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Aim: The hydrolytic degradation behavior of degradable aliphatic polyester-based polymers is strongly influenced by the uptake or transport of water into the polymer matrix and also the hydrolysis rate of ester bonds.
Methods: We examined the volumetric swelling behavior of poly[(rac-lactide)-co-glycolide] (PLGA) and PLGA-based polyurethanes (PLGA-PU) with water contents of 0 wt%, 2 wt% and 7 wt% water at 310 K using a molecular modeling approach. Polymer systems with a number average molecular weight of M-n = 10,126 g.mol(-1) were constructed from PLGA with a lactide content of 67 mol%, whereby PLGA-PU systems were composed of five PLGA segments with M-n = 2052 g.mol(-1), which were connected via urethane linkers originated from 2,2,4-trimethyl hexamethylene-1,6-diisocyanate (TMDI), hexamethyl-1,6-diisocyanate (HDI), or L-lysine-1,6-diisocyanate (LDI).
Results: The calculated densities of the dry PLGA-PU systems were found to be lower than for pure PLGA. The obtained volumetric swelling of the PLGA-PU was depending on the type of urethane linker, whereby all swollen PLGA-PUs contained larger free volume distribution compared to pure PLGA. The mean square displacement curves for dry PLGA and PLGA-PUs showed that urethane linker units reduce the mobility of the polymer chains, while an increase in backbone atoms mobility was found, when water was added to these systems. Consequently, an increased water uptake of PLGA-PU matrices combined with a higher mobility of the chain segments should result in an accelerated hydrolytic chain scission rate in comparison to PLGA.
Conclusions: It can be anticipated that the incorporation of urethane linkers might be a helpful tool to adjust the degradation behavior of polyesters.
The global warming potential of nitrous oxide (N2O) and its long atmospheric lifetime mean its presence in the atmosphere is of major concern, and that methods are required to measure and reduce emissions. Large spatial and temporal variations means, however, that simple extrapolation of measured data is inappropriate, and that other methods of quantification are required. Although process-based models have been developed to simulate these emissions, they often require a large amount of input data that is not available at a regional scale, making regional and global emission estimates difficult to achieve. The spatial extent of organic soils means that quantification of emissions from these soil types is also required, but will not be achievable using a process-based model that has not been developed to simulate soil water contents above field capacity or organic soils. The ECOSSE model was developed to overcome these limitations, and with a requirement for only input data that is readily available at a regional scale, it can be used to quantify regional emissions and directly inform land-use change decisions. ECOSSE includes the major processes of nitrogen (N) turnover, with material being exchanged between pools of SOM at rates modified by temperature, soil moisture, soil pH and crop cover. Evaluation of its performance at site-scale is presented to demonstrate its ability to adequately simulate soil N contents and N2O emissions from cropland soils in Europe. Mitigation scenarios and sensitivity analyses are also presented to demonstrate how ECOSSE can be used to estimate the impact of future climate and land-use change on N2O emissions.
Two novel and simple approaches to N-triflyl guanidines are elaborated. Owing to very strong conjugation the formally double C=N bond of TIN=C(NHR)(2) is longer than the formally single N-C bonds. Energetic effect of the triflylgroup on the conjugation in the N-C=N moiety is estimated to be >= 150 kcal/mol.
A number of ionogels - silica-ionic liquid (IL) hybrid materials - were synthesized and studied for their ionic conductivity. The materials are based on a sulfonated IL, 1-methyl-3-(3-sulfopropyl-)-imidazolium p-toluenesulfonate, [PmimSO(3)H][PTS], which contains a sulfonic acid/sulfonate group both in the IL anion and in the side chain of the IL cation. By way of the sulfonate-sulfonic acid proton transfer, the IL imparts the ionogel with a high ionic conductivity of ca. 10(-2) S cm(-1) in the as-synthesized state at 120 degrees C and 10(-3) S cm(-1) in the dry state at 120 degrees C. The ionogels are stable up to ca. 150 degrees C in dynamic thermogravimetric analysis. This suggests that these materials, which are relatively cheap and easily fabricated, could find application in fuel cells in intermediate temperature ranges where many other membrane materials are not suitable.
This thesis contains several theoretical studies on optomechanical systems, i.e. physical devices where mechanical degrees of freedom are coupled with optical cavity modes. This optomechanical interaction, mediated by radiation pressure, can be exploited for cooling and controlling mechanical resonators in a quantum regime. The goal of this thesis is to propose several new ideas for preparing meso- scopic mechanical systems (of the order of 10^15 atoms) into highly non-classical states. In particular we have shown new methods for preparing optomechani-cal pure states, squeezed states and entangled states. At the same time, proce-dures for experimentally detecting these quantum effects have been proposed. In particular, a quantitative measure of non classicality has been defined in terms of the negativity of phase space quasi-distributions. An operational al- gorithm for experimentally estimating the non-classicality of quantum states has been proposed and successfully applied in a quantum optics experiment. The research has been performed with relatively advanced mathematical tools related to differential equations with periodic coefficients, classical and quantum Bochner’s theorems and semidefinite programming. Nevertheless the physics of the problems and the experimental feasibility of the results have been the main priorities.
1. The complex, nonlinear response of dryland systems to grazing and climatic variations is a challenge to management of these lands. Predicted climatic changes will impact the desertification of drylands under domestic livestock production. Consequently, there is an urgent need to understand the response of drylands to grazing under climate change. 2. We enhanced and parameterized an ecohydrological savanna model to assess the impacts of a range of climate change scenarios on the response of a semi-arid African savanna to grazing. We focused on the effects of temperature and CO2 level increase in combination with changes in inter- and intra-annual precipitation patterns on the long-term dynamics of three major plant functional types. 3. We found that the capacity of the savanna to sustain livestock grazing was strongly influenced by climate change. Increased mean annual precipitation and changes in intra-annual precipitation pattern have the potential to slightly increase carrying capacities of the system. In contrast, decreased precipitation, higher interannual variation and temperature increase are leading to a severe decline of carrying capacities owing to losses of the perennial grass biomass. 4. Semi-arid rangelands will be at lower risk of shrub encroachment and encroachment will be less intense under future climatic conditions. This finding holds in spite of elevated levels of atmospheric CO2 and irrespective of changes in precipitation pattern, because of the drought sensitivity of germination and establishment of encroaching species. 5. Synthesis and applications. Changes in livestock carrying capacities, both positive and negative, mainly depend on the highly uncertain future rainfall conditions. However, independent of the specific changes, shrub encroachment becomes less likely and in many cases less severe. Thus, managers of semi-arid rangelands should shift their focus from woody vegetation towards perennial grass species as indicators for rangeland degradation. Furthermore, the resulting reduced competition from woody vegetation has the potential to facilitate ecosystem restoration measures such as re-introduction of desirable plant species that are only little promising or infeasible under current climatic conditions. On a global scale, the reductions in standing biomass resulting from altered degradation dynamics of semi-arid rangelands can have negative impacts on carbon sequestration.
Investigating the neuronal network underlying language processing may contribute to a better understanding of how the brain masters this complex cognitive function with surprising ease and how language is acquired at a fast pace in infancy. Modern neuroimaging methods permit to visualize the evolvement and the function of the language network. The present paper focuses on a specific methodology, functional near-infrared spectroscopy (fNIRS), providing an overview over studies on auditory language processing and acquisition. The methodology detects oxygenation changes elicited by functional activation of the cerebral cortex. The main advantages for research on auditory language processing and its development during infancy are an undemanding application, the lack of instrumental noise, and its potential to simultaneously register electrophysiological responses. Also it constitutes an innovative approach for studying developmental issues in infants and children. The review will focus on studies on word and sentence processing including research in infants and adults.
Shape-memory properties of polyetherurethane foams prepared by thermally induced phase separation
(2012)
In this study, we report the preparation of two structurally different shape-memory polymer foams by thermally induced phase separation (TIPS) from amorphous polyetherurethanes. Foams with either a homogeneous, monomodal, or with a hierarchically structured, bimodal, pore size distribution are obtained by adoption of the cooling protocol. The shape-memory properties have been investigated for both foam structures by cyclic, thermomechanical experiments, while the morphological changes on the micro scale (pore level) have been compared to the macro scale by an in situ micro compression device experiment. The results show that the hierarchically structured foam achieves higher shape-recovery rates and a higher total recovery as compared to the homogeneous foam, which is due to an increased energy storage capability by micro scale bending of the hierarchically structured foam compared to pure compression of the homogeneous foam.
Shape-memory properties of magnetically active compositives based on multiphase polymer networks
(2012)
The objective was to investigate the effects of high-velocity strength training on isometric strength of the leg extensors and jump height in female and male adolescents. Twenty-eight students (13 boys, 15 girls) ages 16 to 17 years participated in this study and were assigned to either a strength training group or a control group. Strength training was conducted over 8 weeks (2 times per week). Pre- and post-training tests included the measurements of maximal isometric force and rate of force development of the leg extensors as well as countermovement jump height. Both girls (effect size = 1.37) and boys (effect size = 0.61) showed significant improvements in jump height. However, significant increases in maximal isometric force (effect size = 1.85) and rate of force development (effect size = 2.23) were found only in girls. In female and male adolescents, high-velocity strength training is an effective training regimen that produced improvements in countermovement jump height in both sexes but higher gains in maximal isometric force and rate of force development in girls.
Background: Hypothyroidism in dogs is often difficult to diagnose owing to nonspecific clinical signs and laboratory test results that can be mimicked by nonthyroidal illness (NTI). Thyroxine (T4) circulates in blood mainly bound to T4-binding globulin and, to a lesser degree, transthyretin (TTR) and albumin. The concentration of total T4 depends on the concentrations of these binding proteins.
Objectives: We hypothesized that dogs with NTI and decreased serum total T4 concentrations would have decreased serum TTR concentrations. The objective of the study was to measure and compare serum TTR concentrations in healthy dogs, in dogs with NTI and low serum T4 concentrations, and in dogs with hypothyroidism.
Methods: Assignment of dogs to 3 groups was based on physical examination and serum concentrations of T4 and TSH (mean +/- SD): for healthy dogs (n = 13), T4 was 24.8 +/- 3.6 nmol/L and TSH was 0.15 +/- 0.08 mu g/L; for dogs with NTI and low T4 (n = 20), T4 was 3.2 +/- 3.0 nmol/L and TSH was 0.18 +/- 0.13 mu g/L; and for hypothyroid dogs (n = 19), T4 was 5.3 +/- 4.3 nmol/L and TSH was 2.33 +/- 1.90 mu g/L). TTR concentrations in serum were determined semiquantitatively using western blot analysis.
Results: Serum TTR concentration (mean +/- SD) was decreased in the dogs with NTI (24.8 +/- 7.9 mg/L) compared with that of hypothyroid dogs (41.1 +/- 21.4 mg/L, P = .0035). Differences were not found between TTR concentrations in clinically healthy dogs (33.3 +/- 10.1 mg/L) and hypothyroid dogs or dogs with NTI.
Conclusions: Serum TTR concentrations were significantly decreased in dogs with NTI and low T4 compared with concentrations in hypothyroid dogs. Additional studies should be done to determine if TTR concentrations can discriminate between dogs with NTI and low T4 and dogs with primary hypothyroidism.
The use of CO2 as a massive and polarizable drift gas is shown to greatly improve peak-to-peak resolution (Rp-p), as compared with N2, for the separation of disaccharides in a Synapt G2 traveling wave ion mobility cell. Near or baseline Rp-p was achieved for three pairs of sodiated molecules of disaccharide isomers, that is, cellobiose and sucrose (Rp-p?=?0.76), maltose and sucrose (Rp-p?=?1.04), and maltose and lactose (Rp-p?=?0.74). Ion mobility mass spectrometry using CO2 as the drift gas offers therefore an attractive alternative for fast and efficient separation of isomeric disaccharides.
This study examined the effects of competing speech on auditory semantic comprehension using a dichotic sentence-word priming paradigm. Lexical decision performance for target words presented in spoken sentences was compared in strongly and weakly biasing semantic contexts. Targets were either congruent or incongruent with the sentential bias. Sentences were presented to one auditory channel (right or left), either in isolation or with competing speech produced by a single talker of the same gender presented simultaneously. The competing speech signal was either presented in the same auditory channel as the sentence context, or in a different auditory channel, and was either meaningful (played forward) or unintelligible (time-reversed).
Biasing contexts presented in isolation facilitated responses to congruent targets and inhibited responses to incongruent targets, relative to a neutral baseline. Facilitation priming was reduced or eliminated by competing speech presented in the same auditory channel, supporting previous findings that semantic activation is highly sensitive to the intelligibility of the context signal. Competing speech presented in a different auditory channel affected facilitation priming differentially depending upon ear of presentation, suggesting hemispheric differences in the processing of the attended and competing signals. Results were consistent with previous claims of a right ear advantage for meaningful speech, as well as with visual word recognition findings implicating the left hemisphere in the generation of semantic predictions and the right hemisphere in the integration of newly encountered words into the sentence-level meaning. Unlike facilitation priming, inhibition was relatively robust to the energetic and informational masking effects of competing speech and was not influenced by the strength of the contextual bias or the meaningfulness of the competing signal, supporting a two-process model of sentence priming in which inhibition reflects later-stage, expectancy-driven strategic processes that may benefit from perceptual reanalysis after initial semantic activation.
Based on newly available data of both, the structural setting and thermal properties, we compare 3D thermal models for the area of Brandenburg, located in the Northeast German Basin, to assess the sensitivity of our model results. The structural complexity of the basin fill is given by the configuration of the Zechstein salt with salt diapirs and salt pillows. This special configuration is very relevant for the thermal calculations because salt has a distinctly higher thermal conductivity than other sediments. We calculate the temperature using a FEMethod to solve the steady state heat conduction equation in 3D. Based on this approach, we evaluate the sensitivity of the steady-state conductive thermal field with respect to different lithospheric configurations and to the assigned thermal properties. We compare three different thermal models: (a) a crustal-scale model including a homogeneous crust, (b) a new lithosphere-scale model including a differentiated crust and (c) a crustal-scale model with a stepwise variation of measured thermal properties. The comparison with measured temperatures from different structural locations of the basin shows a good fit to the temperature predictions for the first two models, whereas the third model is distinctly colder. This indicates that effective thermal conductivities may be different from values determined by measurements on rock samples. The results suggest that conduction is the main heat transport mechanism in the Brandenburg area.
Applications based on Forster resonance energy transfer (FRET) play an important role for the determination of concentrations and distances within nanometer-scale systems in vitro and in vivo in many fields of biotechnology. Semiconductor nanocrystals (Quantum dots - QDs) possess ideal properties for their application as FRET acceptors when the donors have long excited state lifetimes and when direct excitation of QDs can be efficiently suppressed. Therefore, luminescent terbium complexes (LTCs) with excited state lifetimes of more than 2 ms are ideal FRET donor candidates for QD-acceptors. This chapter will give a short overview of theoretical and practical background of FRET, QDs and LTCs, and present some recent applications of LTC-QD FRET pairs for multiplexed ultra-sensitive in vitro diagnostics and nanometer-resolution molecular distance measurements.
A discrete analogue of the Witten Laplacian on the n-dimensional integer lattice is considered. After rescaling of the operator and the lattice size we analyze the tunnel effect between different wells, providing sharp asymptotics of the low-lying spectrum. Our proof, inspired by work of B. Helffer, M. Klein and F. Nier in continuous setting, is based on the construction of a discrete Witten complex and a semiclassical analysis of the corresponding discrete Witten Laplacian on 1-forms. The result can be reformulated in terms of metastable Markov processes on the lattice.
It is well known that the spacetime diagrams of some cellular automata have a self-similar fractal structure: for instance Wolfram's rule 90 generates a Sierpinski triangle. Explaining the self-similarity of the spacetime diagrams of cellular automata is a well-explored topic, but virtually all of the results revolve around a special class of automata, whose typical features include irreversibility, an alphabet with a ring structure, a global evolution that is a ring homomorphism, and a property known as (weakly) p-Fermat. The class of automata that we study in this article has none of these properties. Their cell structure is weaker, as it does not come with a multiplication, and they are far from being p-Fermat, even weakly. However, they do produce self-similar spacetime diagrams, and we explain why and how.