@phdthesis{Kuhrts,
  author    = {Kuhrts, Lucas},
  title     = {The effect of Polycations on the Formation of Magnetite Nanoparticles},
  address   = {Potsdam},
  school      = {Universit{\"a}t Potsdam},
  pages     = {VIII, 99},
  abstract  = {Nanoparticles of magnetite (Fe3O4) are envisioned to find used in diverse applications, ranging from magnetic data storage, inks, ferrofluids as well as in magnetic resonance imaging, drug delivery, and hyperthermia cancer treatment. Their magnetic properties strongly depend on their size and morphology, two properties that can be synthetically controlled. Achieving appropriate control under soft chemical conditions has so far remained a challenging endeavor. One proven way of exerting this desired control has been using a biomimetic approach that emulates the proteome of magnetotactic bacteria by adding poly-L-arginine in the co- precipitation of ferrous and ferric chloride. The objective of the work presented here is to understand the impact of this polycation on the formation mechanism of magnetite and, through rational design, to enhance the control we can exert on magnetite nanoparticle size and morphology. We developed a SAXS setup to temporally and structurally resolve the formation of magnetite in the presence of poly-L-arginine in situ. Using analytical scattering models, we were able to separate the scattering contribution of a low-density 5 nm iron structure from the contribution of the growing nanoparticles. We identified that the low-density iron structure is a metastable precursor to the magnetite particles and that it is electrostatically stabilized by poly-L-arginine. In a process analogous to biomineralization, the presence of the charged macromolecule thus shifts the reaction mechanism from a thermodynamically controlled one to a kinetically controlled one. We identify this shift in reactions mechanism as the cornerstone of the proposed mechanism and as the crucial step in the paradigm of this extraordinary nanoparticle morphology and size control. Based on SAXS data, theoretical considerations suggest that an observed morphological transition between spherical, solid, and sub-structured mesocrystalline magnetite nanoparticles is induced through a pH-driven change in the wettability of the nanoparticle surface. With these results, we further demonstrate that SAXS can be an invaluable tool for investigating nanoparticle formation. We were able to change particle morphology from spherically solid particles to sub-structured mesocrystals merely by changing the precipitation pH. Improving the synthesis sustainability by substituting poly-L-arginine with renewable, polysaccharide-based polycations produced at the metric ton scale, we demonstrated that the ability to alter the reaction mechanism of magnetite can be generically attributed to the presence of polycations. Through meticulous analysis and the understanding of the formation mechanism, we were able to exert precise control over particle size and morphology, by adapting crucial synthesis parameters. We were thus able to grow mesocrystals up to 200 nm and solid nanocrystals of 100 nm by adding virtually any strong polycation. We further found a way to produce stable single domain magnetite at only slightly increased alkalinity, as magnetotactic bacteria do it. Thus through the understanding of the biological system, the consecutive biomimetic synthesis of magnetite and the following understanding of the mechanism involved in the in vitro synthesis, we managed to improve the synthetic control over the co-precipitation of magnetite, coming close biomineralization of magnetite in magnetotactic bacteria. Polyanions, in both natural as well as in synthetic systems, have been in the spotlight of recent research, yet our work shows the pivotal influence polycations have on the nucleation of magnetite. This work will contribute significantly to our ability to tailor magnetite nanoparticle size and morphology; in addition, we presume it will provide us with a model system for studying biomineralization of magnetite in vitro, putting the spotlight on the important influence of polycations, which have not had the scientific attention they deserve.},
  language  = {en}
}
@article{TeixeiraBlanzatKoetzetal.2006,
  author    = {Teixeira, C. V. and Blanzat, Muriel and Koetz, Joachim and Rico-Lattes, I. and Brezesinski, Gerald},
  title     = {In-plane miscibility and mixed bilayer microstructure in mixtures of catanionic glycolipids and zwitterionic phospholipids},
  series = {Biochimica et biophysica acta : Biomembranes},
  volume    = {1758},
  journal   = {Biochimica et biophysica acta : Biomembranes},
  publisher = {Elsevier},
  address   = {Amsterdam},
  issn      = {0005-2736},
  doi       = {10.1016/j.bbamem.2006.05.025},
  pages     = {1797 -- 1808},
  year      = {2006},
  abstract  = {SAXS/WAXS studies were performed in combination with freeze fracture electron microscopy using mixtures of a new Gemini catanionic surfactant (Gem 16-12, formed by two sugar groups bound by a hydrocarbon spacer with 12 carbons and two 16-carbon chains) and the zwitterionic phospholipid 1,2-dipalmitoyl-sn-glycero-3-phosphocholine(DPPC) to establish the phase diagram. Gem 16-12 in water forms bilayers with the same amount of hydration water as DPPC. A frozen interdigitated phase with a low hydration number is observed below room temperature. The kinetics of the formation of this crystalline phase is very slow. Above the chain melting temperature, multilayered vesicles are formed. Mixing with DPPC produces mixed bilayers above the corresponding chain melting temperature. At room temperature, partially lamellar aggregates with local nematic order are observed. Splitting of infinite lamellae into discs is linked to immiscibility in frozen state. The ordering process is always accompanied by dehydration of the system. As a consequence, an unusual order-disorder phase transition upon cooling is observed.},
  language  = {en}
}
@article{YanFangNoecheletal.2016,
  author    = {Yan, Wan and Fang, Liang and N{\"o}chel, Ulrich and Kratz, Karl and Lendlein, Andreas},
  title     = {Influence of programming strain rates on the shape-memory performance of semicrystalline multiblock copolymers},
  series = {Journal of polymer science : B, Polymer physics},
  volume    = {54},
  journal   = {Journal of polymer science : B, Polymer physics},
  publisher = {Wiley-Blackwell},
  address   = {Hoboken},
  issn      = {0887-6266},
  doi       = {10.1002/polb.24097},
  pages     = {1935 -- 1943},
  year      = {2016},
  abstract  = {Multiblock copolymers named PCL-PIBMD consisting of crystallizable poly(epsilon-caprolactone) segments and crystallizable poly[oligo(3S-iso-butylmorpholine-2,5-dione)] segments coupled by trimethyl hexamethylene diisocyanate provide a versatile molecular architecture for achieving shape-memory effects (SMEs) in polymers. The mechanical properties as well as the SME performance of PCL-PIBMD can be tailored by the variation of physical parameters during programming such as deformation strain or applied temperature protocols. In this study, we explored the influence of applying different strain rates during programming on the resulting nanostructure of PCL-PIBMD. Programming was conducted at 50 degrees C by elongation to epsilon(m)=50\% with strain rates of 1 or 10 or 50 mmmin(-1). The nanostructural changes were visualized by atomic force microscopy (AFM) measurements and investigated by in situ wide and small angle X-ray scattering experiments. With increasing the strain rate, a higher degree of orientation was observed in the amorphous domains. Simultaneously the strain-induced formation of new PIBMD crystals as well as the fragmentation of existing large PIBMD crystals occurred. The observed differences in shape fixity ratio and recovery stress of samples deformed with various strain rates can be attributed to their different nanostructures. The achieved findings can be relevant parameters for programming the shape-memory polymers with designed recovery forces. (c) 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016, 54, 1935-1943},
  language  = {en}
}
@article{WessigBudachThuenemann2015,
  author    = {Wessig, Pablo and Budach, Dennis B. and Th{\"u}nemann, Andreas F.},
  title     = {Dendrimers with Oligospiroketal (OSK) Building Blocks: Synthesis and Properties},
  series = {Chemistry - a European journal},
  volume    = {21},
  journal   = {Chemistry - a European journal},
  number    = {29},
  publisher = {Wiley-VCH},
  address   = {Weinheim},
  issn      = {0947-6539},
  doi       = {10.1002/chem.201501386},
  pages     = {10466 -- 10471},
  year      = {2015},
  abstract  = {The development of novel dendrimers containing oligospiroketal (OSK) rods as building blocks is described. The linkage between the core unit (CU), branching units (BU), and OSK rods relies on the CuAAC reaction between terminal alkynes and azides. Two different strategies of dendrimer synthesis were investigated and it was found that the convergent approach is clearly superior to the divergent one. SAXS measurements and MD simulations indicate that the obtained dendrimer features a globular structure with very low density. Obviously, the OSK rods stabilize a rather loose mass-fractal structure.},
  language  = {en}
}
@article{ZhongAdelsbergerNiedermeieretal.2013,
  author    = {Zhong, Qi and Adelsberger, Joseph and Niedermeier, M. A. and Golosova, Anastasi and Bivigou Koumba, Achille Mayelle and Laschewsky, Andr{\´e} and Funari, S. S. and Papadakis, Christine M. and M{\"u}ller-Buschbaum, Peter},
  title     = {The influence of selective solvents on the transition behavior of poly(styrene-b-monomethoxydiethylenglycol-acrylate-b-styrene) thick films},
  series = {Colloid and polymer science : official journal of the Kolloid-Gesellschaft},
  volume    = {291},
  journal   = {Colloid and polymer science : official journal of the Kolloid-Gesellschaft},
  number    = {6},
  publisher = {Springer},
  address   = {New York},
  issn      = {0303-402X},
  doi       = {10.1007/s00396-012-2879-4},
  pages     = {1439 -- 1451},
  year      = {2013},
  abstract  = {Thick poly(styrene-b-monomethoxydiethylenglycol-acrylate-b-styrene) [P(S-b-MDEGA-b-S)] films (thickness 5 mu m) are prepared from different solvents on flexible substrates by solution casting and investigated with small-angle X-ray scattering. As the solvents are either PS- or PMDEGA-selective, micelles with different core-shell micellar structures are formed. In PMDEGA-selective solvents, the PS block is the core and PMDEGA is the shell, whereas in PS-selective solvents, the order is reversed. After exposing the films to liquid D2O, the micellar structure inside the films prepared from PMDEGA-selective solvents remains unchanged and only the PMDEGA (shell part) swells. On the contrary, in the films prepared from PS-selective solvents, the micelles revert the core and the shell. This reversal causes more entanglements of the PMDEGA chains between the micelles. Moreover, the thermal collapse transition of the PMDEGA block in liquid D2O is significantly broadened. Irrespective of the solvent used for film preparation, the swollen PMDEGA shell does not show a prominent shrinkage when passing the phase transition, and the transition process occurs via compaction. The collapsed micelles have a tendency to densely pack above the transition temperature.},
  language  = {en}
}
@article{SchulzeTierschZenkeetal.2013,
  author    = {Schulze, Nicole and Tiersch, B. and Zenke, I. and Koetz, Joachim},
  title     = {Polyampholyte-tuned lyotrop lamellar liquid crystalline systems},
  series = {COLLOID AND POLYMER SCIENCE},
  volume    = {291},
  journal   = {COLLOID AND POLYMER SCIENCE},
  number    = {11},
  publisher = {SPRINGER},
  address   = {NEW YORK},
  issn      = {0303-402X},
  doi       = {10.1007/s00396-013-2999-5},
  pages     = {2551 -- 2559},
  year      = {2013},
  abstract  = {The influence of a polyampholyte, i.e., poly(N,N\’-diallyl-N,N\’-dimethyl-altmaleamic carboxylate) (PalH), on the lamellar liquid crystalline (LC) system sodium dodecyl sulfate (SDS)/decanol/water was investigated by means of microdifferential scanning calorimetry, small-angle X-ray diffraction (SAXS), and cryo-scanning electron microscopy. After incorporating PalH into the lamellar liquid crystalline system, SAXS measurements show that three different LC phases exist: i.e., a swelling, slightly swelling, and non-swelling one. At pH 4, the positively charged polymer with an extended conformation can directly adsorb at the anionic head groups of the surfactant and more compact vesicles are formed at room temperature. At pH 9, the electrostatic interactions between the polyampholyte (in a more coiled conformation) and the sulfate head groups of the SDS are leveled off and incompact vesicles are formed at room temperature. That means in presence of the polyampholyte the morphology of the LC phase, i.e., the supramolecular vesicle structure, can be tuned by varying the pH and/or the temperature.},
  language  = {en}
}