@phdthesis{Fandrich2016,
  author    = {Fandrich, Artur},
  title     = {Untersuchung des Verhaltens von thermoresponsiven Polymeren auf Elektroden in Interaktion mit biomolekularen Systemen},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-396551},
  school      = {Universit{\"a}t Potsdam},
  pages     = {111},
  year      = {2016},
  abstract  = {Diese Arbeit befasst sich mit der Herstellung und Charakterisierung von thermoresponsiven Filmen auf Goldelektroden durch Fixierung eines bereits synthetisierten thermoresponsiven Polymers. Als Basis f{\"u}r die Entwicklung der responsiven Grenzfl{\"a}che dienten drei unterschiedliche Copolymere (Polymere I, II und III) aus der Gruppe der thermisch schaltbaren Poly(oligo(ethylenglykol)methacrylate). Die turbidimetrischen Messungen der Copolymere in L{\"o}sungen haben gezeigt, dass der Tr{\"u}bungspunkt vom pH-Wert, der Gegenwart von Salzen sowie von der Ionenst{\"a}rke der L{\"o}sung abh{\"a}ngig ist. Nach der Charakterisierung der Polymere in L{\"o}sung wurden Experimente der kovalenten Kopplung der Polymere I bis III an die Oberfl{\"a}che der Gold-Elektroden durchgef{\"u}hrt. W{\"a}hrend bei Polymeren I und II die Ankopplung auf einer Amidverbr{\"u}ckung basierte, wurde bei Polymer III als alternative Methode zur Immobilisierung eine photoinduzierte Anbindung unter gleichzeitiger Vernetzung gew{\"a}hlt. Der Nachweis der erfolgreichen Ankopplung erfolgte bei allen Polymeren elektrochemisch mittels Cyclovoltammetrie und Impedanzspektroskopie in K3/4[Fe(CN)6]-L{\"o}sungen. Wie die Ellipsometrie-Messungen zeigten, waren die erhaltenen Polymer-Filme unterschiedlich dick. Die Ankopplung {\"u}ber Amidverbr{\"u}ckung lieferte d{\"u}nne Filme (10 - 15 nm), w{\"a}hrend der photovernetzte Film deutlich dicker war (70-80 nm) und die darunter liegende Oberfl{\"a}che relativ gut isolierte. Elektrochemische Temperaturexperimente an Polymer-modifizierten Oberfl{\"a}chen in L{\"o}sungen in Gegenwart von K3/4[Fe(CN)6] zeigten, dass auch die immobilisierten Polymere I bis III responsives Temperaturverhalten zeigen. Bei Elektroden mit den immobilisierten Polymeren I und II ist der Temperaturverlauf der Parameterwerte diskontinuierlich - ab einem kritischen Punkt (37 °C f{\"u}r Polymer I und 45 °C f{\"u}r Polymer II) wird zun{\"a}chst langsame Zunahme der Peakstr{\"o}me wird deutlich schneller. Das Temperaturverhalten von Polymer III ist dagegen bis 50 °C kontinuierlich, der Peakstrom sinkt hier durchgehend. Weiterhin wurde mit den auf Polymeren II und III basierten Elektroden deren Anwendung als responsive Matrix f{\"u}r Bioerkennungsreaktionen untersucht. Es wurde die Ankopplung von kleinen Biorezeptoren, TAG-Peptiden, an Polymer II- und Polymer III-modifizierten Elektroden durchgef{\"u}hrt. Das hydrophile FLAG-TAG-Peptid ver{\"a}ndert das Temperaturverhalten des Polymer II-Films unwesentlich, da es die Hydrophilie des Netzwerkes nicht beeinflusst. Weiterhin wurde der Effekt der Ankopplung der ANTI-FLAG-TAG-Antik{\"o}rper an FLAG-TAG-modifizierte Polymer II-Filme untersucht. Es konnte gezeigt werden, dass die Antik{\"o}rper spezifisch an FLAG-TAG-modifiziertes Polymer II binden. Es wurde keine unspezifische Anbindung von ANTI-FLAG-TAG an Polymer II beobachtet. Die Temperaturexperimente haben gezeigt, dass die thermische Restrukturierung des Polymer II-FLAG-TAG-Filmes auch nach der Antik{\"o}rper-Ankopplung noch stattfindet. Der Einfluss der ANTI-FLAG-TAG-Ankopplung ist gering, da der Unterschied in der Hydrophilie zwischen Polymer II und FLAG-TAG bzw. ANTI-FLAG-TAG zu gering ist. F{\"u}r die Untersuchungen mit Polymer III-Elektroden wurde neben dem hydrophilen FLAG-TAG-Peptid das deutlich hydrophobere HA-TAG-Peptid ausgew{\"a}hlt. Wie im Falle der Polymer II Elektrode beeinflusst das gekoppelte FLAG-TAG-Peptid das Temperaturverhalten des Polymer III-Netzwerkes nur geringf{\"u}gig. Die gemessenen Stromwerte sind geringer als bei der Polymer III-Elektrode. Das Temperaturverhalten der FLAG-TAG-Elektrode {\"a}hnelt dem der reinen Polymer III-Elektrode - die Stromwerte sinken kontinuierlich bis die Temperatur von ca. 40 °C erreicht ist, bei der ein Plateau beobachtet wird. Offensichtlich ver{\"a}ndert FLAG-TAG auch in diesem Fall nicht wesentlich die Hydrophilie des Polymer III-Netzwerkes. Das an Polymer III-Elektroden gekoppelte hydrophobe HA-TAG-Peptid beeinflusst dagegen im starken Maße den Quellzustand des Netzwerkes. Die Str{\"o}me f{\"u}r die HA-TAG-Elektroden sind deutlich geringer als die f{\"u}r die FLAG-TAG-Polymer III-Elektroden, was auf geringeren Wassergehalt und dickeren Film zur{\"u}ckzuf{\"u}hren ist. Bereits ab 30 °C erfolgt der Anstieg von Stromwerten, der bei Polymer III- bzw. bei Polymer III-FLAG-TAG-Elektroden nicht beobachtet werden kann. Das gekoppelte hydrophobe HA-TAG-Peptid verdr{\"a}ngt Wasser aus dem Polymer III-Netzwerk, was in der Stauchung des Films bereits bei Raumtemperatur resultiert. Dies f{\"u}hrt dazu, dass der Film im Laufe des Temperaturanstieges kaum noch komprimiert. Die Stromwerte steigen in diesem Fall entsprechend des Anstiegs der temperaturabh{\"a}ngigen Diffusion des Redoxpaares. Diese Untersuchungen zeigen, dass das HA-TAG-Peptid als Ankermolek{\"u}l deutlich besser f{\"u}r eine potentielle Verwendung der Polymer III-Filme f{\"u}r sensorische Zwecke geeignet ist, da es sich deutlich in der Hydrophilie von Polymer III unterscheidet.},
  language  = {de}
}
@phdthesis{Tan2018,
  author    = {Tan, Li},
  title     = {Synthesis, assembly and thermo-responsivity of polymer-functionalized magnetic cobalt nanoparticles},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-418153},
  school      = {Universit{\"a}t Potsdam},
  pages     = {X, 111},
  year      = {2018},
  abstract  = {This thesis mainly covers the synthesis, surface modification, magnetic-field-induced assembly and thermo-responsive functionalization of superparamagnetic Co NPs initially stabilized by hydrophobic small molecules oleic acid (OA) and trioctylphosphine oxide (TOPO), as well as the synthesis of both superparamagnetic and ferromagnetic Co NPs by using end-functionalized-polystyrene as stabilizer. Co NPs, due to their excellent magnetic and catalytic properties, have great potential application in various fields, such as ferrofluids, catalysis, and magnetic resonance imaging (MRI). Superparamagnetic Co NPs are especially interesting, since they exhibit zero coercivity. They get magnetized in an external magnetic field and reach their saturation magnetization rapidly, but no magnetic moment remains after removal of the applied magnetic field. Therefore, they do not agglomerate in the body when they are used in biomedical applications. Normally, decomposition of metallic precursors at high temperature is one of the most important methods in preparation of monodisperse magnetic NPs, providing tunability in size and shape. Hydrophobic ligands like OA, TOPO and oleylamine are often used to both control the growth of NPs and protect them from agglomeration. The as-prepared magnetic NPs can be used in biological applications as long as they are transferred into water. Moreover, their supercrystal assemblies have the potential for high density data storage and electronic devices. In addition to small molecules, polymers can also be used as surfactants for the synthesis of ferromagnetic and superparamagnetic NPs by changing the reaction conditions. Therefore, chapter 2 gives an overview on the basic concept of synthesis, surface modification and self-assembly of magnetic nanoparticles. Various examples were used to illustrate the recent work. The hydrophobic Co NPs synthesized with small molecules as surfactants limit their biological applications, which require a hydrophilic or aqueous environment. Surface modification (e.g., ligand exchange) is a general idea for either phase transition or surface-functionalization. Therefore, in chapter 3, a ligand exchange process was conducted to functionalize the surface of Co NPs. PNIPAM is one of the most popular smart polymers and its lower critical solution temperature (LCST) is around 32 °C, with a reversible change in the conformation structure between hydrophobic and hydrophilic. The novel nanocomposites of superparamagnetic Co NPs and thermo-responsive PNIPAM are of great interest. Thus, well-defined superparamagnetic Co NPs were firstly synthesized through the thermolysis of cobalt carbonyl by using OA and TOPO as surfactants. A functional ATRP initiator, containing an amine (as anchoring group) and a 2-bromopropionate group (SI-ATRP initiator), was used to replace the original ligands. This process is rapid and facial for efficient surface functionalization and afterwards the Co NPs can be dispersed into polar solvent DMF without aggregation. FT-IR spectroscopy showed that the TOPO was completely replaced, but a small amount of OA remained on the surface. A TGA measurement allowed the calculation of the grafting density of the initiator as around 3.2 initiator/nm2. Then, the surface-initiated ATRP was conducted for the polymerization of NIPAM on the surface of Co NPs and rendered the nanocomposites water-dispersible. A temperature-dependent dynamic light scattering study showed the aggregation behavior of PNIPAM-coated Co NPs upon heating and this process was proven to be reversible. The combination of superparamagnetic and thermo-responsive properties in these hybrid nanoparticles is promising for future applications e.g. in biomedicine. In chapter 4, the magnetic-field-induced assembly of superparamagnetic cobalt nanoparticles both on solid substrates and at liquid-air interface was investigated. OA- and TOPO-coated Co NPs were synthesized via the thermolysis of cobalt carbonyl and dispersed into either hexane or toluene. The Co NP dispersion was dropped onto substrates (e.g., TEM grid, silicon wafer) and at liquid-air (water-air or ethylene glycol-air) interface. Due to the attractive dipolar interaction, 1-D chains formed in the presence of an external magnetic field. It is known that the concentration and the strength of the magnetic field can affect the assembly behavior of superparamagnetic Co NPs. Therefore, the influence of these two parameters on the morphology of the assemblies was studied. The formed 1-D chains were shorter and flexible at either lower concentration of the Co NP dispersion or lower strength of the external magnetic field due to thermal fluctuation. However, by increasing either the concentration of the NP dispersion or the strength of the applied magnetic field, these chains became longer, thicker and straighter. The reason could be that a high concentration led to a high fraction of short dipolar chains, and their interaction resulted in longer and thicker chains under applied magnetic field. On the other hand, when the magnetic field increased, the induced moments of the magnetic nanoparticles became larger, which dominated over the thermal fluctuation. Thus, the formed short chains connected to each other and grew in length. Thicker chains were also observed through chain-chain interaction. Furthermore, the induced moments of the NPs tended to direct into one direction with increased magnetic field, thus the chains were straighter. In comparison between the assembly on substrates, at water-air interface and at ethylene glycol-air interface, the assembly of Co NPs in hexane dispersion at ethylene glycol-air interface showed the most regular and homogeneous chain structures due to the better spreading of the dispersion on ethylene glycol subphase than on water subphase and substrates. The magnetic-field-induced assembly of superparamagnetic nanoparticles could provide a powerful approach for applications in data storage and electronic devices. Chapter 5 presented the synthesis of superparamagnetic and ferromagnetic cobalt nanoparticles through a dual-stage thermolysis of cobalt carbonyl (Co2(CO)8) by using polystyrene as surfactant. The amine end-functionalized polystyrene surfactants with different molecular weight were prepared via atom transfer radical polymerization technique. The molecular weight determination of polystyrene was conducted by gel permeation chromatography (GPC) and matrix-assisted laser desorption/ionization time-of-flight (MALDI-ToF) mass spectrometry techniques. The results showed that, when the molecular weight distribution is low (Mw/Mn < 1.2), the measurement by GPC and MALDI-ToF MS provided nearly similar results. For example, the molecular weight of 10600 Da was obtained by MALDI-ToF MS, while GPC gave 10500 g/mol (Mw/Mn = 1.17). However, if the polymer is poly distributed, MALDI-ToF MS cannot provide an accurate value. This was exemplified for a polymer with a molecular weight of 3130 Da measured by MALDI-TOF MS, while GPC showed 2300 g/mol (Mw/Mn = 1.38). The size, size distribution and magnetic properties of the hybrid particles were different by changing either the molecular weight or concentration of the polymer surfactants. The analysis from TEM characterization showed that the size of cobalt nanoparticles stabilized with polystyrene of lower molecular weight (Mn = 2300 g/mol) varied from 12-22 nm, while the size with middle (Mn = 4500 g/mol) and higher molecular weight (Mn = 10500 g/mol) of polystyrene-coated cobalt nanoparticles showed little change. Magnetic measurements exhibited that the small cobalt particles (12 nm) were superparamagnetic, while larger particles (21 nm) were ferromagnetic and assembled into 1-D chains. The grafting density calculated from thermogravimetric analysis showed that a higher grafting density of polystyrene was obtained with lower molecular weight (Mn = 2300 g/mol) than those with higher molecular weight (Mn = 10500 g/mol). Due to the larger steric hindrance, polystyrene with higher molecular weight cannot form a dense shell on the surface of the nanoparticles, which resulted in a lower grafting density. Wide angle X-ray scattering measurements revealed the epsilon cobalt crystalline phases of both superparamagnetic Co NPs coated with polystyrene (Mn = 2300 g/mol) and ferromagnetic Co NPs coated with polystyrene (Mn = 10500 g/mol). Furthermore, a stability study showed that PS-Co NPs prepared with higher polymer concentration and polymer molecular weight exhibited a better stability.},
  language  = {en}
}
@phdthesis{Hentschel2008,
  author    = {Hentschel, Jens},
  title     = {Synthese und kontrollierte Mikrostrukturbildung funktionaler Peptid-Polymerkonjugate in organischen L{\"o}sungsmitteln},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-19840},
  school      = {Universit{\"a}t Potsdam},
  year      = {2008},
  abstract  = {In der vorliegenden Arbeit wurde ein Ansatz verfolgt, die besonderen Eigenschaften der Strukturbildung sequenzdefinierter Peptide mit den vielseitigen Materialeigenschaften synthetischer Blockcopolymere zu kombinieren. Dazu wurde ein synthetisches Polymer kovalent mit einer definierten Peptidsequenz verkn{\"u}pft. Der Peptidblock (die Organisationseinheit) wurde speziell designt, um sp{\"a}ter die Strukturbildung des Peptid-Polymerkonjugates induzieren und leiten zu k{\"o}nnen. Als Organisationsmotiv diente hierbei das aus der Natur bekannte β-Faltblatt Strukturmotiv. Das Peptidsegment wurde in einer festphasengebundenen Synthese aufgebaut. Dabei wurden tempor{\"a}re St{\"o}r-Segmente (Switch-Segmente) in die Peptidsequenz integriert. Diese Segmente unterdr{\"u}cken die Aggregationstendenz w{\"a}hrend der Synthese und k{\"o}nnen durch einen pH-abh{\"a}ngigen Schaltvorgang in das nat{\"u}rliche Peptidr{\"u}ckgrat {\"u}berf{\"u}hrt werden. Zus{\"a}tzlich zu der verbesserten Ausbeute und Reinheit der entsprechenden Peptide war auf diese Weise eine kontrollierte Aktivierung der Mikrostrukturbildung m{\"o}glich. Mit Hilfe zwei verschiedener Synthesestrategien (Kupplungs- bzw. Polymerisationsstrategie) wurde ein Satz von definierten Peptid-Polymerkonjugaten mit unterschiedlich großen Polymersegmenten synthetisiert. Diese wurden anschließend im Hinblick auf ihre Strukturbildungseigenschaften in organischen L{\"o}sungsmitteln untersucht. Durch mikroskopische Verfahren (AFM, TEM), konnte f{\"u}r alle Konjugate, die Bildung faserartiger Aggregate mit Dimensionen im Nano- bis Mikrometerbereich beobachtet werden. Genauere Untersuchungen zeigten, dass die Peptidsegmente in diesen Faserstrukturen ein β-Faltblatt ausbilden. Dies ist ein deutlicher Hinweis darauf, dass die Strukturbildung der Konjugate tats{\"a}chlich durch den Peptidblock gesteuert und kontrolliert wurde.},
  language  = {de}
}
@phdthesis{Saatchi2023,
  author    = {Saatchi, Mersa},
  title     = {Study on manufacturing of multifunctional bilayer systems},
  doi       = {10.25932/publishup-60196},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-601968},
  school      = {Universit{\"a}t Potsdam},
  pages     = {116},
  year      = {2023},
  abstract  = {Layered structures are ubiquitous in nature and industrial products, in which individual layers could have different mechanical/thermal properties and functions independently contributing to the performance of the whole layered structure for their relevant application. Tuning each layer affects the performance of the whole layered system. Pores are utilized in various disciplines, where low density, but large surfaces are demanded. Besides, open and interconnected pores would act as a transferring channel for guest chemical molecules. The shape of pores influences compression behavior of the material. Moreover, introducing pores decreases the density and subsequently the mechanical strength. To maintain defined mechanical strength under various stress, porous structure can be reinforced by adding reinforcement agent such as fiber, filler or layered structure to bear the mechanical stress on demanded application. In this context, this thesis aimed to generate new functions in bilayer systems by combining layers having different moduli and/or porosity, and to develop suitable processing techniques to access these structures. Manufacturing processes of layered structures employ often organic solvents mostly causing environmental pollution. In this regard, the studied bilayer structures here were manufactured by processes free of organic solvents. In this thesis, three bilayer systems were studied to answer the individual questions. First, while various methods of introducing pores in melt-phase are reported for one-layer constructs with simple geometry, can such methods be applied to a bilayer structure, giving two porous layers? This was addressed with Bilayer System 1. Two porous layers were obtained from melt-blending of two different polyurethanes (PU) and polyvinyl alcohol (PVA) in a co-continuous phase followed by sequential injection molding and leaching the PVA phase in deionized water. A porosity of 50 ± 5\% with a high interconnectivity was obtained, in which the pore sizes in both layers ranged from 1 µm to 100 µm with an average of 22 µm in both layers. The obtained pores were tailored by applying an annealing treatment at relevant high temperatures of 110 °C and 130 °C, which allowed the porosity to be kept constant. The disadvantage of this system is that a maximum of 50\% porosity could be reached and removal of leaching material in the weld line section of both layers is not guaranteed. Such a construct serves as a model for bilayer porous structure for determining structure-property relationships with respect to the pore size, porosity and mechanical properties of each layer. This fabrication method is also applicable to complex geometries by designing a relevant mold for injection molding. Secondly, utilizing scCO2 foaming process at elevated temperature and pressure is considered as a green manufacturing process. Employing this method as a post-treatment can alter the history orientation of polymer chains created by previous fabrication methods. Can a bilayer structure be fabricated by a combination of sequential injection molding and scCO2 foaming process, in which a porous layer is supported by a compact layer? Such a construct (Bilayer System 2) was generated by sequential injection molding of a PCL (Tm ≈ 58 °C) layer and a PLLA (Tg ≈ 58 °C) layer. Soaking this structure in the autoclave with scCO2 at T = 45 °C and P = 100 bar led to the selective foaming of PCL with a porosity of 80\%, while the PLA layer was kept compact. The scCO2 autoclave led to the formation of a porous core and skin layer of the PCL, however, the degree of crystallinity of PLLA layer increased from 0 to 50\% at the defined temperature and pressure. The microcellular structure of PCL as well as the degree of crystallinity of PLLA were controlled by increasing soaking time. Thirdly, wrinkles on surfaces in micro/nano scale alter the properties, which are surface-related. Wrinkles are formed on a surface of a bilayer structure having a compliant substrate and a stiff thin film. However, the reported wrinkles were not reversible. Moreover, dynamic wrinkles in nano and micro scale have numerous examples in nature such as gecko foot hair offering reversible adhesion and an ability of lotus leaves for self-cleaning altering hydrophobicity of the surface. It was envisioned to imitate this biomimetic function on the bilayer structure, where self-assembly on/off patterns would be realized on the surface of this construct. In summary, developing layered constructs having different properties/functions in the individual layer or exhibiting a new function as the consequence of layered structure can give novel insight for designing layered constructs in various disciplines such as packaging and transport industry, aerospace industry and health technology.},
  language  = {en}
}
@phdthesis{Hain2022,
  author    = {Hain, Tobias Martin},
  title     = {Structure formation and identification in geometrically driven soft matter systems},
  doi       = {10.25932/publishup-55880},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-558808},
  school      = {Universit{\"a}t Potsdam},
  pages     = {xviii, 171},
  year      = {2022},
  abstract  = {Subdividing space through interfaces leads to many space partitions that are relevant to soft matter self-assembly. Prominent examples include cellular media, e.g. soap froths, which are bubbles of air separated by interfaces of soap and water, but also more complex partitions such as bicontinuous minimal surfaces. Using computer simulations, this thesis analyses soft matter systems in terms of the relationship between the physical forces between the system's constituents and the structure of the resulting interfaces or partitions. The focus is on two systems, copolymeric self-assembly and the so-called Quantizer problem, where the driving force of structure formation, the minimisation of the free-energy, is an interplay of surface area minimisation and stretching contributions, favouring cells of uniform thickness. In the first part of the thesis we address copolymeric phase formation with sharp interfaces. We analyse a columnar copolymer system "forced" to assemble on a spherical surface, where the perfect solution, the hexagonal tiling, is topologically prohibited. For a system of three-armed copolymers, the resulting structure is described by solutions of the so-called Thomson problem, the search of minimal energy configurations of repelling charges on a sphere. We find three intertwined Thomson problem solutions on a single sphere, occurring at a probability depending on the radius of the substrate. We then investigate the formation of amorphous and crystalline structures in the Quantizer system, a particulate model with an energy functional without surface tension that favours spherical cells of equal size. We find that quasi-static equilibrium cooling allows the Quantizer system to crystallise into a BCC ground state, whereas quenching and non-equilibrium cooling, i.e. cooling at slower rates then quenching, leads to an approximately hyperuniform, amorphous state. The assumed universality of the latter, i.e. independence of energy minimisation method or initial configuration, is strengthened by our results. We expand the Quantizer system by introducing interface tension, creating a model that we find to mimic polymeric micelle systems: An order-disorder phase transition is observed with a stable Frank-Caspar phase. The second part considers bicontinuous partitions of space into two network-like domains, and introduces an open-source tool for the identification of structures in electron microscopy images. We expand a method of matching experimentally accessible projections with computed projections of potential structures, introduced by Deng and Mieczkowski (1998). The computed structures are modelled using nodal representations of constant-mean-curvature surfaces. A case study conducted on etioplast cell membranes in chloroplast precursors establishes the double Diamond surface structure to be dominant in these plant cells. We automate the matching process employing deep-learning methods, which manage to identify structures with excellent accuracy.},
  language  = {en}
}
@article{LuetzowWeigelLendlein2020,
  author    = {L{\"u}tzow, Karola and Weigel, Thomas and Lendlein, Andreas},
  title     = {Solvent-based fabrication method for magnetic, shape-memory nanocomposite foams},
  series = {MRS advances},
  volume    = {5},
  journal   = {MRS advances},
  number    = {14-15},
  publisher = {Cambridge Univ. Press},
  address   = {Cambridge},
  issn      = {2059-8521},
  doi       = {10.1557/adv.2019.422},
  pages     = {785 -- 795},
  year      = {2020},
  abstract  = {This paper presents shape-memory foams that can be temporarily fixed in their compressed state and be expanded on demand. Highly porous, nanocomposite foams were prepared from a solution of polyetherurethane with suspended nanoparticles (mean aggregate size 90 nm) which have an iron(III) oxide core with a silica shell. The polymer solution with suspended nanoparticles was cooled down to -20 degrees C in a two-stage process, which was followed by freeze-drying. The average pore size increases with decreasing concentration of nanoparticles from 158 mu m to 230 mu m while the foam porosity remained constant. After fixation of a temporary form of the nanocomposite foams, shape recovery can be triggered either by heat or by exposure to an alternating magnetic field. Compressed foams showed a recovery rate of up to 76 +/- 4\% in a thermochamber at 80 degrees C, and a slightly lower recovery rate of up to 65 +/- 4\% in a magnetic field.},
  language  = {en}
}
@phdthesis{Uyaver2004,
  author    = {Uyaver, Sahin},
  title     = {Simulation of annealed polyelectrolytes in poor solvents},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-0001488},
  school      = {Universit{\"a}t Potsdam},
  year      = {2004},
  abstract  = {Polymere sind lange kettenartige Molek{\"u}le. Sie bestehen aus vielen elementaren chemischen Einheiten, den Monomeren, die durch kovalente Bindungen aneinander gekettet sind. Polyelektrolyte sind Polymere, die ionisierbare Monomeren enthalten. Aufgrund ihrer speziellen Eigenschaften sind Polyelektrolyte sowohl in der Molekular- und Zellbiologie von großen Bedeutung als auch in der Chemie großtechnisch relevant. Verglichen mit ungeladenen Polymeren sind Polyelektrolyte theoretisch noch wenig verstanden. Insbesondere gilt dies f{\"u}r Polyelektrolyte in sogenanntem schlechten L{\"o}sungsmittel. Ein schlechtes L{\"o}sungsmittel bewirkt eine effektive Anziehung zwischen den Monomeren. F{\"u}r Polyelektrolyte in schlechtem L{\"o}sungsmittel kommt es daher zu einer Konkurrenz zwischen dieser Anziehung und der elektrostatischen Abstoßung. Geladene Polymere werden im Rahmen der chemischen Klassifikation in starke und schwache Polyelektrolyte unterschieden. Erstere zeigen vollst{\"a}ndige Dissoziation unabh{\"a}ngig vom pH-Wert der L{\"o}sung. Die Position der Ladungen auf der Kette wird ausschließlich w{\"a}hrend der Polymersynthese festgelegt. In der Physik spricht man deshalb von Polyelektrolyten mit eingefrorener Ladungsverteilung (quenched polyelectrolytes). Im Falle von schwachen Polyelektrolyten ist die Ladungsdichte auf der Kette nicht konstant, sondern wird durch der pH-Wert der L{\"o}sung kontrolliert. Durch Rekombinations- und Dissoziationsprozesse sind die Ladungen auf der Kette beweglich. Im allgemeinen stellt sich eine inhomogene Gleichgewichtsverteilung ein, die mit der Struktur der Kette gekoppelt ist. Diese Polymere werden deshalb auch Polyelektrolyte mit Gleichgewichtsladungsverteilung (annealed polyelectrolytes) genannt. Wegen des zus{\"a}tzlichen Freiheitsgrades in der Ladungsverteilung werden eine Reihe ungew{\"o}hnlicher Eigenschaften theoretisch vorhergesagt. Mit Hilfe von Simulationen ist es zum ersten Mal gelungen, zu zeigen daß 'annealed' Polyelektrolyte in relativ schlechtem L{\"o}sungsmittel einen diskontinuierlichen Phasen{\"u}bergang durchlaufen, wenn ein kritischer pH-Werts der L{\"o}sung {\"u}berschritten wird. Bei diesem Phasen{\"u}bergang, gehen die Polyelektolyte von einer schwach geladenen kompakten globul{\"a}ren Struktur zu einer stark geladenen gestreckten Konfiguration {\"u}ber. Aufgrund theoretischer Vorhersagen wird erwartet, daß die globul{\"a}re Struktur in weniger schlechtem L{\"o}sungsmittel instabil wird und sich eine Perlenkettenkonfiguration ausbildet. Diese Vorhersage konnte f{\"u}r 'annealed' Polyelektrolyte mit den durchgef{\"u}hrten Simulationen zum ersten Mal best{\"a}tigt werden - inzwischen auch durch erste experimentelle Ergebnisse. Schließlich zeigen die Simulationen auch, daß annealed Polyelektrolyte bei einer kritischen Salzkonzentration in der L{\"o}sung einen scharfen {\"U}bergang zwischen einem stark geladenen gestreckten Zustand und einem schwach geladenen globul{\"a}ren Zustand aufweisen, wiederum in {\"U}bereinstimmung mit theoretischen Erwartungen.},
  language  = {en}
}
@phdthesis{Noack2019,
  author    = {Noack, Sebastian},
  title     = {Poly(lactide)-based amphiphilic block copolymers},
  doi       = {10.25932/publishup-43616},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-436168},
  school      = {Universit{\"a}t Potsdam},
  pages     = {xvii, 148},
  year      = {2019},
  abstract  = {Due to its bioavailability and (bio)degradability, poly(lactide) (PLA) is an interesting polymer that is already being used as packaging material, surgical seam, and drug delivery system. Dependent on various parameters such as polymer composition, amphiphilicity, sample preparation, and the enantiomeric purity of lactide, PLA in an amphiphilic block copolymer can affect the self-assembly behavior dramatically. However, sizes and shapes of aggregates have a critical effect on the interactions between biological and drug delivery systems, where the general understanding of these polymers and their ability to influence self-assembly is of significant interest in science. The first part of this thesis describes the synthesis and study of a series of linear poly(L-lactide) (PLLA) and poly(D-lactide) (PDLA)-based amphiphilic block copolymers with varying PLA (hydrophobic), and poly(ethylene glycol) (PEG) (hydrophilic) chain lengths and different block copolymer sequences (PEG-PLA and PLA-PEG). The PEG-PLA block copolymers were synthesized by ring-opening polymerization of lactide initiated by a PEG-OH macroinitiator. In contrast, the PLA-PEG block copolymers were produced by a Steglich-esterification of modified PLA with PEG-OH. The aqueous self-assembly at room temperature of the enantiomerically pure PLLA-based block copolymers and their stereocomplexed mixtures was investigated by dynamic light scattering (DLS), transmission electron microscopy (TEM), wide-angle X-ray diffraction (WAXD), and differential scanning calorimetry (DSC). Spherical micelles and worm-like structures were produced, whereby the obtained self-assembled morphologies were affected by the lactide weight fraction in the block copolymer and self-assembly time. The formation of worm-like structures increases with decreasing PLA-chain length and arises from spherical micelles, which become colloidally unstable and undergo an epitaxial fusion with other micelles. As shown by DSC experiments, the crystallinity of the corresponding PLA blocks increases within the self-assembly time. However, the stereocomplexed self-assembled structures behave differently from the parent polymers and result in irregular-shaped clusters of spherical micelles. Additionally, time-dependent self-assembly experiments showed a transformation, from already self-assembled morphologies of different shapes to more compact micelles upon stereocomplexation. In the second part of this thesis, with the objective to influence the self-assembly of PLA-based block copolymers and its stereocomplexes, poly(methyl phosphonate) (PMeP) and poly(isopropyl phosphonate) (PiPrP) were produced by ring-opening polymerization to implement an alternative to the hydrophilic block PEG. Although, the 1,8 diazabicyclo[5.4.0]unde 7 ene (DBU) or 1,5,7 triazabicyclo[4.4.0]dec-5-ene (TBD) mediated synthesis of the corresponding poly(alkyl phosphonate)s was successful, however, not so the polymerization of copolymers with PLA-based precursors (PLA-homo polymers, and PEG-PLA block copolymers). Transesterification, obtained by 1H-NMR spectroscopy, between the poly(phosphonate)- and PLA block caused a high-field shifted peak split of the methine proton in the PLA polymer chain, with split intensities depending on the used catalyst (DBU for PMeP, and TBD for PiPrP polymerization). An additional prepared block copolymer PiPrP-PLLA that wasn't affected in its polymer sequence was finally used for self-assembly experiments with PLA-PEG and PEG-PLA mixing. This work provides a comprehensive study of the self-assembly behavior of PLA-based block copolymers influenced by various parameters such as polymer block lengths, self-assembly time, and stereocomplexation of block copolymer mixtures.},
  language  = {en}
}
@article{JainWheelerEssetal.2019,
  author    = {Jain, Varun and Wheeler, Joshua J. and Ess, Daniel H. and Noack, Sebastian and Vacogne, Charlotte D. and Schlaad, Helmut and Bahr, Stephan and Dietrich, Paul and Meyer, Michael and Thissen, Andreas and Linford, Matthew R.},
  title     = {Poly(gamma-benzyl l-glutamate), by near-ambient pressure XPS},
  series = {Surface science spectra : SSS : an international journal \& database devoted to archiving spectra from surfaces \& interfaces},
  volume    = {26},
  journal   = {Surface science spectra : SSS : an international journal \& database devoted to archiving spectra from surfaces \& interfaces},
  number    = {2},
  publisher = {American Institute of Physics},
  address   = {Melville},
  issn      = {1055-5269},
  doi       = {10.1116/1.5109121},
  pages     = {10},
  year      = {2019},
  abstract  = {Near-ambient pressure x-ray photoelectron spectroscopy (NAP-XPS) is a less traditional form of XPS that allows samples to be analyzed at relatively high pressures, i. e., at greater than 2500 Pa. In this study, poly(.- benzyl L- glutamate) (PBLG) with a molar mass of 11.3 kg/mol was analyzed by NAP-XPS; here, we show the survey, C 1s, N 1s, and O 1s narrow scans of PBLG. The C 1s peak envelope was fitted in three different ways, to five, six, or seven synthetic peaks. In each fit, there was also a shake-up signal. The O 1s narrow scan was well fit with three peaks: CZO and CvO in a 1:2 ratio from the polymer, and a higher energy signal from water vapor. Hartree-Fock orbital energies of a model monomer served as a guide to an additional fit of the C 1s envelope.},
  language  = {en}
}
@article{BehlBalkMansfeldetal.2021,
  author    = {Behl, Marc and Balk, Maria and Mansfeld, Ulrich and Lendlein, Andreas},
  title     = {Phase morphology of multiblock copolymers differing in sequence of blocks},
  series = {Macromolecular materials and engineering},
  volume    = {306},
  journal   = {Macromolecular materials and engineering},
  number    = {3},
  publisher = {Wiley-VCH},
  address   = {Weinheim},
  issn      = {1439-2054},
  doi       = {10.1002/mame.202000672},
  pages     = {9},
  year      = {2021},
  abstract  = {The chemical nature, the number length of integrated building blocks, as well as their sequence structure impact the phase morphology of multiblock copolymers (MBC) consisting of two non-miscible block types. It is hypothesized that a strictly alternating sequence should impact phase segregation. A library of well-defined MBC obtained by coupling oligo(epsilon-caprolactone) (OCL) of different molecular weights (2, 4, and 8 kDa) with oligotetrahydrofuran (OTHF, 2.9 kDa) via Steglich esterification results in strictly alternating (MBCalt) or random (MBCran) MBC. The three different series has a weight average molecular weight (M-w) of 65 000, 165 000, and 168 000 g mol(-1) for MBCalt and 80 500, 100 000, and 147 600 g mol(-1) for MBCran. When the chain length of OCL building blocks is increased, the tendency for phase segregation is facilitated, which is attributed to the decrease in chain mobility within the MBC. Furthermore, it is found that the phase segregation disturbs the crystallization by causing heterogeneities in the semi-crystalline alignment, which is attributed to an increase of the disorder of the OCL semi-crystalline alignment.},
  language  = {en}
}