Near-Plasma Chemical Surface Engineering.

As a new trend in plasma surface engineering, plasma conditions that allow more-defined chemical reactions at the surface are being increasingly investigated. This is achieved by avoiding high energy deposition via ion bombardment during direct plasma exposure (DPE) causing destruction, densification, and a broad variety of chemical reactions. In this work, a novel approach is introduced by placing a polymer mesh with large open area close to the plasma-sheath boundary above the plasma-treated sample, thus enabling near-plasma chemistry (NPC).

Wicking dynamics in yarns.

Unlabelled: The spontaneous imbibition of a liquid within porous media, known as wicking, can display uncommon features in textiles and yarns. Yarns exhibited step-wise wicking dynamics not captured by current models.

Hypothesis: Wicking dynamics in yarns not only depend on inter-fiber pore filling, but are mainly determined by the pore-to-pore transition processes and the structure of the pore network.

pH-Responsive Chitosan/Alginate Polyelectrolyte Complexes on Electrospun PLGA Nanofibers for Controlled Drug Release.

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.

Four-dimensional imaging and free-energy analysis of sudden pore-filling events in wicking of yarns.

What are the mechanisms at play in the spontaneous imbibition dynamics in polyethylene terephthalate filament yarns at pore scale? Processes at pore scale such as waiting times between the filling of two neighboring pores, as observed in special irregular porous media, like yarns, may overrule the predicted behavior by well-known laws such as Washburn's law. While the imbibition physics are well known, classic models like Washburn's law cannot explain the dynamics observed for yarns. The stepwise dynamics is discussed in terms of the interplay of thermodynamic free energy and viscous dissipation.

Plasma Processing of Low Vapor Pressure Liquids to Generate Functional Surfaces.

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.

How the dynamics of subsurface hydration regulates protein-surface interactions.

The role of water structure near surfaces has been scrutinized extensively because it is accepted to control protein-surface interactions, however, often avoiding effects of hydration dynamics. Relating to this, we have recently discussed how the amount and state of water, accumulated within various hydrophobic-to-hydrophilic subsurface gradients of plasma polymer films, influence the magnitude of adsorbed bovine serum albumin, spurring the hypothesis of the presence of a subsurface dipolar field. This study now analyzes the kinetics of hydration by systematically introducing modified gradient architectures and relating different hydration times to the adsorption of a dipolar probing protein.

Grafting of calcium chelating functionalities onto PLA monofilament fiber surfaces.

Polymer surface grafting is widely used in the field of bone regeneration to increase calcium phosphate (CaP) adhesion, with the intent of improving mechanical properties of CaP-polymer composite cements. Reinforcement can be achieved using multiple combined functional groups and/or complex surface geometries that, however, concurrently influence multiple effects such as wetting, roughness, and interfacial strengthening. This study focused on the influence of a chelating group, namely aspartic acid, on the adsorption of divalent ions such as Ba or Ca onto poly-l-lactic acid (PLA) films.

Energy conversion efficiency in low- and atmospheric-pressure plasma polymerization processes with hydrocarbons.

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, Em. Both of our laboratories have developed methods for measuring Em (or somewhat equivalent, the apparent activation energy, Ea) 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.

Tailored antimicrobial activity and long-term cytocompatibility of plasma polymer silver nanocomposites.

The deposition of coatings enabling antibacterial properties in combination with cytocompatibility remains a challenge for biomaterial applications, such as in medical devices. Silver is one of the most utilized antibacterial surface components, due to its efficacy and extensive applicability. In this work, silver-containing plasma polymer nanocomposites (single layer and multilayers) were developed and tested, with a focus on cytotoxicity and bactericidal function, on the NIH3T3 mammalian cell line as well as Gram-negative ( Pseudomonas aeruginosa) and Gram-positive ( Staphylococcus aureus) bacterial strains.

Nanoconfined water can orient and cause long-range dipolar interactions with biomolecules.

Surface properties are generally determined by the top most surface layer also defining how molecules adsorb onto it. By exploring effects due to interactions with deeper subsurface layers, however, long-range interaction forces were found to also significantly contribute to molecular adsorption, in which hydration of the subsurface region is the key factor. Water molecules confined to a subsurface amphiphilic gradient are confirmed to cause these long-range dipolar interactions by preferential orientation, thus significantly changing the way how a protein interacts with the surface.

Improving the Stability of Amino-Containing Plasma Polymer Films in Aqueous Environments.

Plasma polymer films that contain amine groups (NH-PPFs) are known to degrade over time, particularly in aqueous environments. To reduce such aging effects, a vertical chemical gradient regarding the amine group density was explored ranging over a few nanometers at the coating surface. The gradient-containing nanofilms were formed in low-pressure plasma by tuning plasma conditions while keeping the plasma "switched on".

Enhancing Surface Plasmon Resonance Detection Using Nanostructured Au Chips.

The increase of the sensitivity of surface plasmon resonance (SPR) refractometers was studied experimentally by forming a periodic relief in the form of a grating with submicron period on the surface of the Au-coated chip. Periodic reliefs of different depths and spatial frequency were formed on the Au film surface using interference lithography and vacuum chalcogenide photoresists. Spatial frequencies of the grating were selected close to the conditions of Bragg reflection of plasmons for the working wavelength of the SPR refractometer and the used environment (solution of glycerol in water).

Suppression of Hydrophobic Recovery by Plasma Polymer Films with Vertical Chemical Gradients.

Vertical chemical gradients extending over a few nanometers were explored. The gradients are based on plasma-polymerized oxygen-containing ethylene (ppOEt) films. Using plasma conditions with low CO2/C2H4 ratio and high energy input, cross-linked films were deposited as base layer, while increasing CO2 and lowering energy input resulted in less cross-linked yet highly functional films as applied as top layer.

Response of Plasma-Polymerized Hexamethyldisiloxane Films to Aqueous Environments.

Thin plasma polymer films were deposited in hexamethyldisiloxane (HMDSO) and HMDSO/O2 low-pressure discharges and their chemical structures analyzed using infrared (IR) spectroscopy and neutron reflectometry (NR). The (plasma-polymerized) ppHMDSO film exhibits hydrophobic, poly(dimethylsiloxane)-like properties, while the retention of carbon groups is reduced by O2 addition, yielding a more inorganic, hydrophilic ppSiOx film. Both films show a minor (vertical) density gradient perpendicular to the substrate, where the exposed film surface seems to be more oxidized, indicating oxidative aging reactions upon contact with air.

Absorbing TiO thin film enabling laser welding of polyurethane membranes and polyamide fibers.

We report on the optical properties of thin titanium suboxide (TiO ) films for applications in laser transmission welding of polymers. Non-absorbing fibers were coated with TiO coatings by reactive magnetron sputtering. Plasma process parameters influencing the chemical composition and morphology of the deposited thin films were investigated in order to optimize their absorption properties.

Long-term aging of Ag/a-C:H:O nanocomposite coatings in air and in aqueous environment.

Nanocomposite coatings of silver particles embedded in a plasma polymer matrix possess interesting properties depending on their microstructure. The film microstructure is affected among others also by the RF power supplied during the deposition, as shown by transmission electron microscopy. The optical properties are characterized by UV-vis-NIR spectroscopy.

Controlling the release from silver electrodes by titanium adlayers for health monitoring.

Unlabelled: Beside cancer, cardiovascular disease is the leading cause of deaths worldwide. For medical diagnosis electrocardiography (ECG) is only a powerful predicting tool if the sensed cardiac cycle involves a high signal to noise ratio and reduced artefacts over a long term. The interface of the electrodes to the biological system is therefore improved with a novel textile system.

Embroidered electrode with silver/titanium coating for long-term ECG monitoring.

For the long-time monitoring of electrocardiograms, electrodes must be skin-friendly and non-irritating, but in addition they must deliver leads without artifacts even if the skin is dry and the body is moving. Today's adhesive conducting gel electrodes are not suitable for such applications. We have developed an embroidered textile electrode from polyethylene terephthalate yarn which is plasma-coated with silver for electrical conductivity and with an ultra-thin titanium layer on top for passivation.

Covalent immobilisation of VEGF on plasma-coated electrospun scaffolds for tissue engineering applications.

Recent findings in the field of biomaterials and tissue engineering provide evidence that surface immobilised growth factors display enhanced stability and induce prolonged function. Cell response can be regulated by material properties and at the site of interest. To this end, we developed scaffolds with covalently bound vascular endothelial growth factor (VEGF) and evaluated their mitogenic effect on endothelial cells in vitro.

Preparation of light-responsive membranes by a combined surface grafting and postmodification process.

In order to modify the surface tension of commercial available track-edged polymer membranes, a procedure of surface-initiated polymerization is presented. The polymerization from the membrane surface is induced by plasma treatment of the membrane, followed by reacting the membrane surface with a methanolic solution of 2-hydroxyethyl methacrylate (HEMA). Special attention is given to the process parameters for the plasma treatment prior to the polymerization on the surface.

Plasma-functionalized electrospun matrix for biograft development and cardiac function stabilization.

Cardiac tissue engineering approaches can deliver large numbers of cells to the damaged myocardium and have thus increasingly been considered as a possible curative treatment to counteract the high prevalence of progressive heart failure after myocardial infarction (MI). Optimal scaffold architecture and mechanical and chemical properties, as well as immune- and bio-compatibility, need to be addressed. We demonstrated that radio-frequency plasma surface functionalized electrospun poly(ɛ-caprolactone) (PCL) fibres provide a suitable matrix for bone-marrow-derived mesenchymal stem cell (MSC) cardiac implantation.

General protocol for the culture of cells on plasma-coated electrospun scaffolds.

As opposed to culture on standard tissue-treated plastic, cell culture on three-dimensional scaffolds impedes additional challenges with respect to substrate preparation, cell seeding, culture maintenance, and analysis. We herewith present a general route for the culture of primary cells, differentiated cells, or stem cells on plasma-coated, electrospun scaffolds. We describe a method to prepare and fix the scaffolds in culture wells and discuss a convenient method for cell seeding and subsequent analysis by scanning electron microscopy or immunohistology.