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A degree course in IT and business administration solely for women (FIW) has been offered since 2009 at the HTW Berlin – University of Applied Sciences. This contribution discusses student motivations for enrolling in such a women only degree course and gives details of our experience over recent years. In particular, the approach to attracting new female students is described and the composition of the intake is discussed. It is shown that the women-only setting together with other factors can attract a new clientele for computer science.
Achilles tendinopathy (AT) is a debilitating injury in athletes, especially for those engaged in repetitive stretch-shortening cycle activities. Clinical risk factors are numerous, but it has been suggested that altered biomechanics might be associated with AT. No systematic review has been conducted investigating these biomechanical alterations in specifically athletic populations. Therefore, the aim of this systematic review was to compare the lower-limb biomechanics of athletes with AT to athletically matched asymptomatic controls. Databases were searched for relevant studies investigating biomechanics during gait activities and other motor tasks such as hopping, isolated strength tasks, and reflex responses. Inclusion criteria for studies were an AT diagnosis in at least one group, cross-sectional or prospective data, at least one outcome comparing biomechanical data between an AT and healthy group, and athletic populations. Studies were excluded if patients had Achilles tendon rupture/surgery, participants reported injuries other than AT, and when only within-subject data was available.. Effect sizes (Cohen's d) with 95% confidence intervals were calculated for relevant outcomes. The initial search yielded 4,442 studies. After screening, twenty studies (775 total participants) were synthesised, reporting on a wide range of biomechanical outcomes. Females were under-represented and patients in the AT group were three years older on average. Biomechanical alterations were identified in some studies during running, hopping, jumping, strength tasks and reflex activity. Equally, several biomechanical variables studied were not associated with AT in included studies, indicating a conflicting picture. Kinematics in AT patients appeared to be altered in the lower limb, potentially indicating a pattern of “medial collapse”. Muscular activity of the calf and hips was different between groups, whereby AT patients exhibited greater calf electromyographic amplitudes despite lower plantar flexor strength. Overall, dynamic maximal strength of the plantar flexors, and isometric strength of the hips might be reduced in the AT group. This systematic review reports on several biomechanical alterations in athletes with AT. With further research, these factors could potentially form treatment targets for clinicians, although clinical approaches should take other contributing health factors into account. The studies included were of low quality, and currently no solid conclusions can be drawn.
Solar photocatalysis is the one of leading concepts of research in the current paradigm of sustainable chemical industry. For actual practical implementation of sunlight-driven catalytic processes in organic synthesis, a cheap, efficient, versatile and robust heterogeneous catalyst is necessary. Carbon nitrides are a class of organic semiconductors who are known to fulfill these requirements.
First, current state of solar photocatalysis in economy, industry and lab research is overviewed, outlining EU project funding, prospective synthetic and reforming bulk processes, small scale solar organic chemistry, and existing reactor designs and prototypes, concluding feasibility of the approach.
Then, the photocatalytic aerobic cleavage of oximes to corresponding aldehydes and ketones by anionic poly(heptazine imide) carbon nitride is discussed. The reaction provides a feasible method of deprotection and formation of carbonyl compounds from nitrosation products and serves as a convenient model to study chromoselectivity and photophysics of energy transfer in heterogeneous photocatalysis.
Afterwards, the ability of mesoporous graphitic carbon nitride to conduct proton-coupled electron transfer was utilized for the direct oxygenation of 1,3-oxazolidin-2-ones to corresponding 1,3-oxazlidine-2,4-diones. This reaction provides an easier access to a key scaffold of diverse types of drugs and agrochemicals.
Finally, a series of novel carbon nitrides based on poly(triazine imide) and poly(heptazine imide) structure was synthesized from cyanamide and potassium rhodizonate. These catalysts demonstrated a good performance in a set of photocatalytic benchmark reactions, including aerobic oxidation, dual nickel photoredox catalysis, hydrogen peroxide evolution and chromoselective transformation of organosulfur precursors.
Concluding, the scope of carbon nitride utilization for net-oxidative and net-neutral photocatalytic processes was expanded, and a new tunable platform for catalyst synthesis was discovered.
In this work, binding interactions between biomolecules were analyzed by a technique that is based on electrically controllable DNA nanolevers. The technique was applied to virus-receptor interactions for the first time. As receptors, primarily peptides on DNA nanostructures and antibodies were utilized. The DNA nanostructures were integrated into the measurement technique and enabled the presentation of the peptides in a controllable geometrical order. The number of peptides could be varied to be compatible to the binding sites of the viral surface proteins.
Influenza A virus served as a model system, on which the general measurability was demonstrated. Variations of the receptor peptide, the surface ligand density, the measurement temperature and the virus subtypes showed the sensitivity and applicability of the technology. Additionally, the immobilization of virus particles enabled the measurement of differences in oligovalent binding of DNA-peptide nanostructures to the viral proteins in their native environment.
When the coronavirus pandemic broke out in 2020, work on binding interactions of a peptide from the hACE2 receptor and the spike protein of the SARS-CoV-2 virus revealed that oligovalent binding can be quantified in the switchSENSE technology. It could also be shown that small changes in the amino acid sequence of the spike protein resulted in complete loss of binding. Interactions of the peptide and inactivated virus material as well as pseudo virus particles could be measured. Additionally, the switchSENSE technology was utilized to rank six antibodies for their binding affinity towards the nucleocapsid protein of SARS-CoV-2 for the development of a rapid antigen test device.
The technique was furthermore employed to show binding of a non-enveloped virus (adenovirus) and a virus-like particle (norovirus-like particle) to antibodies. Apart from binding interactions, the use of DNA origami levers with a length of around 50 nm enabled the switching of virus material. This proved that the technology is also able to size objects with a hydrodynamic diameter larger than 14 nm.
A theoretical work on diffusion and reaction-limited binding interactions revealed that the technique and the chosen parameters enable the determination of binding rate constants in the reaction-limited regime.
Overall, the applicability of the switchSENSE technique to virus-receptor binding interactions could be demonstrated on multiple examples. While there are challenges that remain, the setup enables the determination of affinities between viruses and receptors in their native environment. Especially the possibilities regarding the quantification of oligo- and multivalent binding interactions could be presented.
Recent research suggests that design thinking practices may foster the development of needed capabilities in new digitalised landscapes. However, existing publications represent individual contributions, and we lack a holistic understanding of the value of design thinking in a digital world. No review, to date, has offered a holistic retrospection of this research. In response, in this bibliometric review, we aim to shed light on the intellectual structure of multidisciplinary design thinking literature related to capabilities relevant to the digital world in higher education and business settings, highlight current trends and suggest further studies to advance theoretical and empirical underpinnings. Our study addresses this aim using bibliometric methods—bibliographic coupling and co-word analysis as they are particularly suitable for identifying current trends and future research priorities at the forefront of the research. Overall, bibliometric analyses of the publications dealing with the related topics published in the last 10 years (extracted from the Web of Science database) expose six trends and two possible future research developments highlighting the expanding scope of the design thinking scientific field related to capabilities required for the (more sustainable and human-centric) digital world. Relatedly, design thinking becomes a relevant approach to be included in higher education curricula and human resources training to prepare students and workers for the changing work demands. This paper is well-suited for education and business practitioners seeking to embed design thinking capabilities in their curricula and for design thinking and other scholars wanting to understand the field and possible directions for future research.
Desperados at Sea
(2023)
Pirates are fortune-seeking fighters at sea. Their exploits fire the imaginations of their victims and admirers, drawing a veil over individuals who rarely bear a real name and pursue their adventurous occupations as buccaneers, filibusters, freebooters, privateers, pirates, or corsairs. Piracy, corsairing, and contraband trade were epidemic among the Egyptians and the Phoenicians, the Greeks and the Vikings, the Spaniards and the Ottomans, the Muslims, and the Christians. And the Jews.
Twenty-four scientists met for the annual Auxological conference held at Krobielowice castle, Poland, to discuss the diverse influences of the environment and of social behavior on growth following last year’s focus on growth and public health concerns (Hermanussen et al., 2022b). Growth and final body size exhibit marked plastic responses to ecological conditions. Among the shortest are the pygmoid people of Rampasasa, Flores, Indonesia, who still live under most secluded insular conditions. Genetics and nutrition are usually considered responsible for the poor growth in many parts of this world, but evidence is accumulating on the prominent impact of social embedding on child growth. Secular trends not only in the growth of height, but also in body proportions, accompany the secular changes in the social, economic and political conditions, with major influences on the emotional and educational circumstances under which the children grow up (Bogin, 2021). Aspects of developmental tempo and aspects of sports were discussed, and the impact of migration by the example of women from Bangladesh who grew up in the UK. Child growth was considered in particular from the point of view of strategic adjustments of individual size within the network of its social group. Theoretical considerations on network characteristics were presented and related to the evolutionary conservation of growth regulating hypothalamic neuropeptides that have been shown to link behavior and physical growth in the vertebrate species. New statistical approaches were presented for the evaluation of short term growth measurements that permit monitoring child growth at intervals of a few days and weeks.
In the past decades, scholars and courts have paid considerable attention to the extraterritorial applicability of human rights treaties. By contrast, the extraterritorial application of constitutional rights has received comparable scholarly attention only in the United States. Specifically, there is a paucity of comparative research in this area, which contributes to the prevailing view that human rights law provides the proper framework under which domestic courts should examine extraterritoriality questions under constitutional law.
This article argues that domestic constitutional regimes and their judicial enforcers can and should provide an important counterweight to the deadlocked extraterritoriality debate at the international level. Using two case studies from Germany and the United States, it shows that domestic constitutional courts are sometimes better suited than treaty bodies to guard the normative values of human dignity and universality in an extraterritoriality context. This is most apparent in the case of Germany, which has a long tradition of integration into international multi-level governance systems and "bottom-up" resistance based on fundamental rights within such systems. Recent cases from the Federal Constitutional Court (Bundesverfassungsgericht) about the extraterritorial application of the Basic Law (Grundgesetz) to foreign intelligence gathering and climate change support this theory. However, an independent constitutional approach can also achieve some normative effects in domestic systems that are more isolated from the international human rights system. Thus, the US Supreme Court likewise used domestic constitutional doctrine to sidestep the American government's strictly territorial interpretation of the ICCPR and employ a functional approach to the extraterritorial applicability of fundamental rights in the case of detention of suspected terrorists in the Guantánamo Bay naval base.
The study of these two examples does not purport to be comprehensive or even representative of the world’s diverse array of constitutions and their relationships with international human rights law. However, the independent power of constitutional frameworks in these two disparate cases should all the more provide an impetus for increased comparative research into constitutional extraterritoriality regimes and their value for the project of human rights.
Earthquake modeling is the key to a profound understanding of a rupture. Its kinematics or dynamics are derived from advanced rupture models that allow, for example, to reconstruct the direction and velocity of the rupture front or the evolving slip distribution behind the rupture front. Such models are often parameterized by a lattice of interacting sub-faults with many degrees of freedom, where, for example, the time history of the slip and rake on each sub-fault are inverted. To avoid overfitting or other numerical instabilities during a finite-fault estimation, most models are stabilized by geometric rather than physical constraints such as smoothing.
As a basis for the inversion approach of this study, we build on a new pseudo-dynamic rupture model (PDR) with only a few free parameters and a simple geometry as a physics-based solution of an earthquake rupture. The PDR derives the instantaneous slip from a given stress drop on the fault plane, with boundary conditions on the developing crack surface guaranteed at all times via a boundary element approach. As a side product, the source time function on each point on the rupture plane is not constraint and develops by itself without additional parametrization. The code was made publicly available as part of the Pyrocko and Grond Python packages. The approach was compared with conventional modeling for different earthquakes. For example, for the Mw 7.1 2016 Kumamoto, Japan, earthquake, the effects of geometric changes in the rupture surface on the slip and slip rate distributions could be reproduced by simply projecting stress vectors. For the Mw 7.5 2018 Palu, Indonesia, strike-slip earthquake, we also modelled rupture propagation using the 2D Eikonal equation and assuming a linear relationship between rupture and shear wave velocity. This allowed us to give a deeper and faster propagating rupture front and the resulting upward refraction as a new possible explanation for the apparent supershear observed at the Earth's surface.
The thesis investigates three aspects of earthquake inversion using PDR: (1) to test whether implementing a simplified rupture model with few parameters into a probabilistic Bayesian scheme without constraining geometric parameters is feasible, and whether this leads to fast and robust results that can be used for subsequent fast information systems (e.g., ground motion predictions). (2) To investigate whether combining broadband and strong-motion seismic records together with near-field ground deformation data improves the reliability of estimated rupture models in a Bayesian inversion. (3) To investigate whether a complex rupture can be represented by the inversion of multiple PDR sources and for what type of earthquakes this is recommended.
I developed the PDR inversion approach and applied the joint data inversions to two seismic sequences in different tectonic settings. Using multiple frequency bands and a multiple source inversion approach, I captured the multi-modal behaviour of the Mw 8.2 2021 South Sandwich subduction earthquake with a large, curved and slow rupturing shallow earthquake bounded by two faster and deeper smaller events. I could cross-validate the results with other methods, i.e., P-wave energy back-projection, a clustering analysis of aftershocks and a simple tsunami forward model.
The joint analysis of ground deformation and seismic data within a multiple source inversion also shed light on an earthquake triplet, which occurred in July 2022 in SE Iran. From the inversion and aftershock relocalization, I found indications for a vertical separation between the shallower mainshocks within the sedimentary cover and deeper aftershocks at the sediment-basement interface. The vertical offset could be caused by the ductile response of the evident salt layer to stress perturbations from the mainshocks.
The applications highlight the versatility of the simple PDR in probabilistic seismic source inversion capturing features of rather different, complex earthquakes. Limitations, as the evident focus on the major slip patches of the rupture are discussed as well as differences to other finite fault modeling methods.
Supporting reflection in preservice during university-based training is, without doubt, a crucial aspect in attaining teacher professionalism. Therefore, an on-campus seminar designed to relate theory to practice and vice versa – the so-called ‘Lehr-Lern-Labor-Seminar (LLLS)’ – was implemented over the course of five terms to stimulate reflective skills of English and Physics teacher trainees. Investigations on the effectiveness of three types of the LLLS (no video and two types of video-supported reflections) compared to a parallel group (PG) and a control group (CG) occurred in a mixed methods quasi-experimental study. Reflective skills were elicited with vignettes, relevant covariates with questionnaires. Reflective development was then traced in the dimensions depth and breadth employing a qualitative content analysis. MANCOVA (Multivariate Analysis of Covariance) and regression analyses revealed a substantive increase of reflective depth for English and Physics teacher trainees and breadth development for English LLLS-participants in contrast to both, a PG and a CG, even when controlling for the subjects’ individual prerequisites.
Human growth data analysis and statistics – the 5th Gülpe International Student Summer School
(2023)
The Summer School in Gülpe (Ecological Station of the University of Potsdam) offers an exceptional learning opportunity for students to apply their knowledge and skills to real-world problems. With the guidance of experienced human biologists, statisticians, and programmers, students have the unique chance to analyze their own data and gain valuable insights. This interdisciplinary setting not only bridges different research areas but also leads to highly valuable outputs. The progress of students within just a few days is truly remarkable, especially when they are motivated and receive immediate feedback on their questions, problems, and results. The Summer School covers a wide range of topics, with this year’s focus mainly on two areas: understanding the impact of socioeconomic and physiological factors on human development and mastering statistical techniques for analyzing data such as changepoint analysis and the St. Nicolas House Analysis (SNHA) to visualize interacting variables. The latter technique, born out of the Summer School’s emphasis on gaining comprehensive data insights and understanding major relationships, has proven to be a valuable tool for researchers in the field. The articles in this special issue demonstrate that the Summer School in Gülpe stands as a testament to the power of practical learning and collaboration. Students who attend not only gain hands-on experience but also benefit from the expertise of professionals and the opportunity to engage with peers from diverse disciplines.
While inequality of opportunity (IOp) in earnings is well studied, the literature on IOp in individual net wealth is scarce to non-existent. This is problematic because both theoretical and empirical evidence show that the position in the wealth and income distribution can significantly diverge.We measure ex-ante IOp in net wealth for Germany using data from the Socio-Economic Panel (SOEP). Ex-ante IOp is defined as the contribution of circumstances to the inequality in net wealth before effort is exerted. The SOEP allows for a direct mapping from individual circumstances to individual net wealth and for a detailed decomposition of net wealth inequality into a variety of circumstances; among them childhood background, intergenerational transfers, and regional characteristics. The ratio of inequality of opportunity to total inequality is stable from 2002 to 2019. This is in sharp contrast to labor earnings, where ex-ante IOp is declining over time. Our estimates suggest that about 62% of the inequality in net wealth is due to circumstances. The most important circumstances are intergenerational transfers, parental occupation, and the region of birth. In contrast, gender and individuals’ own education are the most important circumstances for earnings.
Under Brazil's ex-president Bolsonaro, deforestation of the Amazon increased dramatically. An Austrian NGO filed a complaint to the Prosecutor of the International Criminal Court (ICC) against Bolsonaro in October 2021, accusing him of crimes against humanity against the backdrop of his involvement in environmental destruction. This paper deals with the question of whether this initi-ative constitutes a promising means of juridification to mitigate conflicts revolving around mass deforestation in Brazil. It thematizes attempts to juridify environmental destruction in international criminal law and examines the Climate Fund Case at the Brazilian Supreme Court. Finally, emerging problems and arguments in favour of starting preliminary examinations at the ICC against Bolsonaro are illuminated. This paper provides arguments as to why the initiative might be a promising undertaking, even though it is unlikely that Bolsonaro will be arrested.
Mothers of Seafaring
(2023)
The article aims to trace the contribution of Jewish women in the Yishuv’s maritime history. Taking the example of Henrietta Diamond, a founding member and chairperson of the Zebulun Seafaring Society, the article seeks to explore the representation and role of women in a growing Jewish maritime domain from the 1930s to the 1950s. It examines Zionist narratives on the ‘New Jew’ and the Jewish body and studies their relevance for the emerging field of maritime activities in the Yishuv. By contextualizing the work and depiction of Henrietta Diamond, the article sheds new light on the gendered notions that underlay the emergence of the Jewish maritime domain and illustrates the patterns of inclusion and exclusion in it.
Functional materials, also called "Smart Materials", are described by their ability to fulfill a desired task through targeted interaction with its environment. Due to this functional integration, such materials are of increased interest, especially in areas where the increasing micronization of components is required. Modern manufacturing processes (e.g. microfluidics) and the availability of a wide variety of functional materials (e.g. shape memory materials) now enable the production of particle-based switching components. This category includes micropumps and microvalves, whose basic function is the active control of liquid flows. One approach in realizing those microcomponents as pursued by this work, enables variable size-switching of water-filled microballoons by implementing a stimulus-sensitive switching motif in the capsule's membrane shell, while being under the influence of a constant driving force. The switching motif with its gatekeeper function has a critical influence on one or more material parameters, which modulate the capsule's resistance against the driving force in microballoon expansion process. The advantage of this concept is that even non-variable analyte conditions, such as concentration levels of ions, can be capitalized to generate external force fields that, under the control of the membrane, cause an inflation of the microballoon by an osmotically driven water influx. In case of osmotic pressure gradients as the driving force for the capsule expansion, material parameters associated with the gatekeeper function are specifically the permeability and the mechanical stiffness of the shell material. While a modulation of the shell permeability could be utilized to kinetically impede the water influx on large time scales, a modulation of the shell's mechanical stiffness even might be utilized to completely prevent the capsule inflation due to a possible non-deformability beneath a certain threshold pressure. In polymer networks, which are a suitable material class for the demanded capsule shell because of their excellent elasticity, both the permeability and the mechanical properties are strongly influenced by the crystallinity of the material. Since the permeability is effectively reduced with increasing crystallinity, while the mechanical stiffness is simultaneously greatly increased, both effects point in the same direction in terms of their functional relationship. For this reason and due to a reversible and contactless modulation of the membrane crystallinity by heat input, crystallites may be suitable switching motifs for controlling the capsule expansion. As second design element of reversible expandable microballoons, the capsule geometry, defined by an aqueous core enveloped by the temperature-sensitive polymer network membrane, should allow an osmotic pressure gradient across the membrane layer. The strength of the inflation pressure and the associated inflation velocity upon membrane melting should be controlled by the salt concentration within the aqueous core, while a turn in the osmotic gradient should furthermore allow the reversible process of capsule deflation. Therefore, it should be possible to build either microvalves and micropumps, while their intended action of either pumping or valving is determined by their state of expansion and the direction of the osmotic pressure gradient.. Microballoons of approximately 300 µm in diameter were formed via droplet-based microfluidics from double-emulsion templates (w/o/w). The elastomeric capsule membrane was formed by photo-crosslinking of methacrylate (MA) functionalized oligo(ε-caprolactone) precursors (≈ 3.8 MA-arms, Mn ≈ 12000 g mol-1) within the organic medium layer (o) via UV-exposure after droplet-formation. After removal of the toluene/chloroform mixture by slow extraction via the continuous aqueous phase, the capsules solidified under the development of a characteristic "mushroom"-like shape at specific experimental conditions (e.g. λ = 308 nm, 57 mJ·s-1·cm-2, 16 min). It could be furthermore shown that in dependency to the process parameters: oligomer concentration and curing-time also spherical capsules were accessible. Long curing-times and high oligomer concentrations at a fixed light-intensity favored the formation of "mushroom"-like capsules, whereas the contrary led to spherical shaped capsules. A comparative study on thin polymer network films of same composition and equal treatment proved a correlation between the film's crosslink density and their contraction capability, while stronger crosslinked polymer networks showed a stronger contraction after solvent removal. In combination with observations during capsule solidification via light-microscopy, where a continuous shaping from almost spherical crosslinked templates to "mushroom"-shaped and solidified capsules was stated, the following mechanism was proposed. In case of low oligomer contents and short curing-times, the contraction of the capsule shell during solvent removal is strongly diminished due to a low degree of crosslinking. Therefore, the solidifying shell could freely collapse onto the aqueous core. In the other case, high oligomer concentrations and long curing-times will favor the formation of highly crosslinked capsule membranes with a strong contraction capability. Due to an observed decentered location of the aqueous core within the swollen polymer network, an uneven radial stress along the capsule's circumference is exerted to the incompressible core. This lead to an uneven contraction during solvent removal and a directed flow of the core fluid into the direction of the minimal stress vector. In consequence, the initially thicker spherical cap contracts, whereas the opposing thinner spherical cap get stretched. The "mushroom"-shape over some advantages over their spherical shaped counterparts, why they were selected for the further experiments. Besides the necessity of a high density of crosslinking for the purpose of extraordinary elasticity and toughness, the form-anisotropy promotes a faster microballoon expandability due to a partial reduction of the membrane thickness. Additionally, pre-stretched regions of thin thickness might provide a better resistance against inflation pressure than spherical but non-stretched capsules of equal membrane thickness. The resulting "mushroom"-shaped microcapsules exhibited a melting point of Tm ≈ 50 - 60 °C and a degree of crystallinity of Xc ≈ 29 - 38 % depending on the membrane thickness and internal salt content, which is slightly lower than for the non-crosslinked oligomer and reasoned by a limited chain mobility upon crosslinking. Nonetheless, the melting transition of the polymer network was associated with a strong drop in its mechanical stiffness, which was shown to have a strong influence on the osmotic driven expansion of the microcapsules. Capsules that were subjected to osmotic pressures between 1.5 and 4.7 MPa did not expand if the temperature was well below the melting point of the capsule's membrane, i.e. at room temperature. In contrast, a continuous expansion, while approaching asymptotically to a final capsule size, was observed if the temperature exceeded the melting point, i.e. 60 °C. Microballoons, which were kept for 56 days at ∆Π = 1.5 MPa and room temperature, did not change significantly in diameter, why the impact of the mechanical stiffness on the expansion behavior is considered to be the greater than the influence of the shell permeability. The time-resolved expansion behavior of the microballoons above their Tm was subsequently modeled, using difusion equations that were corrected for shape anisotropy and elastic restoring forces. A shape-related and expansion dependent pre-factor was used to dynamically address the influence of the shell thickness differences along the circumference on the inflation velocity, whereas the microballoon's elastic contraction upon inflation was rendered by the inclusion of a hyperelastic constitutive model. An important finding resulting from this model was the pronounced increase in inflation velocity compared to hypothetical capsules with a homogeneous shell thickness, which stresses the benefit of employing shape anisotropic balloon-like capsules in this study. Furthermore, the model was able to predict the finite expandability on basis of entropy-elastic recovery forces and strain-hardening effects. A comparison of six different microballoons with different shell thicknesses and internal salt contents showed the linear relationship between the volumetric expansion, the shell thickness and the applied osmotic pressure, as represented by the model. As the proposed model facilitates the prediction of the expansion kinetics depending on the membranes mechanical and diffusional characteristics, it might be a screening tool for future material selections. In course of the microballoon expansion process, capsules of intermediate diameters could be isolated by recrystallization of the membrane, which is mainly caused by a restoration of the membrane's mechanical stiffness and is otherwise difficult to achieve with other stimuli-sensitive systems. The capsule's crystallinity of intermediate expansion states was nearly unchanged, whereas the lamellar crystal size tends to decreased with the expansion ratio. Therefore, it was assumed that the elastic modulus was only minimally altered and might increased due to the networks segment-chain extension. In addition to the volume increase achieved by inflation, a turn in the osmotic gradient also facilitated the reversible deflation, which was shown in inflation/deflation cycles. These both characteristics of the introduced microballoons are important parameter regarding the realization of micropumps and microvalves. The fixation of expanded microcapsules via recrystallization enabled the storage of entropy-elastic strain-energy, which could be utilized for pumping actions in non-aqueous media. Here, the pumping velocity depended on both, the type of surrounding medium and the applied temperature. Surrounding media that supported the fast transport of pumped liquid showed an accelerated deflation, while high temperatures further accelerate the pumping velocity. Very fast rejection of the incorporated payload was furthermore realized with pierced expanded microballoons, which were subjected to temperatures above their Tm. The possible fixation of intermediate particle sizes provide opportunities for vent constructions that allowed the precise adjustment of specific flow-rates and multiple valve openings and closings. A valve construction was realized by the insertion of a single or multiple microballoons in a microfluidic channel. A complete and a partial closing of the microballoon-valves was demonstrated as a function of the heating period. In this context, a difference between the inflation and deflation velocity was stated, summarizing slower expansion kinetics. Overall, microballoons, which presented both on-demand pumping and reversible valving by a temperature-triggered change in the capsule's volume, might be suitable components that help to design fully integrated LOC devices, due to the implementation of the control switch and controllable inflation/deflation kinetics. In comparison to other state of the art stimuli-sensitive materials, one has to highlight the microballoons capability of stabilizing almost continuously intermediate capsule sizes by simple recrystallization of the microballoon's membrane.
Complex emulsions are dispersions of kinetically stabilized multiphasic emulsion droplets comprised of two or more immiscible liquids that provide a novel material platform for the generation of active and dynamic soft materials. In recent years, the intrinsic reconfigurable morphological behavior of complex emulsions, which can be attributed to the unique force equilibrium between the interfacial tensions acting at the various interfaces, has become of fundamental and applied interest. As such, particularly biphasic Janus droplets have been investigated as structural templates for the generation of anisotropic precision objects, dynamic optical elements or as transducers and signal amplifiers in chemo- and bio-sensing applications. In the present thesis, switchable internal morphological responses of complex droplets triggered by stimuli-induced alterations of the balance of interfacial tensions have been explored as a universal building block for the design of multiresponsive, active, and adaptive liquid colloidal systems. A series of underlying principles and mechanisms that influence the equilibrium of interfacial tensions have been uncovered, which allowed the targeted design of emulsion bodies that can alter their shape, bind and roll on surfaces, or change their geometrical shape in response to chemical stimuli. Consequently, combinations of the unique triggerable behavior of Janus droplets with designer surfactants, such as a stimuli-responsive photosurfactant (AzoTAB) resulted for instance in shape-changing soft colloids that exhibited a jellyfish inspired buoyant motion behavior, holding great promise for the design of biological inspired active material architectures and transformable soft robotics.
In situ observations of spherical Janus emulsion droplets using a customized side-view microscopic imaging setup with accompanying pendant dropt measurements disclosed the sensitivity regime of the unique chemical-morphological coupling inside complex emulsions and enabled the recording of calibration curves for the extraction of critical parameters of surfactant effectiveness. The deduced new "responsive drop" method permitted a convenient and cost-efficient quantification and comparison of the critical micelle concentrations (CMCs) and effectiveness of various cationic, anionic, and nonionic surfactants. Moreover, the method allowed insightful characterization of stimuli-responsive surfactants and monitoring of the impact of inorganic salts on the CMC and surfactant effectiveness of ionic and nonionic surfactants. Droplet functionalization with synthetic crown ether surfactants yielded a synthetically minimal material platform capable of autonomous and reversible adaptation to its chemical environment through different supramolecular host-guest recognition events. Addition of metal or ammonium salts resulted in the uptake of the resulting hydrophobic complexes to the hydrocarbon hemisphere, whereas addition of hydrophilic ammonium compounds such as amino acids or polypeptides resulted in supramolecular assemblies at the hydrocarbon-water interface of the droplets. The multiresponsive material platform enabled interfacial complexation and
thus triggered responses of the droplets to a variety of chemical triggers including metal ions, ammonium compounds, amino acids, antibodies, carbohydrates as well as amino-functionalized solid surfaces.
In the final chapter, the first documented optical logic gates and combinatorial logic circuits based on complex emulsions are presented. More specifically, the unique reconfigurable and multiresponsive properties of complex emulsions were exploited to realize droplet-based logic gates of varying complexity using different stimuli-responsive surfactants in combination with diverse readout methods. In summary, different designs for multiresponsive, active, and adaptive liquid colloidal systems were presented and investigated, enabling the design of novel transformative chemo-intelligent soft material platforms.