Influence of immobilized quaternary ammonium group surface density on antimicrobial efficacy and cytotoxicity.

Bacterial colonization of medical devices causes infections and is a significant problem in healthcare. The use of antibacterial coatings is considered as a potential solution to this problem and has attracted a great deal of attention. Using concentration density gradients of immobilized quaternary ammonium compounds it was demonstrated that a specific threshold of surface concentration is required to induce significant bacterial death. It was determined that this threshold was 4.18% NR4(+) bonded nitrogen with a surface potential of + 120.4 mV. Furthermore, it is shown for the first time that adhesion of constituents of the culture medium to the quaternary ammonium modified surface eliminated any cytotoxicity towards eukaryotic cells such as primary human fibroblasts. The implications of this type of surface fouling on the antimicrobial efficacy of surface coatings are also discussed.

Versatile gradients of chemistry, bound ligands and nanoparticles on alumina nanopore arrays.

Nanoporous alumina (PA) arrays produced by self-ordering growth, using electrochemical anodization, have been extensively explored for potential applications based upon the unique thermal, mechanical and structural properties, and high surface-to-volume ratio of these materials. However, the potential applications and functionality of these materials may be further extended by molecular-level engineering of the surface of the pore rims. In this paper we present a method for the generation of chemical gradients on the surface of PA arrays based upon plasma co-polymerization of two monomers. We further extend these chemical gradients, which are also gradients of surface charge, to those of bound ligands and number density gradients of nanoparticles. The latter represent a highly exotic new class of materials, comprising aligned PA, capped by gold nanoparticles around the rim of the pores. Gradients of chemistry, ligands and nanoparticles generated by our method retain the porous structure of the substrate, which is important in applications that take advantage of the inherent properties of these materials. This method can be readily extended to other porous materials.

Plasma polymer facilitated magnetic technology for removal of oils from contaminated waters.

Oil pollution of waters is one of the most serious environmental problems globally. The long half-life and persistence within the environment makes oil particularly toxic and difficult to remediate. There is a significant need for efficient and cost-effective oil recovery technologies to be brought in to practice. In this study, we developed a facile and efficient magnetic separation method. The surface of 316L stainless steel nanoparticles was modified by plasma deposition of 1,7-octadiene and perfluorooctane, producing relatively hydrophobic coatings having water contact angles of 86 and 100°, respectively. Both coatings had high oil removal efficiency (ORE) of >99%. The captured oil could be easily separated by applying an external magnetic force. The ease of material preparation and separation from the water after the oil is captured, and its high ORE is a compelling argument for further development and optimization of the technology to possible utilization into practice. Furthermore, the capacity of plasma polymerization to deliver desired surface properties can extend the application of the technology to removing other chemical and biological contaminants from polluted waters.

The Role of Surface Nanotopography and Chemistry on Primary Neutrophil and Macrophage Cellular Responses.

Synthetic materials employed for enhancing, replacing, or restoring biological functionality may be compromised by the host immune responses that they evoke. Surface modification has attracted substantial attention as a tool to modulate the host response to synthetic materials; however, how surface nanotopography combined with chemistry affects immune effector cell responses is still poorly understood. To address this open question, a unique set of model surfaces with controlled surface nanotopography in the range of 16, 38, and 68 nm has been generated. Tailored outermost surface chemistry that was amine, carboxyl, or methyl group rich has been provided. The combinations of these properties yield 12 surface types that are subject to functional assays assessing key immune effector cells, namely, primary neutrophil and macrophage responses in vitro. The data demonstrate that surface nanotopography leads to enhanced matrix metalloproteinase-9 production from primary neutrophils, and a decrease in pro-inflammatory cytokine secretion from primary macrophages. Together, these results are the first to directly compare the immunomodulatory effects of the cooperative interplay between surface nanotopography and chemistry.

Hybrid core/shell microparticles and their use for understanding biological processes.

Hybrid micro and nanoparticles have become a topic of intense research in recent years. This is due to the special properties of these materials that open new avenues in advanced applications. Herein, we report a novel method for the generation of hybrid particles utilising plasma polymerization. Poly (methyl methacrylate) (PMMA) beads were first coated with a thin allylamine based plasma polymer layer. Gold nanoparticles of engineered size and surface structure were then attached in a controlled manner to the plasma polymer coated beads. To generate uniform chemistry on the outermost surface and to preserve the nanotopography, we deposited a 5-10 nm thin layer of Acpp. We demonstrated that these particles can be utilized in in vivo models to interrogate important biological phenomena. Specifically, we used them in mice to study the inflammatory and foreign body responses to surface nanotopography. The data strongly indicates that surface nanotopography and chemistry can modulate collagen production and the number of adhering immune cells. The method for generating hybrid particles reported here is solvent free and can open new opportunities in fields such as tissue engineering, drug delivery, biosensors, and regenerative medicine.

The influence of substrate stiffness gradients on primary human dermal fibroblasts.

Materials mechanical properties are known to be an important regulator of cellular processes such as proliferation, differentiation and migration, and have seen increasing attention in recent years. At present, there are only few approaches where the mechanical properties of thin films can be controllably varied across an entire surface. In this work, we present a technique for controlled generation of gradients of surface elastic moduli involving a weak polyelectrolyte multilayer (PEM) system of approximately 100 nm thickness and time dependent immersion in a solution of 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDC) as a crosslinking agent. Uniform surface chemistry across the gradient and wettability was provided by the addition of a 10 nm thick plasma polymer layer deposited from vapour of either allylamine or acrylic acid. We used the resultant stiffness gradients (0.5-110 MPa in hydrated state) to investigate the adhesion, morphology and proliferation on human dermal fibroblasts (HDFs). We show that substrate mechanical properties strongly influence HDF cell fate. We also found that in the experimental range of surface properties used in this study, the surface stiffness was a stronger driving force to cells fate compared to chemistry and wettability.

Creating gradients of two proteins by differential passive adsorption onto a PEG-density gradient.

Many fundamental biological processes, including early embryo development, immune responses and the progression of pathogens, are mediated by gradients of biological molecules. Understanding these vital physiological processes requires the development of biomaterial platforms that can mimic them in-vitro. Such platforms include laboratory generated surface gradients of biological molecules. In this work, we report a method for the generation of surface gradients of two proteins. We used a surface grafting density gradient of polyethylene glycol (PEG) to control protein adsorption. In addition, we used protein size as a tool to control the position and the adsorbed amount of both proteins. To demonstrate our concept, we used fibrinogen as an example of a large protein and lysozyme as an example of a small protein. However, we speculate that the same strategy could be extended to any other pair of large and small proteins. We used X-ray photoelectron spectroscopy and sessile drop contact angle measurements to determine the chemical composition and wettability of the gradients. Protein adsorption was studied by surface plasmon resonance imaging.