Low Surface Energy Fluorocarbon Coatings Via Plasma Polymerization Process: Process Optimization and Protein Repellent Study

In the present study, low surface energy perfluorodecyl acrylate (PFDA) coatings and their copolymer coatings with diethylene glycol dimethyl ether (DEGDME) (i.e. PFDA-co-DEGDME) have been deposited through plasma enhanced chemical vapor deposition (PECVD) onto thermanox coverslips in a low pressure tubular inductively coupled RF plasma reactor. The influence of plasma parameters on surface chemical properties of the coatings were investigated by using fourier transform infrared spectroscopy (FTIR), field emission scanning electron microscopy (FESEM), x-ray photoelectron spectroscopy (XPS) and water contact angle (WCA). The protein repellent properties of the plasma polymer coatings have been investigated using quartz crystal microbalance (QCM).JRC.DG.I.5-Nanobioscience

Radio-Frequency Plasma Polymerized Biodegradable Carrier for in vivo Release of Cis-Platinum

A low pressure plasma process based on plasma deposition has been used to develop a drug delivery strategy. In this study, a drug delivery system based on different layers of plasma co-polymerized Poly ε-caprolactone-Polyethylene glycol (PCL-PEG) co-polymers was deposited on biocompatible substrates. Cis-platinum (118 μgm/cm2) was used as an anti-cancer drug and incorporated for local delivery of the chemotherapeutic agent. The co-polymer layers and their interaction with cancer cells were analyzed by scanning electron microscopy. Our study showed that the plasma-PCL-PEG coated cellophane membranes, in which the drug, was included did not modify the flexibility and appearance of the membranes. This system was actively investigated as an alternative method of controlling localized delivery of drug in vivo. The loading of the anti-cancer drug was investigated by UV-VIS spectroscopy and its release from plasma deposited implants against BALB/c mice liver tissues were analyzed through histological examination and apoptosis by TUNEL assay. The histological examination of liver tissues revealed that when the plasma-modified membranes encapsulated the cis-platinum, the Glisson\u27s capsule and liver parenchyma were damaged. In all cases, inflammatory tissues and fibrosis cells were observed in contact zones between the implant and the liver parenchyma. In conclusion, low pressure plasma deposited uniform nano-layers of the co-polymers can be used for controlled release of the drug in vivo

Design of calcium phosphate scaffolds with controlled simvastatin release by plasma polymerisation

Calcium Phosphates (CaPs) have excellent bone regeneration capacity, and their combination with specific drugs is of interest because it allows adding new functionalities. In CaPs, drug release is mainly driven by diffusion, which is strongly affected by the porosity of the matrix and the drug-material interaction. Therefore, it is very difficult to tune their drug release properties beyond their intrinsic properties. Furthermore, when the CaPs are designed as scaffolds, the increased complexity of the macrostructure further complicates the issue.; This work investigates for the first time the use of biocompatible plasma-polymers to provide a tool to control drug release from drug-loaded CaP scaffolds with complex surfaces and intricate 3D structure. Two different CaPs were selected displaying great differences in microstructure: low-temperature CaPs (Calcium-deficient hydroxyapatite cements, CDHA) and sintered CaP ceramics (beta-Tricalcium Phosphate, beta-TCP). The deposition of PCL-co-PEG (1: 4) copolymers on CaPs was achieved by a low pressure plasma process, which allowed coating the inner regions of the scaffolds up to a certain depth. The coating covered the micro and nanopores of the CaPs surface and produced complex geometries presenting a nano and micro rough morphology which lead to low wettability despite the hydrophilicity of the copolymer. Plasma coating with PCL-co-PEG on scaffolds loaded with Simvastatin acid (potentially osteogenic and angiogenic) allowed delaying and modulating the drug release from the bone scaffolds depending on the thickness of the layer deposited, which, in turn depends on the initial specific surface area of the CaP. (C) 2016 Elsevier Ltd. All rights reserved.Peer ReviewedPostprint (author's final draft

Development of silver nanoparticle loaded antibacterial polymer mesh using plasma polymerization process

Plasma polymerized polyacrylic acid (PPAA) was deposited on a polymer substrate, namely polyethylene terephthalate (PET) mesh, for entrapment of silver nanoparticle (Ag-NP) in order to achieve antibacterial property to the material. Carboxylic groups of PPAA act as anchor as well as capping and stabilizing agents for Ag-NPs synthesized by chemical reduction method using NaBH4 as a reducing agent. Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy (XPS), and water contact angle analysis were used to characterize the PPAA coatings. The Ag-NPs loaded polymer samples were characterized by UV–visible spectroscopy, field emission scanning electron microscopy, energy dispersive X-ray, and XPS techniques. XPS analysis showed ∼1.0 at.% loading of Ag-NPs on to the PPAA-PET-mesh, which was composed of 79% zero-valent (Ag°) and 21% oxidized nano-Ag (Ag+). The plasma processed PET meshes samples were tested for antibacterial activity against two bacterial strains, namely Staphylococcus aureus (Gram positive) and Escherichia coli (Gram negative). Qualitative and quantitative tests showed that silver containing PPAA-PET meshes exhibit excellent antibacterial property against the tested bacteria with percent reduction of bacterial concentration >99%, compared to the untreated PET mesh

Catalyst-Free Plasma-Assisted Copolymerization of Poly(ε-caprolactone)-poly(ethylene glycol) for Biomedical Applications

Catalyst-free ring-opening polymerization (ROP) strategy was developed to overcome the disadvantage of incomplete and expensive removal of catalyst used during the multistep wet chemical processes. Nano-sized biocompatible and low molecular weight poly­(ε-carolactone)-poly­(ethylene glycol) (PCL-PEG) copolymer coatings were deposited via a single-step, low-pressure, pulsed-plasma polymerization process. Experiments were performed at different monomer feed ratio and effective plasma power. The coatings were analyzed by XPS, as well as MALDI ToF. Ellipsometric measurement showed deposition rates ranging from 1.3 to 3 nm/min, depending on the ratio of the PCL/PEG precursors introduced in the reactor. Our results have demonstrated that plasma copolymerized PCL-PEG coatings can be tailored in such a way to be cell adherent, convenient for biomedical implants such as artificial skin substrates, or cell repellent, which can be used as antibiofouling surfaces for urethral catheters, cardiac stents, and so on. The global objective of this study is to tailor the surface properties of PCL by copolymerizing it with PEG in the pulsed plasma environment to improve their applicability in tissue engineering and biomedical science

Preventing Biofilm Formation on Biomedical Surfaces

This chapter introduces the problem of biofilm formation on material surfaces, which is not only important in the biomedical field, but also for other industrial applications including food and beverage processing, pharmaceutical and cosmetics manufacturing. The different steps and the most important factors related to the formation of a biofilm (e.g., conditioning film, physicochemical characteristics of biomaterial surface, characteristics of the microorganism, environmental factors, etc.) are discussed. The discussion is followed by an overview of various plausible strategies that are useful to prevent biofilm formation on biomaterial surfaces, i.e., presurgery precautionary measures, the use of antimicrobial releasing materials, surface engineering methods, and an anti-biofilm approach. Surface modification by plasma processing is introduced as a particularly versatile surface engineering approach to prevent biofilm formation, and the important role of plasma processing of polymers in the prevention of biofouling and biofilm formation is emphasized. Finally, a specific case study is presented, which discusses the use of plasma-deposited poly(ethylene oxide)-like films for the prevention of biofilm formation.JRC.DG.I.5-Nanobioscience

Nanostructure Protein Repellant Amphiphilic Copolymer Coatings with Optimized Surface Energy by Inductively Excited Low Pressure Plasma

Statistically designed amphiphilic copolymer coatings were deposited onto Thermanox, Si wafer, and quartz crystal microbalance (QCM) substrates via Plasma Enhanced Chemical Vapor Deposition of 1H,1H,2H,2H-perfluorodecyl acrylate and diethylene glycol vinyl ether in an Inductively Excited Low Pressure Plasma reactor. Plasma deposited amphiphilic coatings were characterized by Field Emission Scanning Electron Microscopy, X-ray Photoelectron Spectroscopy, Atomic Force Microscopy, and Water Contact Angle techniques. The surface energy of the coatings can be adjusted between 12 and 70 mJ/m2. The roughness of the coatings can be tailored depending on the plasma mode used. A very smooth coating was deposited with a CW (continuous wave) power, whereas a rougher surface with Ra in the range of 2 to 12 nm was deposited with the PW (pulsed wave) mode. The nanometer scale roughness of amphiphilic PFDA-co-DEGVE coatings was found to be in the range of the size of the two proteins namely BSA and lysozyme used to examine for the antifouling properties of the surfaces. The results show that the statistically designed surfaces, presenting a surface energy around 25 mJ/m2, present no adhesion with respect to both proteins measured by QCM.JRC.I.4-Nanobioscience

Design of calcium phosphate scaffolds with controlled simvastatin release by plasma polymerisation

Calcium Phosphates (CaPs) have excellent bone regeneration capacity, and their combination with specific drugs is of interest because it allows adding new functionalities. In CaPs, drug release is mainly driven by diffusion, which is strongly affected by the porosity of the matrix and the drug-material interaction. Therefore, it is very difficult to tune their drug release properties beyond their intrinsic properties. Furthermore, when the CaPs are designed as scaffolds, the increased complexity of the macrostructure further complicates the issue.; This work investigates for the first time the use of biocompatible plasma-polymers to provide a tool to control drug release from drug-loaded CaP scaffolds with complex surfaces and intricate 3D structure. Two different CaPs were selected displaying great differences in microstructure: low-temperature CaPs (Calcium-deficient hydroxyapatite cements, CDHA) and sintered CaP ceramics (beta-Tricalcium Phosphate, beta-TCP). The deposition of PCL-co-PEG (1: 4) copolymers on CaPs was achieved by a low pressure plasma process, which allowed coating the inner regions of the scaffolds up to a certain depth. The coating covered the micro and nanopores of the CaPs surface and produced complex geometries presenting a nano and micro rough morphology which lead to low wettability despite the hydrophilicity of the copolymer. Plasma coating with PCL-co-PEG on scaffolds loaded with Simvastatin acid (potentially osteogenic and angiogenic) allowed delaying and modulating the drug release from the bone scaffolds depending on the thickness of the layer deposited, which, in turn depends on the initial specific surface area of the CaP. (C) 2016 Elsevier Ltd. All rights reserved.Peer Reviewe

Visible Light Water Splitting via Oxidized TiN Thin Films

Thin films of TiN were prepared via RF magnetron reactive sputtering at various deposition pressures. The characteristics of the plasmas were measured by optical emission spectroscopy to optimize the conditions for the deposition of TiN coatings. After deposition, the thin films were annealed in a closed furnace at several different temperatures, and revealed the formation of different phases of TiO₂. The resulting TiN/TiO₂ thin films showed drastic changes in their crystal structure, optical properties, and photoelectrochemical performance. By examining how the deposition pressure and postdeposition annealing conditions affected the TiN film structure and performance, samples were prepared to optimize visible light absorption and activity. A model for the oxidation process was proposed which described the structural change from TiN to TiO₂ through optical, morphological, and crystalline characterization. This study has systematically shown the ability to tailor the optical, crystalline, and photoactive properties of TiO₂ by tailoring the intrinsic properties of TiN thin films and subsequent annealing. These results can be utilized for many solar driven optoelectronic devices