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Herein we present an efficient synthesis of a biomimetic probe with modular construction that can be specifically bound by the mannose binding FimH protein – a surface adhesion protein of E. coli bacteria. The synthesis combines the new and interesting DBD dye with the carbohydrate ligand mannose via a Click reaction. We demonstrate the binding to E. coli bacteria over a large concentration range and also present some special characteristics of those molecules that are of particular interest for the application as a biosensor. In particular, the mix-and-measure ability and the very good photo-stability should be highlighted here.
Die Gründung des Europäischen Stabilitätsmechanismus (ESM) durch einen völkerrechtlichen Vertrag außerhalb der EU-Verträge ist mit mehreren Nachteilen verbunden. So schwächt die Zersplitterung der Rechtsquellen die europäischen Institutionen und deren Legitimation. Auch kann der ESM nicht ohne weiteres auf die Strukturen und das Personal der Europäischen Kommission zurückgreifen. Daher ist eine Integration des ESM in das Gemeinschaftsrecht sinnvoll. Dies setzt eine Rechtsgrundlage voraus. Die Arbeit kommt unter Berücksichtigung der deutschen und französischen Positionen sowie der einschlägigen Rechtsprechung des EuGH zu dem Ergebnis, dass die bestehenden EUVerträge keine Rechtsgrundlage für die Integration des ESM in das Gemeinschaftsrecht enthalten. Vor diesem Hintergrund ist eine Änderung des AEUV gemäß dem ordentlichen Vertragsänderungsverfahren unumgänglich. Damit sollte eine ausdrückliche Rechtsgrundlage für einen gemeinschaftsrechtlichen Stabilitätsmechanismus geschaffen werden. In der Arbeit wird ein konkreter Formulierungsvorschlag für eine derartige Rechtsgrundlage entwickelt, auf deren Basis der Rat mit einer Verordnung einen gemeinschaftsrechtlichen Stabilitätsmechanismus schaffen kann. Außerdem werden die wesentlichen Strukturprinzipien für den gemeinschaftsrechtlichen Stabilitätsmechanismus entwickelt, im Hinblick auf Trägerschaft, Governance, Finanzierung, demokratische Kontrolle und die verfügbaren Finanzhilfeinstrumente.
Die Kategorie des jurodstvo im Russlandbild Tadeusz Micińskis am Beispiel des Dramas Kniaź Patiomkin
(2016)
Als Folge der demografischen Entwicklungen und der finanziellen Engpässe vieler Bundesländer kommt es seit einigen Jahren in den meisten Flächenländern der Bundesrepublik Deutschland erneut zu tiefgreifenden Verwaltungsreformen auf kommunaler Ebene. Mit Hilfe von Verwaltungsstruktur-, Funktional- und Kreisgebietsreformen wird versucht, die Verwaltungseffektivität zu erhöhen sowie die kreislichen Aufgaben- und Territorialstrukturen an die veränderten Rahmenbedingungen anzupassen. Nach Auffassung vieler Reformer kann die angestrebte Effektivitätssteigerung, die insbesondere zu Kostenersparnissen und Synergieeffekten führen soll, v. a. durch eine deutliche Vergrößerung der Verwaltungsräume erreicht werden.
Neben dem Ziel, die Leistungsfähigkeit der lokalen Verwaltungsstrukturen zu erhöhen, das zumeist im Mittelpunkt der Reformvorhaben steht, gilt es jedoch gleichermaßen, die Legitimität lokalen Handelns durch Demokratie und bürgerschaftliche Teilhabe zu erhalten. Der Gesetzgeber steht daher vor der Aufgabe, beide Zielvorstellungen in einem Reformprozess zu berücksichtigen und die Größe der administrativen Einheiten so zu gestalten, dass in ihnen ein ausgewogenes Verhältnis zwischen Effizienz und Bürgernähe entsteht.
Ausgehend von dieser Problematik werden jene Thesen und Annahmen aufgegriffen, die im Zusammenhang mit dem Urteil des LVerfG M-V vom 26. Juli 2007 im Kontext von Effizienz und Partizipation stehen, und auf die Kreisgebietsreform im Freistaat Sachsen übertragen. Konkret werden die Auswirkungen des territorialen Neuzuschnitts der sächsischen Landkreise auf die Wahrnehmung des kommunalpolitischen Ehrenamts erstmals auch durch eine breite Empirie untersucht.
Ende September 1910 erschütterten schwere Straßenkämpfe zwischen Bevölkerung und Polizei den Berliner Stadtteil Moabit. Die mehrtägigen Unruhen hatten unter anderem eine Vielzahl Verletzter auf beiden Seiten, zwei Tote, diplomatische Beschwerden und zwei Mammutprozesse vor Berliner Gerichten zur Folge.
Ausgehend von dem Gedanken Wilhelm Mommsens „nichts versetzt so leicht in die Atmosphäre einer Zeit als ihre Zeitungen und nichts zeigt so gut, was die Zeitgenossen beschäftigt und hauptsächlich interessiert hat,“ soll in dieser Arbeit der Versuch unternommen werden, den die Moabiter Unruhen begleitenden Diskurs in den Tageszeitungen nachzuzeichnen, um somit anhand der zeitnahen zeitgenössischen Rezeption dieser zugespitzten Ausnahmesituation Wesen und Charakter der öffentlichen Diskussion in der wilhelminischen Gesellschaft sichtbar zu machen.
In der vorliegenden Arbeit sollen zunächst kurz der Bezirk Moabit sowie seine Bewohner vorgestellt werden, ehe daran anknüpfend der Verlauf von Streik und Auseinandersetzungen überblicksartig vorgestellt werden. Daran anschließend soll ein Bild der zeitnahen Berichterstattung während der Entwicklung der Ereignisse in der deutschen Presselandschaft entworfen werden.
Um ein detailliertes Bild des die in dieser Arbeit vorgestellten Ereignisse begleitenden Diskurses zu erhalten, wurden für diese Arbeit die Ausgaben der nachstehenden deutschen Tageszeitung von Beginn des die Unruhen auslösenden Streiks am 19. September bis zum Ende der Prozesse im Februar 1911 systematisch durchgesehen. Die detaillierte Diskussion der Berichterstattung beschränkt sich in dieser Arbeit jedoch auf den Zeitraum von Beginn des Streiks bis zu dessen Ende im Oktober 1910.
Seitens der liberal ausgerichteten Blätter wurden das liberal-bürgerliche Berliner Tageblatt sowie die Frankfurter Zeitung gesichtet. Als Vertreter der katholischen Zentrumspartei wurde die Germania durchgesehen. Als führendes Organ der Sozialdemokratie wurde der Vorwärts hinzugezogen. Von der konservativen Presse wurden der Berliner Lokal‑Anzeiger und die protestantische Neue Preußische Zeitung begutachtet.
Die Museumsbesucher
(2016)
Ökonomen wie Wirtschaftspolitiker berufen sich auf die Neutralitätstheorie des Geldes, wenn sie eine Entpolitisierung der Geldpolitik fordern. Sowohl die Theorie der Geldneutralität als auch das Paradigma der Entpolitisierung der Geldpolitik sind jedoch problematisch. Die politökonomischen Entwicklungen nach der globalen Finanz- und Wirtschaftskrise 2007/2008 und die jüngsten Kontroversen über die Rolle und Bedeutung von Geld haben dies deutlich vor Augen geführt. Die vorliegende Arbeit diskutiert zunächst die konzeptionellen Grundlagen und theoretischen Modelle der Geldneutralität. Anschließend werden die zentralen theoretischen Annahmen und Aussagen der Neutralitätstheorie aus einer kritischen heterodoxen Perspektive hinterfragt. Es wird argumentiert, dass Geld eine nicht-neutrale Produktionskraft ist, die weder ökonomisch noch sozial neutral ist. Die Bedingungen, unter denen Geld verfügbar ist und zirkuliert, sind richtungsweisend für die ökonomische Entwicklung. Daher kann es auch kein neutrales Geld oder gar eine apolitische Geldpolitik geben.
Die Empirie des beginnenden 21. Jahrhunderts weist mehr autoritäre Regime aus als am Ende des 20. Jahrhunderts angenommen. Die gegenwärtige Autoritarismusforschung versucht die Fortdauer dieses Regimetyps in Hinblick auf die politischen Institutionen zu erklären – dabei bleiben politische Akteure, die nicht zum Herrschaftszentrum gehören, außen vor.
Das vorliegende Projekt untersucht die Rolle und Funktion politischer Opposition in autoritären Regimen. Es wird davon ausgegangen, dass sich an der Opposition eine signifikante Charakteristik autoritärer Regime manifestiert. Das akteurszentrierte Projekt ist der qualitativ orientierten Politikwissenschaft zuzurechnen und verknüpft das Autoritarismuskonzept von Juan Linz mit klassischen Ansätzen der Oppositionsforschung und macht diese Theorien für die gegenwärtige Autoritarismusforschung nutzbar.
Die eigens entwickelte elitenorientierte Oppositionstypologie wird am Beispiel Kenias im Zeitraum 1990-2005 angewendet. Die Oppositionsgruppen werden im Institutionengefüge autoritärer Regime verortet und ihr politisches Agieren in den Dimensionen Handlungsstatus, Handlungsüberzeugung und Handlungsstrategie analysiert. Unter Beachtung der historisch gewachsenen regionalen und kulturellen Spezifika wird angenommen, dass generelle, Regionen übergreifende Aussagen zur Opposition in autoritären Regimen getroffen werden können: Kein Oppositionstyp kann allein einen Herrschaftswechsel bewirken. Der Wechsel bzw. die Fortdauer der Herrschaft hängt von der Dominanz bestimmter Oppositionstypen im Oppositionsgeflecht sowie der gleichzeitigen Schwäche anderer Oppositionstypen ab.
Durch die konzeptionelle Beschäftigung mit Opposition sowie deren empirische Erschließung soll ein substantieller Beitrag für die notwendige Debatte um autoritäre Regime im 21. Jahrhundert geleistet werden.
Die vorliegende Arbeit untersucht die Politik der Zentralbankunabhängigkeit (ZBU) am Beispiel der Türkei. Im Mittelpunkt der Arbeit stehen theoretische und empirische Fragen und Probleme, die sich im Zusammenhang mit der ZBU stellen und anhand der türkischen Geldpolitik diskutiert werden. Ein zentrales Ziel der Arbeit besteht darin, zu untersuchen, ob und inwiefern die türkische Zentralbank nach Erlangung der de jure institutionellen Unabhängigkeit tatsächlich als unabhängig und entpolitisiert eingestuft werden kann. Um diese Forschungsfrage zu beantworten, werden die institutionellen Bedingungen, die Ziele und die Regeln, nach denen sich die türkische Geldpolitik richtet, geklärt. Anschließend wird empirisch überprüft, ob die geldpolitische Praxis der CBRT sich an dem offiziell vorgegebenen Regelwerk orientiert. Die Hauptthese dieser Arbeit lautet, dass die formelle Unabhängigkeit der CBRT und die regelorientierte Geldpolitik nicht mit einer Entpolitisierung der Geldpolitik in der Türkei gleichzusetzen ist. Als Alternative schlägt die vorliegende Studie vor, den institutionellen Status der CBRT als einen der relativen Autonomie zu untersuchen. Auch eine de jure unabhängige Zentralbank kann sich nicht von politischen Eingriffen abkoppeln, wie das Fallbeispiel Türkei zeigen wird.
Der deutsche Zeitungsmarkt ist von einem breiten Angebot überregionaler Tageszeitungen gekennzeichnet, denen innerhalb der Bevölkerung unterschiedliche politische Ausrichtungen zugeschrieben werden. Als konservatives Blatt gilt die „Frankfurter Allgemeine Zeitung“ (F.A.Z.), wohingegen sich die „taz.die tageszeitung“ (taz) durch eine linksalternative Orientierung auszeichnet. Ausgehend von diesem Unterschied untersucht die Arbeit die sprachliche Gestaltung der Überschriften, Unter- und Zwischenzeilen der F.A.Z. und der taz zu den Themen „Alternative für Deutschland“ (AfD), „Nationalsozialistischer Untergrund“ (NSU) und „Front National“ (FN). Die qualitativ-quantitative Korpusuntersuchung fokussiert neben lexikalischen und syntaktischen auch sprachstilistische Faktoren, die eine Stellungnahme zu der Forschungsthese, dass mit der sprachlichen Formulierung der Haupt-, Unter- und Zwischenzeilen die politische Ausrichtung und ideologische Grundhaltung der Zeitungen deutlich wird, erlauben. Die Grundlage für die Analysen bildet ein konstruktivistischer Ansatz, der auf systemtheoretischen Annahmen beruht. Dadurch kann zum einen gezeigt werden, wie sich die Ergebnisse der sprachlichen Analysen mit den unterschiedlichen zugrunde liegenden Wirklichkeitskonstruktionen der Zeitungen verbinden lassen, zum anderen wird deutlich, dass sich die Formulierung der Überschriften auch auf die individuelle Realitätskonstruktion der Rezipienten auswirkt. Die vergleichenden Auswertungen geben unterschiedlich gewichtete Hinweise auf die Einstellung der Kommunikatoren und bestätigen, dass die jeweiligen Perspektivierungen der Wirklichkeit sowie ideologischen Grundhaltungen der F.A.Z. und der taz bereits in der sprachlichen Gestaltung ihrer Titelkomplexe deutlich werden.
Im Graduiertenkolleg NatRiskChange der Universität Potsdam und anderen Forschungseinrichtungen werden beobachtete sowie zukünftig mögliche Veränderungen von Naturgefahren untersucht. Teil des strukturierten Doktorandenprogramms sind sogenannte Task-Force-Einsätze, bei denen die Promovierende zeitlich begrenzt ein aktuelles Ereignis auswerten. Im Zuge dieser Aktivität wurde die Sturzflut vom 29.05.2016 in Braunsbach (Baden-Württemberg) untersucht.
In diesem Bericht werden erste Auswertungen zur Einordnung der Niederschläge, zu den hydrologischen und geomorphologischen Prozessen im Einzugsgebiet des Orlacher Bachs sowie zu den verursachten Schäden beleuchtet.
Die Region war Zentrum extremer Regenfälle in der Größenordnung von 100 mm innerhalb von 2 Stunden. Das 6 km² kleine Einzugsgebiet hat eine sehr schnelle Reaktionszeit, zumal bei vorgesättigtem Boden. Im steilen Bachtal haben mehrere kleinere und größere Hangrutschungen über 8000 m³ Geröll, Schutt und Schwemmholz in das Gewässer eingetragen und möglicherweise kurzzeitige Aufstauungen und Durchbrüche verursacht. Neben den großen Wassermengen mit einer Abflussspitze in einer Größenordnung von 100 m³/s hat gerade die Geschiebefracht zu großen Schäden an den Gebäuden entlang des Bachlaufs in Braunsbach geführt.
Z,E-Diene sind ein häufig auftretendes Strukturmerkmal in Naturstoffen. Aus diesem Grund ist die einfache Darstellung dieser Struktureinheit von großen Interesse in der organischen Chemie.
Das erste Ziel der vorliegenden Arbeit war daher die Weiterentwicklung der Ringschlussmetathese-/ baseninduzierten Ringöffnungs-/ Veresterungssequenz (RBRV-Sequenz) zur Synthese von (2Z,4E)-Diencarbonsäureethylestern ausgehend von Butenoaten. Dazu wurde zunächst die RBRV-Sequenz optimiert. Diese aus drei Schritten bestehende Sequenz konnte in einem Eintopf-Verfahren angewendet werden. Die Ringschlussmetathese gelang mit einer Katalysatorbeladung von 1 mol% des GRUBBS-Katalysators der zweiten Generation in Dichlormethan. Für die baseninduzierte Ringöffnung des β,γ-ungesättigten δ Valerolactons wurde NaHMDS verwendet. Die Alkylierung der Carboxylatspezies gelang mit dem MEERWEIN-Reagenz. Die Anwendbarkeit der Sequenz wurde für verschiedene Substrate demonstriert.
Die Erweiterung der Methode auf α-substituierte Butenoate unterlag starken Einschränkungen. So konnte der Zugang für α Hydroxyderivate realisiert werden. Bei der Anwendung der RBRV-Sequenz auf die α-substituierten Butenoate wurde festgestellt, dass diese sich nur in moderaten Ausbeuten umsetzen ließen und zudem nicht selektiv zu den (2E,4E)-konfigurierten α-substituierten-Dienestern reagierten.
Der Einsatz von Eninen unter den Standardbedingungen der RBRV-Sequenz gelang nicht. Erst nach Modifizierung der Sequenz (höhere Katalysatorbeladung, Wechsel des Lösungsmittels) konnten die [3]Dendralen-Produkte in geringen Ausbeuten erhalten werden.
Im zweiten Teil der Arbeit wurde der Einsatz von (2Z,4E)-Diencarbonsäureethylestern in der Totalsynthese von Naturstoffen untersucht. Dazu wurden zunächst die Transformationsmöglichkeiten der Ester geprüft. Es konnte gezeigt werden, dass sich (2Z,4E)-Diencarbonsäureethylester insbesondere zur Synthese von (2Z,4E)-Aldehyden sowie zum Aufbau der (3Z,5E)-Dien-1-in-Struktur eignen.
Anhand dieser Ergebnisse wurde im Anschluss die RBRV-Sequenz in der Totalsynthese eingesetzt. Dazu wurde zunächst der (2Z,4E)-Dienester Microsphaerodiolin in seiner ersten Totalsynthese auf drei verschiedene Routen hergestellt. Im Anschluss wurden sechs verschiedene Polyacetylene mit einer (3Z,5E)-Dien-1-in-Einheit hergestellt. Schlüsselschritte in ihrer Synthese waren immer die RBRV-Sequenz zum Aufbau der Z,E-Dien-Einheit, die Transformation des Esters in ein terminales Alkin sowie die CADIOT-CHODKIEWICZ-Kupplung zum Aufbau unsymmetrischer Polyine. Alle sechs Polyacetylene wurden zum ersten Mal in einer Totalsynthese synthetisiert. Drei Polyacetylene wurden ausgehend von (S)-Butantriol enantiomerenrein dargestellt. Anhand ihrer Drehwerte konnte eine Revision der von YAO und Mitarbeitern vorgenommen Zuordnung der Absolutkonfiguration der Naturstoffe vorgenommen werden.
Universitäten erbringen wohlfahrtsfördernde Leistungen für die Gesellschaft, insbesondere indem sie Studierende ausbilden, über Forschung neues Wissen erzeugen sowie den Wissens- und Technologietransfer in Wirtschaft und Gesellschaft hinein betreiben. Die Erbringung dieser Leistungen wird ermöglicht durch eine größtenteils öffentliche Finanzierung, die nicht nur in Zeiten wirtschaftlicher Krisen und Spargebote gerne hinterfragt wird. Die Politik ist daher ebenso wie die Hochschulen gut beraten, die Mittelzuweisungen immer wieder neu zu legitimieren. Die vorliegende Studie untersucht die sozioökonomischen Effekte der Universität Potsdam und schließt so vorhandene Informationslücken. Die Autoren zeigen, dass auch indirekte und unerwartete Effekte eine große Rolle spielen können, was die Wirkung einer Universität auf Wirtschaft und Wohlstand angeht.
Robust appraisals of climate impacts at different levels of global-mean temperature increase are vital to guide assessments of dangerous anthropogenic interference with the climate system. The 2015 Paris Agreement includes a two-headed temperature goal: "holding the increase in the global average temperature to well below 2 degrees C above pre-industrial levels and pursuing efforts to limit the temperature increase to 1.5 degrees C". Despite the prominence of these two temperature limits, a comprehensive overview of the differences in climate impacts at these levels is still missing. Here we provide an assessment of key impacts of climate change at warming levels of 1.5 degrees C and 2 degrees C, including extreme weather events, water availability, agricultural yields, sea-level rise and risk of coral reef loss. Our results reveal substantial differences in impacts between a 1.5 degrees C and 2 degrees C warming that are highly relevant for the assessment of dangerous anthropogenic interference with the climate system. For heat-related extremes, the additional 0.5 degrees C increase in global-mean temperature marks the difference between events at the upper limit of present-day natural variability and a new climate regime, particularly in tropical regions. Similarly, this warming difference is likely to be decisive for the future of tropical coral reefs. In a scenario with an end-of-century warming of 2 degrees C, virtually all tropical coral reefs are projected to be at risk of severe degradation due to temperature-induced bleaching from 2050 onwards. This fraction is reduced to about 90% in 2050 and projected to decline to 70% by 2100 for a 1.5 degrees C scenario. Analyses of precipitation-related impacts reveal distinct regional differences and hot-spots of change emerge. Regional reduction in median water availability for the Mediterranean is found to nearly double from 9% to 17% between 1.5 degrees C and 2 degrees C, and the projected lengthening of regional dry spells increases from 7 to 11%. Projections for agricultural yields differ between crop types as well as world regions. While some (in particular high-latitude) regions may benefit, tropical regions like West Africa, South-East Asia, as well as Central and northern South America are projected to face substantial local yield reductions, particularly for wheat and maize. Best estimate sea-level rise projections based on two illustrative scenarios indicate a 50cm rise by 2100 relative to year 2000-levels for a 2 degrees C scenario, and about 10 cm lower levels for a 1.5 degrees C scenario. In a 1.5 degrees C scenario, the rate of sea-level rise in 2100 would be reduced by about 30% compared to a 2 degrees C scenario. Our findings highlight the importance of regional differentiation to assess both future climate risks and different vulnerabilities to incremental increases in global-mean temperature. The article provides a consistent and comprehensive assessment of existing projections and a good basis for future work on refining our understanding of the difference between impacts at 1.5 degrees C and 2 degrees C warming.
Services that operate over the Internet are under constant threat of being exposed to fraudulent use. Maintaining good user experience for legitimate users often requires the classification of entities as malicious or legitimate in order to initiate countermeasures. As an example, inbound email spam filters decide for spam or non-spam. They can base their decision on both the content of each email as well as on features that summarize prior emails received from the sending server. In general, discriminative classification methods learn to distinguish positive from negative entities. Each decision for a label may be based on features of the entity and related entities. When labels of related entities have strong interdependencies---as can be assumed e.g. for emails being delivered by the same user---classification decisions should not be made independently and dependencies should be modeled in the decision function. This thesis addresses the formulation of discriminative classification problems that are tailored for the specific demands of the following three Internet security applications. Theoretical and algorithmic solutions are devised to protect an email service against flooding of user inboxes, to mitigate abusive usage of outbound email servers, and to protect web servers against distributed denial of service attacks.
In the application of filtering an inbound email stream for unsolicited emails, utilizing features that go beyond each individual email's content can be valuable. Information about each sending mail server can be aggregated over time and may help in identifying unwanted emails. However, while this information will be available to the deployed email filter, some parts of the training data that are compiled by third party providers may not contain this information. The missing features have to be estimated at training time in order to learn a classification model. In this thesis an algorithm is derived that learns a decision function that integrates over a distribution of values for each missing entry. The distribution of missing values is a free parameter that is optimized to learn an optimal decision function.
The outbound stream of emails of an email service provider can be separated by the customer IDs that ask for delivery. All emails that are sent by the same ID in the same period of time are related, both in content and in label. Hijacked customer accounts may send batches of unsolicited emails to other email providers, which in turn might blacklist the sender's email servers after detection of incoming spam emails. The risk of being blocked from further delivery depends on the rate of outgoing unwanted emails and the duration of high spam sending rates. An optimization problem is developed that minimizes the expected cost for the email provider by learning a decision function that assigns a limit on the sending rate to customers based on the each customer's email stream.
Identifying attacking IPs during HTTP-level DDoS attacks allows to block those IPs from further accessing the web servers. DDoS attacks are usually carried out by infected clients that are members of the same botnet and show similar traffic patterns. HTTP-level attacks aim at exhausting one or more resources of the web server infrastructure, such as CPU time. If the joint set of attackers cannot increase resource usage close to the maximum capacity, no effect will be experienced by legitimate users of hosted web sites. However, if the additional load raises the computational burden towards the critical range, user experience will degrade until service may be unavailable altogether. As the loss of missing one attacker depends on block decisions for other attackers---if most other attackers are detected, not blocking one client will likely not be harmful---a structured output model has to be learned. In this thesis an algorithm is developed that learns a structured prediction decoder that searches the space of label assignments, guided by a policy.
Each model is evaluated on real-world data and is compared to reference methods. The results show that modeling each classification problem according to the specific demands of the task improves performance over solutions that do not consider the constraints inherent to an application.
Recombination of free charge is a key process limiting the performance of solar cells. For low mobility materials, such as organic semiconductors, the kinetics of non-geminate recombination (NGR) is strongly linked to the motion of charges. As these materials possess significant disorder, thermalization of photogenerated carriers in the inhomogeneously broadened density of state distribution is an unavoidable process. Despite its general importance, knowledge about the kinetics of NGR in complete organic solar cells is rather limited. We employ time delayed collection field (TDCF) experiments to study the recombination of photogenerated charge in the high-performance polymer:fullerene blend PCDTBT:PCBM. NGR in the bulk of this amorphous blend is shown to be highly dispersive, with a continuous reduction of the recombination coefficient throughout the entire time scale, until all charge carriers have either been extracted or recombined. Rapid, contact-mediated recombination is identified as an additional loss channel, which, if not properly taken into account, would erroneously suggest a pronounced field dependence of charge generation. These findings are in stark contrast to the results of TDCF experiments on photovoltaic devices made from ordered blends, such as P3HT:PCBM, where non-dispersive recombination was proven to dominate the charge carrier dynamics under application relevant conditions.
DNA origami nanostructures are a versatile tool to arrange metal nanostructures and other chemical entities with nanometer precision. In this way gold nanoparticle dimers with defined distance can be constructed, which can be exploited as novel substrates for surface enhanced Raman scattering (SERS). We have optimized the size, composition and arrangement of Au/Ag nanoparticles to create intense SERS hot spots, with Raman enhancement up to 1010, which is sufficient to detect single molecules by Raman scattering. This is demonstrated using single dye molecules (TAMRA and Cy3) placed into the center of the nanoparticle dimers. In conjunction with the DNA origami nanostructures novel SERS substrates are created, which can in the future be applied to the SERS analysis of more complex biomolecular targets, whose position and conformation within the SERS hot spot can be precisely controlled.
Surface-enhanced Raman scattering (SERS) is a promising tool to obtain rich chemical information about analytes at trace levels. However, in order to perform selective experiments on individual molecules, two fundamental requirements have to be fulfilled. On the one hand, areas with high local field enhancement, so-called “hot spots”, have to be created by positioning the supporting metal surfaces in close proximity to each other. In most cases hot spots are formed in the gap between adjacent metal nanoparticles (NPs). On the other hand, the analyte has to be positioned directly in the hot spot in order to profit from the highest signal amplification. The use of DNA origami substrates provides both, the arrangement of AuNPs with nm precision as well as the ability to bind analyte molecules at predefined positions. Consequently, the present cumulative doctoral thesis aims at the development of a novel SERS substrate based on a DNA origami template. To this end, two DNA-functionalized gold nanoparticles (AuNPs) are attached to one DNA origami substrate resulting in the formation of a AuNP dimer and thus in a hot spot within the corresponding gap. The obtained structures are characterized by correlated atomic force microscopy (AFM) and SERS imaging which allows for the combination of structural and chemical information.
Initially, the proof-of principle is presented which demonstrates the potential of the novel approach. It is shown that the Raman signal of 15 nm AuNPs coated with dye-modified DNA
(dye: carboxytetramethylrhodamine (TAMRA)) is significantly higher for AuNP dimers arranged on a DNA origami platform in comparison to single AuNPs. Furthermore, by attaching single TAMRA molecules in the hot spot between two 5 nm AuNPs and optimizing the size of the AuNPs by electroless gold deposition, SERS experiments at the few-molecule level are presented. The initially used DNA origami-AuNPs design is further optimized in many respects. On the one hand, larger AuNPs up to a diameter of 60 nm are used which are additionally treated with a silver enhancement solution to obtain Au-Ag-core-shell NPs. On the other hand, the arrangement of both AuNPs is altered to improve the position of the dye molecule within the hot spot as well as to decrease the gap size between the two particles. With the optimized design the detection of single dye molecules (TAMRA and cyanine 3 (Cy3)) by means of SERS is demonstrated. Quantitatively, enhancement factors up to 10^10 are estimated which is sufficiently high to detect single dye molecules.
In the second part, the influence of graphene as an additional component of the SERS substrate is investigated. Graphene is a two-dimensional material with an outstanding combination of electronical, mechanical and optical properties. Here, it is demonstrated that
single layer graphene (SLG) replicates the shape of underlying non-modified DNA origami
substrates very well, which enables the monitoring of structural alterations by AFM imaging.
In this way, it is shown that graphene encapsulation significantly increases the structural
stability of bare DNA origami substrates towards mechanical force and prolonged exposure
to deionized water.
Furthermore, SLG is used to cover DNA origami substrates which are functionalized with a
40 nm AuNP dimer. In this way, a novel kind of hybrid material is created which exhibits
several advantages compared to the analogue non-covered SERS substrates. First, the fluorescence background of dye molecules that are located in between the AuNP surface and SLG is efficiently reduced. Second, the photobleaching rate of the incorporated dye molecules is decreased up to one order of magnitude. Third, due to the increased photostability of the investigated dye molecules, the performance of polarization-dependent series measurements on individual structures is enabled. This in turn reveals extensive information about the dye molecules in the hot spot as well as about the strain induced within the graphene lattice.
Although SLG can significantly influence the SERS substrate in the aforementioned ways, all
those effects are strongly related to the extent of contact with the underlying AuNP dimer.
Dokumentarische Kunstwerke
(2016)
Das vorliegende Werk ist das Ergebnis der 3. Woche des Russischen Rechts an der Juristischen Fakultät der Universität Potsdam. Namhafte Wissenschaftlerinnen und Wissenschaftler der Moskauer Staatlichen Juristischen Universität O. E. Kutafin hielten Vorträge zum Völkerrecht, Verfassungs- und Staatsangehörigkeitsrecht, Bürgerlichen Recht, Unternehmens- und Gesellschaftsrecht, Finanzrecht und Bankrecht. Das russische Recht befindet sich nach dem Ende der Sowjetunion im Wandel. Die Beiträge zeugen vom hohen Stand der Jurisprudenz an der Moskauer Staatlichen Juristischen Universität O. E. Kutafin. Die Wochen des Russischen Rechts tragen dazu bei, das Recht der Russischen Föderation bei uns in Deutschland bekannt zu machen und rechtsvergleichend zur Diskussion zu stellen.
Dropping Out or Keeping Up?
(2016)
The aim of this study was to examine how automatic evaluations of exercising (AEE) varied according to adherence to an exercise program. Eighty-eight participants (24.98 years ± 6.88; 51.1% female) completed a Brief-Implicit Association Task assessing their AEE, positive and negative associations to exercising at the beginning of a 3-month exercise program. Attendance data were collected for all participants and used in a cluster analysis of adherence patterns. Three different adherence patterns (52 maintainers, 16 early dropouts, 20 late dropouts; 40.91% overall dropouts) were detected using cluster analyses. Participants from these three clusters differed significantly with regard to their positive and negative associations to exercising before the first course meeting (η2p = 0.07). Discriminant function analyses revealed that positive associations to exercising was a particularly good discriminating factor. This is the first study to provide evidence of the differential impact of positive and negative associations on exercise behavior over the medium term. The findings contribute to theoretical understanding of evaluative processes from a dual-process perspective and may provide a basis for targeted interventions.
Drugs as instruments
(2016)
Neuroenhancement (NE) is the non-medical use of psychoactive substances to produce a subjective enhancement in psychological functioning and experience. So far empirical investigations of individuals' motivation for NE however have been hampered by the lack of theoretical foundation. This study aimed to apply drug instrumentalization theory to user motivation for NE. We argue that NE should be defined and analyzed from a behavioral perspective rather than in terms of the characteristics of substances used for NE. In the empirical study we explored user behavior by analyzing relationships between drug options (use over-the-counter products, prescription drugs, illicit drugs) and postulated drug instrumentalization goals (e.g., improved cognitive performance, counteracting fatigue, improved social interaction). Questionnaire data from 1438 university students were subjected to exploratory and confirmatory factor analysis to address the question of whether analysis of drug instrumentalization should be based on the assumption that users are aiming to achieve a certain goal and choose their drug accordingly or whether NE behavior is more strongly rooted in a decision to try or use a certain drug option. We used factor mixture modeling to explore whether users could be separated into qualitatively different groups defined by a shared "goal X drug option" configuration. Our results indicate, first, that individuals decisions about NE are eventually based on personal attitude to drug options (e.g., willingness to use an over-the-counter product but not to abuse prescription drugs) rather than motivated by desire to achieve a specific goal (e.g., fighting tiredness) for which different drug options might be tried. Second, data analyses suggested two qualitatively different classes of users. Both predominantly used over-the-counter products, but "neuroenhancers" might be characterized by a higher propensity to instrumentalize over-the-counter products for virtually all investigated goals whereas "fatigue-fighters" might be inclined to use over-the-counter products exclusively to fight fatigue. We believe that psychological investigations like these are essential, especially for designing programs to prevent risky behavior.
Duldung und Diskriminierung
(2016)
Proteins are amphiphilic and adsorb at liquid interfaces. Therefore, they can be efficient stabilizers of foams and emulsions. β-lactoglobulin (BLG) is one of the most widely studied proteins due to its major industrial applications, in particular in food technology.
In the present work, the influence of different bulk concentration, solution pH and ionic strength on the dynamic and equilibrium pressures of BLG adsorbed layers at the solution/tetradecane (W/TD) interface has been investigated. Dynamic interfacial pressure (Π) and interfacial dilational elastic modulus (E’) of BLG solutions for various concentrations at three different pH values of 3, 5 and 7 at a fixed ionic strength of 10 mM and for a selected fixed concentration at three different ionic strengths of 1 mM, 10 mM and 100 mM are measured by Profile Analysis Tensiometer PAT-1 (SINTERFACE Technologies, Germany). A quantitative data analysis requires additional consideration of depletion due to BLG adsorption at the interface at low protein bulk concentrations. This fact makes experiments more efficient when oil drops are studied in the aqueous protein solutions rather than solution drops formed in oil. On the basis of obtained experimental data, concentration dependencies and the effect of solution pH on the protein surface activity was qualitatively analysed. In the presence of 10 mM buffer, we observed that generally the adsorbed amount is increasing with increasing BLG bulk concentration for all three pH values. The adsorption kinetics at pH 5 result in the highest Π values at any time of adsorption while it exhibits a less active behaviour at pH 3.
Since the experimental data have not been in a good agreement with the classical diffusion controlled model due to the conformational changes which occur when the protein molecules get in contact with the hydrophobic oil phase in order to adapt to the interfacial environment, a new theoretical model is proposed here. The adsorption kinetics data were analysed with the newly proposed model, which is the classical diffusion model but modified by assuming an additional change in the surface activity of BLG molecules when adsorbing at the interface. This effect can be expressed through the adsorption activity constant in the corresponding equation of state. The dilational visco-elasticity of the BLG adsorbed interfacial layers is determined from measured dynamic interfacial tensions during sinusoidal drop area variations. The interfacial tension responses to these harmonic drop oscillations are interpreted with the same thermodynamic model which is used for the corresponding adsorption isotherm.
At a selected BLG concentration of 2×10-6 mol/l, the influence of the ionic strength using different buffer concentration of 1, 10 and 100 mM on the interfacial pressure was studied. It is affected weakly at pH 5, whereas it has a strong impact by increasing buffer concentration at pH 3 and 7. In conclusion, the structure formation of BLG adsorbed layer in the early stage of adsorption at the W/TD interface is similar to those of the solution/air (W/A) surface. However, the equation of state at the W/TD interface provides an adsorption activity constant which is almost two orders of magnitude higher than that for the solution/air surface.
At the end of this work, a new experimental tool called Drop and Bubble Micro Manipulator DBMM (SINTERFACE Technologies, Germany) has been introduced to study the stability of protein covered bubbles against coalescence. Among the available protocols the lifetime between the moment of contact and coalescence of two contacting bubble is determined for different BLG concentrations. The adsorbed amount of BLG is determined as a function of time and concentration and correlates with the observed coalescence behaviour of the contacting bubbles.
Dynamics of mantle plumes
(2016)
Mantle plumes are a link between different scales in the Earth’s mantle: They are an important part of large-scale mantle convection, transporting material and heat from the core-mantle boundary to the surface, but also affect processes on a smaller scale, such as melt generation and transport and surface magmatism. When they reach the base of the lithosphere, they cause massive magmatism associated with the generation of large igneous provinces, and they can be related to mass extinction events (Wignall, 2001) and continental breakup (White and McKenzie, 1989).
Thus, mantle plumes have been the subject of many previous numerical modelling studies (e.g. Farnetani and Richards, 1995; d’Acremont et al., 2003; Lin and van Keken, 2005; Sobolev et al., 2011; Ballmer et al., 2013). However, complex mechanisms, such as the development and implications of chemical heterogeneities in plumes, their interaction with mid-ocean ridges and global mantle flow, and melt ascent from the source region to the surface are still not very well understood; and disagreements between observations and the predictions of classical plume models have led to a challenge of the plume concept in general (Czamanske et al., 1998; Anderson, 2000; Foulger, 2011). Hence, there is a need for more sophisticated models that can explain the underlying physics, assess which properties and processes are important, explain how they cause the observations visible at the Earth’s surface and provide a link between the different scales.
In this work, integrated plume models are developed that investigate the effect of dense recycled oceanic crust on the development of mantle plumes, plume–ridge interaction under the influence of global mantle flow and melting and melt migration in form of two-phase flow.
The presented analysis of these models leads to a new, updated picture of mantle plumes: Models considering a realistic depth-dependent density of recycled oceanic crust and peridotitic mantle material show that plumes with excess temperatures of up to 300 K can transport up to 15% of recycled oceanic crust through the whole mantle. However, due to the high density of recycled crust, plumes can only advance to the base of the lithosphere directly if they have high excess temperatures, high plume volumes and the lowermost mantle is subadiabatic, or plumes rise from the top or edges of thermo-chemical piles. They might only cause minor surface uplift, and instead of the classical head–tail structure, these low-buoyancy plumes are predicted to be broad features in the lower mantle with much less pronounced plume heads. They can form a variety of shapes and regimes, including primary plumes directly advancing to the base of the lithosphere, stagnating plumes, secondary plumes rising from the core–mantle boundary or a pool of eclogitic material in the upper mantle and failing plumes. In the upper mantle, plumes are tilted and deflected by global mantle flow, and the shape, size and stability of the melting region is influenced by the distance from nearby plate boundaries, the speed of the overlying plate and the movement of the plume tail arriving from the lower mantle. Furthermore, the structure of the lithosphere controls where hot material is accumulated and melt is generated. In addition to melting in the plume tail at the plume arrival position, hot plume material flows upwards towards opening rifts, towards mid-ocean ridges and towards other regions of thinner lithosphere, where it produces additional melt due to decompression. This leads to the generation of either broad ridges of thickened magmatic crust or the separation into multiple thinner lines of sea mount chains at the surface. Once melt is generated within the plume, it influences its dynamics, lowering the viscosity and density, and while it rises the melt volume is increased up to 20% due to decompression. Melt has the tendency to accumulate at the top of the plume head, forming diapirs and initiating small-scale convection when the plume reaches the base of the lithosphere. Together with the introduced unstable, high-density material produced by freezing of melt, this provides an efficient mechanism to thin the lithosphere above plume heads.
In summary, this thesis shows that mantle plumes are more complex than previously considered, and linking the scales and coupling the physics of different processes occurring in mantle plumes can provide insights into how mantle plumes are influenced by chemical heterogeneities, interact with the lithosphere and global mantle flow, and are affected by melting and melt migration. Including these complexities in geodynamic models shows that plumes can also have broad plume tails, might produce only negligible surface uplift, can generate one or several volcanic island chains in interaction with a mid–ocean ridge, and can magmatically thin the lithosphere.
Solar-like stars maintain their magnetic fields thanks to a dynamo mechanism. The Babcock-Leighton dynamo is one possible dynamo that has the particularity to require magnetic flux tubes. Magnetic flux tubes are assumed to form at the bottom of the convective zone and rise buoyantly to the surface. A delayed dynamo model has been suggested, where the delay accounts for the rise time of the magnetic flux tubes; a time, that has been ignored by former studies.
The present thesis aims to study the applicability of the flux tube/Babcock-Leighton dynamo to other stars. To do so, we attempt to constrain the rise time of magnetic flux tubes thanks to the first fully compressible MHD simulations of rising magnetic flux tubes in stratified rotating spherical shells.
Such simulations are limited to an unrealistic parameter space, therefore, a scaling relation is required to scale the results to realistic physical regimes. We extended earlier works on 2D scaling relations and derived a general scaling law valid for both 2D and 3D. We then carried out two large series of numerical experiments and verified that the scaling law we have derived indeed applies to the fully non-linear case. It allowed us to extract a constraint for the rise time of magnetic flux tubes that is valid for any solar-like star. We finally introduced this constraint to a delayed dynamo model.
By carrying out simulations of a mean-field, delayed, flux tube/Babcock-Leighton dynamo, we were able to identify a new dynamo regime resulting from the delay. This regime requires delays about an entire cycle and exhibits subequipartition magnetic activity. Revealing this new regime shows that even for long delays the flux tube/Babcock-Leighton dynamo can still deliver non-decaying solutions and remains a good candidate for a wide range of solar-like stars.
Infants start learning the prosodic properties of their native language before 12 months, as shown by the emergence of a trochaic bias in English-learning infants between 6 and 9 months (Jusczyk et al., 1993), and in German-learning infants between 4 and 6 months (Huhle et al., 2009, 2014), while French-learning infants do not show a bias at 6 months (Hohle et al., 2009). This language-specific emergence of a trochaic bias is supported by the fact that English and German are languages with trochaic predominance in their lexicons, while French is a language with phrase-final lengthening but lacking lexical stress. We explored the emergence of a trochaic bias in bilingual French/German infants, to study whether the developmental trajectory would be similar to monolingual infants and whether amount of relative exposure to the two languages has an impact on the emergence of the bias. Accordingly, we replicated Hohle et al. (2009) with 24 bilingual 6-month-olds learning French and German simultaneously. All infants had been exposed to both languages for 30 to 70% of the time from birth. Using the Head Preference Procedure, infants were presented with two lists of stimuli, one made up of several occurrences of the pseudoword /GAba/ with word-initial stress (trochaic pattern), the second one made up of several occurrences of the pseudoword /gaBA/ with word-final stress (iambic pattern). The stimuli were recorded by a native German female speaker. Results revealed that these French/German bilingual 6-month olds have a trochaic bias (as evidenced by a preference to listen to the trochaic pattern). Hence, their listening preference is comparable to that of monolingual German-learning 6-month-olds, but differs from that of monolingual French-learning 6-month-olds who did not show any preference (Noble et al., 2009). Moreover, the size of the trochaic bias in the bilingual infants was not correlated with their amount of exposure to German. The present results thus establish that the development of a trochaic bias in simultaneous bilinguals is not delayed compared to monolingual German-learning infants (Hohle et al., 2009) and is rather independent of the amount of exposure to German relative to French.
Earthquakes deform Earth's surface, building long-lasting topographic features and contributing to landscape and mountain formation.
However, seismic waves produced by earthquakes may also destabilize hillslopes, leading to large amounts of soil and bedrock moving downslope. Moreover, static deformation and shaking are suspected to damage the surface bedrock and therefore alter its future properties, affecting hydrological and erosional dynamics. Thus, earthquakes participate both in mountain building and stimulate directly or indirectly their erosion. Moreover, the impact of earthquakes on hillslopes has important implications for the amount of sediment and organic matter delivered to rivers, and ultimately to oceans, during episodic catastrophic seismic crises, the magnitude of life and property losses associated with landsliding, the perturbation and recovery of landscape properties after shaking, and the long term topographic evolution of mountain belts. Several of these aspects have been addressed recently through individual case studies but additional data compilation as well as theoretical or numerical modelling are required to tackle these issues in a more systematic and rigorous manner.
This dissertation combines data compilation of earthquake characteristics, landslide mapping, and seismological data interpretation with physically-based modeling in order to address how earthquakes impact on erosional processes and landscape evolution. Over short time scales (10-100 s) and intermediate length scales (10 km), I have attempted to improve our understanding and ability to predict the amount of landslide debris triggered by seismic shaking in epicentral areas. Over long time scales (1-100 ky) and across a mountain belt (100 km) I have modeled the competition between erosional unloading and building of topography associated with earthquakes. Finally, over intermediate time scales (1-10 y) and at the hillslope scale (0.1-1 km) I have collected geomorphological and seismological data that highlight persistent effects of earthquakes on landscape properties and behaviour.
First, I compiled a database on earthquakes that produced significant landsliding, including an estimate of the total landslide volume and area, and earthquake characteristics such as seismic moment and source depth. A key issue is the accurate conversion of landslide maps into volume estimates. Therefore I also estimated how amalgamation - when mapping errors lead to the bundling of multiple landslide into a single polygon - affects volume estimates from various earthquake-induced landslide inventories and developed an algorithm to automatically detect this artifact. The database was used to test a physically-based prediction of the total landslide area and volume caused by earthquakes, based on seismological scaling relationships and a statistical description of the landscape properties. The model outperforms empirical fits in accuracy, with 25 out of 40 cases well predicted, and allows interpretation of many outliers in physical terms. Apart from seismological complexities neglected by the model I found that exceptional rock strength properties or antecedent conditions may explain most outliers.
Second, I assessed the geomorphic effects of large earthquakes on landscape dynamics by surveying the temporal evolution of precipitation-normalized landslide rate. I found strongly elevated landslide rates following earthquakes that progressively recover over 1 to 4 years, indicating that regolith strength drops and recovers. The relaxation is clearly non-linear for at least one case, and does not seem to correlate with coseismic landslide reactivation, water table level increase or tree root-system recovery. I suggested that shallow bedrock is damaged by the earthquake and then heals on annual timescales. Such variations in ground strength must be translated into shallow subsurface seismic velocities that are increasingly surveyed with ambient seismic noise correlations. With seismic noise autocorrelation I computed the seismic velocity in the epicentral areas of three earthquakes where I constrained a change in landslide rate. We found similar recovery dynamics and timescales, suggesting that seismic noise correlation techniques could be further developed to meaningfully assess ground strength variations for landscape dynamics. These two measurements are also in good agreement with the temporal dynamics of post-seismic surface displacement measured by GPS. This correlation suggests that the surface healing mechanism may be driven by tectonic deformation, and that the surface regolith and fractured bedrock may behave as a granular media that slowly compacts as it is sheared or vibrated.
Last, I compared our model of earthquake-induced landsliding with a standard formulation of surface deformation caused by earthquakes to understand which parameters govern the competition between the building and destruction of topography caused by earthquakes. In contrast with previous studies I found that very large (Mw>8) earthquakes always increase the average topography, whereas only intermediate (Mw ~ 7) earthquakes in steep landscapes may reduce topography. Moreover, I illustrated how the net effect of earthquakes varies with depth or landscape steepness implying a complex and ambivalent role through the life of a mountain belt. Further I showed that faults producing a Gutenberg-Richter distribution of earthquake sizes, will limit topography over a larger range of fault sizes than faults producing repeated earthquakes with a characteristic size.
Editorial
(2016)
A series of new sulfobetaine methacrylates, including nitrogen-containing saturated heterocycles, was synthesised by systematically varying the substituents of the zwitterionic group. Radical polymerisation via the RAFT (reversible addition–fragmentation chain transfer) method in trifluoroethanol proceeded smoothly and was well controlled, yielding polymers with predictable molar masses. Molar mass analysis and control of the end-group fidelity were facilitated by end-group labeling with a fluorescent dye. The polymers showed distinct thermo-responsive behaviour of the UCST (upper critical solution temperature) type in an aqueous solution, which could not be simply correlated to their molecular structure via an incremental analysis of the hydrophilic and hydrophobic elements incorporated within them. Increasing the spacer length separating the ammonium and the sulfonate groups of the zwitterion moiety from three to four carbons increased the phase transition temperatures markedly, whereas increasing the length of the spacer separating the ammonium group and the carboxylate ester group on the backbone from two to three carbons provoked the opposite effect. Moreover, the phase transition temperatures of the analogous polyzwitterions decreased in the order dimethylammonio > morpholinio > piperidinio alkanesulfonates. In addition to the basic effect of the polymers’ precise molecular structure, the concentration and the molar mass dependence of the phase transition temperatures were studied. Furthermore, we investigated the influence of added low molar mass salts on the aqueous-phase behaviour for sodium chloride and sodium bromide as well as sodium and ammonium sulfate. The strong effects evolved in a complex way with the salt concentration. The strength of these effects depended on the nature of the anion added, increasing in the order sulfate < chloride < bromide, thus following the empirical Hofmeister series. In contrast, no significant differences were observed when changing the cation, i.e. when adding sodium or ammonium sulfate.
A majority of studies documented a reduced ankle muscle activity, particularly of the peroneus longus muscle (PL), in patients with functional ankle instability (FI). It is considered valid that foot orthoses as well as sensorimotor training have a positive effect on ankle muscle activity in healthy individuals and those with lower limb overuse injuries or flat arched feet (reduced reaction time by sensorimotor exercises; increased ankle muscle amplitude by orthoses use). However, the acute- and long-term influence of foot orthoses on ankle muscle activity in individuals with FI is unknown.
AIMS: The present thesis addressed (1a) acute- and (1b) long-term effects of foot orthoses compared to sensorimotor training on ankle muscle activity in patients with FI. (2) Further, it was investigated if the orthosis intervention group demonstrate higher ankle muscle activity by additional short-term use of a measurement in-shoe orthosis (compared to short-term use of “shoe only”) after intervention. (3) As prerequisite, it was evaluated if ankle muscle activity can be tested reliably and (4) if this differs between healthy individuals and those with FI.
METHODS: Three intervention groups (orthosis group [OG], sensorimotor training group [SMTG], control group [CG]), consisting of both, healthy individuals and those with FI, underwent one longitudinal investigation (randomised controlled trial). Throughout 6 weeks of intervention, OG wore an in-shoe orthosis with a specific “PL stimulation module”, whereas SMTG conducted home-based exercises. CG served to measure test-retest reliability of ankle muscle activity (PL, M. tibialis anterior [TA] and M. gastrocnemius medialis [GM]). Pre- and post-intervention, ankle muscle activity (EMG amplitude) was recorded during “normal” unperturbed (NW) and perturbed walking (PW) on a split-belt treadmill (stimulus 200 ms post initial heel contact [IC]) as well as during side cutting (SC), each while wearing “shoes only” and additional measurement in-shoe orthoses (randomized order). Normalized RMS values (100% MVC, mean±SD) were calculated pre- (100-50 ms) and post (200-400 ms) - IC.
RESULTS: (3) Test-retest reliability showed a high range of values in healthy individuals and those with FI. (4) Compared to healthy individuals, patients with FI demonstrated lower PL pre-activity during SC, however higher PL pre-activity for NW and PW. (1a) Acute orthoses use did not influence ankle muscle activity. (1b) For most conditions, sensorimotor training was more effective in individuals with FI than long-term orthotic intervention (increased: PL and GM pre-activity and TA reflex-activity for NW, PL pre-activity and TA, PL and GM reflex-activity for SC, PL reflex-activity for PW). However, prolonged orthoses use was more beneficial in terms of an increase in GM pre-activity during SC. For some conditions, long-term orthoses intervention was as effective as sensorimotor training for individuals with FI (increased: PL pre-activity for PW, TA pre-activity for SC, PL and GM reflex-activity for NW). Prolonged orthoses use was also advantageous in healthy individuals (increased: PL and GM pre-activity for NW and PW, PL pre-activity for SC, TA and PL reflex-activity for NW, PL and GM reflex-activity for PW). (2) The orthosis intervention group did not present higher ankle muscle activity by the additional short-term use of a measurement in-shoe orthosis at re-test after intervention.
CONCLUSION: High variations of reproducibility reflect physiological variability in muscle activity during gait and therefore deemed acceptable. The main findings confirm the presence of sensorimotor long-term effects of specific foot orthoses in healthy individuals (primary preventive effect) and those with FI (therapeutic effect). Neuromuscular compensatory feedback- as well as anticipatory feedforward adaptation mechanism to prolonged orthoses use, specifically of the PL muscle, underpins the key role of PL in providing essential dynamic ankle joint stability. Due to its advantages over sensorimotor training (positive subjective feedback in terms of comfort, time-and-cost-effectiveness), long-term foot orthoses use can be recommended as an applicable therapy alternative in the treatment of FI. Long-term effect of foot orthoses in a population with FI must be validated in a larger sample size with longer follow-up periods to substantiate the generalizability of the existing outcomes.
Studies investigating the effect of increasing CO2 levels on the phosphorus cycle in natural waters are lacking although phosphorus often controls phytoplankton development in many aquatic systems. The aim of our study was to analyse effects of elevated CO2 levels on phosphorus pool sizes and uptake. The phosphorus dynamic was followed in a CO2-manipulation mesocosm experiment in the Storfjarden (western Gulf of Finland, Baltic Sea) in summer 2012 and was also studied in the surrounding fjord water. In all mesocosms as well as in surface waters of Storfjarden, dissolved organic phosphorus (DOP) concentrations of 0.26aEuro-+/- aEuro-0.03 and 0.23aEuro-+/- aEuro-0.04aEuro-A mu molaEuro-L-1, respectively, formed the main fraction of the total P-pool (TP), whereas phosphate (PO4) constituted the lowest fraction with mean concentration of 0.15aEuro-A +/- aEuro-0.02 in the mesocosms and 0.17aEuro-A +/- aEuro-0.07aEuro-A mu molaEuro-L-1 in the fjord. Transformation of PO4 into DOP appeared to be the main pathway of PO4 turnover. About 82aEuro-% of PO4 was converted into DOP whereby only 18aEuro-% of PO4 was transformed into particulate phosphorus (PP). PO4 uptake rates measured in the mesocosms ranged between 0.6 and 3.9aEuro-nmolaEuro-L(-1)aEuro-h(-1). About 86aEuro-% of them was realized by the size fraction < aEuro-3aEuro-A mu m. Adenosine triphosphate (ATP) uptake revealed that additional P was supplied from organic compounds accounting for 25-27aEuro-% of P provided by PO4 only. CO2 additions did not cause significant changes in phosphorus (P) pool sizes, DOP composition, and uptake of PO4 and ATP when the whole study period was taken into account. However, significant short-term effects were observed for PO4 and PP pool sizes in CO2 treatments > aEuro-1000aEuro-A mu atm during periods when phytoplankton biomass increased. In addition, we found significant relationships (e.g., between PP and Chl a) in the untreated mesocosms which were not observed under high fCO(2) conditions. Consequently, it can be hypothesized that the relationship between PP formation and phytoplankton growth changed with CO2 elevation. It can be deduced from the results, that visible effects of CO2 on P pools are coupled to phytoplankton growth when the transformation of PO4 into POP was stimulated. The transformation of PO4 into DOP on the other hand does not seem to be affected. Additionally, there were some indications that cellular mechanisms of P regulation might be modified under CO2 elevation changing the relationship between cellular constituents.
Background
It has been demonstrated that core strength training is an effective means to enhance trunk muscle strength (TMS) and proxies of physical fitness in youth. Of note, cross-sectional studies revealed that the inclusion of unstable elements in core strengthening exercises produced increases in trunk muscle activity and thus provide potential extra training stimuli for performance enhancement. Thus, utilizing unstable surfaces during core strength training may even produce larger performance gains. However, the effects of core strength training using unstable surfaces are unresolved in youth. This randomized controlled study specifically investigated the effects of core strength training performed on stable surfaces (CSTS) compared to unstable surfaces (CSTU) on physical fitness in school-aged children.
Methods
Twenty-seven (14 girls, 13 boys) healthy subjects (mean age: 14 ± 1 years, age range: 13–15 years) were randomly assigned to a CSTS (n = 13) or a CSTU (n = 14) group. Both training programs lasted 6 weeks (2 sessions/week) and included frontal, dorsal, and lateral core exercises. During CSTU, these exercises were conducted on unstable surfaces (e.g., TOGU© DYNAIR CUSSIONS, THERA-BAND© STABILITY TRAINER).
Results
Significant main effects of Time (pre vs. post) were observed for the TMS tests (8-22%, f = 0.47-0.76), the jumping sideways test (4-5%, f = 1.07), and the Y balance test (2-3%, f = 0.46-0.49). Trends towards significance were found for the standing long jump test (1-3%, f = 0.39) and the stand-and-reach test (0-2%, f = 0.39). We could not detect any significant main effects of Group. Significant Time x Group interactions were detected for the stand-and-reach test in favour of the CSTU group (2%, f = 0.54).
Conclusions
Core strength training resulted in significant increases in proxies of physical fitness in adolescents. However, CSTU as compared to CSTS had only limited additional effects (i.e., stand-and-reach test). Consequently, if the goal of training is to enhance physical fitness, then CSTU has limited advantages over CSTS.
Effects of data and model simplification on the results of a wetland water resource management model
(2016)
This paper presents the development of a wetland water balance model for use in a large river basin with many different wetlands. The basic model was primarily developed for a single wetland with a complex water management system involving large amounts of specialized input data and water management details. The aim was to simplify the model structure and to use only commonly available data as input for the model, with the least possible loss of accuracy. Results from different variants of the model and data adaptation were tested against results from a detailed model. This shows that using commonly available data and unifying and simplifying the input data is tolerable up to a certain level. The simplification of the model has greater effects on the evaluated water balance components than the data adaptation. Because this simplification was necessary for large-scale use, we suggest that, for reasons of comparability, simpler models should always be applied with uniform data bases for large regions, though these should only be moderately simplified. Further, we recommend using these simplified models only for large-scale comparisons and using more specific, detailed models for investigations on smaller scales.
Difficulties with object relative clauses (ORC), as compared to subject relative clauses (SR), are widely attested across different languages, both in adults and in children. This SR-ORC asymmetry is reduced, or even eliminated, when the embedded constituent in the ORC is a pronoun, rather than a lexical noun phrase. The studies included in this thesis were designed to explore under what circumstances the pronoun facilitation occurs; whether all pronouns have the same effect; whether SRs are also affected by embedded pronouns; whether children perform like adults on such structures; and whether performance is related to cognitive abilities such as memory or grammatical knowledge. Several theoretical approaches that explain the pronoun facilitation in relative clauses are evaluated. The experimental data have been collected in three languages–German, Italian and Hebrew–stemming from both children and adults.
In the German study (Chapter 2), ORCs with embedded 1st- or 3rd-person pronouns are compared to ORCs with an embedded lexical noun phrase. Eye-movement data from 5-year-old children show that the 1st-person pronoun facilitates processing, but not the 3rd-person pronoun. Moreover, children’s performance is modulated by additive effects of their memory and grammatical skills. In the Italian study (Chapter 3), the 1st-person pronoun advantage over the 3rd-person pronoun is tested in ORCs and SRs that display a similar word order. Eye-movement data from 5-year-olds and adult controls and reading times data from adults are pitted against the outcome of a corpus analysis, showing that the 1st-/3rd-person pronoun asymmetry emerges in the two relative clause types to an equal extent. In the Hebrew study (Chapter 4), the goal is to test the effect of a special kind of pronoun–a non-referential arbitrary subject pronoun–on ORC comprehension, in the light of potential confounds in previous studies that used this pronoun. Data from a referent-identification task with 4- to 5-year-olds indicate that, when the experimental material is controlled, the non-referential pronoun does not necessarily facilitate ORC comprehension. Importantly, however, children have even more difficulties when the embedded constituent is a referential pronoun. The non-referentiality / referentiality asymmetry is emphasized by the relation between children’s performance on the experimental task and their memory skills.
Together, the data presented in this thesis indicate that sentence processing is not only driven by structural (or syntactic) factors, but also by discourse-related ones, like pronouns’ referential properties or their discourse accessibility mechanism, which is defined as the level of ease or difficulty with which referents of pronouns are identified and retrieved from the discourse model. Although independent in essence, these structural and discourse factors can in some cases interact in a way that affects sentence processing. Moreover, both types of factors appear to be strongly related to memory. The data also support the idea that, from early on, children are sensitive to the same factors that affect adults’ sentence processing, and that the processing strategies of both populations are qualitatively similar.
In sum, this thesis suggests that a comprehensive theory of human sentence processing needs to account for effects that are due to both structural and discourse-related factors, which operate as a function of memory capacity.
Rhythm perception is assumed to be guided by a domain-general auditory principle, the Iambic/Trochaic Law, stating that sounds varying in intensity are grouped as strong-weak, and sounds varying in duration are grouped as weak-strong. Recently, Bhatara et al. (2013) showed that rhythmic grouping is influenced by native language experience, French listeners having weaker grouping preferences than German listeners. This study explores whether L2 knowledge and musical experience also affect rhythmic grouping. In a grouping task, French late learners of German listened to sequences of coarticulated syllables varying in either intensity or duration. Data on their language and musical experience were obtained by a questionnaire. Mixed-effect model comparisons showed influences of musical experience as well as L2 input quality and quantity on grouping preferences. These results imply that adult French listeners' sensitivity to rhythm can be enhanced through L2 and musical experience.
Previous research on the interplay between static manual postures and visual attention revealed enhanced visual selection near the hands (near-hand effect). During active movements there is also superior visual performance when moving toward compared to away from the stimulus (direction effect). The "modulated visual pathways" hypothesis argues that differential involvement of magno- and parvocellular visual processing streams causes the near-hand effect. The key finding supporting this hypothesis is an increase in temporal and a reduction in spatial processing in near-hand space (Gozli et al., 2012). Since this hypothesis has, so far, only been tested with static hand postures, we provide a conceptual replication of Gozli et al.'s (2012) result with moving hands, thus also probing the generality of the direction effect. Participants performed temporal or spatial gap discriminations while their right hand was moving below the display. In contrast to Gozli et al (2012), temporal gap discrimination was superior at intermediate and not near hand proximity. In spatial gap discrimination, a direction effect without hand proximity effect suggests that pragmatic attentional maps overshadowed temporal/spatial processing biases for far/near-hand space.
About a quarter of anthropogenic CO2 emissions are currently taken up by the oceans, decreasing seawater pH. We performed a mesocosm experiment in the Baltic Sea in order to investigate the consequences of increasing CO2 levels on pelagic carbon fluxes. A gradient of different CO2 scenarios, ranging from ambient (similar to 370 mu atm) to high (similar to 1200 mu atm), were set up in mesocosm bags (similar to 55m(3)). We determined standing stocks and temporal changes of total particulate carbon (TPC), dissolved organic carbon (DOC), dissolved inorganic carbon (DIC), and particulate organic carbon (POC) of specific plankton groups. We also measured carbon flux via CO2 exchange with the atmosphere and sedimentation (export), and biological rate measurements of primary production, bacterial production, and total respiration. The experiment lasted for 44 days and was divided into three different phases (I: t0-t16; II: t17-t30; III: t31-t43). Pools of TPC, DOC, and DIC were approximately 420, 7200, and 25 200 mmol Cm-2 at the start of the experiment, and the initial CO2 additions increased the DIC pool by similar to 7% in the highest CO2 treatment. Overall, there was a decrease in TPC and increase of DOC over the course of the experiment. The decrease in TPC was lower, and increase in DOC higher, in treatments with added CO2. During phase I the estimated gross primary production (GPP) was similar to 100 mmol C m(-2) day(-1), from which 75-95% was respired, similar to 1% ended up in the TPC (including export), and 5-25% was added to the DOC pool. During phase II, the respiration loss increased to similar to 100% of GPP at the ambient CO2 concentration, whereas respiration was lower (85-95% of GPP) in the highest CO2 treatment. Bacterial production was similar to 30% lower, on average, at the highest CO2 concentration than in the controls during phases II and III. This resulted in a higher accumulation of DOC and lower reduction in the TPC pool in the elevated CO2 treatments at the end of phase II extending throughout phase III. The "extra" organic carbon at high CO2 remained fixed in an increasing biomass of small-sized plankton and in the DOC pool, and did not transfer into large, sinking aggregates. Our results revealed a clear effect of increasing CO2 on the carbon budget and mineralization, in particular under nutrient limited conditions. Lower carbon loss processes (respiration and bacterial remineralization) at elevated CO2 levels resulted in higher TPC and DOC pools than ambient CO2 concentration. These results highlight the importance of addressing not only net changes in carbon standing stocks but also carbon fluxes and budgets to better disentangle the effects of ocean acidification.
Effects of resistance training in youth athletes on muscular fitness and athletic performance
(2016)
During the stages of long-term athlete development (LTAD), resistance training (RT) is an important means for (i) stimulating athletic development, (ii) tolerating the demands of long-term training and competition, and (iii) inducing long-term health promoting effects that are robust over time and track into adulthood. However, there is a gap in the literature with regards to optimal RT methods during LTAD and how RT is linked to biological age. Thus, the aims of this scoping review were (i) to describe and discuss the effects of RT on muscular fitness and athletic performance in youth athletes, (ii) to introduce a conceptual model on how to appropriately implement different types of RT within LTAD stages, and (iii) to identify research gaps from the existing literature by deducing implications for future research. In general, RT produced small -to -moderate effects on muscular fitness and athletic performance in youth athletes with muscular strength showing the largest improvement. Free weight, complex, and plyometric training appear to be well -suited to improve muscular fitness and athletic performance. In addition, balance training appears to be an important preparatory (facilitating) training program during all stages of LTAD but particularly during the early stages. As youth athletes become more mature, specificity, and intensity of RT methods increase. This scoping review identified research gaps that are summarized in the following and that should be addressed in future studies: (i) to elucidate the influence of gender and biological age on the adaptive potential following RT in youth athletes (especially in females), (ii) to describe RT protocols in more detail (i.e., always report stress and strain based parameters), and (iii) to examine neuromuscular and tendomuscular adaptations following RT in youth athletes.
Effektivität frühzeitiger Interventionen zur Prävention von Lese- und Rechtschreibschwierigkeiten
(2016)
Die vorliegende Studie beschäftigt sich mit der Förderung der Lese- und Schreibkompetenz in der Anfangsphase des Schriftspracherwerbs. Ziel der Untersuchung ist die Erprobung und Evaluierung frühzeitiger, diagnosegeleiteter Interventionen zur Prävention von Lese- und Rechtschreibschwierigkeiten. Im Unterschied zu vielen Studien in diesem Bereich werden alle Maßnahmen unter realen schulischen Bedingungen im Rahmen des Erstlese- und Schreibunterrichts durch die Klassenlehrer selbst durchgeführt, wobei diese von der Autorin unterstützt und begleitet werden. Förder- und Prozessdiagnose sowie Elemente diagnosegeleiteter Förderung werden aus Theorien und Forschungslage abgeleitet und zu einem Interventionsset verbunden. Die Effektivität der evidenzbasierten Maßnahmen wird durch Parallelgruppenvergleiche überprüft.
An der empirischen Untersuchung nahmen insgesamt 25 Schulklassen mit 560 Erstklässlern teil, geteilt in Versuchs- und Kontrollgruppe. Mit der Eingangsdiagnose am Schulbeginn wurden Voraussetzungen für den Schriftspracherwerb erhoben und mit der Evaluierungsdiagnose am Ende der ersten Schulstufe entwicklungsadäquate schriftsprachliche Kompetenzen auf der Wortebene überprüft. Zusätzlich erfasst wurden internale und externale Einflussfaktoren, deren Wirkung in der statistischen Auswertung berücksichtigt wurde. Alle Datenerhebungen wurden in Versuchs- und Kontrollgruppe durchgeführt, während die evidenzbasierten Treatments nur in der Versuchsgruppe stattfanden.
Die Auswertung bestätigt mit signifikanten Ergebnissen den engen Zusammenhang zwischen der Phonologischen Bewusstheit zu Beginn des Schriftspracherwerbs und der Lese- und Rechtschreibfähigkeit am Ende der ersten Schulstufe sowie zwischen Familiärer Literalität und Lesefertigkeit. Schriftsprachliche Vorkenntnisse weisen eine Tendenz zur Signifikanz hinsichtlich ihrer positiven Wirkung auf die Basale Lesefertigkeit auf. Eine höchst signifikante positive Wirkung auf die Basale Lesefertigkeit zeigt die Druckschrift als Ausgangsschrift.
Die Ergebnisse deuten auf eine Überlegenheit vorschulischer präliteraler Fertigkeiten hinsichtlich ihrer Wirkung auf die Lese- und Rechtschreibfertigkeit am Ende der ersten Schulstufe gegenüber Fördermaßnahmen unter realen schulischen Bedingungen hin. Die positive Wirkung einer unverbundenen Ausgangsschrift auf den Leseerwerb betont die Wichtigkeit der Wahl der Ausgangsschrift. Im frühen Schriftspracherwerb sollte die Druckschrift für das Lesen und Schreiben verwendet werden.