Computational Study of Acidic and Basic Functionalized Crystalline Silica Surfaces as a Model for Biomaterial Interfaces.

In silico modeling of acidic (CH2COOH) or basic (CH2NH2) functionalized silica surfaces has been carried out by means of a density functional approach based on a gradient-corrected functional to provide insight into the characterization of experimentally functionalized surfaces via a plasma method. Hydroxylated surfaces of crystalline cristobalite (sporting 4.8 OH/nm(2)) mimic an amorphous silica interface as unsubstituted material. To functionalize the silica surface we transformed the surface Si-OH groups into Si-CH2COOH and Si-CH2NH2 moieties to represent acidic/basic chemical character for the substitution. Structures, energetics, electronic, and vibrational properties were computed and compared as a function of the increasing loading of the functional groups (from 1 to 4 per surface unit cell). Classical molecular dynamics simulations of selected cases have been performed through a Reax-FF reactive force field to assess the mobility of the surface added chains. Both DFT and force field calculations identify the CH2NH2 moderate surface loading (1 group per unit cell) as the most stable functionalization, at variance with the case of the CH2COOH group, where higher loadings are preferred (2 groups per unit cell). The vibrational fingerprints of the surface functionalities, which are the ν(C═O) stretching and δ(NH2) bending modes for acidic/basic cases, have been characterized as a function of substitution percentage in order to guide the assignment of the experimental data. The final results highlighted the different behavior of the two types of functionalization. On the one hand, the frequency associated with the ν(C═O) mode shifts to lower wavenumbers as a function of the H-bond strength between the surface functionalities (both COOH and SiOH groups), and on the other hand, the δ(NH2) frequency shift seems to be caused by a subtle balance between the H-bond donor and acceptor abilities of the NH2 moiety. Both sets of data are in general agreement with experimental measurements on the corresponding silica-functionalized materials and provide finer details for a deeper interpretation of experimental spectra.

Thermoresponsive Water-Soluble Polymer Layers and Water-Stable Copolymer Layers Synthesized by Atmospheric Plasma Initiated Chemical Vapor Deposition.

The growth of thermoresponsive layers with the atmospheric pressure plasma-initiated chemical vapor deposition (AP-PiCVD) process is reported for the first time. N-vinyl caprolactam (NVCL) was successfully homopolymerized and copolymerized with ethylene glycol dimethacrylate (EGDMA), yielding water-soluble and water-stable thermoresponsive thin films, respectively. Strong chemical retention and high thermoresponsivity were achieved, highlighting the ability of AP-PiCVD to grow functional conventional homopolymers and copolymers.

Anti-biofouling activity of Ranaspumin-2 bio-surfactant immobilized on catechol-functional PMMA thin layers prepared by atmospheric plasma deposition.

The deposition of polymeric thin layers bearing reactive functional groups is a promising solution to provide functionality on otherwise inert surfaces, for instance, for bioconjugation purposes. Atmospheric pressure plasma (AP plasma) deposition technology offers many advantages, such as fast deposition rates, low costs, low waste generation and suitability for coating various kind of material surfaces. In this work, the AP plasma-assisted copolymerization of methyl methacrylate (MMA) with a vinyl derivative of L-DOPA was studied in order to deposit coatings with reactive catechol/quinone groups suitable for protein covalent immobilization. The effect of adding a chemical cross-linker, between 0 and 2 mol%, to the monomer mixture is also studied in order to prepare robust plasma PMMA-based layers in liquid physiological media. The layer prepared with 0.2 mol% of cross-linker shows the best balance between stability in saline-buffered media and surface functionalization. Bioconjugation via the grafting of Ranaspumin-2 recombinant, a naturally occurring surfactant protein, is carried out in a single step after plasma deposition. Protein immobilization is corroborated by Quartz Crystal Microbalance with Dissipation (QCM-D) and Surface Plasmon Resonance (SPR) analyses and confirmed via Epicocconone staining, X-Ray Photoemission Spectroscopy (XPS) and Time of Flight Secondary Ion Mass Spectrometry (ToF-SIMS) measurements and surface wettability characterizations. The bio-functionalized layers presented an enhanced activity against the adhesion of Human Serum Albumin (HSA), indicating the grafting potential of the Ranaspumin-2 bio-surfactant to produce anti-biofouling functional coatings.

Atmospheric Aerosol Assisted Pulsed Plasma Polymerization: An Environmentally Friendly Technique for Tunable Catechol-Bearing Thin Films.

In this work, an atmospheric aerosol assisted pulsed plasma process is reported as an environmentally friendly technique for the preparation of tunable catechol-bearing thin films under solvent and catalyst free conditions. The approach relies on the direct injection of dopamine acrylamide dissolved in 2-hydroxyethylmethacrylate as comonomer into the plasma zone. By adjusting the pulsing of the electrical discharge, the reactive plasma process can be alternatively switch ON (tON) and OFF (tOFF) during different periods of time, thus allowing a facile and fine tuning of the catechol density, morphology and deposition rate of the coating. An optimal tON/tOFF ratio is established, that permits maximizing the catechol content in the deposited film. Finally, a diagram, based on the average energy input into the process, is proposed allowing for easy custom synthesis of layers with specific chemical and physical properties, thus highlighting the utility of the developed dry plasma route.

Anti-biofouling and antibacterial surfaces via a multicomponent coating deposited from an up-scalable atmospheric-pressure plasma-assisted CVD process.

Prevention of bacterial adhesion and biofilm formation on the surfaces of materials is a topic of major medical and societal importance. In this study, an up-scalable atmospheric-pressure plasma assisted deposition method is introduced to produce a multicomponent coating towards the elaboration of antibacterial and anti-biofilm surfaces. Interestingly, from a single catechol-based monomer, high deposition rates of highly chemically reactive functional thin films bearing catechol as well as quinone groups are achieved. The catechol-bearing thin film allows the in situ silver nanoparticle formation, assessed by scanning electron microscopy and EDX, whilst the enriched-quinone thin film is exploited for immobilizing dispersine B, an enzyme. In vitro functional assays demonstrated the dual antibacterial and anti-biofouling resistance properties of the coatings due to the antibacterial effect of silver and the fouling resistance of grafted dispersine B, respectively. Surfaces coated only with silver provide an antibacterial effect but fail to inhibit bacterial attachment, highlighting the usefulness of such dual-action surfaces. The approach presented here provides a simple and effective chemical pathway to construct powerful antibacterial surfaces for various industrial applications.

Atmospheric Plasma Deposition of Methacrylate Layers Containing Catechol/Quinone Groups: An Alternative to Polydopamine Bioconjugation for Biomedical Applications.

Bioconjugation of enzymes on coatings based on polydopamine (PDA) layers is an appealing approach to control biological responses on biomedical implant surfaces. As alternative to PDA wet deposition, a fast, solvent-free, and dynamic deposition approach based on atmospheric-pressure plasma dielectric barrier discharge process is considered to deposit on metallic surfaces acrylic-based interlayers containing highly chemically reactive catechol/quinone groups. A biomimetic approach based on covalent immobilization of Dispersin B, an enzyme with antibiofilm properties, shows the bioconjugation potential of the novel plasma polymer layers. The excellent antibiofilm activity against Staphylococcus epidermidis is comparable to the PDA-based layers prepared by wet chemical methods with slow deposition rates. A study of preosteoblastic MG-63 human cell line viability and adhesion properties on plasma polymer layers demonstrates early interaction required for biomedical applications.

Robust bio-inspired antibacterial surfaces based on the covalent binding of peptides on functional atmospheric plasma thin films.

Here, we describe a robust process aiming at conferring antibacterial properties on stainless steel through the covalent grafting of nisin, a natural antimicrobial peptide, onto a functional plasma thin film deposited by an atmospheric pressure dielectric barrier discharge process. The three different steps of the procedure, namely the deposition of a carboxyl rich thin layer, the surface activation by using a zero-length crosslinking agent and the nisin immobilisation, are reported and thoroughly characterised. A correlation between the carboxylic group surface concentration and the surface roughness onto the antibacterial properties of the layers is evidenced. Finally, IR analyses appear as a powerful analytical tool allowing us to validate the different chemical surface modifications, to confirm the relevance of the activation step to achieve a stable and homogenous peptide grafting over all the surfaces, as well as to investigate the secondary structure of immobilized peptides.

A novel dry chemical path way for diene and dienophile surface functionalization toward thermally responsive metal-polymer adhesion.

In this paper, we report a new and easily up-scalable dry chemical method to functionalize with diene and dienophile groups a large range of surfaces, such as metal, polymer, or glass, and we demonstrate the potentiality of this technique to realize thermally responsive adhesion between these materials. A complete and extensive surface chemistry analysis of the grafted surfaces, based on the deposition of an anhydride-rich thin plasma polymer layer by using an atmospheric pressure dielectric barrier discharge (DBD) plasma process, and its subsequent gas phase aminolysis reaction with specific diene or dienophile compound is discussed. The optimization of the assembling condition for these tailored surfaces has led to achieve a Diels-Alder adhesion force up to 0.6 N/mm at ambient temperature, which can be reduced by a factor of 50 when the retro Diels-Alder is ignited at a heating temperature around 200 °C. The study of the failure interface produced after peeling tests is presented and a mechanism of failure is proposed, based on forensic analyses involving surface analytical techniques such as XPS, ToF-SIMS, and SEM combined to AFM analyses for the retrieving of chemical and morphological information.