Microfluidics for Micromotors: Fabrication, Environments

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. Erklärun