@phdthesis{Xie2023, author = {Xie, Dongjiu}, title = {Nanostructured Iron-based compounds as sulfur host material for lithium-sulfur batteries}, doi = {10.25932/publishup-61036}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-610369}, school = {Universit{\"a}t Potsdam}, pages = {viii, 142}, year = {2023}, abstract = {The present thesis focuses on the synthesis of nanostructured iron-based compounds by using β-FeOOH nanospindles and poly(ionic liquid)s (PILs) vesicles as hard and soft templates, respectively, to suppress the shuttle effect of lithium polysulfides (LiPSs) in Li-S batteries. Three types of composites with different nanostructures (mesoporous nanospindle, yolk-shell nanospindle, and nanocapsule) have been synthesized and applied as sulfur host material for Li-S batteries. Their interactions with LiPSs and effects on the electrochemical performance of Li-S batteries have been systematically studied. In the first part of the thesis, carbon-coated mesoporous Fe3O4 (C@M-Fe3O4) nanospindles have been synthesized to suppress the shuttle effect of LiPSs. First, β-FeOOH nanospindles have been synthesized via the hydrolysis of iron (III) chloride in aqueous solution and after silica coating and subsequent calcination, mesoporous Fe2O3 (M-Fe2O3) have been obtained inside the confined silica layer through pyrolysis of β-FeOOH. After the removal of the silica layer, electron tomography (ET) has been applied to rebuild the 3D structure of the M-Fe2O3 nanospindles. After coating a thin layer of polydopamine (PDA) as carbon source, the PDA-coated M-Fe2O3 particles have been calcinated to synthesize C@M-Fe3O4 nanospindles. With the chemisorption of Fe3O4 and confinement of mesoporous structure to anchor LiPSs, the composite C@M-Fe3O4/S electrode delivers a remaining capacity of 507.7 mAh g-1 at 1 C after 600 cycles. In the second part of the thesis, a series of iron-based compounds (Fe3O4, FeS2, and FeS) with the same yolk-shell nanospindle morphology have been synthesized, which allows for the direct comparison of the effects of compositions on the electrochemical performance of Li-S batteries. The Fe3O4-carbon yolk-shell nanospindles have been synthesized by using the β-FeOOH nanospindles as hard template. Afterwards, Fe3O4-carbon yolk-shell nanospindles have been used as precursors to obtain iron sulfides (FeS and FeS2)-carbon yolk-shell nanospindles through sulfidation at different temperatures. Using the three types of yolk-shell nanospindles as sulfur host, the effects of compositions on interactions with LiPSs and electrochemical performance in Li-S batteries have been systematically investigated and compared. Benefiting from the chemisorption and catalytic effect of FeS2 particles and the physical confinement of the carbon shell, the FeS2-C/S electrode exhibits the best electrochemical performance with an initial specific discharge capacity of 877.6 mAh g-1 at 0.5 C and a retention ratio of 86.7\% after 350 cycles. In the third part, PILs vesicles have been used as soft template to synthesize carbon nanocapsules embedded with iron nitride particles to immobilize and catalyze LiPSs in Li-S batteries. First, 3-n-decyl-1-vinylimidazolium bromide has been used as monomer to synthesize PILs nanovesicles by free radical polymerization. Assisted by PDA coating route and ion exchange, PIL nanovesicles have been successfully applied as soft template in morphology-maintaining carbonization to prepare carbon nanocapsules embedded with iron nitride nanoparticles (FexN@C). The well-dispersed iron nitride nanoparticles effectively catalyze the conversion of LiPSs to Li2S, owing to their high electrical conductivity and strong chemical binding to LiPSs. The constructed FexN@C/S cathode demonstrates a high initial discharge capacity of 1085.0 mAh g-1 at 0.5 C with a remaining value of 930.0 mAh g-1 after 200 cycles. The results in the present thesis demonstrate the facile synthetic routes of nanostructured iron-based compounds with controllable morphologies and compositions using soft and hard colloidal templates, which can be applied as sulfur host to suppress the shuttle behavior of LiPSs. The synthesis approaches developed in this thesis are also applicable to fabricating other transition metal-based compounds with porous nanostructures for other applications.}, language = {en} } @article{GeorgievGrafmuellerBlegeretal.2018, author = {Georgiev, Vasil N. and Grafm{\"u}ller, Andrea and Bl{\´e}ger, David and Hecht, Stefan and Kunstmann, Sonja and Barbirz, Stefanie and Lipowsky, Reinhard and Dimova, Rumiana}, title = {Area increase and budding in giant vesicles triggered by light}, series = {Advanced science}, volume = {5}, journal = {Advanced science}, number = {8}, publisher = {Wiley}, address = {Hoboken}, issn = {2198-3844}, doi = {10.1002/advs.201800432}, pages = {9}, year = {2018}, abstract = {Biomembranes are constantly remodeled and in cells, these processes are controlled and modulated by an assortment of membrane proteins. Here, it is shown that such remodeling can also be induced by photoresponsive molecules. The morphological control of giant vesicles in the presence of a water-soluble ortho-tetrafluoroazobenzene photoswitch (F-azo) is demonstrated and it is shown that the shape transformations are based on an increase in membrane area and generation of spontaneous curvature. The vesicles exhibit budding and the buds can be retracted by using light of a different wavelength. In the presence of F-azo, the membrane area can increase by more than 5\% as assessed from vesicle electrodeformation. To elucidate the underlying molecular mechanism and the partitioning of F-azo in the membrane, molecular dynamics simulations are employed. Comparison with theoretically calculated shapes reveals that the budded shapes are governed by curvature elasticity, that the spontaneous curvature can be decomposed into a local and a nonlocal contribution, and that the local spontaneous curvature is about 1/(2.5 mu m). The results show that exo- and endocytotic events can be controlled by light and that these photoinduced processes provide an attractive method to change membrane area and morphology.}, language = {en} } @misc{GeorgievGrafmuellerBlegeretal.2018, author = {Georgiev, Vasil N. and Grafm{\"u}ller, Andrea and Bl{\´e}ger, David and Hecht, Stefan and Kunstmann, Ruth Sonja and Barbirz, Stefanie and Lipowsky, Reinhard and Dimova, Rumiana}, title = {Area increase and budding in giant vesicles triggered by light}, series = {Postprints der Universit{\"a}t Potsdam : Mathematisch-Naturwissenschaftliche Reihe}, volume = {5}, journal = {Postprints der Universit{\"a}t Potsdam : Mathematisch-Naturwissenschaftliche Reihe}, number = {733}, issn = {1866-8372}, doi = {10.25932/publishup-42629}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-426298}, pages = {9}, year = {2018}, abstract = {Biomembranes are constantly remodeled and in cells, these processes are controlled and modulated by an assortment of membrane proteins. Here, it is shown that such remodeling can also be induced by photoresponsive molecules. The morphological control of giant vesicles in the presence of a water-soluble ortho-tetrafluoroazobenzene photoswitch (F-azo) is demonstrated and it is shown that the shape transformations are based on an increase in membrane area and generation of spontaneous curvature. The vesicles exhibit budding and the buds can be retracted by using light of a different wavelength. In the presence of F-azo, the membrane area can increase by more than 5\% as assessed from vesicle electrodeformation. To elucidate the underlying molecular mechanism and the partitioning of F-azo in the membrane, molecular dynamics simulations are employed. Comparison with theoretically calculated shapes reveals that the budded shapes are governed by curvature elasticity, that the spontaneous curvature can be decomposed into a local and a nonlocal contribution, and that the local spontaneous curvature is about 1/(2.5 mu m). The results show that exo- and endocytotic events can be controlled by light and that these photoinduced processes provide an attractive method to change membrane area and morphology.}, language = {en} } @misc{LiebigSarhanPrietzeletal.2016, author = {Liebig, Ferenc and Sarhan, Radwan Mohamed and Prietzel, Claudia Christina and Reinecke, Antje and Koetz, Joachim}, title = {"Green" gold nanotriangles: synthesis, purification by polyelectrolyte/micelle depletion flocculation and performance in surface-enhanced Raman scattering}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-394430}, pages = {33561 -- 33568}, year = {2016}, abstract = {The aim of this study was to develop a one-step synthesis of gold nanotriangles (NTs) in the presence of mixed phospholipid vesicles followed by a separation process to isolate purified NTs. Negatively charged vesicles containing AOT and phospholipids, in the absence and presence of additional reducing agents (polyampholytes, polyanions or low molecular weight compounds), were used as a template phase to form anisotropic gold nanoparticles. Upon addition of the gold chloride solution, the nucleation process is initiated and both types of particles, i.e., isotropic spherical and anisotropic gold nanotriangles, are formed simultaneously. As it was not possible to produce monodisperse nanotriangles with such a one-step procedure, the anisotropic nanoparticles needed to be separated from the spherical ones. Therefore, a new type of separation procedure using combined polyelectrolyte/micelle depletion flocculation was successfully applied. As a result of the different purification steps, a green colored aqueous dispersion was obtained containing highly purified, well-defined negatively charged flat nanocrystals with a platelet thickness of 10 nm and an edge length of about 175 nm. The NTs produce promising results in surface-enhanced Raman scattering.}, language = {en} } @article{BrosnanSchlaadAntonietti2015, author = {Brosnan, Sarah M. and Schlaad, Helmut and Antonietti, Markus}, title = {Aqueous Self-Assembly of Purely Hydrophilic Block Copolymers into Giant Vesicles}, series = {Angewandte Chemie : a journal of the Gesellschaft Deutscher Chemiker ; International edition}, volume = {54}, journal = {Angewandte Chemie : a journal of the Gesellschaft Deutscher Chemiker ; International edition}, number = {33}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1433-7851}, doi = {10.1002/anie.201502100}, pages = {9715 -- 9718}, year = {2015}, abstract = {Self-assembly of macromolecules is fundamental to life itself, and historically, these systems have been primitively mimicked by the development of amphiphilic systems, driven by the hydrophobic effect. Herein, we demonstrate that self-assembly of purely hydrophilic systems can be readily achieved with similar ease and success. We have synthesized double hydrophilic block copolymers from polysaccharides and poly(ethylene oxide) or poly(sarcosine) to yield high molar mass diblock copolymers through oxime chemistry. These hydrophilic materials can easily assemble into nanosized (<500nm) and microsized (>5m) polymeric vesicles depending on concentration and diblock composition. Because of the solely hydrophilic nature of these materials, we expect them to be extraordinarily water permeable systems that would be well suited for use as cellular mimics.}, language = {en} } @phdthesis{Linke2005, author = {Linke, Gunnar Torsten}, title = {Eigenschaften fluider Vesikeln bei endlichen Temperaturen}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-5835}, school = {Universit{\"a}t Potsdam}, year = {2005}, abstract = {In der vorliegenden Arbeit werden die Eigenschaften geschlossener fluider Membranen, sogenannter Vesikeln, bei endlichen Temperaturen untersucht. Dies beinhaltet Betrachtungen zur Form freier Vesikeln, eine Untersuchung des Adh{\"a}sionsverhaltens von Vesikeln an planaren Substraten sowie eine Untersuchung der Eigenschaften fluider Vesikeln in eingeschr{\"a}nkten Geometrien. Diese Untersuchungen fanden mit Hilfe von Monte-Carlo-Simulationen einer triangulierten Vesikeloberfl{\"a}che statt. Die statistischen Eigenschaften der fluktuierenden fluiden Vesikeln wurden zum Teil mittels Freier-Energie-Profile analysiert. In diesem Zusammenhang wurde eine neuartige Histogrammethode entwickelt.
Die Form f{\"u}r eine freie fluide Vesikel mit frei ver{\"a}nderlichem Volumen, die das Konfigurationsenergie-Funktional minimiert, ist im Falle verschwindender Temperatur eine Kugel. Mit Hilfe von Monte-Carlo-Simulationen sowie einem analytisch behandelbaren Modellsystem konnte gezeigt werden, daß sich dieses Ergebnis nicht auf endliche Temperaturen verallgemeinern l{\"a}sst und statt dessen leicht prolate und oblate Vesikelformen gegen{\"u}ber der Kugelgestalt {\"u}berwiegen. Dabei ist die Wahrscheinlichkeit f{\"u}r eine prolate Form ein wenig gr{\"o}oßer als f{\"u}r eine oblate. Diese spontane Asph{\"a}rizit{\"a}t ist entropischen Ursprungs und tritt nicht bei zweidimensionalen Vesikeln auf. Durch osmotische Dr{\"u}cke in der Vesikel, die gr{\"o}ßer sind als in der umgebenden Fl{\"u}ssigkeit, l{\"a}sst sich die Asph{\"a}rizit{\"a}t reduzieren oder sogar kompensieren. Die {\"U}berg{\"a}nge zwischen den beobachteten prolaten und oblaten Formen erfolgen im Bereich von Millisekunden in Abwesenheit osmotisch aktiver Partikel. Bei Vorhandensein derartiger Partikel ergeben sich {\"U}bergangszeiten im Bereich von Sekunden. Im Rahmen der Untersuchung des Adh{\"a}sionsverhaltens fluider Vesikeln an planaren, homogenen Substraten konnte mit Hilfe von Monte-Carlo-Simulationen festgestellt werden, dass die Eigenschaften der Kontaktfl{\"a}che der Vesikeln stark davon abh{\"a}ngen, welche Kr{\"a}fte den Kontakt bewirken. F{\"u}r eine dominierende attraktive Wechselwirkung zwischen Substrat und Vesikelmembran sowie im Falle eines Massendichteunterschieds der Fl{\"u}ssigkeiten innerhalb und außerhalb der Vesikel, der die Vesikel auf das Substrat sinken l{\"a}sst, fndet man innerhalb der Kontakt � ache eine ortsunabh� angige Verteilung des Abstands zwischen Vesikelmembran und Substrat. Dr{\"u}ckt die Vesikel ohne Ber{\"u}cksichtigung osmotischer Effekte auf Grund einer Differenz der Massendichten der Membran und der umgebenden Fl{\"u}ssigkeit gegen das Substrat, so erh{\"a}lt man eine Abstandsverteilung zwischen Vesikelmembran und Substrat, die mit dem Abstand vom Rand der Kontaktfl{\"a}che variiert. Dieser Effekt ist zudem temperaturabh{\"a}ngig. Ferner wurde die Adh{\"a}sion fluider Vesikeln an chemisch strukturierten planaren Substraten untersucht. Durch das Wechselspiel von entropischen Effekten und Konfigurationsenergien entsteht eine komplexe Abh{\"a}ngigkeit der Vesikelform von Biegesteifigkeit, osmotischen Bedingungen und der Geometrie der attraktiven Dom{\"a}nen. F{\"u}r die Bestimmung der Biegesteifigkeit der Vesikelmembranen liefern die existierenden Verfahren stark voneinander abweichende Ergebnisse. In der vorliegenden Arbeit konnte mittels Monte-Carlo-Simulationen zur Bestimmung der Biegesteifigkeit anhand des Mikropipettenverfahrens von Evans gezeigt werden, dass dieses Verfahren die a priori f{\"u}r die Simulation vorgegebene Biegesteifigkeit im wesentlichen reproduzieren kann. Im Hinblick auf medizinisch-pharmazeutische Anwendungen ist der Durchgang fluider Vesikeln durch enge Poren relevant. In Monte-Carlo-Simulationen konnte gezeigt werden, dass ein spontaner Transport der Vesikel durch ein Konzentrationsgef{\"a}lle osmotisch aktiver Substanzen, das den physiologischen Bedingungen entspricht, induziert werden kann. Es konnten die hierf{\"u}r notwendigen osmotischen Bedingungen sowie die charakteristischen Zeitskalen abgesch{\"a}tzt werden. Im realen Experiment sind Eindringzeiten in eine enge Pore im Bereich weniger Minuten zu erwarten. Ferner konnte beobachtet werden, dass bei Vesikeln mit einer homogenen, positiven spontanen Kr{\"u}mmung Deformationen hin zu prolaten Formen leichter erfolgen als bei Vesikeln ohne spontane Kr{\"u}mmung. Mit diesem Effekt ist eine Verringerung der Energiebarriere f{\"u}r das Eindringen in eine Pore verbunden, deren Radius nur wenig kleiner als der Vesikelradius ist.}, subject = {Membran}, language = {de} } @phdthesis{Kukula2001, author = {Kukula, Hildegard}, title = {Lineare und verzweigte Blockcopolymere aus Polypeptiden und synthetischen Polymeren}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-0000040}, school = {Universit{\"a}t Potsdam}, year = {2001}, abstract = {Die vorliegende Arbeit besch{\"a}ftigt sich mit der Synthese und den Eigenschaften von linearen und verzweigten amphiphilen Polypeptid-Blockcopolymeren. Die Frage nach dem Einfluss der Topologie und Konformation der Blockcopolymere auf die supramolekularen und kolloidalen Eigenschaften bildete einen wichtigen Aspekt bei den Untersuchungen. Die Blockcopolymere wurden nach einem mehrstufigen Reaktionsschema durch Kombination von anionischer und ring{\"o}ffnender Polymerisation von Aminos{\"a}uren-N-Carboxyanhydriden (NCA) synthetisiert. Die Untersuchung der Polypeptid-Blockcopolymere hinsichtlich ihres Aggregationsverhaltens in fester Phase sowie in verd{\"u}nnter w{\"a}ssriger L{\"o}sung erfolgte mittels Streumethoden (SAXS, WAXS, DLS) sowie abbildender Methoden (TEM). Durch Einsatz der Blockcopolymere als polymere Stabilisatoren in der Emulsionspolymerisation wurden Oberfl{\"a}chen funktionalisierte Latizes erhalten. Als Beispiel f{\"u}r eine pharmazeutische Anwendung wurden biovertr{\"a}gliche Polypeptid-Blockcopolymere als Wirkstoff-Tr{\"a}gersysteme in der Krebstherapie eingesetzt.}, language = {de} }