging procedure for data recorded across a well-constrained 2D target. We finally apply our method to a large five-offset data set acquired in an agricultural study. The final pseudo-3D model of electrical resistivity is in accordance with borehole data available for the surveyed area. Our results demonstrate the applicability and the versatility of the presented inversion approach for large-scale data sets as they are typically collected with such rolling electrode systems. (C) 2017 Elsevier B.V. All rights reserved.
5-Jahres-Verlauf der LRS
(2017)
Wyschkon, Anne ; Schulz, Franziska ; Gallit, Finja Sunnyi ; Poltz, Nadine ; Kohn-Henkel, Juliane ; Moraske, Svenja ; Bondue, Rebecca ; von Aster, Michael G. ; Esser, Günter
Fragestellung: Untersucht wird der Verlauf von Kindern mit Lese-Rechtschreibstörungen (LRS) über gut 5 Jahre unter Berücksichtigung des Einflusses des Geschlechts der Betroffenen. Außerdem werden Auswirkungen der LRS auf das spätere Schriftsprachniveau und den Schulerfolg überprüft. Methodik: Eingangs wurden 995 Schüler zwischen 6 und 16 Jahren untersucht. Ein Teil dieser Kinder ist nach 43 sowie 63 Monaten nachuntersucht worden. Eine LRS wurde diagnostiziert, wenn für das Lesen bzw. Rechtschreiben das doppelte Diskrepanzkriterium von 1.5 Standardabweichungen zur nonverbalen Intelligenz und dem Mittelwert der Klassenstufe erfüllt war und gleichzeitig keine Minderbegabung vorlag. Ergebnisse: Die LRS weist über einen Zeitraum von 63 Monaten eine hohe Störungspersistenz von knapp 70 % auf. Der 5-Jahres-Verlauf der mittleren Lese- und Rechtschreibleistungen wurde nicht vom Geschlecht beeinflusst. Trotz durchschnittlicher Intelligenz blieben die LRS-Schüler in der Schriftsprache mindestens eine Standardabweichung hinter durchschnittlich und etwa 0.5 Standardabweichungseinheiten hinter unterdurchschnittlich intelligenten Kindern zurück. Der Schulerfolg der LRS-Schüler glich dem unterdurchschnittlich intelligenter Kinder und fiel deutlich schlechter aus als bei durchschnittlich intelligenten Kontrollkindern. Schlussfolgerungen: Eine LRS stellt ein erhebliches Entwicklungsrisiko dar, was frühzeitige Diagnostik- und Therapiemaßnahmen erfordert. Dafür sind reliable und im Hinblick auf die resultierenden Prävalenzraten sinnvolle, allgemein anerkannte Diagnosekriterien essenziell.
Wolff, Martin ; Zhang-Haagen, Bo ; Decker, Christina ; Barz, Bogdan ; Schneider, Mario ; Biehl, Ralf ; Radulescu, Aurel ; Strodel, Birgit ; Willbold, Dieter ; Nagel-Steger, Luitgard
Spekkers, Matthieu ; Roezer, Viktor ; Thieken, Annegret ; ten Veldhuis, Marie-Claire ; Kreibich, Heidi
Introduction
Varus knee alignment has been identified as a risk factor for the progression of medial knee osteoarthritis. However, the underlying mechanisms have not been elucidated yet in children. Thus, the aims of the present study were to examine differences in ground reaction forces, loading rate, impulses, and free moment values during running in children with and without genu varus.
Methods
Thirty-six boys aged 9–14 volunteered to participate in this study. They were divided in two age-matched groups (genu varus versus healthy controls). Body weight adjusted three dimensional kinetic data (Fx, Fy, Fz) were collected during running at preferred speed using two Kistler force plates for the dominant and non-dominant limb.
Results
Individuals with knee genu varus produced significantly higher (p = .01; d = 1.09; 95%) body weight adjusted ground reaction forces in the lateral direction (Fx) of the dominant limb compared to controls. On the non-dominant limb, genu varus patients showed significantly higher body weight adjusted ground reaction forces values in the lateral (p = .01; d = 1.08; 86%) and medial (p < .001; d = 1.55; 102%) directions (Fx). Further, genu varus patients demonstrated 55% and 36% greater body weight adjusted loading rates in the dominant (p < .001; d = 2.09) and non-dominant (p < .001; d = 1.02) leg, respectively. No significant between-group differences were observed for adjusted free moment values (p>.05).
Discussion
Higher mediolateral ground reaction forces and vertical loading rate amplitudes in boys with genu varus during running at preferred running speed may accelerate the development of progressive joint degeneration in terms of the age at knee osteoarthritis onset. Therefore, practitioners and therapists are advised to conduct balance and strength training programs to improve lower limb alignment and mediolateral control during dynamic movements.
A comparison of running kinetics in children with and without genu varus: A cross sectional study
(2017)
Introduction Varus knee alignment has been identified as a risk factor for the progression of medial knee osteoarthritis. However, the underlying mechanisms have not been elucidated yet in children. Thus, the aims of the present study were to examine differences in ground reaction forces, loading rate, impulses, and free moment values during running in children with and without genu varus. Methods Thirty-six boys aged 9-14 volunteered to participate in this study. They were divided in two age-matched groups (genu varus versus healthy controls). Body weight adjusted three dimensional kinetic data (Fx, Fy, Fz) were collected during running at preferred speed using two Kistler force plates for the dominant and non-dominant limb. Results Individuals with knee genu varus produced significantly higher (p = .01; d = 1.09; 95%) body weight adjusted ground reaction forces in the lateral direction (Fx) of the dominant limb compared to controls. On the non-dominant limb, genu varus patients showed significantly higher body weight adjusted ground reaction forces values in the lateral (p = .01; d = 1.08; 86%) and medial (p < .001; d = 1.55; 102%) directions (Fx). Further, genu varus patients demonstrated 55% and 36% greater body weight adjusted loading rates in the dominant (p < .001; d = 2.09) and non-dominant (p < .001; d = 1.02) leg, respectively. No significant between-group differences were observed for adjusted free moment values (p>.05). Discussion Higher mediolateral ground reaction forces and vertical loading rate amplitudes in boys with genu varus during running at preferred running speed may accelerate the development of progressive joint degeneration in terms of the age at knee osteoarthritis onset. Therefore, practitioners and therapists are advised to conduct balance and strength training programs to improve lower limb alignment and mediolateral control during dynamic movements.
Niemeyer, Bastian ; Epp, Laura Saskia ; Stoof-Leichsenring, Kathleen Rosemarie ; Pestryakova, Luidmila Agafyevna ; Herzschuh, Ulrike
Reliable information on past and present vegetation is important to project future changes, especially for rapidly transitioning areas such as the boreal treeline. To study past vegetation, pollen analysis is common, while current vegetation is usually assessed by field surveys. Application of detailed sedimentary DNA (sedDNA) records has the potential to enhance our understanding of vegetation changes, but studies systematically investigating the power of this proxy are rare to date. This study compares sedDNA metabarcoding and pollen records from surface sediments of 31 lakes along a north-south gradient of increasing forest cover in northern Siberia (Taymyr peninsula) with data from field surveys in the surroundings of the lakes. sedDNA metabarcoding recorded 114 plant taxa, about half of them to species level, while pollen analyses identified 43 taxa, both exceeding the 31 taxa found by vegetation field surveys. Increasing Larix percentages from north to south were consistently recorded by all three methods and principal component analyses based on percentage data of vegetation surveys and DNA sequences separated tundra from forested sites. Comparisons of the ordinations using procrustes and protest analyses show a significant fit among all compared pairs of records. Despite similarities of sedDNA and pollen records, certain idiosyncrasies, such as high percentages of Alnus and Betula in all pollen and high percentages of Salix in all sedDNA spectra, are observable. Our results from the tundra to single-tree tundra transition zone show that sedDNA analyses perform better than pollen in recording site-specific richness (i.e., presence/absence of taxa in the vicinity of the lake) and perform as well as pollen in tracing vegetation composition.
Although the general development of mathematical abilities in primary school has been the focus of many researchers, the development of place value understanding has rarely been investigated to date. This is possibly due to the lack of conceptual approaches and empirical studies related to this topic. To fill this gap, a theory-driven and empirically validated model was developed that describes five sequential conceptual levels of place value understanding. The level sequence model gives us the ability to estimate general abilities and difficulties in primary school pupils in the development of a conceptual place value understanding. The level sequence model was tried and tested in Germany, and given that number words are very differently constructed in German and in the languages used in South African classrooms, this study aims to investigate whether this level sequence model can be transferred to South Africa. The findings based on the responses of 198 Grade 2-4 learners show that the English translation of the test items results in the same item level allocation as the original German test items, especially for the three basic levels. Educational implications are provided, in particular concrete suggestions on how place value might be taught according to the model and how to collect specific empirical data related to place value understanding.
Accurate time series representation of paleoclimatic proxy records is challenging because such records involve dating errors in addition to proxy measurement errors. Rigorous attention is rarely given to age uncertainties in paleoclimatic research, although the latter can severely bias the results of proxy record analysis. Here, we introduce a Bayesian approach to represent layer-counted proxy records - such as ice cores, sediments, corals, or tree rings - as sequences of probability distributions on absolute, error-free time axes. The method accounts for both proxy measurement errors and uncertainties arising from layer-counting-based dating of the records. An application to oxygen isotope ratios from the North Greenland Ice Core Project (NGRIP) record reveals that the counting errors, although seemingly small, lead to substantial uncertainties in the final representation of the oxygen isotope ratios. In particular, for the older parts of the NGRIP record, our results show that the total uncertainty originating from dating errors has been seriously underestimated. Our method is next applied to deriving the overall uncertainties of the Suigetsu radiocarbon comparison curve, which was recently obtained from varved sediment cores at Lake Suigetsu, Japan. This curve provides the only terrestrial radiocarbon comparison for the time interval 12.5-52.8 kyr BP. The uncertainties derived here can be readily employed to obtain complete error estimates for arbitrary radiometrically dated proxy records of this recent part of the last glacial interval.
Despite the fact that development aid has broadened from economic growth theory to include human and social capital, there is a lack of a general agreement as to its benefits. This critical review and analyses of the development aid academic and institutional discourse identifies some major shortcomings. The dominance of economics at the expense of politics, and the imposition of development aid neoliberal conditionalities act as barriers to socio-economic development in aid recipient countries. An inference is offered to recast development aid through reconciliation within critical frameworks of different sides of the political spectrum.
Lotze-Campen, Hermann ; Verburg, Peter H. ; Popp, Alexander ; Lindner, Marcus ; Verkerk, Pieter J. ; Moiseyev, Alexander ; Schrammeijer, Elizabeth ; Helming, John ; Tabeau, Andrzej ; Schulp, Catharina J. E. ; van der Zanden, Emma H. ; Lavalle, Carlo ; Batista e Silva, Filipe ; Walz, Ariane ; Bodirsky, Benjamin Leon
Protection of natural or semi-natural ecosystems is an important part of societal strategies for maintaining biodiversity, ecosystem services, and achieving overall sustainable development. The assessment of multiple emerging land use trade-offs is complicated by the fact that land use changes occur and have consequences at local, regional, and even global scale. Outcomes also depend on the underlying socio-economic trends. We apply a coupled, multi-scale modelling system to assess an increase in nature protection areas as a key policy option in the European Union (EU). The main goal of the analysis is to understand the interactions between policy-induced land use changes across different scales and sectors under two contrasting future socio-economic pathways. We demonstrate how complementary insights into land system change can be gained by coupling land use models for agriculture, forestry, and urban areas for Europe, in connection with other world regions. The simulated policy case of nature protection shows how the allocation of a certain share of total available land to newly protected areas, with specific management restrictions imposed, may have a range of impacts on different land-based sectors until the year 2040. Agricultural land in Europe is slightly reduced, which is partly compensated for by higher management intensity. As a consequence of higher costs, total calorie supply per capita is reduced within the EU. While wood harvest is projected to decrease, carbon sequestration rates increase in European forests. At the same time, imports of industrial roundwood from other world regions are expected to increase. Some of the aggregate effects of nature protection have very different implications at the local to regional scale in different parts of Europe. Due to nature protection measures, agricultural production is shifted from more productive land in Europe to on average less productive land in other parts of the world. This increases, at the global level, the allocation of land resources for agriculture, leading to a decrease in tropical forest areas, reduced carbon stocks, and higher greenhouse gas emissions outside of Europe. The integrated modelling framework provides a method to assess the land use effects of a single policy option while accounting for the trade-offs between locations, and between regional, European, and global scales.