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Biological and biomimetic formation and organization of magnetic nanoparticles

Biological materials have ever been used by humans because of their remarkable properties. This is surprising since the materials are formed under physiological conditions and with commonplace constituents. Nature thus not only provides us with inspiration for designing new materials but also teaches us how to use soft molecules to tune interparticle and external forces to structure and assemble simple building blocks into functional entities. Magnetotactic bacteria and their chain of magnetosomes represent a striking example of such an accomplishment where a very simple living organism controls the properties of inorganics via organics at the nanometer-scale to form a single magnetic dipole that orients the cell in the Earth magnetic field lines.
My group has developed a biological and a bio-inspired research based on these bacteria. My research, at the interface between chemistry, materials science, physics, and biology focuses on how biological systems synthesize, organize and use minerals. We apply the design principles to sustainably form hierarchical materials with controlled properties that can be used e.g. as magnetically directed nanodevices towards applications in sensing, actuating, and transport.
In this thesis, I thus first present how magnetotactic bacteria intracellularly form magnetosomes and assemble them in chains. I developed an assay, where cells can be switched from magnetic to non-magnetic states. This enabled to study the dynamics of magnetosome and magnetosome chain formation. We found that the magnetosomes nucleate within minutes whereas chains assembles within hours. Magnetosome formation necessitates iron uptake as ferrous or ferric ions. The transport of the ions within the cell leads to the formation of a ferritin-like intermediate, which subsequently is transported and transformed within the magnetosome organelle in a ferrihydrite-like precursor. Finally, magnetite crystals nucleate and grow toward their mature dimension.
In addition, I show that the magnetosome assembly displays hierarchically ordered nano- and microstructures over several levels, enabling the coordinated alignment and motility of entire populations of cells. The magnetosomes are indeed composed of structurally pure magnetite. The organelles are partly composed of proteins, which role is crucial for the properties of the magnetosomes. As an example, we showed how the protein MmsF is involved in the control of magnetosome size and morphology. We have further shown by 2D X-ray diffraction that the magnetosome particles are aligned along the same direction in the magnetosome chain. We then show how magnetic properties of the nascent magnetosome influence the alignment of the particles, and how the proteins MamJ and MamK coordinate this assembly. We propose a theoretical approach, which suggests that biological forces are more important than physical ones for the chain formation. All these studies thus show how magnetosome formation and organization are under strict biological control, which is associated with unprecedented material properties. Finally, we show that the magnetosome chain enables the cells to find their preferred oxygen conditions if the magnetic field is present.
The synthetic part of this work shows how the understanding of the design principles of magnetosome formation enabled me to perform biomimetic synthesis of magnetite particles within the highly desired size range of 25 to 100 nm. Nucleation and growth of such particles are based on aggregation of iron colloids termed primary particles as imaged by cryo-high resolution TEM. I show how additives influence magnetite formation and properties. In particular, MamP, a so-called magnetochrome proteins involved in the magnetosome formation in vivo, enables the in vitro formation of magnetite nanoparticles exclusively from ferrous iron by controlling the redox state of the process. Negatively charged additives, such as MamJ, retard magnetite nucleation in vitro, probably by interacting with the iron ions. Other additives such as e.g. polyarginine can be used to control the colloidal stability of stable-single domain sized nanoparticles.
Finally, I show how we can “glue” magnetic nanoparticles to form propellers that can be actuated and swim with the help of external magnetic fields. We propose a simple theory to explain the observed movement. We can use the theoretical framework to design experimental conditions to sort out the propellers depending on their size and effectively confirm this prediction experimentally. Thereby, we could image propellers with size down to 290 nm in their longer dimension, much smaller than what perform so far. / Biologische Materialien wie Knochen, Muscheln und Holz wurden von den Menschen seit den ältesten Zeiten verwendet. Diese biologisch gebildeten Materialien haben bemerkenswerte Eigenschaften. Dies ist besonders überraschend, da sie unter physiologischen Bedingungen und mit alltäglichen Bestandteilen gebildet sind. Die Natur liefert uns also nicht nur mit Inspiration für die Entwicklung neuer Materialien, sondern lehrt uns auch, wie biologische Additiven benutzen werden können, um einfache synthetische Bausteine in funktionale Einheiten zu strukturieren.
Magnetotaktischen Bakterien und ihre Kette von Magnetosomen sind ein Beispiel, wo einfache Lebewesen die Eigenschaften von anorganischen Materialien steuern, um sich entlang den magnetischen Feldlinien der Erde zu orientieren. Die von den Bakterien gebildeten Magnetosomen sind von besonderem Interesse, da mit magnetischen Eisenoxid-Nanopartikeln in den letzten zehn Jahren einer Vielzahl von Bio-und nanotechnologischen Anwendungen entwickelt worden sind.
In dieser Arbeit stelle ich eine biologische und eine bio-inspirierte Forschung auf der Grundlage der magnetotaktischen Bakterien vor. Diese Forschung verbindet die neuesten Entwicklungen von Nanotechnik in der chemischen Wissenschaft, die neuesten Fortschritte der Molekularbiologie zusammen mit modernen Messverfahren. Mein Forschungsschwerpunkt liegt somit an der Schnittstelle zwischen Chemie, Materialwissenschaften, Physik und Biologie. Ich will verstehen, wie biologische Systeme Materialien synthetisieren und organisieren, um Design-Prinzipien zu extrahieren, damit hierarchischen Materialien mit kontrollierten Eigenschaften nachhaltig gebildet werden.

Identiferoai:union.ndltd.org:Potsdam/oai:kobv.de-opus-ubp:7202
Date January 2014
CreatorsFaivre, Damien
PublisherUniversität Potsdam, Mathematisch-Naturwissenschaftliche Fakultät. Institut für Chemie
Source SetsPotsdam University
LanguageEnglish
Detected LanguageEnglish
TypeText.Thesis.Habilitation
Formatapplication/pdf
Rightshttp://creativecommons.org/licenses/by-nc-nd/4.0/deed.de

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