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A contemporary challenge in Ecology and Evolutionary Biology is to anticipate the fate of populations of organisms in the context of a changing world. Climate change and landscape changes due to anthropic activities have been of major concern in the contemporary history. Organisms facing these threats are expected to respond by local adaptation (i.e., genetic changes or phenotypic plasticity) or by shifting their distributional range (migration). However, there are limits to their responses. For example, isolated populations will have more difficulties in developing adaptive innovations by means of genetic changes than interconnected metapopulations. Similarly, the topography of the environment can limit dispersal opportunities for crawling organisms as compared to those that rely on wind. Thus, populations of species with different life history strategy may differ in their ability to cope with changing environmental conditions. However, depending on the taxon, empirical studies investigating organisms’ responses to environmental change may become too complex, long and expensive; plus, complications arising from dealing with endangered species. In consequence, eco-evolutionary modeling offers an opportunity to overcome these limitations and complement empirical studies, understand the action and limitations of underlying mechanisms, and project into possible future scenarios. In this work I take a modeling approach and investigate the effect and relative importance of evolutionary mechanisms (including phenotypic plasticity) on the ability for local adaptation of populations with different life strategy experiencing climate change scenarios. For this, I performed a review on the state of the art of eco-evolutionary Individual-Based Models (IBMs) and identify gaps for future research. Then, I used the results from the review to develop an eco-evolutionary individual-based modeling tool to study the role of genetic and plastic mechanisms in promoting local adaption of populations of organisms with different life strategies experiencing scenarios of climate change and environmental stochasticity. The environment was simulated through a climate variable (e.g., temperature) defining a phenotypic optimum moving at a given rate of change. The rate of change was changed to simulate different scenarios of climate change (no change, slow, medium, rapid climate change). Several scenarios of stochastic noise color resembling different climatic conditions were explored. Results show that populations of sexual species will rely mainly on standing genetic variation and phenotypic plasticity for local adaptation. Population of species with relatively slow growth rate (e.g., large mammals) – especially those of small size – are the most vulnerable, particularly if their plasticity is limited (i.e., specialist species). In addition, whenever organisms from these populations are capable of adaptive plasticity, they can buffer fitness losses in reddish climatic conditions. Likewise, whenever they can adjust their plastic response (e.g., bed-hedging strategy) they will cope with bluish environmental conditions as well. In contrast, life strategies of high fecundity can rely on non-adaptive plasticity for their local adaptation to novel environmental conditions, unless the rate of change is too rapid. A recommended management measure is to guarantee interconnection of isolated populations into metapopulations, such that the supply of useful genetic variation can be increased, and, at the same time, provide them with movement opportunities to follow their preferred niche, when local adaptation becomes problematic. This is particularly important for bluish and reddish climatic conditions, when the rate of change is slow, or for any climatic condition when the level of stress (rate of change) is relatively high.
Das Preußische Erbrecht in der Judikatur des Berliner Obertribunals in den Jahren 1836 bis 1865
(2019)
Die Dissertation befasst sich mit dem Allgemeinen Preußischen Landrecht von 1794 und der hierzu ergangenen Rechtsprechung des Berliner Obertribunals. Im Fokus der Untersuchung stehen die erbrechtlichen Regelungen des Landrechts und deren Anwendung sowie Auslegung in der Judikatur des höchsten preußischen Gerichts. Der Forschungsgegenstand ergibt sich aus dem im Landrecht kodifizierten speziellen Gesetzesverständnisses. Nach diesem sollte die Gesetzesauslegung durch die Rechtsprechung auf ein Minimum, nämlich die Auslegung allein anhand des Wortlauts der Regelung reduziert werden, um dem absolutistischen Regierungsanspruch der preußischen Monarchen, namentlich Friedrich des Großen, hinreichend Rechnung zu tragen. In diesem Kontext wird der Frage nachgegangen, inwieweit das preußische Obertribunal das im Landrecht statuierte „Auslegungsverbot“ beachtet hat und in welchen Fällen sich das Gericht von der Vorgabe emanzipierte und weitere Auslegungsmethoden anwendete und sich so eine unabhängige Rechtsprechung entwickeln konnte.
Die Arbeit gliedert sich in drei Hauptabschnitte. Im Anschluss an die Einleitung, in der zunächst die rechtshistorische Bedeutung des Landrechts und des Erbrechts sowie der Untersuchungsgegenstand umrissen werden, folgt die Darstellung der Entstehungsgeschichte des Landrechts und des Berliner Obertribunals.
Hieran schließt sich in einem dritten Abschnitt eine Analyse der erbrechtlichen Vorschriften des Landrechts an. In dieser wird auf die Entstehungsgeschichte der verschiedenen erbrechtlichen Institute wie beispielsweise der gesetzlichen und gewillkürten Erbfolge, dem Pflichtteilsrecht etc., unter Berücksichtigung des zeitgenössischen wissenschaftlichen Diskurses eingegangen.
Im vierten Abschnitt geht es um die Judikate des Berliner Obertribunals aus den Jahren 1836-1865 in denen die zuvor dargestellten erbrechtlichen Regelungen entscheidungserheblich waren. Dabei wird der Forschungsfrage, inwieweit das Obertribunal das im Landrecht statuierte Auslegungsverbot beachtet hat und in welchen Fällen es von diesem abwich bzw. weitere Auslegungsmethoden anwendete, konkret nachgegangen wird. Insgesamt werden 26 Entscheidungen des Obertribunals unter dem Aspekt der Auslegungspraxis, der Kontinuität und der Beschleunigung der Rechtsprechung analysiert und ausgewertet.
Binaries play an important role in observational and theoretical astrophysics. Since the mass and the chemical composition are key ingredients for stellar evolution, high-resolution spectroscopy is an important and necessary tool to derive those parameters to high confidence in binaries. This involves carefully measured orbital motion by the determination of radial velocity (RV) shifts and sophisticated techniques to derive the abundances of elements within the stellar atmosphere.
A technique superior to conventional cross-correlation methods to determine RV shifts in known as spectral disentangling. Hence, a major task of this thesis was the design of a sophisticated software package for this approach. In order to investigate secondary effects, such as flux and line-profile variations, imprinting changes on the spectrum the behavior of spectral disentangling on such variability is a key to understand the derived values, to improve them, and to get information about the variability itself. Therefore, the spectral disentangling code presented in this thesis and available to the community combines multiple advantages: separation of the spectra for detailed chemical analysis, derivation of orbital elements, derivation of individual RVs in order to investigate distorted systems (either by third body interaction or relativistic effects), the suppression of telluric contaminations, the derivation of variability, and the possibility to apply the technique to eclipsing binaries (important for orbital inclination) or in general to systems that undergo flux-variations.
This code in combination with the spectral synthesis codes MOOG and SME was used in order to derive the carbon 12C/13C isotope ratio (CIR) of the benchmark binary Capella. The observational result will be set into context with theoretical evolution by the use of MESA models and resolves the discrepancy of theory and observations existing since the first measurement of Capella's CIR in 1976.
The spectral disentangling code has been made available to the community and its applicability to completely different behaving systems, Wolf-Rayet stars, have also been investigated and resulted in a published article.
Additionally, since this technique relies strongly on data quality, continues development of scientific instruments to achieve best observational data is of great importance in observational astrophysics. That is the reason why there has also been effort in astronomical instrumentation during the work on this thesis.
Plasmonic metal nanostructures can be tuned to efficiently interact with light, converting the photons into energetic charge carriers and heat. Therefore, the plasmonic nanoparticles such as gold and silver nanoparticles act as nano-reactors, where the molecules attached to their surfaces benefit from the enhanced electromagnetic field along with the generated energetic charge carriers and heat for possible chemical transformations. Hence, plasmonic chemistry presents metal nanoparticles as a unique playground for chemical reactions on the nanoscale remotely controlled by light. However, defining the elementary concepts behind these reactions represents the main challenge for understanding their mechanism in the context of the plasmonically assisted chemistry.
Surface-enhanced Raman scattering (SERS) is a powerful technique employing the plasmon-enhanced electromagnetic field, which can be used for probing the vibrational modes of molecules adsorbed on plasmonic nanoparticles. In this cumulative dissertation, I use SERS to probe the dimerization reaction of 4-nitrothiophenol (4-NTP) as a model example of plasmonic chemistry. I first demonstrate that plasmonic nanostructures such as gold nanotriangles and nanoflowers have a high SERS efficiency, as evidenced by probing the vibrations of the rhodamine dye R6G and the 4-nitrothiophenol 4-NTP. The high signal enhancement enabled the measurements of SERS spectra with a short acquisition time, which allows monitoring the kinetics of chemical reactions in real time.
To get insight into the reaction mechanism, several time-dependent SERS measurements of the 4-NTP have been performed under different laser and temperature conditions. Analysis of the results within a mechanistic framework has shown that the plasmonic heating significantly enhances the reaction rate, while the reaction is probably initiated by the energetic electrons. The reaction was shown to be intensity-dependent, where a certain light intensity is required to drive the reaction. Finally, first attempts to scale up the plasmonic catalysis have been performed showing the necessity to achieve the reaction threshold intensity. Meanwhile, the induced heat needs to quickly dissipate from the reaction substrate, since otherwise the reactants and the reaction platform melt. This study might open the way for further work seeking the possibilities to quickly dissipate the plasmonic heat generated during the reaction and therefore, scaling up the plasmonic catalysis.
The current thesis examined how second language (L2) speakers of German predict upcoming input during language processing. Early research has shown that the predictive abilities of L2 speakers relative to L1 speakers are limited, resulting in the proposal of the Reduced Ability to Generate Expectations (RAGE) hypothesis. Considering that prediction is assumed to facilitate language processing in L1 speakers and probably plays a role in language learning, the assumption that L1/L2 differences can be explained in terms of different processing mechanisms is a particularly interesting approach. However, results from more recent studies on the predictive processing abilities of L2 speakers have indicated that the claim of the RAGE hypothesis is too broad and that prediction in L2 speakers could be selectively limited. In the current thesis, the RAGE hypothesis was systematically put to the test.
In this thesis, German L1 and highly proficient late L2 learners of German with Russian as L1 were tested on their predictive use of one or more information sources that exist as cues to sentence interpretation in both languages, to test for selective limits. The results showed that, in line with previous findings, L2 speakers can use the lexical-semantics of verbs to predict the upcoming noun. Here the level of prediction was more systematically controlled for than in previous studies by using verbs that restrict the selection of upcoming nouns to the semantic category animate or inanimate. Hence, prediction in L2 processing is possible. At the same time, this experiment showed that the L2 group was slower/less certain than the L1 group. Unlike previous studies, the experiment on case marking demonstrated that L2 speakers can use this morphosyntactic cue for prediction. Here, the use of case marking was tested by manipulating the word order (Dat > Acc vs. Acc > Dat) in double object constructions after a ditransitive verb. Both the L1 and the L2 group showed a difference between the two word order conditions that emerged within the critical time window for an anticipatory effect, indicating their sensitivity towards case. However, the results for the post-critical time window pointed to a higher uncertainty in the L2 group, who needed more time to integrate incoming information and were more affected by the word order variation than the L1 group, indicating that they relied more on surface-level information. A different cue weighting was also found in the experiment testing whether participants predict upcoming reference based on implicit causality information. Here, an additional child L1 group was tested, who had a lower memory capacity than the adult L2 group, as confirmed by a digit span task conducted with both learner groups. Whereas the children were only slightly delayed compared to the adult L1 group and showed the same effect of condition, the L2 speakers showed an over-reliance on surface-level information (first-mention/subjecthood). Hence, the pattern observed resulted more likely from L1/L2 differences than from resource deficits.
The reviewed studies and the experiments conducted show that L2 prediction is affected by a range of factors. While some of the factors can be attributed to more individual differences (e.g., language similarity, slower processing) and can be interpreted by L2 processing accounts assuming that L1 and L2 processing are basically the same, certain limits are better explained by accounts that assume more substantial L1/L2 differences. Crucially, the experimental results demonstrate that the RAGE hypothesis should be refined: Although prediction as a fast-operating mechanism is likely to be affected in L2 speakers, there is no indication that prediction is the dominant source of L1/L2 differences. The results rather demonstrate that L2 speakers show a different weighting of cues and rely more on semantic and surface-level information to predict as well as to integrate incoming information.
For millennia, humans have affected landscapes all over the world. Due to horizontal expansion, agriculture plays a major role in the process of fragmentation. This process is caused by a substitution of natural habitats by agricultural land leading to agricultural landscapes. These landscapes are characterized by an alternation of agriculture and other land use like forests. In addition, there are landscape elements of natural origin like small water bodies. Areas of different land use are beside each other like patches, or fragments. They are physically distinguishable which makes them look like a patchwork from an aerial perspective. These fragments are each an own ecosystem with conditions and properties that differ from their adjacent fragments. As open systems, they are in exchange of information, matter and energy across their boundaries. These boundary areas are called transition zones. Here, the habitat properties and environmental conditions are altered compared to the interior of the fragments. This changes the abundance and the composition of species in the transition zones, which in turn has a feedback effect on the environmental conditions.
The literature mainly offers information and insights on species abundance and composition in forested transition zones. Abiotic effects, the gradual changes in energy and matter, received less attention. In addition, little is known about non-forested transition zones. For example, the effects on agricultural yield in transition zones of an altered microclimate, matter dynamics or different light regimes are hardly researched or understood. The processes in transition zones are closely connected with altered provisioning and regulating ecosystem services. To disentangle the mechanisms and to upscale the effects, models can be used.
My thesis provides insights into these topics: literature was reviewed and a conceptual framework for the quantitative description of gradients of matter and energy in transition zones was introduced. The results of measurements of environmental gradients like microclimate, aboveground biomass and soil carbon and nitrogen content are presented that span from within the forest into arable land. Both the measurements and the literature review could not validate a transition zone of 100 m for abiotic effects. Although this value is often reported and used in the literature, it is likely to be smaller.
Further, the measurements suggest that on the one hand trees in transition zones are smaller compared to those in the interior of the fragments, while on the other hand less biomass was measured in the arable lands’ transition zone. These results support the hypothesis that less carbon is stored in the aboveground biomass in transition zones. The soil at the edge (zero line) between adjacent forest and arable land contains more nitrogen and carbon content compared to the interior of the fragments. One-year measurements in the transition zone also provided evidence that microclimate is different compared to the fragments’ interior.
To predict the possible yield decreases that transition zones might cause, a modelling approach was developed. Using a small virtual landscape, I modelled the effect of a forest fragment shading the adjacent arable land and the effects of this on yield using the MONICA crop growth model. In the transition zone yield was less compared to the interior due to shading. The results of the simulations were upscaled to the landscape level and exemplarily calculated for the arable land of a whole region in Brandenburg, Germany.
The major findings of my thesis are: (1) Transition zones are likely to be much smaller than assumed in the scientific literature; (2) transition zones aren’t solely a phenomenon of forested ecosystems, but significantly extend into arable land as well; (3) empirical and modelling results show that transition zones encompass biotic and abiotic changes that are likely to be important to a variety of agricultural landscape ecosystem services.
Emotions are a central element of human experience. They occur with high frequency in everyday life and play an important role in decision making. However, currently there is no consensus among researchers on what constitutes an emotion and on how emotions should be investigated. This dissertation identifies three problems of current emotion research: the problem of ground truth, the problem of incomplete constructs and the problem of optimal representation. I argue for a focus on the detailed measurement of emotion manifestations with computer-aided methods to solve these problems. This approach is demonstrated in three research projects, which describe the development of methods specific to these problems as well as their application to concrete research questions.
The problem of ground truth describes the practice to presuppose a certain structure of emotions as the a priori ground truth. This determines the range of emotion descriptions and sets a standard for the correct assignment of these descriptions. The first project illustrates how this problem can be circumvented with a multidimensional emotion perception paradigm which stands in contrast to the emotion recognition paradigm typically employed in emotion research. This paradigm allows to calculate an objective difficulty measure and to collect subjective difficulty ratings for the perception of emotional stimuli. Moreover, it enables the use of an arbitrary number of emotion stimuli categories as compared to the commonly used six basic emotion categories. Accordingly, we collected data from 441 participants using dynamic facial expression stimuli from 40 emotion categories. Our findings suggest an increase in emotion perception difficulty with increasing actor age and provide evidence to suggest that young adults, the elderly and men underestimate their emotion perception difficulty. While these effects were predicted from the literature, we also found unexpected and novel results. In particular, the increased difficulty on the objective difficulty measure for female actors and observers stood in contrast to reported findings. Exploratory analyses revealed low relevance of person-specific variables for the prediction of emotion perception difficulty, but highlighted the importance of a general pleasure dimension for the ease of emotion perception.
The second project targets the problem of incomplete constructs which relates to vaguely defined psychological constructs on emotion with insufficient ties to tangible manifestations. The project exemplifies how a modern data collection method such as face tracking data can be used to sharpen these constructs on the example of arousal, a long-standing but fuzzy construct in emotion research. It describes how measures of distance, speed and magnitude of acceleration can be computed from face tracking data and investigates their intercorrelations. We find moderate to strong correlations among all measures of static information on one hand and all measures of dynamic information on the other. The project then investigates how self-rated arousal is tied to these measures in 401 neurotypical individuals and 19 individuals with autism. Distance to the neutral face was predictive of arousal ratings in both groups. Lower mean arousal ratings were found for the autistic group, but no difference in correlation of the measures and arousal ratings could be found between groups. Results were replicated in a high autistic traits group consisting of 41 participants. The findings suggest a qualitatively similar perception of arousal for individuals with and without autism. No correlations between valence ratings and any of the measures could be found which emphasizes the specificity of our tested measures for the construct of arousal.
The problem of optimal representation refers to the search for the best representation of emotions and the assumption that there is a one-fits-all solution. In the third project we introduce partial least squares analysis as a general method to find an optimal representation to relate two high-dimensional data sets to each other. The project demonstrates its applicability to emotion research on the question of emotion perception differences between men and women. The method was used with emotion rating data from 441 participants and face tracking data computed on 306 videos. We found quantitative as well as qualitative differences in the perception of emotional facial expressions between these groups. We showed that women’s emotional perception systematically captured more of the variance in facial expressions. Additionally, we could show that significant differences exist in the way that women and men perceive some facial expressions which could be visualized as concrete facial expression sequences. These expressions suggest differing perceptions of masked and ambiguous facial expressions between the sexes. In order to facilitate use of the developed method by the research community, a package for the statistical environment R was written. Furthermore, to call attention to the method and its usefulness for emotion research, a website was designed that allows users to explore a model of emotion ratings and facial expression data in an interactive fashion.
Vom Monomer zum Glykopolymer
(2019)
Glykopolymere sind synthetische und natürlich vorkommende Polymere, die eine Glykaneinheit in der Seitenkette des Polymers tragen. Glykane sind durch die Glykan-Protein-Wechselwirkung verantwortlich für viele biologische Prozesse. Die Beteiligung der Glykanen in diesen biologischen Prozessen ermöglicht das Imitieren und Analysieren der Wechselwirkungen durch geeignete Modellverbindungen, z.B. der Glykopolymere. Dieses System der Glykan-Protein-Wechselwirkung soll durch die Glykopolymere untersucht und studiert werden, um die spezifische und selektive Bindung der Proteine an die Glykopolymere nachzuweisen. Die Proteine, die in der Lage sind, Kohlenhydratstrukturen selektiv zu binden, werden Lektine genannt.
In dieser Dissertationsarbeit wurden verschiedene Glykopolymere synthetisiert. Dabei sollte auf einen effizienten und kostengünstigen Syntheseweg geachtet werden.
Verschiedene Glykopolymere wurden durch funktionalisierte Monomere mit verschiedenen Zuckern, wie z.B. Mannose, Laktose, Galaktose oder N-Acetyl-Glukosamin als funktionelle Gruppe, hergestellt. Aus diesen funktionalisierten Glykomonomeren wurden über ATRP und RAFT-Polymerisation Glykopolymere synthetisiert.
Die erhaltenen Glykopolymere wurden in Diblockcopolymeren als hydrophiler Block angewendet und die Selbstassemblierung in wässriger Lösung untersucht. Die Polymere formten in wässriger Lösung Mizellen, bei denen der Zuckerblock an der Oberfläche der Mizellen sitzt. Die Mizellen wurden mit einem hydrophoben Fluoreszenzfarbstoff beladen, wodurch die CMC der Mizellenbildung bestimmt werden konnte.
Außerdem wurden die Glykopolymere als Oberflächenbeschichtung über „Grafting from“ mit SI-ATRP oder über „Grafting to“ auf verschiedene Oberflächen gebunden. Durch die glykopolymerbschichteten Oberflächen konnte die Glykan Protein Wechselwirkung über spektroskopische Messmethoden, wie SPR- und Mikroring Resonatoren untersucht werden. Hierbei wurde die spezifische und selektive Bindung der Lektine an die Glykopolymere nachgewiesen und die Bindungsstärke untersucht.
Die synthetisierten Glykopolymere könnten durch Austausch der Glykaneinheit für andere Lektine adressierbar werden und damit ein weites Feld an anderen Proteinen erschließen. Die bioverträglichen Glykopolymere wären alternativen für den Einsatz in biologischen Prozessen als Transporter von Medikamenten oder Farbstoffe in den Körper. Außerdem könnten die funktionalisierten Oberflächen in der Diagnostik zum Erkennen von Lektinen eingesetzt werden. Die Glykane, die keine selektive und spezifische Bindung zu Proteinen eingehen, könnten als antiadsorptive Oberflächenbeschichtung z.B. in der Zellbiologie eingesetzt werden.
This is a publication-based dissertation comprising three original research stud-ies (one published, one submitted and one ready for submission; status March 2019). The dissertation introduces a generic computer model as a tool to investigate the behaviour and population dynamics of animals in cyclic environments. The model is further employed for analysing how migratory birds respond to various scenarios of altered food supply under global change. Here, ecological and evolutionary time-scales are considered, as well as the biological constraints and trade-offs the individual faces, which ultimately shape response dynamics at the population level. Further, the effect of fine-scale temporal patterns in re-source supply are studied, which is challenging to achieve experimentally. My findings predict population declines, altered behavioural timing and negative carry-over effects arising in migratory birds under global change. They thus stress the need for intensified research on how ecological mechanisms are affected by global change and for effective conservation measures for migratory birds. The open-source modelling software created for this dissertation can now be used for other taxa and related research questions. Overall, this thesis improves our mechanistic understanding of the impacts of global change on migratory birds as one prerequisite to comprehend ongoing global biodiversity loss. The research results are discussed in a broader ecological and scientific context in a concluding synthesis chapter.
The fabrication of 1D nanostrands composed of stimuli responsive microgels has been shown in this work. Microgels are well known materials able to respond to various stimuli from outer environment. Since these microgels respond via a volume change to an external stimulus, a targeted mechanical response can be achieved. Through carefully choosing the right composition of the polymer matrix, microgels can be designed to react precisely to the targeted stimuli (e.g. drug delivery via pH and temperature changes, or selective contractions through changes in electrical current125).
In this work, it was aimed to create flexible nano-filaments which are capable of fast anisotropic contractions similar to muscle filaments. For the fabrication of such filaments or strands, nanostructured templates (PDMS wrinkles) were chosen due to a facile and low-cost fabrication and versatile tunability of their dimensions. Additionally, wrinkling is a well-known lithography-free method which enables the fabrication of nanostructures in a reproducible manner and with a high long-range periodicity.
In Chapter 2.1, it was shown for the first time that microgels as soft matter particles can be aligned to densely packed microgel arrays of various lateral dimensions. The alignment of microgels with different compositions (e.g. VCL/AAEM, NIPAAm, NIPAAm/VCL and charged microgels) was shown by using different assembly techniques (e.g. spin-coating, template confined molding). It was chosen to set one experimental parameter constant which was the SiOx surface composition of the templates and substrates (e.g. oxidized PDMS wrinkles, Si-wafers and glass slides). It was shown that the fabrication of nanoarrays was feasible with all tested microgel types. Although the microgels exhibited different deformability when aligned on a flat surface, they retained their thermo-responsivity and swelling behavior.
Towards the fabrication of 1D microgel strands interparticle connectivity was aspired. This was achieved via different cross-linking methods (i.e. cross-linking via UV-irradiation and host-guest complexation) discussed in Chapter 2.2. The microgel arrays created by different assembly methods and microgel types were tested for their cross-linking suitability. It was observed that NIPAAm based microgels cannot be cross-linked with UV light. Furthermore, it was found that these microgels exhibit a strong surface-particle-interaction and therefore could not be detached from the given substrates. In contrast to the latter, with VCL/AAEM based microgels it was possible to both UV cross-link them based on the keto-enol tautomerism of the AAEM copolymer, and to detach them from the substrate due to the lower adhesion energy towards SiOx surfaces. With VCL/AAEM microgels long, one-dimensional microgel strands could be re-dispersed in water for further analysis. It has also been shown that at least one lateral dimension of the free dispersed 1D microgel strands is easily controllable by adjusting the wavelength of the wrinkled template. For further work, only VCL/AAEM based microgels were used to focus on the main aim of this work, i.e. the fabrication of 1D microgel nanostrands.
As an alternative to the unspecific and harsh UV cross-linking, the host-guest complexation via diazobenzene cross-linkers and cyclodextrin hosts was explored. The idea behind this approach was to give means to a future construction kit-like approach by incorporation of cyclodextrin comonomers in a broad variety of particle systems (e.g. microgels, nanoparticles). For this purpose, VCL/AAEM microgels were copolymerized with different amounts of mono-acrylate functionalized β-cyclodextrin (CD). After successfully testing the cross-linking capability in solution, the cross-linking of aligned VCL/AAEM/CD microgels was tried. Although the cross-linking worked well, once the single arrays came into contact to each other, they agglomerated. As a reason for this behavior residual amounts of mono-complexed diazobenzene linkers were suspected. Thus, end-capping strategies were tried out (e.g. excess amounts of β-cyclodextrin and coverage with azobenzene functionalized AuNPs) but were unsuccessful. With deeper thought, entropy effects were taken into consideration which favor the release of complexed diazobenzene linker leading to agglomerations. To circumvent this entropy driven effect, a multifunctional polymer with 50% azobenzene groups (Harada polymer) was used. First experiments with this polymer showed promising results regarding a less pronounced agglomeration (Figure 77). Thus, this approach could be pursued in the future. In this chapter it was found out that in contrast to pearl necklace and ribbon like formations, particle alignment in zigzag formation provided the best compromise in terms of stability in dispersion (see Figure 44a and Figure 51) while maintaining sufficient flexibility.
For this reason, microgel strands in zigzag formation were used for the motion analysis described in Chapter 2.3. The aim was to observe the properties of unrestrained microgel strands in solution (e.g. diffusion behavior, rotational properties and ideally, anisotropic contraction after temperature increase). Initially, 1D microgel strands were manipulated via AFM in a liquid cell setup. It could be observed that the strands required a higher load force compared to single microgels to be detached from the surface. However, with the AFM it was not possible to detach the strands in a controllable manner but resulted in a complete removal of single microgel particles and a tearing off the strands from the surface, respectively. For this reason, to observe the motion behavior of unrestrained microgel strands in solution, confocal microscopy was used. Furthermore, to hinder an adsorption of the strands, it was found out that coating the surface of the substrates with a repulsive polymer film was beneficial. Confocal and wide-field microscopy videos showed that the microgel strands exhibit translational and rotational diffusive motion in solution without perceptible bending. Unfortunately, with these methods the detection of the anisotropic stimuli responsive contraction of the free moving microgel strands was not possible. To summarize, the flexibility of microgel strands is more comparable to the mechanical behavior of a semi flexible cable than to a yarn. The strands studied here consist of dozens or even hundreds of discrete submicron units strung together by cross-linking, having few parallels in nanotechnology.
With the insights gained in this work on microgel-surface interactions, in the future, a targeted functionalization of the template and substrate surfaces can be conducted to actively prevent unwanted microgel adsorption for a given microgel system (e.g. PVCL and polystyrene coating235). This measure would make the discussed alignment methods more diverse. As shown herein, the assembly methods enable a versatile microgel alignment (e.g. microgel meshes, double and triple strands). To go further, one could use more complex templates (e.g. ceramic rhombs and star shaped wrinkles (Figure 14) to expand the possibilities of microgel alignment and to precisely control their aspect ratios (e.g. microgel rods with homogeneous size distributions).