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- ItemNanoporous Block Copolymer Membranes with Enhanced Solvent Resistance Via UV-Mediated Cross-Linking Strategies(Weinheim : Wiley-VCH, 2021) Frieß, Florian V.; Hu, Qiwei; Mayer, Jannik; Gemmer, Lea; Presser, Volker; Balzer, Bizan N.; Gallei, MarkusIn this work, a block copolymer (BCP) consisting of poly((butyl methacrylate-co-benzophenone methacrylate-co-methyl methacrylate)-block-(2-hydroxyethyl methacrylate)) (P(BMA-co-BPMA-co-MMA)-b-P(HEMA)) is prepared by a two-step atom-transfer radical polymerization (ATRP) procedure. BCP membranes are fabricated applying the self-assembly and nonsolvent induced phase separation (SNIPS) process from a ternary solvent mixture of tetrahydrofuran (THF), 1,4-dioxane, and dimethylformamide (DMF). The presence of a porous top layer of the integral asymmetric membrane featuring pores of about 30 nm is confirmed via scanning electron microscopy (SEM). UV-mediated cross-linking protocols for the nanoporous membrane are adjusted to maintain the open and isoporous top layer. The swelling capability of the noncross-linked and cross-linked BCP membranes is investigated in water, water/ethanol mixture (1:1), and pure ethanol using atomic force microscopy, proving a stabilizing effect of the UV cross-linking on the porous structures. Finally, the influence of the herein described cross-linking protocols on water-flux measurements for the obtained membranes is explored. As a result, an increased swelling resistance for all tested solvents is found, leading to an increased water flux compared to the pristine membrane. The herein established UV-mediated cross-linking protocol is expected to pave the way to a new generation of porous and stabilized membranes within the fields of separation technologies.
- ItemKinetic Control over Self-Assembly of Semiconductor Nanoplatelets(Washington, DC : American Chemical Society, 2020) Momper, R.; Zhang, H.; Chen, S.; Halim, H.; Johannes, E.; Yordanov, S.; Braga, D.; Blülle, B.; Doblas, D.; Kraus, T.; Kraus, T.; Bonn, M.; Wang, H.I.; Riedinger, A.Semiconductor nanoplatelets exhibit spectrally pure, directional fluorescence. To make polarized light emission accessible and the charge transport effective, nanoplatelets have to be collectively oriented in the solid state. We discovered that the collective nanoplatelets orientation in monolayers can be controlled kinetically by exploiting the solvent evaporation rate in self-assembly at liquid interfaces. Our method avoids insulating additives such as surfactants, making it ideally suited for optoelectronics. The monolayer films with controlled nanoplatelets orientation (edge-up or face-down) exhibit long-range ordering of transition dipole moments and macroscopically polarized light emission. Furthermore, we unveil that the substantial in-plane electronic coupling between nanoplatelets enables charge transport through a single nanoplatelets monolayer, with an efficiency that strongly depends on the orientation of the nanoplatelets. The ability to kinetically control the assembly of nanoplatelets into ordered monolayers with tunable optical and electronic properties paves the way for new applications in optoelectronic devices.
- ItemSynthesis and Biopharmaceutical Characterization of Amphiphilic Squalenyl Derivative Based Versatile Drug Delivery Platform(Lausanne : Frontiers Media, 2020) Ho, Duy-Khiet; Christmann, Rebekka; Murgia, Xabier; De Rossi, Chiara; Frisch, Sarah; Koch, Marcus; Schaefer, Ulrich F.; Loretz, Brigitta; Desmaele, Didier; Couvreur, Patrick; Lehr, Claus-MichaelLimited drug loading capacity (LC), mostly below 5% w/w, is a significant drawback of nanoparticulate drug delivery systems (DDS). Squalenoylation technology, which employs bioconjugation of squalenyl moiety and drug, allows self-assemble of nanoparticles (NPs) in aqueous media with significantly high LC (>30% w/w). The synthesis and particle preparation of squalenoylated prodrugs are, however, not facile for molecules with multiple reactive groups. Taking a different approach, we describe the synthesis of amphiphilic squalenyl derivatives (SqDs) as well as the physicochemical and biopharmaceutical characterizations of their self-assembled NPs as DDSs. The SqDs included in this study are (i) cationic squalenyl diethanolamine (ii) PEGylated SqD (PEG 750 Da), (iii) PEGylated SqD (PEG 3,000 Da), and (iv) anionic squalenyl hydrogen sulfate. All four SqDs self-assemble into NPs in a size range from 100 to 200 nm in an aqueous solution. Furthermore, all NP derivatives demonstrate appropriate biocompatibility and adequate colloidal stability in physiological relevant pH environments. The mucoprotein binding of PEGylated NPs is reduced compared to the charged NPs. Most importantly, this technology allows excellent LC (at maximum of 45% w/w) of a wide range of multifunctional compounds, varying in physicochemical properties and molecular weight. Interestingly, the drug release profile can be tuned by different loading methods. In summary, the SqD-based NPs appear as versatile drug delivery platforms.
- ItemThermo-Responsive Ultrafiltration Block Copolymer Membranes Based on Polystyrene-block-poly(diethyl acrylamide)(Weinheim : Wiley-VCH GmbH, 2023) Frieß, Florian V.; Hartmann, Frank; Gemmer, Lea; Pieschel, Jens; Niebuur, Bart‐Jan; Faust, Matthias; Kraus, Tobias; Presser, Volker; Gallei, MarkusWithin the present work, a thermo-responsive ultrafiltration membrane is manufactured based on a polystyrene-block-poly(diethyl acrylamide) block copolymer (BCP). The poly(diethyl acrylamide) block segment features a lower critical solution temperature (LCST) in water, similar to the well-known poly(N-isopropylacrylamide), but having increased biocompatibility and without exhibiting a hysteresis of the thermally induced switching behavior. The BCP is synthesized via sequential “living” anionic polymerization protocols and analyzed by 1H-NMR spectroscopy, size exclusion chromatography, and differential scanning calorimetry. The resulting morphology in the bulk state is investigated by transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS) revealing the intended hexagonal cylindrical morphology. The BCPs form micelles in a binary mixture of tetrahydrofuran and dimethylformamide, where BCP composition and solvent affinities are discussed in light of the expected structure of these micelles and the resulting BCP membrane formation. The membranes are manufactured using the non-solvent induced phase separation (NIPS) process and are characterized via scanning electron microscopy (SEM) and water permeation measurements. The latter are carried out at room temperature and at 50 °C revealing up to a 23-fold increase of the permeance, when crossing the LCST of the poly(diethyl acrylamide) block segment in water.
- ItemDye-Loaded Mechanochromic and pH-Responsive Elastomeric Opal Films(Weinheim : Wiley-VCH, 2021) Winter, Tamara; Boehm, Anna; Presser, Volker; Gallei, MarkusIn this work, the preparation and fabrication of elastomeric opal films revealing reversible mechanochromic and pH-responsive features are reported. The core–interlayer–shell (CIS) particles are synthesized via stepwise emulsion polymerization leading to hard core (polystyrene), crosslinked interlayer (poly(methyl methacrylate-co-allyl methacrylate), and soft poly(ethyl acrylate-co-butyl acrylate-co-(2-hydroxyethyl) methacrylate) shell particles featuring a size of 294.9 ± 14.8 nm. This particle architecture enables the application of the melt-shear organization technique leading to elastomeric opal films with orange, respectively, green brilliant reflection colors dependent on the angle of view. Moreover, the hydroxyl moieties as part of the particle shell are advantageously used for subsequent thermally induced crosslinking reactions enabling the preparation of reversibly tunable mechanochromic structural colors based on Bragg's law of diffraction. Additionally, the CIS particles can be loaded upon extrusion or chemically by a postfunctionalization strategy with organic dyes implying pH-responsive features. This convenient protocol for preparing multi-responsive, reversibly stretch-tunable opal films is expected to enable a new material family for anti-counterfeiting applications based on external triggers.
- ItemNanoscale Faceting and Ligand Shell Structure Dominate the Self-Assembly of Nonpolar Nanoparticles into Superlattices(Weinheim : Wiley-VCH, 2022) Bo, Arixin; Liu, Yawei; Kuttich, Björn; Kraus, Tobias; Widmer-Cooper, Asaph; de Jonge, NielsSelf-assembly of nanoscale structures at liquid–solid interfaces occurs in a broad range of industrial processes and is found in various phenomena in nature. Conventional theory assumes spherical particles and homogeneous surfaces, but that model is oversimplified, and nanoscale in situ observations are needed for a more complete understanding. Liquid-phase scanning transmission electron microscopy (LP-STEM) is used to examine the interactions that direct the self-assembly of superlattices formed by gold nanoparticles (AuNPs) in nonpolar liquids. Varying the molecular coating of the substrate modulates short-range attraction and leads to switching between a range of different geometric structures, including hexagonal close-packed (hcp), simple hexagonal (sh), dodecahedral quasi-crystal (dqc), and body-centered cubic (bcc) lattices, as well as random distributions. Langevin dynamics simulations explain the experimental results in terms of the interplay between nanoparticle faceting, ligand shell structure, and substrate–NP interactions.