Hans J. Griesser

Surfaces that resist bioadhesion

Abstract The search for surfaces that resist bioadhesion has continued with the pursuit of a number of avenues. A large part of the studies has investigated PEG coatings. Nevertheless, there is still controversy about what exactly the properties and modes of action of an ‘ideal’ PEG coating should be. While some studies have reported no irreversible protein adsorption, other, very similar coatings appear less able to resist bioadhesion. Of great interest are results showing that PEG surfaces with very short chains are capable of rejecting proteins. As it is very difficult to obtain direct information about the microstructure of the coatings, studies typically employ plausible models to interpret observations. New analytical techniques and the direct measurement of interfacial forces between proteins and surfaces open up the possibility of improved, guided design and feedback in the optimization of surfaces intended to resist bioadhesion.

Effect of polysaccharide structure on protein adsorption

Abstract Using X-ray photoelectron spectroscopy for quantification, the adsorption has been studied of chicken egg lysozyme, human serum albumin (HSA), bovine colostrum lactoferrin, and γ-globulin (IgG) from single solutions onto surface-immobilised polysaccharide coatings, which were produced by the covalent attachment of a series of carboxymethyldextrans (CMDs) onto aminated fluoropolymer surfaces. CMDs with differing degrees of carboxymethyl substitution were synthesized by the reaction of dextran with bromoacetic acid under different reactant ratios. Substantial amounts of protein adsorption onto these coatings were observed with the majority of the coating/protein combinations. On the most extensively substituted CMD (1 carboxyl group per 2 dextran units), lysozyme and lactoferrin adsorbed to approximately monolayer amounts whereas there was minimal adsorption of HSA, indicating the importance of electrostatic interfacial interactions. CMD 1:14 was similar whereas the least substituted, least dense coating, from CMD 1:30, adsorbed less lysozyme and lactoferrin but more HSA. Adsorption of the large multidomain protein IgG varied little with the coating. Grazing angle XPS data indicated that for the CMD 1:30 coating there occurred significant in-diffusion of the lower molecular weight proteins. The data suggest that elimination of adsorption of a broad spectrum of proteins is not straightforward with negatively charged polysaccharide coatings; elimination of protein accumulation onto/into such coatings may not be achievable solely with a balance of electrostatic and steric–entropic interfacial forces.

Characterization of the Ageing of Plasma-deposited Polymer Films: Global Analysis of X-ray Photoelectron Spectroscopy Data

A protocol for global analysis of x-ray photoelectron spectra of plasma-deposited polymer films is presented. These materials are difficult to analyse because of the multitude of different chemical groups present. The combination of different primary and secondary binding energy shifts results in relatively broad, featureless photoelectron peaks. The protocol is based on fitting a series of spectra obtained by monitoring the surface composition of a plasma polymer film over extended periods of time after deposition. Information obtained from this first round of curve-fitting is used in the form of additional constraints for a second round of fitting. This leads to a self-consistent procedure which is akin to a global approach to curve-fitting. To illustrate application of this method, results of a study of ann-heptylamine plasma polymer are described. The spectral changes on ageing provided clear evidence for radical-initiated oxidation reactions. These reactions generated additional radicals, which sustained the oxidation process for many months and not only led to substantial incorporation of oxygen into the material (forming a variety of carbon–oxygen functionalities) but also to conversion of most of the existing carbon–nitrogen functionalities to an oxidized form.

Small scale reactor for plasma processing of moving substrate web

A simple, inexpensive and versatile custom built reactor for experimental plasma deposition and surface treatment is presented. The two outstanding features are a compact web conveyancing system with a web speed that is variable in the range 0.15–6 m min−1, and a defined gas flow path. The web transport accepts rolls containing of the order of 100 m of flexible thin substrate and is reversible in order to enable multistep plasma processing without breaking the vacuum. The reactor provides stable and uniform plasma conditions for extended coating of thin polymer films by plasma polymerization.

Evolution of the surface composition and topography of perfluorinated polymers following ammonia-plasma treatment

Treatment of fluorinated ethylene propylene (FEP) and polytetrafluoroethylene (PTFE) in ammonia plasmas produced surfaces with very high wettability by water, but on storage in air at ambient temperature, the air/water contact angles increased markedly. The evolution of the surface composition and topography was studied by angle-dependent X-ray photoelectron spectroscopy (XPS), derivatization of amine groups with fluorescein isothiocyanate, scanning tunelling microscopy (STM), and atomic force microscopy (AFM). XPS demonstrated a continuous increase in the oxygen content over periods of weeks; this was assigned to oxidation of trapped radicals and subsequent secondary reactions. In addition, the fluorine content also changed markedly on storage; the XPS fluorine signal suggested that there was a substantial amount of fluoride in the freshly treated surfaces, and this component disappeared rapidly on storage. STM and AFM showed no changes in topography with aging but suggested surface hardening on plasma t...

Aging of 1,3‐diaminopropane plasma‐deposited polymer films: Mechanisms and reaction pathways

In the course of plasma deposition of organic–polymeric thin films, radicals are incorporated into the growing film. These radicals initiate spontaneous oxidation reactions that continue over many weeks when the plasma polymers are stored in air. These reactions and their products have been previously studied in detail for spectroscopically simple, hydrocarbon-based plasma polymers. In this investigation, the aging of 1,3-diaminopropane (DAP) plasma polymer samples was monitored by XPS and FTIR in order to study how the oxidative reaction pathways might differ in a plasma-deposited material that is initially rich in amine groups. The freshly deposited DAP plasma polymer consisted of a random hydrocarbon network with a considerable amount of unsaturation and a high concentration of nitrogen-containing functional groups, mainly primary/secondary amines and imines. These groups strongly influenced the aging reactions: in contrast to hydrocarbon-based material where hydrogen abstraction and reaction of carbon-centered radicals with in-diffusing oxygen result in a wide range of oxidative products, both XPS and FTIR identified a rather narrow range of products (mainly amides and similar groups) in DAP plasma polymers even after extensive aging for more than 2 years. Reaction routes based on oxidation and/or hydrolysis of nitrogen functional groups, and involving primary as well as secondary reactions, are proposed to account for the spectroscopic data. The structure of the aged DAP plasma polymer appeared to be stable, and did not undergo more extensive oxidation, in contrast to hydrocarbon plasma polymers. In particular, carboxylic acid groups and carbamates were not detected.

Surface modification of poly(tetrafluoroethylene) by gas plasma treatment

Abstract Poly(tetrafluoroethylene) (PTFE) samples were surface modified in gas plasma atmospheres of air, oxygen, argon and water vapour in order to increase the surface energy. Its dispersive and polar components were determined by contact angle measurements after various treatment times. Plasma treatment times of only 15s were sufficient in all gases studied for substantial surface modification of PTFE. The chemical composition of the surfaces was studied by X-ray photoelectron spectroscopy (X.p.s.). The main results of all the plasma treatments were the abstraction of fluorine and the production of surface crosslinks, whereas only a low level of oxygen-containing groups was attached into the surface layer.

Biomedical coatings by the covalent immobilization of polysaccharides onto gas‐plasma‐activated polymer surfaces

As the surface properties of polymeric biomaterials play an important role in the performance of biomedical devices, highly hydrophilic, ultrathin coatings were applied onto hydrophobic, perfluorinated and organosilicon polymers by the covalent immobilization of polysaccharides using a reductive amination reaction. Gas plasma (r.f. glow discharge) methods were employed to equip the surfaces of these normally unreactive polymeric substrates with chemical groups capable of reacting with polysaccharides in aqueous solution. In one variant, ammonia plasmas were used to introduce into the polymer surfaces a submonolayer of amine groups. Alternatively, an n-heptylamine process vapour was used to deposit a thin plasma polymer film that possessed surface amine groups. The polysaccharides were activated for covalent immobilization by periodate oxidation, which produced hemiacetal structures, as revealed by NMR and XPS. The hemiacetal structures in the polysaccharide chains were reacted with the surface amine groups on the polymers. The resulting Schiff base linkages were stabilized by reduction to secondary amine linkages using sodium cyanoborohydride. Detailed surface analysis is important for verification that the intended chemistries have indeed been achieved in such multilayer coating schemes. X-ray photoelectron spectroscopy provided a thickness estimate of 1 ± 0.3 nm for the polysaccharide coatings in the dehydrated state. Copyright

Correlation of the Nitrogen 1s and Oxygen 1s XPS Binding Energies with Compositional Changes During Oxidation of Ethylene Diamine Plasma Polymers

In the course of plasma deposition of organic-polymeric thin films, radicals are incorporated into the growing film. These radicals initiate spontaneous oxidation reactions that continue over many weeks when the plasma polymers are stored in air. The resultant changes to the composition with time were monitored by XPS for ethylene diamine plasma polymer samples in order to improve understanding of the products of the oxidative reactions. The broadness of all the peaks, and the multitude of functional groups expected to be present, precluded the obtainment of detailed compositional information by curve fitting for components, but shifts in the binding energies (BEs) of the N 1s and O 1s peaks with time provided useful evidence of compositional changes. As the oxygen content of the plasma polymer increased upon oxidation, the binding energy of the N 1s photoelectrons increased from 399.1 to 399.8 eV. Concurrently, the amount of nitrogen in relation to carbon (N/C) decreased from 0.42 to 0.34. As the nitrogen content of the plasma polymer decreased, the binding energy of the O 1s photoelectrons increased from 531.1 to 531.8 eV. The BE values and their shifts with time/compositional changes suggested that the oxidation process predominantly caused oxidation of the carbon atoms that had amine groups attached to them, leading to the formation of amide groups and perhaps also some imides.

Post-deposition ageing reactions differ markedly between plasma polymers deposited from siloxane and silazane monomers

Abstract Plasma polymer coatings deposited from hexamethyldisiloxane (HMDSO) and hexamethyldisilazane (HMDSA) were monitored by XPS, FTIR and contact angle (CA) measurements as they aged in air after fabrication. Of particular interest was the influence of the monomer structure on the long term properties of the plasma deposited materials: in conventionally synthesized organosilicon materials, the siloxane unit provides very good long-term stability whereas the silazane structure is prone to hydrolytic attack. During plasma deposition of both coatings, abstraction of methyl groups was the major activation mechanism and the monomer structure was retained to a substantial extent. In the case of plasma polymerised (pp) HMDSA, however, other reactions such as Si–N bond cleavage resulted in considerably more structural diversity. During storage in air, the ppHMDSO film underwent minor chemical changes such as incorporation of additional siloxane cross-links and a small extent of loss of methyl groups. The chemical structure of both the freshly deposited material and the aged coating were unusually homogeneous, compared with the broad range of chemical structures typically found in most other plasma polymers. The structure of the ppHMDSA coating, in contrast, changed dramatically on ageing: almost all silazane moieties were lost after one year and substantial amounts of oxygen incorporated, mainly in the form of siloxane links. In spite of the initial chemical differences, the two materials became more similar over time, with the final structures of the aged materials based on a cross-linked siloxane backbone. The wettability data reflected the structural differences between the two materials. However, correlations between structures and surface properties were not predictable. The overall wettability of these surfaces was determined by a complex balance of several factors such as chemical structure, topography and mobility.