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Liposomes that are surface-bound to a biomaterial such as a contact lens are of interest for localized delivery of therapeutic agents, but it is not known whether such liposome layers are sufficiently robust. The stability of a dense, PEG-functionalized layer of liposomes, affinity-bound onto a multilayer coated surface, was tested under various stress conditions using colloid-probe atomic force miscroscopy (AFM). The different stress effects were generated by varying the applied normal load of the probe and the impinging fluid shear through different approach velocities and by varying the applied lateral forces by scanning under increasing force loads. The effect of applied forces (normal and lateral) was further investigated by coating the probe with a layer of albumin. The liposomes remained intact following the ramping of both protein-coated and uncoated probes under the normal and lateral loads. The low-fouling nature of these liposomes, with respect to nonspecific protein adsorption, was also demonstrated from the interaction force measurements which showed only weak adhesion from the protein layer during the contact period of the albumin-coated probe. The observed adhesive interactions were concluded to be a direct result of the applied load from the probe, during the force measurements, rather than from attraction of the protein molecules for the surface-bound liposomes. The low frictional response of the liposome layer indicated the viscoelastic nature of these molecules, which enabled liposome structure retention during the continuous load application. The demonstrated stability of the liposomes presents a system of viable and localized drug delivery in, for example, ophthalmic applications. [ABSTRACT FROM AUTHOR]

Porous silicon has received considerable interest in recent years in a range of biomedical applications, with its performance determined by surface chemistry. In this work, we investigate the PEGylation of porous silicon wafers using click chemistry. The porous silicon wafer surface chemistry was monitored at each stage of the reaction via photoacoustic Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy, whereas sessile drop contact angle and model protein adsorption measurements were used to characterize the final PEGylated surface. This work highlights the simplicity of click-chemistry-based functionalization in tailoring the porous silicon surface chemistry and controlling protein−porous silicon interactions. [ABSTRACT FROM AUTHOR]

Successful implantation of any biomaterial depends on its mechanical, architectural, and surface properties. Materials with good bulk properties seldom possess the appropriate surface characteristics required for good biointegration. The present study investigates the results of surface modification of a highly porous, fully fluorinated polymeric substrate, expanded poly(tetrafluoroethylene) (ePTFE), with a view to improving the surface bioactivity and hence ultimately its biointegration. Modification involved gamma irradiation-induced graft copolymerization with the monomers monoacryloxyethyl phosphate (MAEP) and methacryloxyethyl phosphate (MOEP) in various solvent systems (water, methanol, methyl ethyl ketone, and mixtures thereof). In order to determine the penetration depth of the graft copolymer into the pores and/or the bulk of the ePTFE membranes, angle-dependent X-ray photoelectron spectroscopy (XPS) and magnetic resonance imaging (MRI) were used. It was found that the penetration depth was critically affected by the choice of monomer and solvent as well as by the technique used to remove dissolved oxygen from the grafting mixture: nitrogen degassing versus vacuum. Difficulties due to the porous nature of the membranes in establishing the lateral position of the graft copolymers were largely overcome by combining data from microattenuated total reflectance Fourier transfer infrared (μ-ATR-FTIR) mapping and time-of-flight secondary ion mass spectrometry (ToF-SIMS) imaging. Results show that the large variation in graft heterogeneity found between different samples is largely an effect of the underlying substrate and choice of monomer. The results from this study provide the necessary knowledge and experimental data to control both the graft copolymer lateral position and depth of penetration in these porous ePTFE membranes. [ABSTRACT FROM AUTHOR]

In this communication we demonstrate that in the initial stages of deposition of ultrathin plasma polymer films, both the growth rate and the chemical composition of the films are affected by the nature of the substrate which is an important question surprisingly neglected until now. [ABSTRACT FROM AUTHOR]

Bacterial infections present an enormous problem causing human suffering and cost burdens to healthcare systems worldwide. Here we present novel tunable antibacterial coatings which completely inhibit bacterial colonization by Staphylococcus epidermidisbut allow normal adhesion and spreading of osteoblastic cells. The coatings are based on amine plasma polymer films loaded with silver nanoparticles. The method of preparation allows flexible control over the amount of loaded silver nanoparticles and the rate of release of silver ions. [ABSTRACT FROM AUTHOR]

The generation of nanosized cavities within thin film layers is of interest for a number of fundamental and applied reasons. One challenge is to make such systems sufficiently robust mechanically. Plasma polymer (pp) films possess excellent mechanical stability if deposition conditions are selected such as to achieve a sufficient density of cross-linking and resistance to extraction of polymeric material by solvents. In this study, gold nanoparticles of 15 and 70 nm diameter were used as sacrificial templates to generate nanocavities in pp films of various thickness values in the tens of nanometers range. A first pp layer was deposited onto substrates using n-heptylamine (HA) to a thickness of 20 nm. Carboxy-thiolated gold nanoparticles were electrostatically bound onto the surface amine groups of the n-heptylamine plasma polymer (HApp) layer. A second HApp layer was then coated to various thicknesses onto the nanoparticle/HApp surface. The template particles embedded thus in-between the two HApp layers were then dissolved using aqueous KCN solution; monitoring of the plasmon resonance band of the gold nanoparticles enabled verification of template stripping and measurement of the kinetics of stripping. AFM topography images showed little change on extraction of the template nanoparticles, indicating that the plasma polymer layer maintained structural integrity upon template extraction and subsequent drying, and thereby prevented collapse of the empty nanocavities. The concept of template stripping to generate controlled size free volume in thin plasma polymer layers is thus shown to produce robust structures. [ABSTRACT FROM AUTHOR]

A block copolymer consisting of a phosphate-containing moiety (poly[2-(methacryloyloxy)ethyl phosphate], PMOEP) and a keto-containing moiety (poly[2-(acetoacetoxy)ethyl methacrylate], PAAEMA) showed good stability after attachment to an APS amine-modified glass slide, as did both of the respective homopolymers. The PAAEMA homopolymer can attach to the APS amine groups via covalent linkages, while the PMOEP homopolymer most likely attaches through electrostatic interactions involving deprotonated phosphate and protonated amine groups. To elucidate the conformation of the block copolymer after attachment, particularly with respect to the PMOEP segment orientation, principal component analysis (PCA) of time-of-flight secondary ion mass spectrometry (ToF-SIMS) spectra of the surface-attached polymer layers was performed. Comparison with the pure homopolymer spectra and interpretation after PCA indicate that the adsorbed conformation is not random. Rather, the copolymer is adsorbed in a conformation that preferentially exposes the PMOEP block toward the outer surface. We thus conclude that the most likely conformation of PMOEP-b-PAAEMA immobilized onto the APS-modified glass slide is via covalent interfacial linkages involving the PAAEMA block with the result that the surface is enriched in PMOEP tails. This in turn implies that under the conditions applied (dry DMF) the covalent coupling of keto groups to the amine groups of the aminated slide is more efficient than the proton transfer required for the generation of electrostatic attractions. This (partially) preferential orientation of the PMOEP-b-PAAEMA copolymer could have significant implications on interfacial interactions such as those involved in nucleation and the subsequent mineralization sequence of events in hydroxyapatite formation. The present study demonstrates that ToF-SIMS is a powerful tool not only for the investigation of the surface composition of adsorbed layers, but also for probing the molecular conformation of such adsorbed block copolymers, though care is required in the PCA analysis of multiple spectra. [ABSTRACT FROM AUTHOR]

Biomimetic coatings offer exciting options to modulate the biocompatibility of biomaterials. The challenge is to create surfaces that undergo specific interactions with cells without promoting nonspecific fouling. This work reports an innovative approach toward biomimetic surfaces based on the covalent immobilization of a carboxylate terminated PEGylated hyaluronan (HA-PEG) onto plasma functionalized NiTi alloy surfaces. The metal substrates were aminated via two different plasma functionalization processes. Hyaluronan, a natural glycosaminoglycan and the major constituent of the extracellular matrix, was grafted to the substrates by reaction of the surface amines with the carboxylic acid terminated PEG spacer using carbodiimide chemistry. The surface modification was monitored at each step by X-ray photoelectron spectroscopy (XPS). HA-immobilized surfaces displayed increased hydrophilicity and reduced fouling, compared to bare surfaces, when exposed to human platelets (PLT) in an in vitro assay with radiolabeled platelets (204.1 ± 123.8 × 10 3PLT/cm 2vs 538.5 ± 100.5 × 10 3PLT/cm 2for bare metal, p< 0.05). Using a robust plasma patterning technique, microstructured hyaluronan surfaces were successfully created as demonstrated by XPS chemical imaging. The bioactive surfaces described present unique features, which result from the synergy between the intrinsic biological properties of hyaluronan and the chemical composition and morphology of the polymer layer immobilized on a metal surface. [ABSTRACT FROM AUTHOR]

A novel plasma functionalization process based on the pulsed plasma polymerization of allyl glycidyl ether is reported for the generation of robust and highly reactive epoxy-functionalized surfaces with well-defined chemical properties. Using a multitechnique approach including X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS), infrared spectroscopy (FT-IR), atomic force microscopy (AFM) and ellipsometry, the effect of the plasma deposition parameters on the creation and retention of epoxy surface functionalities was characterized systematically. Under optimal plasma polymerization conditions (duty cycle: 1 ms/20 ms and 1 ms/200 ms), reactive uniform films with a high level of reproducibility were prepared and successfully used to covalently immobilize the model protein lysozyme. Surface derivatization was also carried out with ethanolamine to probe for epoxy groups. The ethanolamine blocked surface resisted nonspecific adsorption of lysozyme. Lysozyme immobilization was also done via microcontact printing. These results show that allyl glycidyl ether plasma polymer layers are an attractive strategy to produce a reactive epoxy functionalized surface on a wide range of substrate materials for biochip and other biotechnology applications. [ABSTRACT FROM AUTHOR]

Plasma polymers deposited from n-heptylamine onto silicon wafers have been found to form a porous microstructure when immersed in water and other solvents, with pores of dimensions and densities that vary considerably between coatings deposited under different plasma conditions. This solvent-induced pore formation was found to correlate with the observed percentage of extractable material. With low radio frequency (rf) power inputs, the resultant softer coatings possess considerably more extractable material than coatings deposited at higher applied power levels. The porosity is thus proposed to result from the formation of voids created by the extraction of soluble low-molecular-weight polymeric material, which produces shrinkage stress that the coating, firmly attached to the substrate, cannot relieve by macroscopic contraction. The microscopic contraction of plasma polymer volume creates voids that appear to span the entire film thickness. The effect of aging plasma polymers in air was also investigated. For films deposited at low power it led to reduced extraction of soluble material and different pore morphology, whereas for films deposited at higher rf power levels, the extracted amounts and pore formation were the same for aged coatings. It was also found that the density of surface amine groups was lower for films deposited under the two lowest power settings, in contrast to the commonly held belief that the use of minimal applied rf power aids retention of functional groups. These porous plasma polymer coatings with surface groups suitable for further interfacial chemical immobilization reactions may be useful for various membrane and biotechnology applications. [ABSTRACT FROM AUTHOR]

A critical requirement toward the clinical use of nanocarriers in drug delivery applications is the development of optimal biointerfacial engineering procedures designed to resist biologically nonspecific adsorption events. Minimization of opsonization increases blood residence time and improves the ability to target solid tumors. We report the electrostatic self-assembly of polyethyleneimine−polyethylene glycol (PEI-PEG) copolymers onto porous silica nanoparticles. PEI-PEG copolymers were synthesized and their adsorption by self-assembly onto silica surfaces were investigated to achieve a better understanding of structure−activity relationships. Quartz-crystal microbalance (QCM) study confirmed the rapid and stable adsorption of the copolymers onto silica-coated QCM sensors driven by strong electrostatic interactions. XPS and FT-IR spectroscopy were used to analyze the coated surfaces, which indicated the presence of dense PEG layers on the silica nanoparticles. Dynamic light scattering was used to optimize the coating procedure. Monodisperse dispersions of the PEGylated nanoparticles were obtained in high yields and the thin PEG layers provided excellent colloidal stability. In vitro protein adsorption tests using 5% serum demonstrated the ability of the self-assembled copolymer layers to resist biologically nonspecific fouling and to prevent aggregation of the nanoparticles in physiological environments. These results demonstrate that the electrostatic self-assembly of PEG copolymers onto silica nanoparticles used as drug nanocarriers is a robust and efficient procedure, providing excellent control of their biointerfacial properties. [ABSTRACT FROM AUTHOR]

Towards a robust and universal functionalization procedure with alkanethiols for gold nanorods and plasmonic nanoparticles, a straightforward two-step approach is described. [ABSTRACT FROM AUTHOR]

The attachment of pathogenic fungal cells onto materials surfaces, which is often followed by biofilm formation, causes adverse consequences in a wide range of areas. Here we have investigated the ability of thin film coatings from chlorinated molecules to deter fungal colonization of solid materials by contact killing of fungal cells reaching the surface of the coating. Coatings were deposited onto various substrate materials via plasma polymerization, which is a substrate-independent process widely used for industrial coating applications, using 1,1,2-trichloroethane as the process vapour. XPS surface analysis showed that the coatings were characterized by a highly chlorinated hydrocarbon polymer nature, with only a very small amount of oxygen incorporated. The activity of these coatings against human fungal pathogens was quantified using a recently developed, modified yeast assay and excellent antifungal activity was observed against Candida albicans and Candida glabrata. Plasma polymer surface coatings derived from chlorinated hydrocarbon molecules may therefore offer a promising solution to preventing yeast and mould biofilm formation on materials surfaces, for applications such as air conditioners, biomedical devices, food processing equipment, and others. [ABSTRACT FROM AUTHOR]

This paper presents a novel and facile method for the generation of efficient antibacterial coatings which can be applied to practically any type of substrate. Silver nanoparticles were stabilized with an adsorbed surface layer of polyvinyl sulphonate (PVS). This steric layer provided excellent colloidal stability, preventing aggregation over periods of months. PVS-coated silver nanoparticles were bound onto amine-containing surfaces, here produced by deposition of an allylamine plasma polymer thin film onto various substrates. SEM imaging showed no aggregation upon surface binding of the nanoparticles; they were well dispersed on amine surfaces. Such nanoparticle-coated surfaces were found to be effective in preventing attachment of Staphylococcus epidermidis bacteria and also in preventing biofilm formation. Combined with the ability of plasma polymerization to apply the thin polymeric binding layer onto a wide range of materials, this method appears promising for the fabrication of a wide range of infection-resistant biomedical devices. [ABSTRACT FROM AUTHOR]