Sandra Gaiser

Liquid‐infused surfaces are based upon the infusion of a liquid phase into a porous solid material to induce slippery and repellent character. In this context, porous SiOx plasma polymer films represent a relevant candidate for a robust nanoporous carrier layer. Intermittent low‐pressure plasma etching of O₂/hexamethyldisiloxane‐derived coatings is investigated to enhance the intrinsic porosity inherent to residual hydrocarbons in the silica matrix. Simulations of the resulting Si–O ring network structure using reactive molecular dynamics indicate formation of interconnected voids with Si–OH functionalized pore walls allowing water penetration with almost Fickian diffusive behavior. The corresponding porosity of up to 18%, well agreeing with simulations, Fourier‐transform infrared spectroscopy, and ellipsometry measurements, was found to be suitable for the liquid infusion of polyethylene glycol molecules into about 80 nm thick SiOx films providing ongoing lubricating properties, thus revealing their suitability as liquid‐infused surfaces.

To enable a rapid‐acting antibacterial mechanism without the release of biocidal substances, TiO₂ catalysts have been considered based on the generation of reactive oxygen species (ROS). Doping with dissimilar metals generates electron‐hole pairs with narrow band gaps promoting the production of ROS. Here, plasma technology is investigated to deposit Ag nano islets on defective TiOx films, stabilized by plasma postoxidation suppressing Ag ion release. Importantly, ROS generation is maintained upon storage in the dark yet with diminishing efficacy; however, it can be restored by exposure to visible light. The rapid‐acting antibacterial properties are found to strongly correlate with ROS generation, which can even be maintained by functionalization with hydrophobic plasma polymer films. The cytocompatible coatings offer promising applications for implants and other medical devices.

Manmade soft materials are important in a wide range of technological applications and play a key role in the development of future technologies, mainly at the interface of synthetic and biological components. They include gels and hydrogels, elastomers, structural and packaging materials, micro and nanoparticles as well as biological materials. Soft materials can be distinguished from liquids owing to their defined shape and from hard materials by the deformability of their shape. This review article provides an overview of recent progress on the plasma engineering and processing of softer materials, especially in the area of synthesis, surface modification, etching, and deposition. The article aims to demonstrate the extensive range of plasma surface engineering as used to form, modify, and coat soft materials focusing on material properties and potential applications. In general, the plasma provides highly energetic, non-equilibrium conditions at material surfaces requiring to adjust the conditions for plasma–surface interaction to account for the specifics of soft matter, which holds independent of the used plasma source. Plasma-induced crosslinking and polymerization of liquids is discussed to transform them into gel-like materials as well as to modify the surface region of viscous liquids. A major field covers the plasma surface engineering of manmade soft materials with the help of gaseous reactive species yielding ablation, nanostructuring, functionalization, crosslinking, stiffening, and/or deposition to obtain demanded surface properties or adhesion to dissimilar materials. Finally, plasma engineering of rigid materials is considered to induce surface softening for the enhanced contact with tissues, to allow interaction in aqueous media, and to support bonding to soft matter. The potential and future perspectives of plasma engineering will be discussed in this review to contribute to a higher knowledge of plasma interaction with sensitive materials such as soft matter.

The surface functionalization of electrospun nanofibers allows for the introduction of additional functionalities while at the same time retaining the membrane properties of high porosity and surface-to-volume ratio. In this work, we sequentially deposited layers of chitosan and alginate to form a polyelectrolyte complex via layer-by-layer assembly on PLGA nanofibers to introduce pH-responsiveness for the controlled release of ibuprofen. The deposition of the polysaccharides on the surface of the fibers was revealed using spectroscopy techniques and ζ-potential measurements. The presence of polycationic chitosan resulted in a positive surface charge (16.2 ± 4.2 mV, pH 3.0) directly regulating the interactions between a model drug (ibuprofen) loaded within the polyelectrolyte complex and the layer-by-layer coating. The release of ibuprofen was slowed down in acidic pH (1.0) compared to neutral pH as a result of the interactions between the drug and the coating. The provided mesh acts as a promising candidate for the design of drug delivery systems required to bypass the acidic environment of the digestive tract.

The concept of depositing solid films on low-vapor pressure liquids is introduced and developed into a top-down approach to functionalize surfaces by attaching liquid polyethylene glycol (PEG). Solid-liquid gradients were formed by low-pressure plasma treatment yielding cross-linking and/or deposition of a plasma polymer film subsequently bound to a flexible polydimethylsiloxane (PDMS) backing. The analysis via optical transmission spectroscopy (OTS), optical, confocal laser scanning (CLSM) and scanning electron microscopy (SEM), Fourier transform infrared (FTIR) and X-ray photoelectron spectroscopy (XPS) as well as by water contact angle (WCA) measurements revealed correlations between optical appearance, chemical composition and surface properties of the resulting water absorbing, covalently bound PEG-functionalized surfaces. Requirements for plasma polymer film deposition on low-vapor pressure liquids and effective surface functionalization are defined. Namely, the thickness of the liquid PEG substrate was a crucial parameter for successful film growth and covalent attachment of PEG. The presented method is a practicable approach for the production of functional surfaces featuring long-lasting strong hydrophilic properties, making them predestined for non-fouling or low-friction applications.

Activation reactions of molecules in plasma are investigated using plasma polymerization of hexamethyldisiloxane as a model system for plasma‐state polymerization. Underlying reaction pathways and film‐forming mechanisms are revisited based on a simplified macroscopic approach, considering the average energy available per monomer particle, E_pl, in relation to the threshold energy, E_th, which represents an activation barrier for plasma polymerization. Basic principles are discussed involving averaged values for collision frequency, cross‐section, and reaction rate to produce film‐forming species combining macroscopic and microscopic quantities. Considering the energy uptake from the electric field by the electrons, the energy transfer from electrons to monomer molecules, and the conversion into film‐forming species, it is demonstrated that E_pl/E_th is equally relevant as the electron energy distribution function for plasma‐chemical activation reactions.

A novel top‐down approach is presented to produce stable functional films from low vapor pressure liquids via plasma processing. Low‐pressure plasma activation and deposition are examined to cross‐link liquid polyethylene glycol (PEG‐400) surfaces. After stabilizing the thus‐obtained films on the liquid with a silicone backing layer, water contact angle measurements, Fourier‐transform infrared spectroscopy and scanning electron microscopy imaging were used for characterization. The results show that PEG molecules are covalently bonded to the solid films providing high hydrophilicity.

Since the earliest days of this field there has been an interest in correlating the structure of plasma polymer (PP) coatings with deposition parameters, most particularly with energy input per monomer molecule, E_m. Both of our laboratories have developed methods for measuring E_m (or somewhat equivalent, the apparent activation energy, E_a) in low- (LP) and atmospheric-pressure (AP) electrical discharge plasmas. We recently proposed a new parameter, energy conversion efficiency (ECE), which for the first time permits direct comparison of LP and AP experiments. Here, we report the case of small hydrocarbons, namely acetylene, ethylene and methane. “Critical” E_m (or E_a) values that demarcate ECE regimes separating different reaction mechanisms are found to agree remarkably well, and to correlate with specific reaction mechanisms, including dissociation, recombination, gas-phase oligomerization, and surface processes.