@phdthesis{Cheng2018,
  author    = {Cheng, Xiao},
  title     = {Controlled solvent vapor annealing of block copolymer films},
  doi       = {10.25932/publishup-42417},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-424179},
  school      = {Universit{\"a}t Potsdam},
  pages     = {X, 166},
  year      = {2018},
  abstract  = {This project was focused on exploring the phase behavior of poly(styrene)187000-block-poly(2-vinylpyridine)203000 (SV390) with high molecular weight (390 kg/mol) in thin films, in which the self-assembly of block copolymers (BCPs) was realized via thermo-solvent annealing. The advanced processing technique of solvent vapor treatment provides controlled and stable conditions. In Chapter 3, the factors to influence the annealing process and the swelling behavior of homopolymers are presented and discussed. The swelling behavior of BCP in films is controlled by the temperature of the vapor and of the substrate, on one hand, and variation of the saturation of the solvent vapor atmosphere (different solvents), on the other hand. Additional factors like the geometry and material of the chamber, the type of flow inside the chamber etc. also influence the reproducibility and stability of the processing. The slightly selective solvent vapor of chloroform gives 10\% more swelling of P2VP than PS in films with thickness of ~40 nm. The tunable morphology in ultrathin films of high molecular weight BCP (SV390) was investigated in Chapter 4. First, the swelling behavior can be precisely tuned by temperature and/or vapor flow separately, which provided information for exploring the multiple-parameter-influenced segmental chain mobility of polymer films. The equilibrium state of SV390 in thin films influenced by temperature was realized at various temperatures with the same degree of swelling. Various methods including characterization with SFM, metallization and RIE were used to identify the morphology of films as porous half-layer with PS dots and P2VP matrix. The kinetic investigations demonstrate that on substrates with either weak or strong interaction the original morphology of the BCP with high molecular weight is changed very fast within 5 min, and the further annealing serves for annihilation of defects. The morphological development of symmetric BCP in films with thickness increasing from half-layer to one-layer influenced by confinement factors of gradient film thicknesses and various surface properties of substrates was studied in Chapter 5. SV390 and SV99 films show bulk lamella-forming morphology after slightly selective solvent vapor (chloroform) treatment. SV99 films show cylinder-forming morphology under strongly selective solvent vapor (toluene) treatment since the asymmetric structure (caused by toluene uptake in PS blocks only) of SV99 block copolymer during annealing. Both kinds of morphology (lamella and cylinder) are influenced by the film thickness. The annealed morphology of SV390 and SV99 influenced by the combination of confined film and substrate property is similar to the morphology on flat silicon wafers. In this chapter the gradients in the film thickness and surface properties of the substrates with regard to their influence on the morphological development in thin BCP films are presented. Directed self-assembly (graphoepitaxy) of this SV390 was also investigated to compare with systematically reported SV99. In Chapter 6 an approach to induced oriented microphase separation in thick block copolymer films via treatment with the oriented vapor flow using mini-extruder is envisaged to be an alternative to existing methodologies, e.g. via non-solvent-induced phase separation. The preliminary tests performed in this study confirm potential perspective of this method, which alters the structure through the bulk of the film (as revealed by SAXS measurements), but more detailed studies have to be conducted in order to optimize the preparation.},
  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}
}
@phdthesis{Pan2023,
  author    = {Pan, Xuefeng},
  title     = {Soft-template directed functional composite nanomaterials},
  doi       = {10.25932/publishup-61270},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-612709},
  school      = {Universit{\"a}t Potsdam},
  pages     = {VI, 185},
  year      = {2023},
  abstract  = {Soft-template strategy enables the fabrication of composite nanomaterials with desired functionalities and structures. In this thesis, soft templates, including poly(ionic liquid) nanovesicles (PIL NVs), self-assembled polystyrene-b-poly(2-vinylpyridine) (PS-b-P2VP) particles, and glycopeptide (GP) biomolecules have been applied for the synthesis of versatile composite particles of PILs/Cu, molybdenum disulfide/carbon (MoS2/C), and GP-carbon nanotubes-metal (GP-CNTs-metal) composites, respectively. Subsequently, their possible applications as efficient catalysts in two representative reactions, i.e. CO2 electroreduction (CO2ER) and reduction of 4-nitrophenol (4-NP), have been studied, respectively. In the first work, PIL NVs with a tunable particle size of 50 to 120 nm and a shell thickness of 15 to 60 nm have been prepared via one-step free radical polymerization. By increasing monomer concentration for polymerization, their nanoscopic morphology can evolve from hollow NVs to dense spheres, and finally to directional worms, in which a multi-lamellar packing of PIL chains occurred in all samples. The obtained PIL NVs with varied shell thickness have been in situ functionalized with ultra-small Cu nanoparticles (Cu NPs, 1-3 nm) and subsequently employed as the electrocatalysts for CO2ER. The hollow PILs/Cu composite catalysts exhibit a 2.5-fold enhancement in selectivity towards C1 products compared to the pristine Cu NPs. This enhancement is primarily attributed to the strong electronic interactions between the Cu NPs and the surface functionalities of PIL NVs. This study casts new aspects on using nanostructured PILs as novel electrocatalyst supports in efficient CO2 conversion. In the second work, a novel approach towards fast degradation of 4-NP has been developed using porous MoS2/C particles as catalysts, which integrate the intrinsically catalytic property of MoS2 with its photothermal conversion capability. Various MoS2/C composite particles have been prepared using assembled PS-b-P2VP block copolymer particles as sacrificed soft templates. Intriguingly, the MoS2/C particles exhibit tailored morphologies including pomegranate-like, hollow, and open porous structures. Subsequently, the photothermal conversion performance of these featured particles has been compared under near infrared (NIR) light irradiation. When employing the open porous MoS2/C particles as the catalyst for the reduction of 4-NP, the reaction rate constant has increased by 1.5-fold under light illumination. This catalytic enhancement mainly results from the open porous architecture and photothermal conversion performance of the MoS2 particles. This proposed strategy offers new opportunities for efficient photothermal-assisted catalysis. In the third work, a facile and green approach towards the fabrication of GP-CNTs-metal composites has been proposed, which utilizes a versatile GP biomolecule both as a stabilizer for CNTs in water and as a reducing agent for noble metal ions. The abundant hydrogen bonds in GP molecules bestow the formed GP-CNTs with excellent plasticity, enabling the availability of polymorphic CNTs species ranging from dispersion to viscous paste, gel, and even dough by increasing their concentration. The GP molecules can reduce metal precursors at room temperature without additional reducing agents, enabling the in situ immobilization of metal NPs (e.g. Au, Ag, and Pd) on the CNTs surface. The combination of excellent catalytic property of Pd NPs with photothermal conversion capability of CNTs makes the GP-CNTs-Pd composite a promising catalyst for the efficient degradation of 4-NP. The obtained composite displays a 1.6-fold increase in conversion under NIR light illumination in the reduction of 4-NP, mainly owing to the strong light-to-heat conversion effect of CNTs. Overall, the proposed method opens a new avenue for the synthesis of CNTs composite as a sustainable and versatile catalyst platform. The results presented in the current thesis demonstrate the significance of using soft templates for the synthesis of versatile composites with tailored nanostructure and functionalities. The investigation of these composite nanomaterials in the catalytic reactions reveals their potential in the development of desired catalysts for emerging catalytic processes, e.g. photothermal-assisted catalysis and electrocatalysis.},
  language  = {en}
}
@phdthesis{Weiss2011,
  author    = {Weiß, Jan},
  title     = {Synthesis and self-assembly of multiple thermoresponsive amphiphilic block copolymers},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-53360},
  school      = {Universit{\"a}t Potsdam},
  year      = {2011},
  abstract  = {In the present thesis, the self-assembly of multi thermoresponsive block copolymers in dilute aqueous solution was investigated by a combination of turbidimetry, dynamic light scattering, TEM measurements, NMR as well as fluorescence spectroscopy. The successive conversion of such block copolymers from a hydrophilic into a hydrophobic state includes intermediate amphiphilic states with a variable hydrophilic-to-lipophilic balance. As a result, the self-organization is not following an all-or-none principle but a multistep aggregation in dilute solution was observed. The synthesis of double thermoresponsive diblock copolymers as well as triple thermoresponsive triblock copolymers was realized using twofold-TMS labeled RAFT agents which provide direct information about the average molar mass as well as residual end group functionality from a routine proton NMR spectrum. First a set of double thermosensitive diblock copolymers poly(N-n-propylacrylamide)-b-poly(N-ethylacrylamide) was synthesized which differed only in the relative size of the two blocks. Depending on the relative block lengths, different aggregation pathways were found. Furthermore, the complementary TMS-labeled end groups served as NMR-probes for the self-assembly of these diblock copolymers in dilute solution. Reversible, temperature sensitive peak splitting of the TMS-signals in NMR spectroscopy was indicative for the formation of mixed star-/flower-like micelles in some cases. Moreover, triple thermoresponsive triblock copolymers from poly(N-n-propylacrylamide) (A), poly(methoxydiethylene glycol acrylate) (B) and poly(N-ethylacrylamide) (C) were obtained from sequential RAFT polymerization in all possible block sequences (ABC, BAC, ACB). Their self-organization behavior in dilute aqueous solution was found to be rather complex and dependent on the positioning of the different blocks within the terpolymers. Especially the localization of the low-LCST block (A) had a large influence on the aggregation behavior. Above the first cloud point, aggregates were only observed when the A block was located at one terminus. Once placed in the middle, unimolecular micelles were observed which showed aggregation only above the second phase transition temperature of the B block. Carrier abilities of such triple thermosensitive triblock copolymers tested in fluorescence spectroscopy, using the solvatochromic dye Nile Red, suggested that the hydrophobic probe is less efficiently incorporated by the polymer with the BAC sequence as compared to ABC or ACB polymers above the first phase transition temperature. In addition, due to the problem of increasing loss of end group functionality during the subsequent polymerization steps, a novel concept for the one-step synthesis of multi thermoresponsive block copolymers was developed. This allowed to synthesize double thermoresponsive di- and triblock copolymers in a single polymerization step. The copolymerization of different N-substituted maleimides with a thermosensitive styrene derivative (4-vinylbenzyl methoxytetrakis(oxyethylene) ether) led to alternating copolymers with variable LCST. Consequently, an excess of this styrene-based monomer allowed the synthesis of double thermoresponsive tapered block copolymers in a single polymerization step.},
  language  = {en}
}
@phdthesis{Nizardo2018,
  author    = {Nizardo, Noverra Mardhatillah},
  title     = {Thermoresponsive block copolymers with UCST-behavior aimed at biomedical environments},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-412217},
  school      = {Universit{\"a}t Potsdam},
  pages     = {xiii, 134},
  year      = {2018},
  abstract  = {Thermoresponsive block copolymers of presumably highly biocompatible character exhibiting upper critical solution temperature (UCST) type phase behavior were developed. In particular, these polymers were designed to exhibit UCST-type cloud points (Tcp) in physiological saline solution (9 g/L) within the physiologically interesting window of 30-50°C. Further, their use as carrier for controlled release purposes was explored. Polyzwitterion-based block copolymers were synthesized by atom transfer radical polymerization (ATRP) via a macroinitiator approach with varied molar masses and co-monomer contents. These block copolymers can self-assemble in the amphiphilic state to form micelles, when the thermoresponsive block experiences a coil-to-globule transition upon cooling. Poly(ethylene glycol) methyl ether (mPEG) was used as the permanently hydrophilic block to stabilize the colloids formed, and polyzwitterions as the thermoresponsive block to promote the temperature-triggered assembly-disassembly of the micellear aggregates at low temperature. Three zwitterionic monomers were used for this studies, namely 3-((2-(methacryloyloxy)ethyl)dimethylammonio)propane-1-sulfonate (SPE), 4-((2-(methacryloyl- oxy)ethyl)dimethylammonio)butane-1-sulfonate (SBE), and 3-((2-(methacryloyloxy)ethyl)- dimethylammonio)propane-1-sulfate) (ZPE). Their (co)polymers were characterized with respect to their molecular structure by proton nuclear magnetic resonance (1H-NMR) and gel permeation chromatography (GPC). Their phase behaviors in pure water as well as in physiological saline were studied by turbidimetry and dynamic light scattering (DLS). These (co)polymers are thermoresponsive with UCST-type phase behavior in aqueous solution. Their phase transition temperatures depend strongly on the molar masses and the incorporation of co-monomers: phase transition temperatures increased with increasing molar masses and content of poorly water-soluble co-monomer. In addition, the presence of salt influenced the phase transition dramatically. The phase transition temperature decreased with increasing salt content in the solution. While the PSPE homopolymers show a phase transition only in pure water, the PZPE homopolymers are able to exhibit a phase transition only in high salinity, as in physiological saline. Although both polyzwitterions have similar chemical structures that differ only in the anionic group (sulfonate group in SPE and sulfate group in ZPE), the water solubility is very different. Therefore, the phase transition temperatures of targeted block copolymers were modulated by using statistical copolymer of SPE and ZPE as thermoresponsive block, and varying the ratio of SPE to ZPE. Indeed, the statistical copolymers of P(SPE-co-ZPE) show phase transitions both in pure water as well as in physiological saline. Surprisingly, it was found that mPEG-b-PSBE block copolymer can display "schizophrenic" behavior in pure water, with the UCST-type cloud point occurring at lower temperature than the LCST-type one. The block copolymer, which satisfied best the boundary conditions, is block copolymer mPEG114-b-P(SPE43-co-ZPE39) with a cloud point of 45°C in physiological saline. Therefore, it was chosen for solubilization studies of several solvatochromic dyes as models of active agents, using the thermoresponsive block copolymer as "smart" carrier. The uptake and release of the dyes were explored by UV-Vis and fluorescence spectroscopy, following the shift of the wavelength of the absorbance or emission maxima at low and high temperature. These are representative for the loaded and released state, respectively. However, no UCST-transition triggered uptake and release of these dyes could be observed. Possibly, the poor affinity of the polybetaines to the dyes in aqueous environtments may be related to the widely reported antifouling properties of zwitterionic polymers.},
  language  = {en}
}