ABSTRACT
Controlling and understanding the electrochemical properties of electroactive polymeric colloids is a highly topical but still a rather unexplored field of research. This is especially true when considering more complex particle architectures like stimuli-responsive microgels, which would entail different kinetic constraints for charge transport within one particle. We synthesize and electrochemically address dual stimuli responsive core-shell microgels, where the temperature-responsiveness modulates not only the internal structure, but also the microgel electroactivity both on an internal and on a global scale. In detail, a facile one-step precipitation polymerization results in architecturally advanced poly(N-isopropylacrylamide-co-vinylferrocene) P(NIPAM-co-VFc) microgels with a ferrocene (Fc)-enriched (collapsed/hard) core and a NIPAM-rich shell. While the remaining Fc units in the shell are electrochemically accessible, the electrochemical activity of Fc in the core is limited due to the restricted mobility of redox active sites and therefore restricted electron transfer in the compact core domain. Still, prolonged electrochemical action and/or chemical oxidation enable a reversible adjustment of the internal microgel structure from core-shell microgels with a dense core to completely oxidized microgels with a highly swollen core and a denser corona. The combination of thermo-sensitive and redox-responsive units being part of the network allows for efficient amplification of the redox response on the overall microgel dimension, which is mainly governed by the shell. Further, it allows for an electrochemical switching of polarity (hydrophilicity/hydrophobicity) of the microgel, enabling an electrochemically triggered uptake and release of active guest molecules. Hence, bactericidal drugs can be released to effectively kill bacteria. In addition, good biocompatibility of the microgels in cell tests suggests suitability of the new microgel system for future biomedical applications.
ABSTRACT
Metallopolymers are a unique class of functional materials because of their redox-mediated optoelectronic and catalytic switching capabilities and, as recently shown, their outstanding structure formation and separation capabilities. Within the present study, (tri)block copolymers of poly(isoprene) (PI) and poly(ferrocenylmethyl methacrylate) having different block compositions and overall molar masses up to 328 kg mol-1 are synthesized by anionic polymerization. The composition and thermal properties of the metallopolymers are investigated by state-of-the-art polymer analytical methods comprising size exclusion chromatography, 1H NMR spectroscopy, differential scanning calorimetry, and thermogravimetric analysis. As a focus of this work, excellent microphase separation of the synthesized (tri)block copolymers is proven by transmission electron microscopy, scanning electron microcopy, energy-dispersive X-ray spectroscopy, small-angle X-ray scattering measurements showing spherical, cylindrical, and lamellae morphologies. As a highlight, the PI domains are subjected to ozonolysis for selective domain removal while maintaining the block copolymer morphology. In addition, the novel metalloblock copolymers can undergo microphase separation on cellulose-based substrates, again preserving the domain order after ozonolysis. The resulting nanoporous structures reveal an intriguing switching capability after oxidation, which is of interest for controlling the size and polarity of the nanoporous architecture.
ABSTRACT
We study the conformation of a polymer (polyethylene glycol) in a nanoscopic soft confinement with attractive walls. The polymer is added to a water-in-oil microemulsion based on the deuterated anionic surfactant AOT, d-octane and D2O. Three different droplet sizes and up to three polymers per droplet are investigated with small angle scattering combining X-rays and neutrons. This allows determining the confinement size and polymer conformation on identical samples. Whereas polymer conformation in bulk is found to be well described with the model of a Gaussian coil its radius of gyration is drastically increased in the droplet. At the same time it is compressed on a local scale. This supports the picture of a polymer strongly adsorbed on the surfactant layer with a thickness of several Angstroms.
ABSTRACT
The design of artificially generated channels featuring distinct remote-switchable functionalities is of critical importance for separation, transport control, and water filtration applications. Here, we focus on the preparation of block copolymers (BCPs) consisting of polystyrene-block-poly(2-hydroxyethyl methacrylate) (PS-b-PHEMA) having molar masses in the range of 91 to 124 kg mol-1 with a PHEMA content of 13 to 21 mol %. The BCPs can be conveniently functionalized with redox-active ferrocene moieties by a postmodification protocol for the hydrophilic PHEMA segments. Up to 66 mol % of the hydroxyl functionalities can be efficiently modified with the reversibly redox-responsive units. For the first time, the ferrocene-containing BCPs are shown to form nanoporous integral asymmetric membranes by self-assembly and application of the non-solvent-induced phase separation (SNIPS) process. Open porous structures are evidenced by scanning electron microscopy (SEM) and water flux measurements, while efficient redox-switching capabilities are investigated after chemical oxidation of the ferrocene moieties. As a result, the porous membranes reveal a tremendously increased polarity after oxidation as reflected by contact angle measurements. Additionally, the initial water flux of the ferrocene-containing membranes decreased after oxidizing the ferrocene moieties because of oxidation-induced pore swelling of the membrane.
