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Die hohe Energieaufnahme durch Fette ist ein Hauptfaktor für die Entstehung von Adipositas, was zu weltweiten Bestrebungen führte, die Fettaufnahme zu verringern. Fettreduzierte Lebensmittel erreichen jedoch, trotz ihrer Weiterentwicklung, nicht die Schmackhaftigkeit ihrer Originale. Die traditionelle Sichtweise, dass die Attraktivität von Fetten allein durch Textur, Geruch, Aussehen und postingestive Effekte bestimmt wird, wird nun durch das Konzept einer gustatorischen Wahrnehmung ergänzt. Bei Nagetieren zeigte sich, dass Lipide unabhängig von den vorgenannten Eigenschaften erkannt werden, sowie, dass Fettsäuren, freigesetzt durch linguale Lipasen, als gustatorische Stimuli fungieren und Fettsäuresensoren in Geschmackszellen exprimiert sind. Die Datenlage für den Menschen erwies sich jedoch als sehr begrenzt, daher war es Ziel der vorliegenden Arbeit molekulare und histologische Voraussetzungen für eine gustatorische Fettwahrnehmung beim Menschen zu untersuchen.
Zunächst wurde humanes Geschmacksgewebe mittels RT-PCR und immunhistochemischen Methoden auf die Expression von Fettsäuresensoren untersucht, sowie exprimierende Zellen in Kofärbeexperimenten charakterisiert und quantifiziert. Es wurde die Expression fettsäuresensitiver Rezeptoren nachgewiesen, deren Agonisten das gesamte Spektrum an kurz- bis langkettigen Fettsäuren abdecken (GPR43, GPR84, GPR120, CD36, KCNA5). Ein zweifelsfreier Nachweis des Proteins konnte für den auf langkettige Fettsäuren spezialisierten Rezeptor GPR120 in Typ-I- und Typ-III-Geschmackszellen der Wallpapillen erbracht werden. Etwa 85 % dieser GPR120-exprimierenden Zellen enthielten keine der ausgewählten Rezeptoren der Geschmacksqualitäten süß (TAS1R2/3), umami (TAS1R1/3) oder bitter (TAS2R38). Somit findet sich in humanen Geschmackspapillen nicht nur mindestens ein Sensor, sondern möglicherweise auch eine spezifische, fettsäuresensitive Zellpopulation. Weitere RT-PCR-Experimente und Untersuchungen mittels In-situ-Hybridisierung wurden zur Klärung der Frage durchgeführt, ob Lipasen in den Von-Ebner-Speicheldrüsen (VED) existieren, die freie Fettsäuren aus Triglyceriden als gustatorischen Stimulus freisetzen können. Es zeigte sich zwar keine Expression der bei Nagetieren gefundenen Lipase F (LIPF), jedoch der eng verwandten Lipasen K, M und N in den serösen Zellen der VED. In-silico-Untersuchungen der Sekundär- und Tertiärstrukturen zeigten die hohe Ähnlichkeit zu LIPF, erwiesen aber auch Unterschiede in den Bindungstaschen der Enzyme, welche auf ein differenziertes Substratspektrum hinweisen. Die Anwesenheit eines spezifischen Signalpeptids macht eine Sekretion der Lipasen in den die Geschmacksporen umspülenden Speichel wahrscheinlich und damit auch eine Bereitstellung von Fettsäuren als Stimuli für Fettsäuresensoren. Die Übertragung des durch diese Stimuli hervorgerufenen Signals von Geschmackszellen auf gustatorische Nervenfasern über P2X-Rezeptormultimere wurde mit Hilfe einer vorherigen Intervention mit einem P2X3 /P2X2/3-spezifischen Antagonisten an der Maus als Modellorganismus im Kurzzeit-Präferenztest untersucht. Es zeigte sich weder eine Beeinträchtigung der Wahrnehmung einer Fettsäurelösung, noch einer zuckerhaltigen Kontrolllösung, wohingegen die Wahrnehmung einer Bitterstofflösung reduziert wurde. Somit ist anhand der Ergebnisse dieser Arbeit eine Beteiligung des P2X3-Homomers bzw. des P2X2/3-Heteromers unwahrscheinlich, jedoch die des P2X2-Homomers und damit der gustatorischen Nervenfasern nicht ausgeschlossen.
Die Ergebnisse dieser Arbeit weisen auf die Erfüllung grundlegender Voraussetzungen für die gustatorische Fett(säure)wahrnehmung hin und tragen zum Verständnis der sensorischen Fettwahrnehmung und der Regulation der Fettaufnahme bei. Das Wissen um die Regulation dieser Mechanismen stellt eine Grundlage zur Aufklärung der Ursachen und damit der Bekämpfung von Adipositas und assoziierten Krankheiten dar.
Molekulare Charakterisierung von CP75, einem neuen centrosomalen Protein in Dictyostelium discoideum
(2016)
Das Centrosom ist ein Zellkern-assoziiertes Organell, das nicht von einer Membran umschlossen ist. Es spielt eine wichtige Rolle in vielen Mikrotubuli- abhängigen Prozessen wie Organellenpositionierung, Zellpolarität oder die Organisation der mitotischen Spindel. Das Centrosom von Dictyostelium besteht aus einer dreischichtigen Core-Struktur umgeben von einer Corona, die Mikrotubuli-nukleierende Komplexe enthält. Die Verdoppelung des Centrosoms in Dictyostelium findet zu Beginn der Mitose statt. In der Prophase vergrößert sich die geschichtete Core-Struktur und die Corona löst sich auf. Anschließend trennen sich die beiden äußeren Lagen der Core-Struktur und bilden in der Metaphase die beiden Spindelpole, die in der Telophase zu zwei vollständigen Centrosomen heranreifen. Das durch eine Proteom-Analyse identifizierte Protein CP75 lokalisiert am Centrosom abhängig von den Mitosephasen. Es dissoziiert von der Core-Struktur in der Prometaphase und erscheint an den Spindelpolen in der Telophase wieder. Dieses Verhalten korreliert mit dem Verhalten der mittleren Lage der Core-Struktur in der Mitose, was darauf hinweist, dass CP75 eine Komponente dieser Schicht sein könnte. Die FRAP-Experimente am Interphase- Centrosom zeigen, dass GFP-CP75 dort nicht mobil ist. Das deutet darauf hin, dass das Protein wichtige Funktionen im Strukturerhalt der centrosomalen Core- Struktur übernehmen könnte. Sowohl die C- als auch die N-terminale Domäne von CP75 enthalten centrosomale Targeting-Domäne. Als GFP-Fusionsproteine (GFP-CP75-N und -C) lokalisieren die beiden Fragmente am Centrosom in der Interphase. Während GFP-CP75-C in der Mitose am Centrosom verbleibt, verschwindet GFP-CP75-N in der Metaphase und kehrt erst in der späten Telophase zurück. GFP-CP75-C und GFP-CP75O/E kolokalisieren mit F-Aktin am Zellcortex, zeigen aber keine Interaktion mit Aktin mit der BioID-Methode. Die N-terminale Domäne von CP75 enthält eine potentielle Plk1- Phosphorylierungssequenz. Die Überexpression der nichtphosphorylierbaren Punktmutante (GFP-CP75-Plk-S143A) ruft verschiedene Phänotypen wie verlängerte oder überzählige Centrosomen, vergrößerte Zellkerne und Anreicherung von detyrosinierten Mikrotubuli hervor. Die ähnlichen Phänotypen konnten auch bei GFP-CP75-N und CP75-RNAi beobachtet werden. Der
Phänotyp der detyrosinierten Mikrotubuli bringt erstmals den Beweis dafür, dass I
in Dictyostelium posttranslationale Modifikation an Tubulinen stattfindet. Außerdem zeigten CP75-RNAi-Zellen Defekte in der Organisation der mitotischen Spindel. Mittels BioID-Methode konnten drei potentielle Interaktionspartner von CP75 identifiziert werden. Diese drei Proteine CP39, CP91 und Cep192 sind ebenfalls Bestandteile des Centrosoms.
Molekulare Charakterisierung des Centrosom-assoziierten Proteins CP91 in Dictyostelium discoideum
(2016)
Das Dictyostelium-Centrosom ist ein Modell für acentrioläre Centrosomen. Es besteht aus einer dreischichtigen Kernstruktur und ist von einer Corona umgeben, welche Nukleationskomplexe für Mikrotubuli beinhaltet. Die Verdoppelung der Kernstruktur wird einmal pro Zellzyklus am Übergang der G2 zur M-Phase gestartet. Durch eine Proteomanalyse isolierter Centrosomen konnte CP91 identifiziert werden, ein 91 kDa großes Coiled-Coil Protein, das in der centrosomalen Kernstruktur lokalisiert. GFP-CP91 zeigte fast keine Mobilität in FRAP-Experimenten während der Interphase, was darauf hindeutet, dass es sich bei CP91 um eine Strukturkomponente des Centrosoms handelt. In der Mitose hingegen dissoziieren das GFP-CP91 als auch das endogene CP91 ab und fehlen an den Spindelpolen von der späten Prophase bis zur Anaphase. Dieses Verhalten korreliert mit dem Verschwinden der zentralen Schicht der Kernstruktur zu Beginn der Centrosomenverdopplung. Somit ist CP91 mit großer Wahrscheinlichkeit ein Bestandteil dieser Schicht. CP91-Fragmente der N-terminalen bzw. C-terminalen Domäne (GFP-CP91 N-Terminus, GFP-CP91 C-Terminus) lokalisieren als GFP-Fusionsproteine exprimiert auch am Centrosom, zeigen aber nicht die gleiche mitotische Verteilung des Volllängenproteins. Das CP91-Fragment der zentralen Coiled-Coil Domäne (GFP-CP91cc) lokalisiert als GFP-Fusionsprotein exprimiert, als ein diffuser cytosolische Cluster, in der Nähe des Centrosoms. Es zeigt eine partiell ähnliche mitotische Verteilung wie das Volllängenprotein. Dies lässt eine regulatorische Domäne innerhalb der Coiled-Coil Domäne vermuten. Die Expression der GFP-Fusionsproteine unterdrückt die Expression des endogenen CP91 und bringt überzählige Centrosomen hervor. Dies war auch eine markante Eigenschaft nach der Unterexpression von CP91 durch RNAi. Zusätzlich zeigte sich in CP91-RNAi Zellen eine stark erhöhte Ploidie verursacht durch schwere Defekte in der Chromosomensegregation verbunden mit einer erhöhten Zellgröße und Defekten im Abschnürungsprozess während der Cytokinese. Die Unterexpression von CP91 durch RNAi hatte auch einen direkten Einfluss auf die Menge an den centrosomalen Proteinen CP39, CP55 und CEP192 und dem Centromerprotein Cenp68 in der Interphase. Die Ergebnisse deuten darauf hin, dass CP91 eine zentrale centrosomale Kernkomponente ist und für den Zusammenhalt der beiden äußeren Schichten der Kernstruktur benötigt wird. Zudem spielt CP91 eine wichtige Rolle für eine ordnungsgemäße Centrosomenbiogenese und, unabhängig davon, bei dem Abschnürungsprozess der Tochterzellen während der Cytokinese.
For the first time a molecularly imprinted polymer (MIP) with direct electron transfer (DET) and bioelectrocatalytic activity of the target protein is presented. Thin films of MIPs for the recognition of a hexameric tyrosine-coordinated heme protein (HTHP) have been prepared by electropolymerization of scopoletin after oriented assembly of HTHP on a self-assembled monolayer (SAM) of mercaptoundecanoic acid (MUA) on gold electrodes. Cavities which should resemble the shape and size of HTHP were formed by template removal. Rebinding of the target protein sums up the recognition by non-covalent interactions between the protein and the MIP with the electrostatic attraction of the protein by the SAM. HTHP bound to the MIP exhibits quasi-reversible DET which is reflected by a pair of well pronounced redox peaks in the cyclic voltammograms (CVs) with a formal potential of -184.4 +/- 13.7 mV vs. Ag/AgCl (1 M KCl) at pH 8.0 and it was able to catalyze the cathodic reduction of peroxide. At saturation the MIP films show a 12-fold higher electroactive surface concentration of HTHP than the non-imprinted polymer (NIP).
The speciation of 2-Mercaptopyridine in aqueous solution has been investigated with nitrogen 1s Near Edge X-ray Absorption Fine Structure spectroscopy and time dependent Density Functional Theory. The prevalence of distinct species as a function of the solvent basicity is established. No indications of dimerization towards high concentrations are found. The determination of different molecular structures of 2-Mercaptopyridine in aqueous solution is put into the context of proton-transfer in keto-enol and thione-thiol tautomerisms. (C) 2016 The Authors. Published by Elsevier B.V.
The speciation of 2-Mercaptopyridine in aqueous solution has been investigated with nitrogen 1s Near Edge X-ray Absorption Fine Structure spectroscopy and time dependent Density Functional Theory. The prevalence of distinct species as a function of the solvent basicity is established. No indications of dimerization towards high concentrations are found. The determination of different molecular structures of 2-Mercaptopyridine in aqueous solution is put into the context of proton-transfer in keto-enol and thione-thiol tautomerisms. (C) 2016 The Authors. Published by Elsevier B.V.
We report on an extension of the previously established concept of oligospiroketal (OSK) rods by replacing a part or all ketal moieties by thioketals leading to oligospirothioketal (OSTK) rods. In this way, some crucial problems arising from the reversible formation of ketals are circumvented. Furthermore, the stability of the rods toward hydrolysis is considerably improved. To successfully implement this concept, we first developed a number of new oligothiol building blocks and improved the synthetic accessibility of known oligothiols, respectively. Another advantage of thioacetals is that terephthalaldehyde (TAA) sleeves, which are too flexible in the case of acetals can be used in OSTK rods. The viability of the OSTK approach was demonstrated by the successful preparation of some OSTK rods with a length of some nanometers.
Molecular paleoclimate reconstructions over the last 9 ka from a peat sequence in South China
(2016)
To achieve a better understanding of Holocene climate change in the monsoon regions of China, we investigated the molecular distributions and carbon and hydrogen isotope compositions delta C-13 and delta D values) of long-chain n-alkanes in a peat core from the Shiwangutian SWGT) peatland, south China over the last 9 ka. By comparisons with other climate records, we found that the delta C-13 values of the long-chain n-alkanes can be a proxy for humidity, while the dD values of the long-chain n-alkanes primarily recorded the moisture source dD signal during 9-1.8 ka BP and responded to the dry climate during 1.8-0.3 ka BP. Together with the average chain length ACL) and the carbon preference index CPI) data, the climate evolution over last 9 ka in the SWGT peatland can be divided into three stages. During the first stage 9-5 ka BP), the delta C-13 values were depleted and CPI and Paq values were low, while ACL values were high. They reveal a period of warm and wet climate, which is regarded as the Holocene optimum. The second stage 5-1.8 ka BP) witnessed a shift to relatively cool and dry climate, as indicated by the more positive delta C-13 values and lower ACL values. During the third stage 1.8-0.3 ka BP), the delta C-13, delta D, CPI and Paq values showed marked increase and ACL values varied greatly, implying an abrupt change to cold and dry conditions. This climate pattern corresponds to the broad decline in Asian monsoon intensity through the latter part of the Holocene. Our results do not support a later Holocene optimum in south China as suggested by previous studies.
Molecular Paleoclimate Reconstructions over the Last 9 ka from a Peat Sequence in South China
(2016)
To achieve a better understanding of Holocene climate change in the monsoon regions of China, we investigated the molecular distributions and carbon and hydrogen isotope compositions delta C-13 and delta D values) of long-chain n-alkanes in a peat core from the Shiwangutian SWGT) peatland, south China over the last 9 ka. By comparisons with other climate records, we found that the delta C-13 values of the long-chain n-alkanes can be a proxy for humidity, while the dD values of the long-chain n-alkanes primarily recorded the moisture source dD signal during 9-1.8 ka BP and responded to the dry climate during 1.8-0.3 ka BP. Together with the average chain length ACL) and the carbon preference index CPI) data, the climate evolution over last 9 ka in the SWGT peatland can be divided into three stages. During the first stage 9-5 ka BP), the delta C-13 values were depleted and CPI and Paq values were low, while ACL values were high. They reveal a period of warm and wet climate, which is regarded as the Holocene optimum. The second stage 5-1.8 ka BP) witnessed a shift to relatively cool and dry climate, as indicated by the more positive delta C-13 values and lower ACL values. During the third stage 1.8-0.3 ka BP), the delta C-13, delta D, CPI and Paq values showed marked increase and ACL values varied greatly, implying an abrupt change to cold and dry conditions. This climate pattern corresponds to the broad decline in Asian monsoon intensity through the latter part of the Holocene. Our results do not support a later Holocene optimum in south China as suggested by previous studies.
Flower development is a model system to understand organ specification in plants. The identities of different types of floral organs are specified by homeotic MADS transcription factors that interact in a combinatorial fashion. Systematic identification of DNA-binding sites and target genes of these key regulators show that they have shared and unique sets of target genes. DNA binding by MADS proteins is not based on ‘simple’ recognition of a specific DNA sequence, but depends on DNA structure and combinatorial interactions. Homeotic MADS proteins regulate gene expression via alternative mechanisms, one of which may be to modulate chromatin structure and accessibility in their target gene promoters.
The main physical features and operating principles of isothermal nanomachines in the microworld, common to both classical and quantum machines, are reviewed. Special attention is paid to the dual, constructive role of dissipation and thermal fluctuations, the fluctuation-dissipation theorem, heat losses and free energy transduction, thermodynamic efficiency, and thermodynamic efficiency at maximum power. Several basic models are considered and discussed to highlight generic physical features. This work examines some common fallacies that continue to plague the literature. In particular, the erroneous beliefs that one should minimize friction and lower the temperature for high performance of Brownian machines, and that the thermodynamic efficiency at maximum power cannot exceed one-half are discussed. The emerging topic of anomalous molecular motors operating subdiffusively but very efficiently in the viscoelastic environment of living cells is also discussed.
Foam fractionation of surfactant and protein solutions is a process dedicated to separate surface active molecules from each other due to their differences in surface activities. The process is based on forming bubbles in a certain mixed solution followed by detachment and rising of bubbles through a certain volume of this solution, and consequently on the formation of a foam layer on top of the solution column. Therefore, systematic analysis of this whole process comprises of at first investigations dedicated to the formation and growth of single bubbles in solutions, which is equivalent to the main principles of the well-known bubble pressure tensiometry. The second stage of the fractionation process includes the detachment of a single bubble from a pore or capillary tip and its rising in a respective aqueous solution. The third and final stage of the process is the formation and stabilization of the foam created by these bubbles, which contains the adsorption layers formed at the growing bubble surface, carried up and gets modified during the bubble rising and finally ends up as part of the foam layer.
Bubble pressure tensiometry and bubble profile analysis tensiometry experiments were performed with protein solutions at different bulk concentrations, solution pH and ionic strength in order to describe the process of accumulation of protein and surfactant molecules at the bubble surface. The results obtained from the two complementary methods allow understanding the mechanism of adsorption, which is mainly governed by the diffusional transport of the adsorbing protein molecules to the bubble surface. This mechanism is the same as generally discussed for surfactant molecules. However, interesting peculiarities have been observed for protein adsorption kinetics at sufficiently short adsorption times. First of all, at short adsorption times the surface tension remains constant for a while before it decreases as expected due to the adsorption of proteins at the surface. This time interval is called induction time and it becomes shorter with increasing protein bulk concentration. Moreover, under special conditions, the surface tension does not stay constant but even increases over a certain period of time. This so-called negative surface pressure was observed for BCS and BLG and discussed for the first time in terms of changes in the surface conformation of the adsorbing protein molecules. Usually, a negative surface pressure would correspond to a negative adsorption, which is of course impossible for the studied protein solutions. The phenomenon, which amounts to some mN/m, was rather explained by simultaneous changes in the molar area required by the adsorbed proteins and the non-ideality of entropy of the interfacial layer. It is a transient phenomenon and exists only under dynamic conditions.
The experiments dedicated to the local velocity of rising air bubbles in solutions were performed in a broad range of BLG concentration, pH and ionic strength. Additionally, rising bubble experiments were done for surfactant solutions in order to validate the functionality of the instrument. It turns out that the velocity of a rising bubble is much more sensitive to adsorbing molecules than classical dynamic surface tension measurements. At very low BLG or surfactant concentrations, for example, the measured local velocity profile of an air bubble is changing dramatically in time scales of seconds while dynamic surface tensions still do not show any measurable changes at this time scale. The solution’s pH and ionic strength are important parameters that govern the measured rising velocity for protein solutions. A general theoretical description of rising bubbles in surfactant and protein solutions is not available at present due to the complex situation of the adsorption process at a bubble surface in a liquid flow field with simultaneous Marangoni effects. However, instead of modelling the complete velocity profile, new theoretical work has been started to evaluate the maximum values in the profile as characteristic parameter for dynamic adsorption layers at the bubble surface more quantitatively.
The studies with protein-surfactant mixtures demonstrate in an impressive way that the complexes formed by the two compounds change the surface activity as compared to the original native protein molecules and therefore lead to a completely different retardation behavior of rising bubbles. Changes in the velocity profile can be interpreted qualitatively in terms of increased or decreased surface activity of the formed protein-surfactant complexes. It was also observed that the pH and ionic strength of a protein solution have strong effects on the surface activity of the protein molecules, which however, could be different on the rising bubble velocity and the equilibrium adsorption isotherms. These differences are not fully understood yet but give rise to discussions about the structure of protein adsorption layer under dynamic conditions or in the equilibrium state.
The third main stage of the discussed process of fractionation is the formation and characterization of protein foams from BLG solutions at different pH and ionic strength. Of course a minimum BLG concentration is required to form foams. This minimum protein concentration is a function again of solution pH and ionic strength, i.e. of the surface activity of the protein molecules. Although at the isoelectric point, at about pH 5 for BLG, the hydrophobicity and hence the surface activity should be the highest, the concentration and ionic strength effects on the rising velocity profile as well as on the foamability and foam stability do not show a maximum. This is another remarkable argument for the fact that the interfacial structure and behavior of BLG layers under dynamic conditions and at equilibrium are rather different. These differences are probably caused by the time required for BLG molecules to adapt respective conformations once they are adsorbed at the surface.
All bubble studies described in this work refer to stages of the foam fractionation process. Experiments with different systems, mainly surfactant and protein solutions, were performed in order to form foams and finally recover a solution representing the foamed material. As foam consists to a large extent of foam lamella – two adsorption layers with a liquid core – the concentration in a foamate taken from foaming experiments should be enriched in the stabilizing molecules. For determining the concentration of the foamate, again the very sensitive bubble rising velocity profile method was applied, which works for any type of surface active materials. This also includes technical surfactants or protein isolates for which an accurate composition is unknown.
The LEA (late embryogenesis abundant) proteins COR15A and COR15B from Arabidopsis thaliana are intrinsically disordered under fully hydrated conditions, but obtain alpha-helical structure during dehydration, which is reversible upon rehydration. To understand this unusual structural transition, both proteins were investigated by circular dichroism (CD) and molecular dynamics (MD) approaches. MD simulations showed unfolding of the proteins in water, in agreement with CD data obtained with both HIS-tagged and untagged recombinant proteins. Mainly intramolecular hydrogen bonds (H-bonds) formed by the protein backbone were replaced by H-bonds with water molecules. As COR15 proteins function in vivo as protectants in leaves partially dehydrated by freezing, unfolding was further assessed under crowded conditions. Glycerol reduced (40%) or prevented (100%) unfolding during MD simulations, in agreement with CD spectroscopy results. H-bonding analysis indicated that preferential exclusion of glycerol from the protein backbone increased stability of the folded state.
The LEA (late embryogenesis abundant) proteins COR15A and COR15B from Arabidopsis thaliana are intrinsically disordered under fully hydrated conditions, but obtain α-helical structure during dehydration, which is reversible upon rehydration. To understand this unusual structural transition, both proteins were investigated by circular dichroism (CD) and molecular dynamics (MD) approaches. MD simulations showed unfolding of the proteins in water, in agreement with CD data obtained with both HIS-tagged and untagged recombinant proteins. Mainly intramolecular hydrogen bonds (H-bonds) formed by the protein backbone were replaced by H-bonds with water molecules. As COR15 proteins function in vivo as protectants in leaves partially dehydrated by freezing, unfolding was further assessed under crowded conditions. Glycerol reduced (40%) or prevented (100%) unfolding during MD simulations, in agreement with CD spectroscopy results. H-bonding analysis indicated that preferential exclusion of glycerol from the protein backbone increased stability of the folded state.
Complementary to the well-established zwitterionic monomer 3-((3-methacrylamidopropyl) dimethylammonio) propane-1-sulfonate (SPP), the closely related monomers 2-hydroxy-3-((3-methacrylamidopropyl) dimethylammonio) propane-1-sulfonate (SHPP) and 4-((3-methacrylamidopropyl) dimethylammonio)butane- 1-sulfonate (SBP) were synthesised and polymerised by reversible addition-fragmentation chain transfer (RAFT) polymerisation, using a fluorophore labeled RAFT agent. The polyzwitterions of systematically varied molar masses were characterised with respect to their solubility in water and aqueous salt solutions. Both poly(sulfobetaine)s show thermoresponsive behaviour in water, exhibiting phase separation at low temperatures and upper critical solution temperatures (UCST). For both polySHPP and polySBP, cloud points depend notably on the molar mass, and are much higher in D2O than in H2O. Also, the cloud points are effectively modulated by the addition of salts. The individual effects can be in parts correlated to the Hofmeister series for the anions studied. Still, they depend in a complex way on the concentration and the nature of the added electrolytes, on the one hand, and on the detailed nature of the spacer group separating the anionic and the cationic charges of the betaine moiety, on the other hand. As anticipated, the cloud points of polySBP are much higher than the ones of the analogous polySPP of identical molar mass. Surprisingly, the cloud points of polySHPP are also somewhat higher than the ones of their polySPP analogues, despite the additional hydrophilic hydroxyl group present in the spacer separating the ammonium and the sulfonate moieties. These findings point to a complicated interplay of the various hydrophilic components in polyzwitterions with respect to their overall hydrophilicity. Thus, the spacer group in the betaine moiety proves to be an effective additional molecular design parameter, apparently small variations of which strongly influence the phase behaviour of the polyzwitterions in specific aqueous environments.
This work is devoted to the convergence analysis of a modified Runge-Kutta-type iterative regularization method for solving nonlinear ill-posed problems under a priori and a posteriori stopping rules. The convergence rate results of the proposed method can be obtained under a Holder-type sourcewise condition if the Frechet derivative is properly scaled and locally Lipschitz continuous. Numerical results are achieved by using the Levenberg-Marquardt, Lobatto, and Radau methods.
In many statistical applications, the aim is to model the relationship between covariates and some outcomes. A choice of the appropriate model depends on the outcome and the research objectives, such as linear models for continuous outcomes, logistic models for binary outcomes and the Cox model for time-to-event data. In epidemiological, medical, biological, societal and economic studies, the logistic regression is widely used to describe the relationship between a response variable as binary outcome and explanatory variables as a set of covariates. However, epidemiologic cohort studies are quite expensive regarding data management since following up a large number of individuals takes long time. Therefore, the case-cohort design is applied to reduce cost and time for data collection. The case-cohort sampling collects a small random sample from the entire cohort, which is called subcohort. The advantage of this design is that the covariate and follow-up data are recorded only on the subcohort and all cases (all members of the cohort who develop the event of interest during the follow-up process).
In this thesis, we investigate the estimation in the logistic model for case-cohort design. First, a model with a binary response and a binary covariate is considered. The maximum likelihood estimator (MLE) is described and its asymptotic properties are established. An estimator for the asymptotic variance of the estimator based on the maximum likelihood approach is proposed; this estimator differs slightly from the estimator introduced by Prentice (1986). Simulation results for several proportions of the subcohort show that the proposed estimator gives lower empirical bias and empirical variance than Prentice's estimator.
Then the MLE in the logistic regression with discrete covariate under case-cohort design is studied. Here the approach of the binary covariate model is extended. Proving asymptotic normality of estimators, standard errors for the estimators can be derived. The simulation study demonstrates the estimation procedure of the logistic regression model with a one-dimensional discrete covariate. Simulation results for several proportions of the subcohort and different choices of the underlying parameters indicate that the estimator developed here performs reasonably well. Moreover, the comparison between theoretical values and simulation results of the asymptotic variance of estimator is presented.
Clearly, the logistic regression is sufficient for the binary outcome refers to be available for all subjects and for a fixed time interval. Nevertheless, in practice, the observations in clinical trials are frequently collected for different time periods and subjects may drop out or relapse from other causes during follow-up. Hence, the logistic regression is not appropriate for incomplete follow-up data; for example, an individual drops out of the study before the end of data collection or an individual has not occurred the event of interest for the duration of the study. These observations are called censored observations. The survival analysis is necessary to solve these problems. Moreover, the time to the occurence of the event of interest is taken into account. The Cox model has been widely used in survival analysis, which can effectively handle the censored data. Cox (1972) proposed the model which is focused on the hazard function. The Cox model is assumed to be
λ(t|x) = λ0(t) exp(β^Tx)
where λ0(t) is an unspecified baseline hazard at time t and X is the vector of covariates, β is a p-dimensional vector of coefficient.
In this thesis, the Cox model is considered under the view point of experimental design. The estimability of the parameter β0 in the Cox model, where β0 denotes the true value of β, and the choice of optimal covariates are investigated. We give new representations of the observed information matrix In(β) and extend results for the Cox model of Andersen and Gill (1982). In this way conditions for the estimability of β0 are formulated. Under some regularity conditions, ∑ is the inverse of the asymptotic variance matrix of the MPLE of β0 in the Cox model and then some properties of the asymptotic variance matrix of the MPLE are highlighted. Based on the results of asymptotic estimability, the calculation of local optimal covariates is considered and shown in examples. In a sensitivity analysis, the efficiency of given covariates is calculated. For neighborhoods of the exponential models, the efficiencies have then been found. It is appeared that for fixed parameters β0, the efficiencies do not change very much for different baseline hazard functions. Some proposals for applicable optimal covariates and a calculation procedure for finding optimal covariates are discussed.
Furthermore, the extension of the Cox model where time-dependent coefficient are allowed, is investigated. In this situation, the maximum local partial likelihood estimator for estimating the coefficient function β(·) is described. Based on this estimator, we formulate a new test procedure for testing, whether a one-dimensional coefficient function β(·) has a prespecified parametric form, say β(·; ϑ). The score function derived from the local constant partial likelihood function at d distinct grid points is considered. It is shown that the distribution of the properly standardized quadratic form of this d-dimensional vector under the null hypothesis tends to a Chi-squared distribution. Moreover, the limit statement remains true when replacing the unknown ϑ0 by the MPLE in the hypothetical model and an asymptotic α-test is given by the quantiles or p-values of the limiting Chi-squared distribution. Finally, we propose a bootstrap version of this test. The bootstrap test is only defined for the special case of testing whether the coefficient function is constant. A simulation study illustrates the behavior of the bootstrap test under the null hypothesis and a special alternative. It gives quite good results for the chosen underlying model.
References
P. K. Andersen and R. D. Gill. Cox's regression model for counting processes: a large samplestudy. Ann. Statist., 10(4):1100{1120, 1982.
D. R. Cox. Regression models and life-tables. J. Roy. Statist. Soc. Ser. B, 34:187{220, 1972.
R. L. Prentice. A case-cohort design for epidemiologic cohort studies and disease prevention trials. Biometrika, 73(1):1{11, 1986.
NO donors and Arg remove dormancy of apple embryos and stimulate germination. Compounds lowering NO level (cPTIO, L -NAME, CAN) strengthen dormancy. Embryo transition from dormancy state to germination is linked to increased nitric oxide synthase (NOS)-like activity. Germination of embryos is associated with declined level of biotin containing proteins and nitrated proteins in soluble protein fraction of root axis. Pattern of nitrated proteins suggest that storage proteins are putative targets of nitration. Nitric oxide (NO) acts as a key regulatory factor in removal of seed dormancy and is a signal necessary for seed transition from dormant state into germination. Modulation of NO concentration in apple (Malus domestica Borkh.) embryos by NO fumigation, treatment with NO donor (S-nitroso-N-acetyl-d,l-penicillamine, SNAP), application of 2-(4-carboxyphenyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide (cPTIO), N (omega)-nitro-l-arginine methyl ester (l-NAME), canavanine (CAN) or arginine (Arg) allowed us to investigate the NO impact on seed dormancy status. Arg analogs and NO scavenger strengthened embryo dormancy by lowering reactive nitrogen species level in embryonic axes. This effect was accompanied by strong inhibition of NOS-like activity, without significant influence on tissue NO2 (-) concentration. Germination sensu stricto of apple embryos initiated by dormancy breakage via short term NO treatment or Arg supplementation were linked to a reduced level of biotinylated proteins in root axis. Decrease of total soluble nitrated proteins was observed at the termination of germination sensu stricto. Also modulation of NO tissue status leads to modification in nitrated protein pattern. Among protein bands that correspond to molecular mass of approximately 95 kDa, storage proteins (legumin A-like and seed biotin-containing protein) were identified, and can be considered as good markers for seed dormancy status. Moreover, pattern of nitrated proteins suggest that biotin containing proteins are also targets of nitration.
During expedition 202 aboard the RV Sonne in 2009, 39 seafloor surface sediment sites were sampled over a wide sector of the North Pacific and adjoining Bering Sea. The data served to infer land-ocean linkages of terrigenous sediment supply in terms of major sources and modes of sediment transport within an over-regional context. This is based on an integrated approach dealing with grain-size analysis, bulk mineralogy and clay mineralogy in combination with statistical data evaluation (end-member modelling of grain-size data, fuzzy cluster analysis of mineralogical data). The findings on clay mineralogy served to update those of earlier work extracted from the literature. Today, two processes of terrigenous sediment supply prevail in the study area: far-distance aeolian sediment supply to the pelagic North Pacific, and hemipelagic sediment dispersal from nearby land sources via ocean currents along the continental margins and island arcs. Aeolian particles show the finest grain sizes (clay and fine silt), whereas hemipelagic sediments have high abundances of coarse silt. Exposed sites on seamounts and the continental slope are partly swept by strong currents, leading to residual enrichment of fine sand. Four sediment sources can be distinguished on the basis of distinct index minerals revealed by statistical data analysis: dust plumes from central Asia (quartz, illite), altered materials from the volcanic regions of Kamchatka and the Aleutian Arc (smectite), detritus from the Alaskan Cordillera (chlorite, hornblende), and fluvial detritus from far-eastern Siberia and the Alaska mainland (quartz, feldspar, illite). These findings confirm those of former studies but considerably expand the geographic range of this suite of proxies as far south as 39A degrees N in the open North Pacific. The present integrated methodological approach proved useful in identifying the major modern processes of terrigenous sediment supply to the study region. This aspect deserves attention in the selection of sediment core sites for future palaeoenvironmental reconstructions related to aeolian and glacial dynamics, as well as the recognition of palaeo-ocean circulation patterns in general.
Die Projektierung und Abwicklung sowie die statische und dynamische Analyse von Geschäftsprozessen im Bereich des Verwaltens und Regierens auf kommunaler, Länder- wie auch Bundesebene mit Hilfe von Informations- und Kommunikationstechniken beschäftigen Politiker und Strategen für Informationstechnologie ebenso wie die Öffentlichkeit seit Langem.
Der hieraus entstandene Begriff E-Government wurde in der Folge aus den unterschiedlichsten technischen, politischen und semantischen Blickrichtungen beleuchtet.
Die vorliegende Arbeit konzentriert sich dabei auf zwei Schwerpunktthemen:
• Das erste Schwerpunktthema behandelt den Entwurf eines hierarchischen Architekturmodells, für welches sieben hierarchische Schichten identifiziert werden können. Diese erscheinen notwendig, aber auch hinreichend, um den allgemeinen Fall zu beschreiben.
Den Hintergrund hierfür liefert die langjährige Prozess- und Verwaltungserfahrung als Leiter der EDV-Abteilung der Stadtverwaltung Landshut, eine kreisfreie Stadt mit rund 69.000 Einwohnern im Nordosten von München. Sie steht als Repräsentant für viele Verwaltungsvorgänge in der Bundesrepublik Deutschland und ist dennoch als Analyseobjekt in der Gesamtkomplexität und Prozessquantität überschaubar.
Somit können aus der Analyse sämtlicher Kernabläufe statische und dynamische Strukturen extrahiert und abstrakt modelliert werden.
Die Schwerpunkte liegen in der Darstellung der vorhandenen Bedienabläufe in einer Kommune. Die Transformation der Bedienanforderung in einem hierarchischen System, die Darstellung der Kontroll- und der Operationszustände in allen Schichten wie auch die Strategie der Fehlererkennung und Fehlerbehebung schaffen eine transparente Basis für umfassende Restrukturierungen und Optimierungen.
Für die Modellierung wurde FMC-eCS eingesetzt, eine am Hasso-Plattner-Institut für Softwaresystemtechnik GmbH (HPI) im Fachgebiet Kommunikationssysteme entwickelte Methodik zur Modellierung zustandsdiskreter Systeme unter Berücksichtigung möglicher Inkonsistenzen (Betreuer: Prof. Dr.-Ing. Werner Zorn [ZW07a, ZW07b]).
• Das zweite Schwerpunktthema widmet sich der quantitativen Modellierung und Optimierung von E-Government-Bediensystemen, welche am Beispiel des Bürgerbüros der Stadt Landshut im Zeitraum 2008 bis 2015 durchgeführt wurden. Dies erfolgt auf Basis einer kontinuierlichen Betriebsdatenerfassung mit aufwendiger Vorverarbeitung zur Extrahierung mathematisch beschreibbarer Wahrscheinlichkeitsverteilungen.
Der hieraus entwickelte Dienstplan wurde hinsichtlich der erzielbaren Optimierungen im dauerhaften Echteinsatz verifiziert.
[ZW07a] Zorn, Werner: «FMC-QE A New Approach in Quantitative Modeling», Vortrag anlässlich: MSV'07- The 2007 International Conference on Modeling, Simulation and Visualization Methods WorldComp2007, Las Vegas, 28.6.2007.
[ZW07b] Zorn, Werner: «FMC-QE, A New Approach in Quantitative Modeling», Veröffentlichung, Hasso-Plattner-Institut für Softwaresystemtechnik an der Universität Potsdam, 28.6.2007.
Die Projektierung und Abwicklung sowie die statische und dynamische Analyse von Geschäftsprozessen im Bereich des Verwaltens und Regierens auf kommunaler, Länder- wie auch Bundesebene mit Hilfe von Informations- und Kommunikationstechniken beschäftigen Politiker und Strategen für Informationstechnologie ebenso wie die Öffentlichkeit seit Langem. Der hieraus entstandene Begriff E-Government wurde in der Folge aus den unterschiedlichsten technischen, politischen und semantischen Blickrichtungen beleuchtet.
Die vorliegende Arbeit konzentriert sich dabei auf zwei Schwerpunktthemen:
> Das erste Schwerpunktthema behandelt den Entwurf eines hierarchischen Architekturmodells, für welches sieben hierarchische Schichten identifiziert werden können. Diese erscheinen notwendig, aber auch hinreichend, um den allgemeinen Fall zu beschreiben. Den Hintergrund hierfür liefert die langjährige Prozess- und Verwaltungserfahrung als Leiter der EDV-Abteilung der Stadtverwaltung Landshut, eine kreisfreie Stadt mit rund 69.000 Einwohnern im Nordosten von München. Sie steht als Repräsentant für viele Verwaltungsvorgänge in der Bundesrepublik Deutschland und ist dennoch als Analyseobjekt in der Gesamtkomplexität und Prozessquantität überschaubar. Somit können aus der Analyse sämtlicher Kernabläufe statische und dynamische Strukturen extrahiert und abstrakt modelliert werden. Die Schwerpunkte liegen in der Darstellung der vorhandenen Bedienabläufe in einer Kommune. Die Transformation der Bedienanforderung in einem hierarchischen System, die Darstellung der Kontroll- und der Operationszustände in allen Schichten wie auch die Strategie der Fehlererkennung und Fehlerbehebung schaffen eine transparente Basis für umfassende Restrukturierungen und Optimierungen. Für die Modellierung wurde FMC-eCS eingesetzt, eine am Hasso-Plattner-Institut für Softwaresystemtechnik GmbH (HPI) im Fachgebiet Kommunikationssysteme entwickelte Methodik zur Modellierung zustandsdiskreter Systeme unter Berücksichtigung möglicher Inkonsistenzen
>Das zweite Schwerpunktthema widmet sich der quantitativen Modellierung und Optimierung von E-Government-Bediensystemen, welche am Beispiel des Bürgerbüros der Stadt Landshut im Zeitraum 2008 bis 2015 durchgeführt wurden. Dies erfolgt auf Basis einer kontinuierlichen Betriebsdatenerfassung mit aufwendiger Vorverarbeitung zur Extrahierung mathematisch beschreibbarer Wahrscheinlichkeitsverteilungen. Der hieraus entwickelte Dienstplan wurde hinsichtlich der erzielbaren Optimierungen im dauerhaften Echteinsatz verifiziert.
Decreasing groundwater levels in many parts of Germany and decreasing low flows in Central Europe have created a need for adaptation measures to stabilize the water balance and to increase low flows. The objective of our study was to estimate the impact of ditch water level management on stream-aquifer interactions in small lowland catchments of the mid-latitudes. The water balance of a ditch-irrigated area and fluxes between the subsurface and the adjacent stream were modeled for three runoff recession periods using the Hydrus-2D software package. The results showed that the subsurface flow to the stream was closely related to the difference between the water level in the ditch system and the stream. Evapotranspiration during the growing season additionally reduced base flow. It was crucial to stop irrigation during a recession period to decrease water withdrawal from the stream and enhance the base flow by draining the irrigated area. Mean fluxes to the stream were between 0.04 and 0.64 ls(-1) for the first 20 days of the low-flow periods. This only slightly increased the flow in the stream, whose mean was 57 ls(-1) during the period with the lowest flows. Larger areas would be necessary to effectively increase flows in mesoscale catchments.
Decreasing groundwater levels in many parts of Germany and decreasing low flows in Central Europe have created a need for adaptation measures to stabilize the water balance and to increase low flows. The objective of our study was to estimate the impact of ditch water level management on stream-aquifer interactions in small lowland catchments of the mid-latitudes. The water balance of a ditch-irrigated area and fluxes between the subsurface and the adjacent stream were modeled for three runoff recession periods using the Hydrus-2D software package. The results showed that the subsurface flow to the stream was closely related to the difference between the water level in the ditch system and the stream. Evapotranspiration during the growing season additionally reduced base flow. It was crucial to stop irrigation during a recession period to decrease water withdrawal from the stream and enhance the base flow by draining the irrigated area. Mean fluxes to the stream were between 0.04 and 0.64 ls(-1) for the first 20 days of the low-flow periods. This only slightly increased the flow in the stream, whose mean was 57 ls(-1) during the period with the lowest flows. Larger areas would be necessary to effectively increase flows in mesoscale catchments.
Polychlorinated biphenyls (PCBs) can cause endocrine disruption, cancer, immunosuppression, or reproductive failure in animals. We used an individual-based model to explore whether and how PCB-associated reproductive failure could affect the dynamics of a hypothetical polar bear (Ursus maritimus) population exposed to PCBs to the same degree as the East Greenland subpopulation. Dose-response data from experimental studies on a surrogate species, the mink (Mustela vision), were used in the absence of similar data for polar bears. Two alternative types of reproductive failure in relation to maternal sum-PCB concentrations were considered: increased abortion rate and increased cub mortality. We found that the quantitative impact of PCB-induced reproductive failure on population growth rate depended largely on the actual type of reproductive failure involved. Critical potencies of the dose-response relationship for decreasing the population growth rate were established for both modeled types of reproductive failure. Comparing the model predictions of the age-dependent trend of sum-PCBs concentrations in females with actual field measurements from East Greenland indicated that it was unlikely that PCB exposure caused a high incidence of abortions in the subpopulation. However, on the basis of this analysis, it could not be excluded that PCB exposure contributes to higher cub mortality. Our results highlight the necessity for further research on the possible influence of PCBs on polar bear reproduction regarding their physiological pathway. This includes determining the exact cause of reproductive failure, i.e., in utero exposure versus lactational exposure of offspring; the timing of offspring death; and establishing the most relevant reference metrics for the dose-response relationship.
Recently, due to an increasing demand on functionality and flexibility, beforehand isolated systems have become interconnected to gain powerful adaptive Systems of Systems (SoS) solutions with an overall robust, flexible and emergent behavior. The adaptive SoS comprises a variety of different system types ranging from small embedded to adaptive cyber-physical systems. On the one hand, each system is independent, follows a local strategy and optimizes its behavior to reach its goals. On the other hand, systems must cooperate with each other to enrich the overall functionality to jointly perform on the SoS level reaching global goals, which cannot be satisfied by one system alone. Due to difficulties of local and global behavior optimizations conflicts may arise between systems that have to be solved by the adaptive SoS.
This thesis proposes a modeling language that facilitates the description of an adaptive SoS by considering the adaptation capabilities in form of feedback loops as first class entities. Moreover, this thesis adopts the Models@runtime approach to integrate the available knowledge in the systems as runtime models into the modeled adaptation logic. Furthermore, the modeling language focuses on the description of system interactions within the adaptive SoS to reason about individual system functionality and how it emerges via collaborations to an overall joint SoS behavior. Therefore, the modeling language approach enables the specification of local adaptive system behavior, the integration of knowledge in form of runtime models and the joint interactions via collaboration to place the available adaptive behavior in an overall layered, adaptive SoS architecture.
Beside the modeling language, this thesis proposes analysis rules to investigate the modeled adaptive SoS, which enables the detection of architectural patterns as well as design flaws and pinpoints to possible system threats. Moreover, a simulation framework is presented, which allows the direct execution of the modeled SoS architecture. Therefore, the analysis rules and the simulation framework can be used to verify the interplay between systems as well as the modeled adaptation effects within the SoS. This thesis realizes the proposed concepts of the modeling language by mapping them to a state of the art standard from the automotive domain and thus, showing their applicability to actual systems. Finally, the modeling language approach is evaluated by remodeling up to date research scenarios from different domains, which demonstrates that the modeling language concepts are powerful enough to cope with a broad range of existing research problems.
BACKROUND: Few studies have been carried out to connect nutrients recovery from wastewater and heavy metals immobilization in contaminated soil. To achieve the goal, ammonia nitrogen (AN) and phosphorus (P) were recovered from rare-earth wastewater by using the formation of struvite, which was used as the amendment with plant ash for copper, lead and chromium immobilization. RESULTS: AN removal efficiency and residual P reached 95.32 +/- 0.73% and 6.14 +/- 1.72mgL(-1) under optimal conditions: pH= 9.0, n(Mg): n(N): n(P)= 1.2: 1: 1.1, which were obtained using response surface methodology (RSM). The minimum available concentrations of Cu, Pb and Cr (CPC) separately reduced to 320.82 mg kg(-1), 190.77 mg kg(-1) and 121.46 mg kg(-1) with increasing immobilization time at the mass ratio of phosphate precipitate (PP)/plant ash (PA) of 1: 3. Humic acid (HA) and fulvic acid (FA) were beneficial to immobilize Cu, both of which showed no effect or even a negative effect on Pb and Cr immobilization.
Answer set programming (ASP) has emerged as an approach to declarative problem solving based on the stable model semantics for logic programs. The basic idea is to represent a computational problem by a logic program, formulating constraints in terms of rules, such that its answer sets correspond to problem solutions. To this end, ASP combines an expressive language for high-level modeling with powerful low-level reasoning capacities, provided by off-the-shelf tools. Compact problem representations take advantage of genuine modeling features of ASP, including (first-order) variables, negation by default, and recursion. In this article, we demonstrate the ASP methodology on two example scenarios, illustrating basic as well as advanced modeling and solving concepts. We also discuss mechanisms to represent and implement extended kinds of preferences and optimization. An overview of further available extensions concludes the article.
The relationship between climate and forest productivity is an intensively studied subject in forest science. This Thesis is embedded within the general framework of future forest growth under climate change and its implications for the ongoing forest conversion. My objective is to investigate the future forest productivity at different spatial scales (from a single specific forest stand to aggregated information across Germany) with focus on oak-pine forests in the federal state of Brandenburg. The overarching question is: how are the oak-pine forests affected by climate change described by a variety of climate scenarios. I answer this question by using a model based analysis of tree growth processes and responses to different climate scenarios with emphasis on drought events. In addition, a method is developed which considers climate change uncertainty of forest management planning.
As a first 'screening' of climate change impacts on forest productivity, I calculated the change in net primary production on the base of a large set of climate scenarios for different tree species and the total area of Germany. Temperature increases up to 3 K lead to positive effects on the net primary production of all selected tree species. But, in water-limited regions this positive net primary production trend is dependent on the length of drought periods which results in a larger uncertainty regarding future forest productivity. One of the regions with the highest uncertainty of net primary production development is the federal state of Brandenburg.
To enhance the understanding and ability of model based analysis of tree growth sensitivity to drought stress two water uptake approaches in pure pine and mixed oak-pine stands are contrasted. The first water uptake approach consists of an empirical function for root water uptake. The second approach is more mechanistic and calculates the differences of soil water potential along a soil-plant-atmosphere continuum. I assumed the total root resistance to vary at low, medium and high total root resistance levels. For validation purposes three data sets on different tree growth relevant time scales are used. Results show that, except the mechanistic water uptake approach with high total root resistance, all transpiration outputs exceeded observed values. On the other hand high transpiration led to a better match of observed soil water content. The strongest correlation between simulated and observed annual tree ring width occurred with the mechanistic water uptake approach and high total root resistance. The findings highlight the importance of severe drought as a main reason for small diameter increment, best supported by the mechanistic water uptake approach with high root resistance. However, if all aspects of the data sets are considered no approach can be judged superior to the other. I conclude that the uncertainty of future productivity of water-limited forest ecosystems under changing environmental conditions is linked to simulated root water uptake.
Finally my study aimed at the impacts of climate change combined with management scenarios on an oak-pine forest to evaluate growth, biomass and the amount of harvested timber. The pine and the oak trees are 104 and 9 years old respectively. Three different management scenarios with different thinning intensities and different climate scenarios are used to simulate the performance of management strategies which explicitly account for the risks associated with achieving three predefined objectives (maximum carbon storage, maximum harvested timber, intermediate). I found out that in most cases there is no general management strategy which fits best to different objectives. The analysis of variance in the growth related model outputs showed an increase of climate uncertainty with increasing climate warming. Interestingly, the increase of climate-induced uncertainty is much higher from 2 to 3 K than from 0 to 2 K.
The notion of model transformation intent is proposed to capture the purpose of a transformation. In this paper, a framework for the description of model transformation intents is defined, which includes, for instance, a description of properties a model transformation has to satisfy to qualify as a suitable realization of an intent. Several common model transformation intents are identified, and the framework is used to describe six of them in detail. A case study from the automotive industry is used to demonstrate the usefulness of the proposed framework for identifying crucial properties of model transformations with different intents and to illustrate the wide variety of model transformation intents that an industrial model-driven software development process typically encompasses.
Based on theories of scientific discovery learning (SDL) and conceptual change, this study explores students' preconceptions in the domain of torques in physics and the development of these conceptions while learning with a computer-based SDL task. As a framework we used a three-space theory of SDL and focused on model space, which is supposed to contain the current conceptualization/model of the learning domain, and on its change through hypothesis testing and experimenting. Three questions were addressed: (1) What are students' preconceptions of torques before learning about this domain? To do this a multiple-choice test for assessing students' models of torques was developed and given to secondary school students (N = 47) who learned about torques using computer simulations. (2) How do students' models of torques develop during SDL? Working with simulations led to replacement of some misconceptions with physically correct conceptions. (3) Are there differential patterns of model development and if so, how do they relate to students’ use of the simulations? By analyzing individual differences in model development, we found that an intensive use of the simulations was associated with the acquisition of correct conceptions. Thus, the three-space theory provided a useful framework for understanding conceptual change in SDL.
The spatial and temporal control over presentation of protein-based biomolecules such as growth factors and hormones is crucial for in vitro applications to mimic the complex in vivo environment. We investigated the interaction of a model protein lysozyme (Lys) with poly(L-lysine)/hyaluronic acid (PLL/HA) multilayer films. We focused on Lys diffusion as well as adsorption and retention within the film as a function of the film deposition conditions and post-treatment. Additionally, an effect of Lys concentration on its mobility was probed. A combination of confocal fluorescence microscopy, fluorescence recovery after photobleaching, and microfluidics was employed for this investigation. Our main finding is that adsorption of PLL and HA after protein loading induces acceleration and reduction of Lys mobility, respectively. These results suggest that a charge balance in the film to a high extent governs the protein-film interaction. We believe that control over protein mobility is a key to reach the full potential of the PLL/HA films as reservoirs for biomolecules depending on the application demand. (C) 2016 The Authors. Published by Elsevier B.V.
We study an array of activity rhythms generated by a half-center oscillator (HCO), represented by a pair of reciprocally coupled neurons with post-inhibitory rebounds (PIR). Such coupling induced bursting possesses two time scales, one for fast spiking and another for slow quiescent periods, is shown to exhibit an array of synchronization properties. We discuss several HCO configurations constituted by two endogenous bursters, by tonic-spiking and quiescent neurons, as well as mixed-mode configurations composed of neurons of different type. We demonstrate that burst synchronization can be accompanied by complex, often chaotic, interactions of fast spikes within synchronized bursts. (C) 2015 Elsevier B.V. All rights reserved.
ATP production requires the establishment of an electrochemical proton gradient across the inner mitochondrial membrane. Mitochondrial uncouplers dissipate this proton gradient and disrupt numerous cellular processes, including vesicular trafficking, mainly through energy depletion. Here we show that Endosidin9 (ES9), a novel mitochondrial uncoupler, is a potent inhibitor of clathrin-mediated endocytosis (CME) in different systems and that ES9 induces inhibition of CME not because of its effect on cellular ATP, but rather due to its protonophore activity that leads to cytoplasm acidification. We show that the known tyrosine kinase inhibitor tyrphostinA23, which is routinely used to block CME, displays similar properties, thus questioning its use as a specific inhibitor of cargo recognition by the AP-2 adaptor complex via tyrosine motif-based endocytosis signals. Furthermore, we show that cytoplasm acidification dramatically affects the dynamics and recruitment of clathrin and associated adaptors, and leads to reduction of phosphatidylinositol 4,5-biphosphate from the plasma membrane.
La siguiente investigación aborda la relación entre mito y modernidad en la obra literaria (poemas, cuentos, novelas y crónicas) del autor chileno Rosamel del Valle (Curacaví, 1901 – Santiago de Chile, 1965). En sus distintos textos existe una tensión entre un proyecto poético basado en una visión mítica del mundo y un contexto histórico que privilegia posturas más racionalistas, relegando lo poético y lo mítico. Ya en el siglo XIX la modernidad y los fenómenos asociados de la modernización producen el desplazamiento de la poesía como discurso y del poeta como persona a una situación deficitaria dentro de la sociedad, lo que se extiende en el siglo XX. Debido a este conflicto Rosamel del Valle cuestiona en su obra los alcances de sus propios postulados, tanto estéticos como vitales. Esto conlleva una vacilación entre la reafirmación de su proyecto poético-vital y la consciencia del fracaso. Es por esto que la obra del poeta chileno contiene un Lebenswissen, que concibe a la poesía como una forma privilegiada de vida. Sin embargo, debido a las dificultades de las condiciones históricas es posible entender este Lebenswissen también como un ÜberLebenswissen (Ette).
En la primera parte del texto se estudia la concepción mítica de la poesía de del Valle y se analiza los distintos niveles en los que aparece el mito en su obra literaria: como pensamiento, como lenguaje y como narración tradicional. La identificación de la poesía como mito muestra las principales características de la poética de del Valle: una concepción ontológica que diferencia entre una dimensión visible y otra invisible de la realidad; la tendencia mística de la poesía; una concepción cíclica del tiempo que funda una relación con los discursos de la memoria y de la muerte, así como la idea de un pasado utópico que por medio de la poesía podría revivir en el presente; además de la figura de la mujer cómo símbolo del amor y de la poesía.
En la segunda parte se investiga la relación y las consecuencias de esta “poesía mítica” en el contexto de la modernidad. Se aborda especialmente el efecto en la poética de Rosamel del Valle de la Entzauberung der Welt (Weber), como experiencia específica de la época. Para esto se destaca ante todo sus impresiones sobre Nueva York. Esta ciudad en la que vivió y trabajó entre 1946 y 1963, se transforma en sus textos en un lugar en el que sería posible el “habitar poético del hombre” en la modernidad.
Mit Korbmachern zum Sieg
(2016)
The current financial reporting environment, with its increasing use of accounting estimates, including fair value estimates, suggests that unethical accounting estimates may be a growing concern. This paper provides explanations and empirical evidence for why some types of accounting estimates in financial reporting may promote a form of ethical blindness. These types of ethical blindness can have an escalating effect that corrupts not only an individual or organization but also the accounting profession and the public interest it serves. Ethical blindness in the standards of professional accountants may be a factor in the extent of misreporting, and may have taken on new urgency as a result of the proposals to change the conceptual framework for financial reporting using international standards. The social consequences for users of financial statements can be huge. The acquittal of former Nortel executives on fraud charges related to accounting manipulations is viewed by many as legitimizing accounting gamesmanship. This decision illustrates that the courts may not be the best place to deal with ethical reporting issues. The courts may be relied on for only the most egregious unethical conduct and, even then, the accounting profession is ill equipped to assist the legal system in prosecuting accounting fraud unless the standards have been clarified. We argue that the problem of unethical reporting should be addressed by the accounting profession itself, preferably as a key part of the conceptual framework that supports accounting and auditing standards, and the codes of ethical conduct that underpin the professionalism of accountants.
Biomimetic binders and catalysts have been generated in order to substitute the biological pendants in separation techniques and bioanalysis. The two major approaches use either "evolution in the test tube" of nucleotides for the preparation of aptamers or total chemical synthesis for molecularly imprinted polymers (MIPs). The reproducible production of aptamers is a clear advantage, whilst the preparation of MIPs typically leads to a population of polymers with different binding sites. The realization of binding sites in the total bulk of the MIPs results in a higher binding capacity, however, on the expense of the accessibility and exchange rate. Furthermore, the readout of the bound analyte is easier for aptamers since the integration of signal generating labels is well established. On the other hand, the overall negative charge of the nucleotides makes aptamers prone to non-specific adsorption of positively charged constituents of the sample and the "biological" degradation of non-modified aptamers and ionic strength-dependent changes of conformation may be challenging in some application.
A new electrochemical MIP sensor for the most frequently used drug paracetamol (PAR) was prepared by electropolymerization of mixtures containing the template molecule and the functional monomers ophenylenediamine, resorcinol and aniline. The imprinting factor of 12 reflects the effective target binding to the MIP as compared with the non-imprinted electropolymer. Combination of the MIP with a nonspecific esterase allows the measurement of phenacetin - another analgesic drug. In the second approach the PAR containing sample solution was pretreated with tyrosinase in order to prevent electrochemical interferences by ascorbic acid and uric acid. Interference-free indication at a very low electrode potential without fouling of the electrode surface was achieved with the o-phenylenediamine: resorcinol-based MIP.
Rainfall in the central Andes associated with the South American Monsoon and the South American Low-Level Jet results from orographic effects on atmospheric circulation exerted by the Andean Plateau and the Eastern Cordillera. However, despite its importance for South American climate, no reliable records exist that allow decoding the evolution of thresholds and interactions between Andean topography and atmospheric circulation, especially regarding the onset of humid conditions in the inherently dry southern central Andes. Here, we employ multi-proxy isotope data of lipid biomarkers, pedogenic carbonates and volcanic glass from the Eastern Cordillera of NW Argentina and present the first long-term evapotranspiration record. We find that regional eco-hydrology and vegetation changes are associated with initiation of moisture transport via the South American Low-Level Jet at 7.6 Ma, and subsequent lateral growth of the orogen at 6.5 Ma. Our results highlight that topographically induced changes in atmospheric circulation patterns, not global climate change, were responsible for late Miocene environmental change in this part of the southern hemisphere. This suggests that mountain building over time fundamentally controlled habitat evolution along the central Andes.
In the present study, we tested a serial mindfulness facets-trait emotional intelligence (TEI)-emotional distress-multiple health behaviors mediation model in a sample of N = 427 German-speaking occupational therapists. The mindfulness facets-TEI-emotional distress section of the mediation model revealed partial mediation for the mindfulness facets Act with awareness (Act/Aware) and Accept without judgment (Accept); inconsistent mediation was found for the Describe facet. The serial two-mediator model included three mediational pathways that may link each of the four mindfulness facets with multiple health behaviors. Eight out of 12 indirect effects reached significance and fully mediated the links between Act/Aware and Describe to multiple health behaviors; partial mediation was found for Accept. The mindfulness facet Observe was most relevant for multiple health behaviors, but its relation was not amenable to mediation. Implications of the findings will be discussed.
Die vorliegende Arbeit beschäftigt sich mit dem Einfluss der Organisationsform von Mikrofinanzinstitutionen (MFIs) auf deren soziale Performance. In diesem Kontext wird die soziale Performance als die direkte Übersetzung der sozialen Mission der MFIs in die Praxis verstanden. Konkret wird die soziale Performance der zwei Organisationsformen Shareholder Owned Firm (SOF) sowie Non-Governmental Organisation (NGO) betrachtet und verglichen. Dieser Vergleich stützt sich auf die in der Fachwelt häufig vertretene Annahme, dass NGO MFIs eine höhere soziale Performance aufweisen als SOF MFIs, da sie dem Nonprofit-Sektor zugeschrieben werden können. Die bis dato vorhandenen relevanten empirischen Forschungen zu dem Thema werden anhand einer Literaturdiskussion analysiert. Bislang existiert nur eine relativ geringe Anzahl an empirischen Forschungen in diesem Themenfeld, da die Erforschung der sozialen Performance von MFIs ein recht neues Forschungsgebiet darstellt. Die Ergebnisse der Literaturdiskussion verdeutlichen zudem, dass hinsichtlich des Einflusses der Organisationsform von MFIs auf deren soziale Performance keine eindeutige Aussage getroffen werden kann, da die betrachteten Studien zu unterschiedlichen Resultaten kommen. Die Ergebnisse deuten jedoch darauf hin, dass in einigen geografischen Regionen der Welt NGO MFIs eine bessere soziale Performance aufweisen als SOF MFIs. Insgesamt liefert die Arbeit einen wichtigen Überblick über den Forschungsstand auf diesem Forschungsgebiet und deckt diverse Forschungslücken auf, welche in zukünftigen Untersuchungen berücksichtigt werden sollten.
Permafrost-related processes drive regional landscape dynamics in the Arctic terrestrial system. A better understanding of past periods indicative of permafrost degradation and aggradation is important for predicting the future response of Arctic landscapes to climate change. Here, we used a multi-proxy approach to analyse a4m long sediment core from a drained thermokarst lake basin on the northern Seward Peninsula in western Arctic Alaska (USA). Sedimentological, biogeochemical, geochronological, micropalaeontological (ostracoda, testate amoebae) and tephra analyses were used to determine the long-term environmental Early-Wisconsin to Holocene history preserved in our core for central Beringia. Yedoma accumulation dominated throughout the Early to Late-Wisconsin but was interrupted by wetland formation from 44.5 to 41.5ka BP. The latter was terminated by the deposition of 1m of volcanic tephra, most likely originating from the South Killeak Maar eruption at about 42ka BP. Yedoma deposition continued until 22.5ka BP and was followed by a depositional hiatus in the sediment core between 22.5 and 0.23ka BP. We interpret this hiatus as due to intense thermokarst activity in the areas surrounding the site, which served as a sediment source during the Late-Wisconsin to Holocene climate transition. The lake forming the modern basin on the upland initiated around 0.23ka BP and drained catastrophically in spring 2005. The present study emphasises that Arctic lake systems and periglacial landscapes are highly dynamic and that permafrost formation as well as degradation in central Beringia was controlled by regional to global climate patterns as well as by local disturbances. Copyright (c) 2015 John Wiley & Sons, Ltd.
para-Substituted aryl prenyl ethers undergo a deprenylation reaction upon microwave irradiation. This offers the opportunity to use a prenyl ether as a thermolabile protecting group in the synthesis of natural products with a chromone structure, which proceeds via a tandem deprenylation/6-endo-cyclization sequence.
Microthlaspi is a predominantly Eurasian genus which also occurs in the northernmost parts of Africa (Maghreb). The most widespread species of the genus is M. perfoliatum, which can be found from Sweden to Algeria and from Portugal to China. The other species are thought to have much more confined distribution ranges, often covering only a few hundred kilometres. This is also believed for the diploid M. erraticum, which was recently re-appraised as a taxon independent from the tetra- to hexaploid M. perfoliatum. Previously, M. erraticum was believed to be present only in Central Europe, from the East of France to Slovenia. In order to gain a deeper understanding of the ecology, evolution and migration history of Microthlaspi it was the focus of the current study to investigate, if M. erraticum is present in habitats outside Central Europe, but with microclimates similar to Central Europe. It is demonstrated that M. erraticum is much more widespread than previously thought, while other lineages apart from M. perfoliatum s.str. and M. erraticum seem to have restricted distribution ranges. The latter species was observed from the Alps and their foreland, the Balkans, the mountainous areas around the Black Sea, Southern Siberia, as well as the Altai and Tien Shan mountains. This demonstrates a widespread occurrence of this easily-overlooked species. (C) 2016 Elsevier GmbH. All rights reserved.
Microstructured hydrogel allows for a new template-guided method to obtain conductive nanowire arrays on a large scale. To generate the template, an imprinting process is used in order to synthesize the hydrogel directly into the grooves of wrinkled polydimethylsiloxane (PDMS). The resulting poly(N-vinylimidazole)-based hydrogel is defined by the PDMS stamp in pattern and size. Subsequently, tetrachloroaurate(III) ions from aqueous solution are coordinated within the humps of the N-vinylimidazole-containing polymer template and reduced by air plasma. After reduction and development of the gold, to achieve conductive wires, the extension perpendicular to the long axis (width) of the gold strings is considerably reduced compared to the dimension of the parental hydrogel wrinkles (from approximate to 1 mu m down to 200-300 nm). At the same time, the wire-to-wire distance and the overall length of the wires is preserved. The PDMS templates and hydrogel structures are analyzed with scanning force microscopy (SFM) and the gold structures via scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy. The conductivity measurements of the gold nanowires are performed in situ in the SEM, showing highly conductive gold leads. Hence, this method can be regarded as a facile nonlithographic top-down approach from micrometer-sized structures to nanometer-sized features.