Therapeutic drug monitoring (TDM) typically requires painful blood drawn from patients. We propose a painless and minimally-invasive alternative for TDM using hollow microneedles suitable to extract extremely small volumes (<1 nL) of interstitial fluid to measure drug concentrations. The inner lumen of a microneedle is functionalized to be used as a micro-reactor during sample collection to trap and bind target drug candidates during extraction, without requirements of sample transfer. An optofluidic device is integrated with this microneedle to rapidly quantify drug analytes with high sensitivity using a straightforward absorbance scheme. Vancomycin is currently detected by using volumes ranging between 50–100 μL with a limit of detection (LoD) of 1.35 μM. The proposed microneedle-optofluidic biosensor can detect vancomycin with a sample volume of 0.6 nL and a LoD of <100 nM, validating this painless point of care system with significant potential to reduce healthcare costs and patients suffering.

Light-induced, spatially well-defined, reversible switching of surface properties enables the creation of remote-controlled smart surfaces. We have taken advantage of the unique high-resolution structuring capabilities of extreme ultraviolet (EUV) interference lithography to produce nanostructured photoresponsive polymer brushes. Patterns of poly(glycidyl methacrylate) (PGMA) and poly(methacrylic acid) (PMAA) were grafted from two different 100 μm thick fluoropolymer substrates by means of a radiation-initiated, grafting-from approach based on free-radical polymerization (FRP). Photochromic properties were introduced via novel one- or two-step postpolymerization modifications with spiropyran (SP) derivatives, which allowed us to control the number of photochromic groups on the polymer brushes. Depending on the degree of functionalization and the local chemical environment, the SP moieties can open upon UV-light exposure to form zwitterionic, deeply colored, and fluorescent merocyanines (MCs) and reclose to the colorless SP configuration via thermal or visible light-induced relaxation. Switching kinetics were studied by means of time-resolved fluorescence microscopy and compared with kinetic measurements of the SP moiety in solution. The results indicated the importance, for the intensity of the switching, of the local chemical environment provided by both the polymer brush and added solvents, and showed the predominant influence on the ring-closing kinetics of polar solvents, which stabilize the MC form. To allow further characterization of the polymer-brush arrangements on a macroscopic scale, similar, but unstructured brush systems were grafted from fluoropolymers after large-area activation using EUV radiation or argon plasma. All steps of the postpolymerization modification were characterized in detail using attenuated total reflection infrared (ATR-IR) spectroscopy. Furthermore, a light-induced reversible static-contact-angle switch with a range of up to 15° for PGMA-SP brushes and up to 30° for PMA-SP brushes was demonstrated upon alternating UV- and visible-light irradiation.

Hydrogels are often used as model systems for articular cartilage due to similarities in their tribological properties. However, neither the structures nor the friction mechanisms of either system are fully understood. A key aspect of hydrogel lubrication is the nature of the polymeric structure at the surface, and the lubricating water film. A combination of neutron reflectometry and infrared spectroscopy is used to probe polymer volume fraction from the interface into the bulk hydrogel and its dependence on the molding material. The depth dependence of the polymer‐network density influences the compressibility of the hydrogel surfaces, as demonstrated by both atomic force microscopy (AFM)‐ and micro indentation. By changing molding materials, substantial differences in the gradient of polymer‐network density are observed with depth. The lower the volume fraction of polymer at the hydrogel surface, the more water it can maintain at its interface as a substantial water film that is stable even under static conditions. Such films render the hydrogel highly lubricious, with a speed‐independent friction coefficient of μ = 0.01, measured in gemini contact. This result provides experimental evidence that the presence of these highly lubricious water films is strongly dependent on the polymer‐network structure at the surface.

We demonstrate a new approach to grafting thiol-reactive nanopatterned copolymer-brush structures on polymeric substrates by means of extreme ultraviolet (EUV) interference lithography. The copolymer brushes were designed to contain maleimide functional groups as thiol-reactive centers. Fluoropolymer films were exposed to EUV radiation at the X-ray interference lithography beamline (XIL-II) at the Swiss Light Source, in order to create radical patterns on their surfaces. The radicals served as initiators for the copolymerization of thiol-ene "clickable" brushes, composed of a furan-protected maleimide monomer (FuMaMA) and different methacrylates, namely, methyl methacrylate (MMA), ethylene glycol methyl ether methacrylate (EGMA), or poly(ethylene glycol) methyl ether methacrylate (PEGMA). Copolymerization with ethylene-glycol-containing monomers provides antibiofouling properties to these surfaces. The number of reactive centers on the grafted brush structures can be tailored by varying the monomer ratios in the feed. Grafted copolymers were characterized by using attenuated total reflection infrared (ATR-IR) spectroscopy. The reactive maleimide methacrylate (MaMA) units were utilized to conjugate thiol-containing moieties using the nucleophilic Michael-addition reaction, which proceeds at room temperature without the need for any metal-based catalyst. Using this approach, a variety of functionalities was introduced to yield polyelectrolytes, as well as fluorescent and light-responsive polymer-brush structures. Functionalization of the brush structures was demonstrated via ATR-IR and UV-vis spectroscopy and fluorescence microscopy, and was also indicated by a color switch. Furthermore, grafted surfaces were generated via plasma activation, showing a strongly increased wettability for polyelectrolytes and a reversible switch in static water contact angle (CA) of up to 18° for P(EGMA-co-MaMA-SP) brushes, upon exposure to alternating visible and UV-light irradiation.