Daniel Klinger

Striped, Ellipsoidal Particles by Controlled Assembly of Diblock Copolymers

Control of interfacial interactions leads to a dramatic change in shape and morphology for particles based on poly(styrene-b-2-vinylpyridine) diblock copolymers. Key to these changes is the addition of Au-based surfactant nanoparticles (SNPs) which are adsorbed at the interface between block copolymer-containing emulsion droplets and the surrounding amphiphilic surfactant to afford asymmetric, ellipsoid particles. The mechanism of formation for these novel nanostructures was investigated by systematically varying the volume fraction of SNPs, with the results showing the critical nature that the segregation of SNPs to specific interfaces plays in controlling structure. A theoretical description of the system allows the size distribution and aspect ratio of the asymmetric block copolymer colloidal particles to be correlated with the experimental results.

A Facile Synthesis of Dynamic, Shape‐Changing Polymer Particles

We herein report a new facile strategy to ellipsoidal block copolymer nanoparticles that exhibit a pH-triggered anistropic swelling profile. In a first step, elongated particles with an axially stacked lamellae structure are selectively prepared by utilizing functional surfactants to control the phase separation of symmetric polystyrene-b-poly(2-vinylpyridine) (PS-b-P2VP) in dispersed droplets. In a second step, the dynamic shape change is realized by cross-linking the P2VP domains, thereby connecting glassy PS discs with pH-sensitive hydrogel actuators.

Photo-sensitive PMMA microgels: light-triggered swelling and degradation

Two classes (type A and type B) of novel photolabile divinyl functionalized crosslinkers based on o-nitrobenzyl derivatives were synthesized and investigated with regard to their photolytic performance upon UV irradiation. The systematic variation of the molecular structure resulted in different degradation rates depending on the irradiation conditions. Thus, the successive and independent cleavage is enabled by either adjusting the applied wavelengths or irradiation times. The respective molecules were used to build up photodegradable PMMA microgels by free radical copolymerization with MMA in a miniemulsion polymerization process. UV light-induced degradation of the swollen microgels was monitored by time dependent turbidity measurements and the resulting kinetics were found to correlate with the photolysis rates of the respective crosslinkers in solution. The irradiation wavelength-controlled selective partial cleavage of type B crosslinking points was achieved by UV irradiation with λ > 315 nm and resulted in particles with extensively increased volumes consisting of highly swollen networks. In addition, the irradiation time-controlled selective complete degradation of particles containing type B crosslinkers was accomplished. By using broadband UV light containing wavelengths of λ < 315 nm, the successive complete particle disintegration of type B and type A microgels was observed. Hence, the specific performance of the synthesized microgels can be precisely triggered by means of the used UV light wavelengths, doses and intensities, thus representing a great potential as new light-responsive nanoscaled materials.

Enzymatically degradable nanogels by inverse miniemulsion copolymerization of acrylamide with dextran methacrylates as crosslinkers

Nanogels consisting of polyacrylamide (PAAm), crosslinked with dextran methacrylate (Dex-MA), were designed to be partially biodegradable by enzymatic cleavage of the methacryl-functionalized polysaccharide chains. Important properties of the described hydrogels such as a low initial degree of swelling and a high crosslinking efficiency—in order to ensure the morphological integrity during nanogel preparation, purification and storage—are highly favored. Primarily, those requirements strongly depend on the amount of crosslinking points, i.e.methacrylate groups in the network. This parameter was adjusted by either increasing the ratio of Dex-MA/AAm for a fixed degree of substitution (DS) of Dex-MA or increasing the DS of Dex-MA for a fixed ratio of Dex-MA/AAm. Secondly, the distribution of crosslinking points in the network is another crucial parameter which was optimized by lowering the molecular weight of the Dex-MA for analogous DS or by simultaneously increasing the Dex-MA/AAm ratio and decreasing the respective DS. This resulted in nanogels with a reduced initial degree of swelling and sol content, therefore indicating a more homogeneous distribution of the same amount of crosslinking points. Degradation of the hybrid gel nanoparticles was examined by turbidity and DLS measurements upon treatment with dextranase. It was found that the degradation behavior depends on the total amount of methacrylate groups in the network and the degree of substitution of the individual Dex-MA chains.

Photoreactive Nanoparticles as Nanometric Building Blocks for the Generation of Self-Healing Hydrogel Thin Films

The use of reversible photo-cross-linkable nanoparticles as nano building blocks for the formulation of nanostructured self-healing thin hydrogel films is shown for the first time. This strategy for the fabrication of autonomous self-healing coatings consisted of various microgels bearing surface cinnamate moieties. The nanoparticles were formed by miniemulsion copolymerization, which was followed by surface functionalization with the cinnamate groups. These nanoparticles were then used to form films by drop-casting, followed by interparticle photo-cross-linking polymerization through the light-induced forward dimerization reaction of the previously incorporated cinnamate groups. The reversibility of this macroscopic network formation was also demonstrated by photoinducing the backward dimerization reaction and carrying out several cycles of photoinduced cross-linking and de-cross-linking. The self-healing ability through swelling of these films following surface damage was also demonstrated. Finally, the ability of these self-healing macroscopic films to incorporate additives of different chemical nature before photo-cross-linking was evaluated.

Engineering Surfaces through Sequential Stop-Flow Photopatterning.

Solution-exchange lithography is a new modular approach to engineer surfaces via sequential photopatterning. An array of lenses reduces features on an inkjet-printed photomask and reproduces arbitrarily complex patterns onto surfaces. In situ exchange of solutions allows successive photochemical reactions without moving the substrate and affords access to hierarchically patterned substrates.

Supramolecular guests in solvent driven block copolymer assembly: from internally structured nanoparticles to micelles

Supramolecular interactions between different hydrogen-bonding guests and poly(2-vinyl pyridine)-block-poly (styrene) can be exploited to prepare remarkably diverse self-assembled nanostructures in dispersion from a single block copolymer (BCP). The characteristics of the BCP can be efficiently controlled by tailoring the properties of a guest which preferentially binds to the P2VP block. For example, the incorporation of a hydrophobic guest creates a hydrophobic BCP complex that forms phase separated nanoparticles upon self-assembly. Conversely, the incorporation of a hydrophilic guest results in an amphiphilic BCP complex that forms spherical micelles in water. The ability to tune the self-assembly behavior and access dramatically different nanostructures from a single BCP substrate demonstrates the exceptional versatility of the self-assembly of BCPs driven by supramolecular interactions. This approach represents a new methodology that will enable the further design of complex, responsive self-assembled nanostructures.

Fully Aromatic High Performance Thermoset via Sydnone–Alkyne Cycloaddition

We have developed an efficient synthetic platform for the preparation of a new class of high performance thermosets based on the 1,3-dipolar cycloaddition of a bifunctional sydnone with a trifunctional alkyne. These processable materials possess outstanding thermal stability, with Td5% of 520 °C and a weight loss of <0.1% per day at 225 °C (both in air). Key to this performance is the stability of the starting functional groups that allows for reactive B-staging via simple thermal activation to give fully aromatic and highly cross-linked polypyrazole-based thermosets.

Polymeric Photoresist Nanoparticles: Light-Induced Degradation of Hydrophobic Polymers in Aqueous Dispersion

Nanoparticles consisting of a photoreactive polymer able to radically switch its hydrophobicity are successfully prepared by miniemulsion polymerization. Irradiation with UV light causes degradation of the particles where at complete dissolution is achieved by changing the initial hydrophobic photoresist polymer into hydrophilic poly(methacrylic acid). Incorporation of the fluorescence-sensitive Nile red serves as a solvatochromic probe to study the particle degradation. Diffusion of either Nile red out from or water into the former hard spherical nanoparticles is studied and not only renders the described material an ideal system for applications, where in situ dissolution of nanoparticles may be needed, but also bears the additional advantage of performing controlled burst release.

Particles with Tunable Porosity and Morphology by Controlling Interfacial Instability in Block Copolymer Emulsions

A series of porous block copolymer (BCP) particles with controllable morphology and pore sizes was fabricated by tuning the interfacial behavior of BCP droplets in oil-in-water emulsions. A synergistic adsorption of polystyrene-b-poly(4-vinylpyridine) (PS-b-P4VP) BCPs and sodium dodecyl sulfate (SDS) to the surface of the emulsion droplet induced a dramatic decrease in the interfacial tension and generated interfacial instability at the particle surface. In particular, the SDS concentration and the P4VP volume fraction of PS-b-P4VP were key parameters in determining the degree of interfacial instability, leading to different types of particles including micelles, capsules, closed-porosity particles, and open-porosity particles with tunable pore sizes ranging from 10 to 500 nm. The particles with open-porosity could be used as pH-responsive, high capacity delivery systems where the uptake and release of multiple dyes could be achieved.