Swimming is a fundamental feature in many living systems. Biological microorganisms move in the search of food, appropriate pH, temperature, mate and for many other elements crucial for life. A classic example is sperm cell, which travels thousands of its body length in the complex genital tract of females to reach the egg. Inspired by such unique character and diversified motion abilities of the biological world, researchers have always been intrigued to create small artificial microbots which could swim and perform complex tasks. In his famous talk ’There is plenty of room at the bottom’ in 1960, Richard Feynman suggested designing swallowable doctors which could travel in the blood vessels and perform the surgery. Although seemingly exquisite and far-fetched, this idea laid the foundation stone to pave the path towards building autonomously propelled artificial machines with applications ranging from targeted drug delivery to environmental remediation. However, considerable challenges are yet to be addressed before developing fully functional artificial machines, especially in the biomedical applications. For instance, directed transport in vivo, using man-made artificial machines face many obstacles starting from their fabrication, fuels for powering them and their interactions with the surroundings. Rapid changes in the environment in vivo, would make it difficult in selecting the ideal material and shape design of the microswimmer and would most probably require a flexible structure which could potentially squeeze itself and easily pass through small cavities. With most of the swimmers, in the past, being designed from inorganic materials, leave them unsuitable for biological applications. In addition, the environments inside an animal body is dominated by various complexity such as flows of bodily fluids, cavities and soft tissues. In laboratory settings, often these peculiarities are ignored as mostly the motion behavior is tested in stagnant conditions on solid substrates and it is unclear how would an artificial machine will behave in such complex environments. In this thesis, we combined the advances in microfluidics to benefit the microswimmer research manifold. In the last few years, microfluidics and micromotors have been used together in various instances because of their co-sharing regime of low Reynolds number and excellent fluid manipulation abilities at the microscale. In addition, microfluidics offer unique opportunities in designing structures with well-engineered shapes. With these points in mind, in this thesis, we used microfluidics to fabricate microswimmers and design custom made environments to mimic the complexity present in vivo, and to study the feedback of artificial swimmers in them. Specifically, in the first part of the thesis, two microfluidic strategies namely droplet microfluidics and stop-flow lithography were investigated to design hydrogel-based micromotors. Besides, in the next part, we developed complex environments and studied the motion behavior of conventional microswimmers in them. In the first subpart of the thesis, using droplet microfluidics, we designed polyacrylamide and poly (ethylene glycol) diacrylate (PEGDA) based Janus droplets using co-flowing phases with enzyme immobilized in one of the phases to confer asymmetry. The droplets were polymerized on-chip using UV polymerization. We found that the polyacrylamide and PEGDA 565 particles did not result into efficient bubble production when suspended in H2O2 solution and we explain this behaviour using the analogy of smaller pore size and possible poisoning of the enzyme by acrylamide. But, when a 10 v/v% PEGDA 700 was selected as the polymer material, it resulted in very efficient bubble evolution, although the Janus geometry was compromised which restricted swimming for these particles. The second subpart dealt with applying stop-flow lithography technique for designing hydrogel micromotors with different shapes and these shapes corresponded to different swimming modes. Exploiting laminar flow in the low Reynolds number region in the microfluidics channels, we fabricated micromotors with variable composition, shape and controlled active regions. Furthermore, we studied the different trajectories resulting from the complex interactions between swimmer body and fluid dynamics around it and connected them to the theoretical findings. We found close agreement between the experimental results and the theoretical outcomes: I-shaped structure behaved as a pump, U-shaped as a propeller and S-shaped as a rotor. Post fabrication, during real applications, the micromotors will be exposed to complex environments for instance interfaces and flows. To evaluate the feedback of microswimmers in these situations, in the next two sections, we designed custom made environments using microfluidics and we studied the response of well-studied Janus microswimmers in them. It should be noted that in the following two sections we used Janus particles rather than the bubble driven swimmers (fabricated in the first section) for simplicity. In this section, we designed an oil-water interface using a special microfluidic trap design and explored the motion behaviour of a very well-studied Pt@SiO2 Janus micromotors on them. The chip geometry facilitated on-demand merging of a droplet of particles and the ‘fuel’ (H2O2) inside the trap. Additionally, the large surface of the trap resulted in high surface energy which was compensated by partial wetting of the glass substrate. This partial wetting created patches of oil on the glass which we refer to as ‘oil dimples’. The dimples gave us the unique opportunity to directly compare the propulsion and performance of Janus motors at both interfaces (oil-water and solid-water) within the same setup and under similar experimental conditions. The swimming pattern and the speed values were found to be similar at the two interfaces and we conjecture an interplay of various factors such as microscale friction, lubrication, surface locking by the surfactant, reaction product absorption by oil and potential Marangoni influences for this similarity. In the next section, we designed a laminar flowing system using a square glass capillary and studied the response of a spherically symmetrical Janus micromotor in the conditions of flow. Previously, in the literature the response of Pt@SiO2, which is a model pusher-type micromotor, has been studied and they have been demonstrated to migrate cross-stream when the flow is imposed. In this thesis, we introduce a Cu@SiO2 colloid which we hypothesize to resemble a puller-type configuration based on theoretical flow field calculations. Additionally, in the literature, it has been predicted that pullers would exhibit upstream migration when placed under the conditions of flow. Indeed, when placed under flow, these particles migrate upstream, resembling many of the swimmers from biological world. These experimental findings are recovered theoretically using a simple squirmer model in puller configuration. The model also predicted a unique jumping behaviour for these particles, at very high flow rate. When increasing the flow rate in the experiments, we actually capture this characteristics. Finally, based on the theoretical flow field calculations and particularly their upstream response in the imposed flow, we conjecture a puller configuration for Cu@SiO2 micromotors. To sum up, this thesis made important advances by creating a number of different shapes of microswimmers and designing complex environments using microfluidics in which microswimmers can be placed and their response can be studied. Although, in this thesis we emphasized on Janus particles, in future, these custom-made environments can be used to assess the behaviour of other microswimmers including biological ones. While still many engineering and medical problems need to be solved before fully functional applications of artificial microswimmers are realized, manifestations of various shape designs and understanding their behaviours in complex surroundings are the first crucial steps.:Contents: Acknowledgements List of Abbreviations 1. Introduction 2. Fundamentals of active matter and microfluidics 2.1. Active matter 2.1.1. Physical fundamentals of motion at microscale 2.1.2. Biological microswimmers 2.2. Review Paper: Microfluidics for microswimmers 3. Aims and Motivation 4. Results and Discussion 4.1. Microfluidics for fabrication of microswimmers 4.1.1. Introduction 4.1.2. Droplet microfluidics 4.1.3. Stop-flow lithography 4.1.4. Paper - Fundamental Modes of Swimming Correspond to Fundamental Modes of Shape: Engineering I–, U–, and S– Shaped Swimmers 4.2. Microfluidics for specific environments: Interfaces 4.2.1. Introduction 4.2.2. Paper - Study of Active Janus Particles in the Presence of an Engineered Oil–Water Interface 4.3. Microfluidics for specific environments: Flow 4.3.1. Introduction 4.3.2. Paper - Upstream rheotaxis of catalytic Janus spheres 5. Summary and Final Remarks 6. Experimental Details 6.1. Fabrication of hydrogel particles using droplet microfluidics 6.2. Characterization of the hydrogel particles 6.3. Motion studies of the hydrogel particles A. Appendix A.1. Droplet microfluidics A.2. Stop-flow lithography A.3. Microfluidics for specific environments: Interfaces A.4. Microfluidics for specific environments: Flow B. List of publications Bibliography C. Erklärung

Lab-on-a-chip systems for point-of-care testing demonstrate a promising development towards more accurate diagnostic tests that are of extreme importance for the future global health. This work presents an agglutination assay performed in micrometer sized well using Janus PS/Ag/AgCl micromotors to enhance the interactions between goat anti-human IgM functionalized particles and Human IgM. The fabricated microwell chips are a suitable platform to analyze the interaction between different particles and to perform the agglutination assays. The interaction between active Janus particles and passive and functionalized particles is studied, as well as the influence of ions on the motion of the Janus particles. Agglutination assays are performed with and without the presence of Janus particles, and in different PBS concentrations. Once illuminated with blue light, passive SiO2 particles were effectively excluded from Janus particles, while SiO2 NH2 particles revealed attraction. In contrast, functionalized SiO2 NH2 Ab particles suspended in PBS did not show any interaction. It was found that the optimal working conditions for antibodies and Janus particles differed and, as a result, the Janus particles did not reveal a desirable interaction between the functionalized particles and IgM. Further experiments should be performed to find the proper conditions in which the antibodies and the Janus particles maintain their activities. It is believed that an effective interaction between the functionalized and Janus particles could be achieved by modifying the parameters that affect their interaction such as the zeta potential and the medium in which the assay is being performed. This preliminary work provides the first steps towards the development of a fully integrated lab on a chip system for point of care testing.:Abstract ........................................................................................................................ iii Acknowledgments.......................................................................................................... v Table of Contents .......................................................................................................... vi List of Tables ............................................................................................................. viii List of Figures ............................................................................................................... ix Abbreviations ................................................................................................................. x 1. Introduction ............................................................................................................ 1 1.1 In vitro diagnostic tests ........................................................................................ 1 1.1.1 Point-of-care tests ......................................................................................... 2 1.2 Agglutination assay .............................................................................................. 2 1.3 Lab-on-a-chip ....................................................................................................... 5 1.4 Self-propelled particles ........................................................................................ 6 1.4.1 Light-driven Ag/AgCl micromotors ............................................................. 6 1.5 Aim ...................................................................................................................... 9 2. Materials and Methods ......................................................................................... 11 2.1 Microwell fabrication .................................................................................... 11 2.2 Microswimmers fabrication .......................................................................... 12 2.3 Functionalization of particles ........................................................................ 12 2.4.1 Scanning electron microscope ............................................................... 14 2.4.2 UV-vis spectroscopy .............................................................................. 14 2.4.3 Zeta potential ......................................................................................... 14 2.4.4 Optical microscopy ................................................................................ 15 2.5 Motion Experiments ...................................................................................... 15 2.6 Agglutination assay ....................................................................................... 16 2.7 Effect of PBS ................................................................................................. 16 2.7.1 Janus particles ........................................................................................ 16 2.7.2 Agglutination assay ................................................................................ 17 2.7.3 Exclusion of functionalized particles ..................................................... 17 3. Results and Discussion ........................................................................................ 18 3.1 Microwell chip with integrated Janus particles ................................................. 18 3.2 Characterization of particles .............................................................................. 19 3.2.1 UV-vis spectroscopy ................................................................................... 19 3.2.2 Zeta potential .............................................................................................. 21 3.2.3 Agglutination assay in PEG-covered glass slides ....................................... 22 3.3 Motion experiments ........................................................................................... 23 3.3.1 Exclusion time ............................................................................................ 23 3.3.2 On/off light cycles....................................................................................... 26 3.4 Agglutination assay ............................................................................................ 28 3.4.1 Assay performed in wells............................................................................ 28 3.4.2 Assay performed in wells with Janus particles ........................................... 29 3.5 Effect of PBS concentration............................................................................... 30 3.5.1 Janus particles ............................................................................................. 30 3.5.2 Agglutination assay ..................................................................................... 32 3.5.3 Exclusion of functionalized particles .......................................................... 33 4. Conclusions .......................................................................................................... 35 References .................................................................................................................... 37 Declaration of Research Integrity and Good Scientific Practice ................................. 42

In this work, photocatalytic bismuth vanadate microparticles of different morphologies were investigated as artificial single.component microswimmers. In the first chapter, the motion mechanism as well as influence factors on the motion behavior such as solution pH and solution conductivity, hydrogen peroxide fuel concentration and decomposition kinetics and the surface charge of the particles were studied in detail. Furthermore, fluid flow profiles around the particles were determined. In the following chapter, interactions between the microswimmers were studied and exploited to create active assemblies that can be used to integrate multiple functionalities in one assembly. Eventually, alternative propulsion mechanisms besides hydrogen peroxide fuel decomposition were studied. The presented approaches include the catalysis of an organic oxidation and photoreduction of noble metals onto the particles, which proved to increase their catalytic activity and enabled propulsion of the modified microswimmers in pure water.:Acknowledgments III List of Abbreviations V 1. Introduction 1 2. Fundamentals of Photocatalysis and Active Matter 5 2.1. Photocatalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 2.1.1. Definition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 2.1.2. Processes in Semiconductor Photocatalysis . . . . . . . . . . . . . . . . 5 2.1.3. Properties of Bismuth Vanadate . . . . . . . . . . . . . . . . . . . . . . 10 2.1.4. Photocatalytic H2O2 decomposition . . . . . . . . . . . . . . . . . . . . 12 2.2. Active Matter . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14 2.2.1. Motion at the Microscale . . . . . . . . . . . . . . . . . . . . . . . . . . 14 2.2.2. Mechanisms of Catalytic Active Motion . . . . . . . . . . . . . . . . . . 18 2.2.3. Light-Driven Active Motion . . . . . . . . . . . . . . . . . . . . . . . . . 22 2.2.4. Origin of Asymmetry . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23 3. Aim and Motivation 27 4. Results and Discussion 29 4.1. Microparticle Synthesis und Characterization . . . . . . . . . . . . . . . . . . . 29 4.1.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29 4.1.2. Syntheses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29 4.1.3. Characterization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35 4.1.4. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41 4.2. Motion Studies and Mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . 43 4.2.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43 4.2.2. Characterization of Active Motion . . . . . . . . . . . . . . . . . . . . . 44 4.2.3. Influence of Experimental Conditions . . . . . . . . . . . . . . . . . . . . 54 4.2.4. Adjustment of Motion Mode by pH . . . . . . . . . . . . . . . . . . . . . 67 4.2.5. Flow Fields Around Single Crystalline Microparticles . . . . . . . . . . . 73 4.2.6. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81 4.3. Interactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83 4.3.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83 4.3.2. Interactions Between BiVO4 Microswimmers . . . . . . . . . . . . . . . 83 4.3.3. Interactions between Spheroidal Microswimmers . . . . . . . . . . . . . 84 4.3.4. Surface Modification of Spheroidal Microswimmers . . . . . . . . . . . . 88 4.3.5. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92 4.4. Towards Alternative Propulsion Reactions . . . . . . . . . . . . . . . . . . . . . 93 4.4.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93 4.4.2. Oxidation of Dibenzylamine . . . . . . . . . . . . . . . . . . . . . . . . . 94 4.4.3. Photodeposition of Metals . . . . . . . . . . . . . . . . . . . . . . . . . . 97 4.4.4. Towards Propulsion in Pure Water . . . . . . . . . . . . . . . . . . . . . 98 4.4.5. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101 5. Summary and Final Remarks 103 6. Experimental Details 113 6.1. Syntheses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113 6.1.1. Microparticle Synthesis and Characterization . . . . . . . . . . . . . . . 113 6.1.2. Motion Studies and Mechanism . . . . . . . . . . . . . . . . . . . . . . . 114 6.1.3. Interactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116 6.1.4. Towards Alternative Propulsion Reactions . . . . . . . . . . . . . . . . . 117 6.2. Apparatus and Measurements . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117 6.2.1. Scanning Electron Microscopy (SEM) . . . . . . . . . . . . . . . . . . . 117 6.2.2. Transmission Electron microscopy (TEM) . . . . . . . . . . . . . . . . . 117 6.2.3. Nitrogen physisorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118 6.2.4. Gas Chromatography (GC) . . . . . . . . . . . . . . . . . . . . . . . . . 118 6.2.5. Powder X-ray Crystallography (XRD) . . . . . . . . . . . . . . . . . . . 118 6.2.6. Absorption Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . 118 6.2.7. Fluorescence Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . 118 6.2.8. Zeta Potential Measurements . . . . . . . . . . . . . . . . . . . . . . . . 119 6.2.9. Fluorescence Microscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . 119 6.2.10. Light Microscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119 A. Appendix 123 Bibliography 139 List of Publications 149 Erklärung 151

What is flagellar swimming? Cilia and flagella are whip-like cell appendages that can exhibit regular bending waves. This active process emerges from the non-equilibrium dynamics of molecular motors distributed along the length of cilia and flagella. Eukaryotic cells can possess many cilia and flagella that beat in a coordinated fashion, thus transporting fluids, as in mammalian airways or the ventricular system inside the brain. Many unicellular organisms posses just one or two flagella, rendering them microswimmers that are propelled through fluids by the flagellar beat including sperm cells and the biflagellate green alga Chlamydomonas. Objectives. In this thesis in theoretical biological physics, we seek to understand the nonlinear dynamics of flagellar swimming and synchronization. We investigate the flow fields induced by beating flagella and how in turn external hydrodynamic flows change speed and shape of the flagellar beat. This flagellar load-response is a prerequisite for flagellar synchronization. We want to find the physical principals underlying stable synchronization of the two flagella of Chlamydomonas cells. Results. First, we employed realistic hydrodynamic simulations of flagellar swimming based on experimentally measured beat patterns. For this, we developed analysis tools to extract flagellar shapes from high-speed videoscopy data. Flow-signatures of flagellated swimmers are analysed and their effect on a neighboring swimmer is compared to the effect of active noise of the flagellar beat. We were able to estimate a chemomechanical energy efficiency of the flagellar beat and determine its waveform compliance by comparing findings from experiments, in which a clamped Chlamydomonas is exposed to external flow, to predictions from an effective theory that we designed. These mechanical properties have interesting consequences for the synchronization dynamics of Chlamydomonas, which are revealed by computer simulations. We propose that direct elastic coupling between the two flagella of Chlamydomonas, as suggested by recent experiments, in combination with waveform compliance is crucial to facilitate in-phase synchronization of the two flagella of Chlamydomonas.

What is flagellar swimming? Cilia and flagella are whip-like cell appendages that can exhibit regular bending waves. This active process emerges from the non-equilibrium dynamics of molecular motors distributed along the length of cilia and flagella. Eukaryotic cells can possess many cilia and flagella that beat in a coordinated fashion, thus transporting fluids, as in mammalian airways or the ventricular system inside the brain. Many unicellular organisms posses just one or two flagella, rendering them microswimmers that are propelled through fluids by the flagellar beat including sperm cells and the biflagellate green alga Chlamydomonas. Objectives. In this thesis in theoretical biological physics, we seek to understand the nonlinear dynamics of flagellar swimming and synchronization. We investigate the flow fields induced by beating flagella and how in turn external hydrodynamic flows change speed and shape of the flagellar beat. This flagellar load-response is a prerequisite for flagellar synchronization. We want to find the physical principals underlying stable synchronization of the two flagella of Chlamydomonas cells. Results. First, we employed realistic hydrodynamic simulations of flagellar swimming based on experimentally measured beat patterns. For this, we developed analysis tools to extract flagellar shapes from high-speed videoscopy data. Flow-signatures of flagellated swimmers are analysed and their effect on a neighboring swimmer is compared to the effect of active noise of the flagellar beat. We were able to estimate a chemomechanical energy efficiency of the flagellar beat and determine its waveform compliance by comparing findings from experiments, in which a clamped Chlamydomonas is exposed to external flow, to predictions from an effective theory that we designed. These mechanical properties have interesting consequences for the synchronization dynamics of Chlamydomonas, which are revealed by computer simulations. We propose that direct elastic coupling between the two flagella of Chlamydomonas, as suggested by recent experiments, in combination with waveform compliance is crucial to facilitate in-phase synchronization of the two flagella of Chlamydomonas.:1 Introduction 1.1 Physics of cell motility: flagellated swimmers as model system 2 1.1.1 Tissue cells and unicellular eukaryotic organisms have cilia and flagella 2 1.1.2 The conserved architecture of flagella 3 1.1.3 Synchronization in collections of flagella 5 1.2 Hydrodynamics at the microscale 9 1.2.1 Navier-Stokes equation 10 1.2.2 The limit of low Reynolds number 10 1.2.3 Multipole expansion of flow fields 11 1.3 Self-propulsion by viscous forces 13 1.3.1 Self propulsion requires broken symmetries 13 1.3.2 Signatures of flowfields: pusher & puller 15 1.4 Overview of the thesis 16 2 Flow signatures of flagellar swimming 2.1 Self-propulsion of flagellated swimmers 20 2.1.1 Representation of flagellar shapes 20 2.1.2 Computation of hydrodynamic friction forces 21 2.1.3 Material frame and rigid-body transformations 22 2.1.4 The grand friction matrix 23 2.1.5 Dynamics of swimming 23 2.2 The hydrodynamic far field: pusher and puller 26 2.2.1 The flow generated by a swimmer 26 2.2.2 Force dipole characterization 27 2.2.3 Flagellated swimmers alternate between pusher and puller 29 2.2.4 Implications for two interacting Chlamydomonas cells 31 2.3 Inertial screening of oscillatory flows 32 2.3.1 Convection and oscillatory acceleration 33 2.3.2 The oscilet: fundamental solution of unsteady flow 35 2.3.3 Screening length of oscillatory flows 35 2.4 Energetics of flagellar self-propulsion 36 2.4.1 Impact of inertial screening on hydrodynamic dissipation 37 2.4.2 Case study: the green alga Chlamydomonas 38 2.4.3 Discussion: evolutionary optimization and the number of molecular motors 38 2.5 Summary 39 3 The load-response of the flagellar beat 3.1 Experimental collaboration: flagellated swimmers exposed to flows 41 3.1.1 Description of the experimental setup 42 3.1.2 Computed flow profile in the micro-fluidic device 43 3.1.3 Image processing and flagellar tracking 43 3.1.4 Mode decomposition and limit-cycle reconstruction 47 3.1.5 Changes of limit-cycle dynamics: deformation, translation, acceleration 49 3.2 An effective theory of flagellar oscillations 50 3.2.1 A balance of generalized forces 50 3.2.2 Hydrodynamic friction in generalized coordinates 51 3.2.3 Intra-flagellar friction 52 3.2.4 Calibration of active flagellar driving forces 52 3.2.5 Stability of the limit cycle of the flagellar beat 53 3.2.6 Equations of motion 55 3.3 Comparison of theory and experiment 56 3.3.1 Flagellar mean curvature 57 3.3.2 Susceptibilities of phase speed and amplitude 57 3.3.3 Higher modes and stalling of the flagellar beat at high external load 59 3.3.4 Non-isochrony of flagellar oscillations 63 3.4 Summary 63 4 Flagellar load-response facilitates synchronization 4.1 Synchronization to external driving 65 4.2 Inter-flagellar synchronization in the green alga Chlamydomonas 67 4.2.1 Equations of motion for inter-flagellar synchronization 68 4.2.2 Synchronization strength for free-swimming and clamped cells 70 4.2.3 The synchronization strength depends on energy efficiency and waveform compliance 73 4.2.4 The case of an elastically clamped cell 74 4.2.5 Basal body coupling facilitates in-phase synchronization 75 4.2.6 Predictions for experiments 78 4.3 Summary 80 5 Active flagellar fluctuations 5.1 Effective description of flagellar oscillations 84 5.2 Measuring flagellar noise 84 5.2.1 Active phase fluctuations are much larger than thermal noise 84 5.2.2 Amplitude fluctuations are correlated 85 5.3 Active flagellar fluctuations result in noisy swimming paths 86 5.3.1 Effective diffusion of swimming circles of sperm cell 86 5.3.2 Comparison of the effect of noise and hydrodynamic interactions 87 5.4 Summary 88 6 Summary and outlook 6.1 Summary of our results 89 6.2 Outlook on future work 90 A Solving the Stokes equation A.1 Multipole expansion 95 A.2 Resistive-force theory 96 A.3 Fast multipole boundary element method 97 B Linearized Navier-Stokes equation B.1 Linearized Navier-Stokes equation 101 B.2 The case of an oscillating sphere 102 B.3 The small radius limit 103 B.4 Greens function 104 C Hydrodynamic friction C.1 A passive particle 107 C.2 Multiple Particles 107 C.3 Generalized coordinates 108 D Data analysis methods D.1 Nematic filter 111 D.1.1 Nemat 111 D.1.2 Nematic correlation 111 D.2 Principal-component analysis 112 D.3 The quality of the limit-cycle projections of experimental data 113 E Adler equation F Sensitivity analysis for computational results F.1 The distance function of basal coupling 117 F.2 Computed synchronization strength for alternative waveform 118 F.3 Insensitivity of computed load-response to amplitude correlation time 118 List of Symbols List of Figures Bibliography

Since the highly cited paper by Purcell postulating the “Scallop theorem” almost 50 years ago, asymmetry is an unavoidable part of micromotors. It is frequently induced by self-shadowing or self-masking, resulting in so-called Janus colloids. This strategy works very reliably, but turns into a bottleneck once up-scaling becomes important. Herein, existing alternatives are discussed and a novel synthetic pathway yielding active swimmers in a one-pot synthesis is presented. To understand the resulting mobility from a single material, the geometric asymmetry is evaluated using a python based algorithm and this process is automated in an open access tool.

Die Fähigkeit künstlicher Mikroschwimmer, auf äußere Reize zu reagieren und deren mechanistische Ursprünge, gehören zu den umstrittensten Fragen der interdisziplinären Wissenschaft. Die Erzeugung chemischer Gradienten ist dabei eine technische Herausforderung, da sie aufgrund von Diffusion schnell abflachen. Inspiriert von ‘Stop-flow’ Experimenten aus der chemischen Kinetik zeigen wir, dass die Erzeugung eines mikrofluidischen Gradienten durch Kombination mit einer Druckrückkopplungsschleife zur präzisen Kontrolle des Stoppens erfolgen kann. Das ermöglicht es uns, die mechanistischen Details der Chemotaxis von künstlichen katalytischen Janus-Mikromotoren zu untersuchen. Wir stellen fest, dass diese Kupfer-Janus-Partikel eine chemotaktische Bewegung entlang des Konzentrationsgradienten sowohl in positiver als auch in negativer Richtung zeigen, und wir demonstrieren die mechanische Reaktion der Partikel auf unausgewogene Widerstandskräfte, die dieses Verhalten erklären.

The ability of artificial microswimmers to respond to external stimuli and the mechanistical details of their origins belong to the most disputed challenges in interdisciplinary science. Therein, the creation of chemical gradients is technically challenging, because they quickly level out due to diffusion. Inspired by pivotal stopped flow experiments in chemical kinetics, we show that microfluidics gradient generation combined with a pressure feedback loop for precisely controlling the stop of the flows, can enable us to study mechanistical details of chemotaxis of artificial Janus micromotors, based on a catalytic reaction. We find that these copper Janus particles display a chemotactic motion along the concentration gradient in both, positive and negative direction and we demonstrate the mechanical reaction of the particles to unbalanced drag forces, explaining this behaviour.

Catalytic microswimmers that move by a phoretic mechanism in response to a self-induced chemical gradient are often obtained by the design of spherical janus microparticles, which suffer from multi-step fabrication and low yields. Approaches that circumvent laborious multi-step fabrication include the exploitation of the possibility of nonuniform catalytic activity along the surface of irregular particle shapes, local excitation or intrinsic asymmetry. Unfortunately, the effects on the generation of motion remain poorly understood. In this work, single crystalline BiVO₄ microswimmers are presented that rely on a strict inherent asymmetry of charge-carrier distribution under illumination. The origin of the asymmetrical flow pattern is elucidated because of the high spatial resolution of measured flow fields around pinned BiVO₄ colloids. As a result the flow from oxidative to reductive particle sides is confirmed. Distribution of oxidation and reduction reactions suggests a dominant self-electrophoretic motion mechanism with a source quadrupole as the origin of the induced flows. It is shown that the symmetry of the flow fields is broken by self-shadowing of the particles and synthetic surface defects that impact the photocatalytic activity of the microswimmers. The results demonstrate the complexity of symmetry breaking in nonspherical microswimmers and emphasize the role of self-shadowing for photocatalytic microswimmers. The findings are leading the way toward understanding of propulsion mechanisms of phoretic colloids of various shapes.