@phdthesis{Elsner2005, author = {Elsner, Nils}, title = {Nanomechanik und Adh{\"a}sion von Polyelektrolytmultischicht-Hohlkapseln}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-5555}, school = {Universit{\"a}t Potsdam}, year = {2005}, abstract = {Die vorliegende Arbeit besch{\"a}ftigte sich mit zwei Themengebieten. Es ging zum einen um die mechanischen Eigenschaften von Polyelektrolythohlkapseln und zum anderen um die Adh{\"a}sion von Polyelektrolythohlkapseln. Die mechanischen Eigenschaften wurden mit der AFM „colloidal probe" Technik untersucht. Dabei zeigte sich, dass die Kraftdeformationskurven f{\"u}r kleine Deformationen den nach der Schalentheorie vorhergesagten linearen Verlauf haben. Ebenso wurde die quadratische Abh{\"a}ngigkeit der Federkonstanten von der Dicke best{\"a}tigt. F{\"u}r PAH/PSS findet man einen E-Modul von 0.25 GPa. Zusammen mit der Tatsache, dass die Deformationskurven unabh{\"a}ngig von der Geschwindigkeit sind und praktisch keine Hysterese zeigen, sowie der M{\"o}glichkeit die Kapseln plastisch zu deformieren, kann man schließen, dass das System in einem glasartigen Zustand vorliegt. Erwartungsgem{\"a}ß zeigte der pH einen starken Einfluss auf die PEM. W{\"a}hrend in einem pH-Bereich zwischen 2 und 11.5 keine morphologischen {\"A}nderungen festgestellt werden konnten, vergr{\"o}ßerte sich der Radius bei pH = 12 um bis zu 50 \%. Diese Radien{\"a}nderung war reversibel und ging einher mit einem sichtbaren Weicherwerden der Kapseln. Eine Abnahme des E-Moduls um mindestens drei Gr{\"o}ßenordungen wurde durch Kraftdeformationsmessungen best{\"a}tigt. Die Kraftdeformationskurven zeigen eine starke Hysterese. Das System befindet sich nun nicht mehr in einem glasartigen Zustand, sondern ist viskos bis gummiartig geworden. Messungen an Kapseln, die mit Glutardialdehyd behandelt wurden, zeigten, dass die Behandlung das pH-abh{\"a}ngige Verhalten ver{\"a}ndert. Dies kann darauf zur{\"u}ckgef{\"u}hrt werden, dass das PAH durch den Glutardialdehyd quervernetzt wird. Bei einem hohen Quervernetzungsgrad, zeigen die Kapseln keine {\"A}nderung des mechanischen Verhaltens bei pH = 12. Schwach quervernetzte Kapseln werden immer noch signifikant weicher bei pH = 12, jedoch {\"a}ndert sich der Radius nicht. Außerdem wurden Multilagenkapseln untersucht, deren Stabilit{\"a}t nicht auf elektrostatischen Wechselwirkungen sondern auf Wasserstoffbr{\"u}ckenbindungen beruhte. Diese Kapseln zeigten eine deutlich h{\"o}here Steifigkeit mit E-Modulen bis zu 1 GPa. Es wurde gefunden, dass auch dieses System f{\"u}r kleine Deformationen ein lineares Kraft-Deformationsverhalten zeigt, und dass die Federkonstante quadratisch von der Dicke abh{\"a}ngt. Die Kapseln l{\"o}sen sich praktisch sofort bei pH = 6.5 auf. In der N{\"a}he dieses pHs konnte das Abnehmen der Federkonstanten verfolgt werden. Außerdem wurde das Adh{\"a}sionsverhalten von PAH/PSS Kapseln auf mit PEI-beschichtetem Glas untersucht. Die Adh{\"a}sionsfl{\"a}chen waren zu einem großen Teil rund und ließen sich quantitativ auswerten. Der Adh{\"a}sionsradius nimmt mit dem Kapselradius zu und mit der Dicke ab. Das Verhalten konnte mit zwei Modellen, einem f{\"u}r die große und einem f{\"u}r die kleine Deformation beschrieben werden. Das große Deformationsmodell liefert um eine Gr{\"o}ßenordung niedrigere Adh{\"a}sionsenergien als das kleine Deformationsmodell, welches mit Werten von ‑0.2 mJ/m2 Werte in einem plausiblen Bereich liefert. Es wurde gefunden, dass bei einem Verh{\"a}ltnis von Dicke zu Deformation von etwa eins "buckling" auftritt. Dieser Punkt markierte zugleich den {\"U}bergang von der großen zur kleinen Deformation.}, subject = {Polyelektrolyt}, language = {de} } @phdthesis{CerdaDonate2020, author = {Cerd{\´a} Do{\~n}ate, Elisa}, title = {Microfluidics for the study of magnetotactic bacteria towards single-cell analysis}, school = {Universit{\"a}t Potsdam}, pages = {X, 92}, year = {2020}, abstract = {Magnetotactic bacteria comprise a heterogeneous group of Gram negative bacteria which share the ability to synthesise intracellular magnetic nanoparticles surrounded by a lipid bilayer, known as magnetosomes, which are arranged in linear chains. The bacteria exert a unique level of control onto the biomineralization of these nanoparticles, which is seen in the controlled size and shape they have. These characteristics have attracted great attention on understanding the process by which the bacteria synthesise the magnetosomes. Moreover, the magnetosome chain impart the bacteria with a net magnetic dipole which makes them susceptible to interact with magnetic fields and thus orient with the Earth's magnetic field. This feature has attracted as well much interest to understand how the swimming motility of these microorganisms is affected by the presence of magnetic fields. Most of the studies performed in these bacteria so far have been conducted in the traditional manner using large populations of cells. Such studies have the disadvantage of averaging many different individuals with heterogeneous behaviours and fail to consider individual variations. In addition, in large populations each bacterium will be subjected to a different microenvironment that will influence the bacterial behaviour, but which cannot be defined using these traditional methods. In this thesis, different microfluidic platforms are proposed to overcome these limitations and to offer the possibility to study magnetotactic bacteria in defined environments and down to a single-cell resolution. First, a sediment-like microfluidic platform is presented with the purpose of mimicking the porous environment they bacteria naturally dwell in. The platform allows to observe via transmitted light microscopy that bacterial navigation in crowded environments is enhanced by the Earth's magnetic field strengths (B = 50 μT) rather than by null (B = 0 μT) or higher magnetic fields (B = 500 μT). Second, a microfluidic system to confine single-bacterial cells in physically defined environments is presented. The system allows to study via transmitted light microscopy the interplay between wall curvature, magnetic fields and bacterial speed affect the motion of a confined bacterium, and shows how bacterial trajectories depend on those three parameters. Third, a microfluidic platform to conduct semi in vivo magnetosome nucleation with a single-cell resolution via X-ray fluorescence is fabricated. It is shown that signal arising from magnetosome full chains can be observed individually in each bacterium. Finally, the iron uptake kinetics of a single bacterium are studied via a fluorescent reporter through confocal microscopy. Two different approaches are used for this: one of the previously mentioned platforms, as well as giant lipid vesicles. It is observed how iron uptake rates vary between cells, as well as how these rates are consistent with magnetosome formation taking place within some hours. The present thesis shows therefore how microfluidic technologies can be implemented for the study of magnetotactic bacteria at different degrees, and the level of resolution that can be attained by going into the single- cell scale.
}, language = {en} } @phdthesis{Sharma2023, author = {Sharma, Anjali}, title = {Optical manipulation of multi-responsive microgels}, school = {Universit{\"a}t Potsdam}, pages = {207}, year = {2023}, abstract = {This dissertation focuses on the understanding of the optical manipulation of microgels dispersed in aqueous solution of azobenzene containing surfactant. The work consists of three parts where each part is a systematic investigation of the (1) photo-isomerization kinetics of the surfactant in complex with the microgel polymer matrix, (2) light driven diffusiosmosis (LDDO) in microgels and (3) photo-responsivity of microgel on complexation with spiropyran. The first part comprises three publications where the first one [P1] investigates the photo-isomerization kinetics and corresponding isomer composition at a photo-stationary state of the photo-sensitive surfactant conjugated with charged polymers or micro sized polymer networks to understand the structural response of such photo-sensitive complexes. We report that the photo-isomerization of the azobenzene-containing cationic surfactant is slower in a polymer complex compared to being purely dissolved in an aqueous solution. The surfactant aggregates near the polyelectrolyte chains at concentrations much lower than the bulk critical micelle concentration. This, along with the inhibition of the photo-isomerization kinetics due to steric hindrance within the densely packed aggregates, pushes the isomer-ratio to a higher trans-isomer concentration for all irradiation wavelengths. The second publication [P2] combines experimental results and non-adiabatic dynamic simulations for the same surfactant molecules embedded in the micelles with absorption spectroscopy measurements of micellar solutions to uncover the reasons responsible for the slowdown in photo induced trans → cis azobenzene isomerization at concentrations higher than the critical micelle concentration (CMC). The simulations reveal a decrease of isomerization quantum yields for molecules inside the micelles and observes a reduction of extinction coefficients upon micellization. These findings explain the deceleration of the trans → cis switching in micelles of the azobenzene-containing surfactants. Finally, the third publication [P3] focusses on the kinetics of adsorption and desorption of the same surfactant within anionic microgels in the dark and under continuous irradiation. Experimental data demonstrate, that microgels can serve as a selective absorber of the trans isomers. The interaction of the isomers with the gel matrix induces a remotely controllable collapse or swelling on appropriate irradiation wavelengths. Measuring the kinetics of the microgel size response and knowing the exact isomer composition under light exposure, we calculate the adsorption rate of the trans-isomers. The second part comprises two publications. The first publication [P4] reports on the phenomenon of light-driven diffusioosmotic (DO) long-range attractive and repulsive interactions between micro-sized objects, whose range extends several times the size of microparticles and can be adjusted to point towards or away from the particle by varying irradiation parameters such as intensity or wavelength of light. The phenomenon is fueled by the aforementioned photosensitive surfactant. The complex interaction of dynamic exchange of isomers and photo-isomerization rate yields to relative concentrations gradients of the isomers in the vicinity of micro-sized object inducing a local diffusioosmotic (DO) flow thereby making a surface act as a micropump. The second publication [P5] exclusively aims the visualization and investigation of the DO flows generated from microgels by using small tracer particles. Similar to micro sized objects, the flow is able to push adjacent tracers over distances several times larger than microgel size. Here we report that the direction and the strength of the l-LDDO depends on the intensity, irradiation wavelength and the amount of surfactant adsorbed by the microgel. For example, the flow pattern around a microgel is directed radially outward and can be maintained quasi-indefinitely under exposure at 455 nm when the trans:cis ratio is 2:1, whereas irradiation at 365 nm, generates a radially transient flow pattern, which inverts at lower intensities. Lastly, the third part consists of one publication [P6] which, unlike the previous works, reports on the study of the kinetics of photo- and thermo-switching of a new surfactant namely, spiropyran, upon exposure with light of different wavelengths and its interaction with p(NIPAM-AA) microgels. The surfactant being an amphiphile, switches between its ring closed spiropyran (SP) form and ring open merocyanine (MC) form which results in a change in the hydrophilic-hydrophobic balance of the surfactant as MC being a zwitterionic form along with the charged head group, generates three charges on the molecule. Therefore, the MC form of the surfactant is more hydrophilic than in the case of the neutral SP state. Here, we investigate the initial shrinkage of the gel particles via charge compensation on first exposure to SP molecules which results from the complex formation of the molecules with the gel matrix, triggering them to become photo responsive. The size and VPTT of the microgels during irradiation is shown to be a combination of heating up of the solution during light absorption by the surfactant (more pronounced in the case of UV irradiation) and the change in the hydrophobicity of the surfactant.}, language = {en} }