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The protective properties of polymethacrylate coatings with different side chain lengths for 2024 aluminum alloys were studied, focusing on the chain length increase but also on the Ar-plasma pretreatment applied to the metal surface. The coatings were obtained by photopolymerization, obtaining reproducible molecular weight polymers during each process that were determined by high-performance liquid chromatography. AA2024 alloy were immersed into the polymethacrylate solution using methyl, butyl, and hexyl as monomers. Their roughness was then evaluated using atomic force microscopy. Surface hydrophobicity and contact angle hysteresis were analyzed in water and diiodomethane. Protective properties were evaluated by electrochemical impedance spectroscopy after 56 days of immersion in a 0.1 M Na2SO4. The alloy cross-sections were examined by field emission scanning electron microscopy and glow discharge optical emission spectroscopy, allowing the estimation of film thickness. Surface analysis revealed that the defect population densities in the coatings increased the monomer alkyl chain length. The immersion thickness increase was consistent with contact angle measurements taken over time, and independent from the chain length. Contradicting expectations, the results showed the protective efficacy was not related to the chain length, since after exposure, the PBMA film revealed the best anti-corrosive coating performance on the AA2024. This was possibly influenced by its polymeric film conformation, hydrophilicity, ordering and lower density of defects on the metal surface.

Violacein is an intensely purple pigment synthesized by various genera of bacteria that has been discovered to have a wide range of interesting biological activities which range from anticarcinogenic to antibacterial. One of the hindrances for its real-life application is that the first microorganisms found to produce the compound may act as opportunistic pathogens. Here, we report the isolation and characterization of violacein from a non-pathogenic Antarctic Iodobacter strain. Its anti-microbial properties were also tested. The method proposed here for the purification of violacein shows high yields, indicating that this Antarctic microorganism could be a valuable source for this important pigment. This is the first characterization of violacein from an Antarctic Iodobacter strain and here we also present a viable method to obtain this pigment for potential biotechnological applications.

To better understand the effect of surface treatments on the efficiency of protective coatings of aluminum alloys, this study assessed different surface treatments for the aluminum alloy AA2024, including mechanical polishing, chemical etching and Ar-plasma pretreatment followed by deposition of poly(methyl methacrylate). Surface morphology, surface chemical analysis and wettability of the treated samples were characterized by scanning electron microscopy, X-ray photoelectron spectroscopy and contact angle, respectively. Open circuit potential and electrochemical impedance spectroscopy were carried out in a 0.1 M solution of Na2SO4 as a function of exposure time. SEM images revealed that a homogeneous and well incorporated poly-(methyl methacrylate) coating was obtained by using Ar-plasma as a pretreatment. XPS spectra showed that the Al O/Al OH intensity ratio of the Ar-plasma pretreated samples does not show clear dependence on angle measurement, which indicates that Al(OH) and Al2O3 are not homogenously distributed on the sample surfaces. Al2O3 does not completely cover the aluminum surface, leaving some areas exposed. The measurements of the hysteresis angle showed that the Ar-plasma pretreatment favors chemical heterogeneity, which in turn increases the hydrophilicity of the coated samples, resulting in lower wettability and a greater hysteresis angle. The electrochemical results showed that the Ar-plasma pretreatment significantly improves the protective capacity of poly(methyl methacrylate).

The factors governing bacterial adhesion to substrates with different topographies are still not fully identified. The present work seeks to elucidate for the first time and with quantitative data the roles of bacterial elasticity and shape and substrate topography in bacterial adhesion. With this aim, populations of three bacterial species

Inhibiting pathogenic bacterial adherence on surfaces is an ongoing challenge to prevent the development of biofilms. Multilayer polyelectrolyte films are feasible antibacterial materials. Here, we have designed new films made of carbohydrate polyelectrolytes to obtain antibacterial coatings that prevent biofilm formation. The polyelectrolyte films were constructed from poly(maleic anhydride- alt-styrene) functionalized with glucofuranose derivatives and quaternized poly(4-vinylpyridine) N-alkyl. These films prevent Pseudomonas aeruginosa and Salmonella Typhimurium, two important bacterial contaminants in clinical environments, from adhering to surfaces. When the film was composed of more than 10 layers, the bacterial population was greatly reduced, while the bacteria remaining on the film were morphologically damaged, as atomic force microscopy revealed. The antibacterial capacity of the polyelectrolyte films was determined by the combination of thickness, wettability, surface energy, and most importantly, the conformation that polyelectrolytes adopt the function of nature of the carbohydrate group. This polyelectrolyte film constitutes the first green approach to preventing pathogenic bacterial surface adherence and proliferation without killing the bacterial pathogen.

The main motivation of this work is to obtain poly (ionic liquids) (PILs) derived from poly (4-vinyl pyridine) of different hydrophobic character containing BF4−, PF6−, (CF3SO2)2 N− and CF3SO3− as counterions. PILs were synthesized from N-alkyl quaternized poly(4-vinylpyridine) P-4VP+-CnBr− with different alkyl chain length, n = 2, 4, 5 and different molecular weights (60.000 and 160.000 g/mol). The systems obtained were compared with the polyelectrolyte of origin, i.e., the N-alkyl quaternized poly(4-vinylpyridine). The molecular characterization of PILs was obtained by FT-IR, 1H NMR and 19F NMR. Moreover, the thermal analysis of these systems was by carried out by differential scanning calorimetry (DSC) and thermogravimetry (TGA) techniques. Thermal degradation profiles obtained from TGA measurements, varied according to the alkyl chain length, which in turn influenced the obtained values of glass transition temperature (Tg), due to greater or lesser segmental movement of the alkyl chain. The results obtained for the PILs studied were analysed according to alkyl chain length, molecular weight and counter-anion effects. Additionally, P-4VP+-C4 BF4− was used in a preliminary study of chromium (VI) removal from aqueous solution, showing a 72.2% removal of Cr (VI).

In this work, we present a solid silicon substrate functionalized with modified β-cyclodextrin monolayers as an optimal surface for organic contaminant uptake. The inclusion and capture of three potential pollutants, 4-chlorophenoxyacetic acid, 4-aminobenzoic acid and phenylethylamine, were studied. 1H-NMR and ROESY studies revealed the complete inclusion and details of the conformational orientation of the three guests in the per-(6-amino-6-deoxy)-β-cyclodextrin matrix, forming three new inclusion complexes that have not yet been reported. Capture assays for the guests were carried out by immersing the substrates in an aqueous pollutant solution and by measuring the UV–vis spectra. This substrate showed a high sorption capacity at equilibrium, between 2.5 × 10−5 and 6.0 × 10−5 mmol/substrate, for the studied pollutants. In addition, this surface can be reused four times with an efficiency equal to the initial use. Therefore, it could be a versatile platform that could be applied for the capture of other organic pollutants from water.

International audience; Surfaces were prepared with polyelectrolyte derivatives of poly(styrene-alt-maleic anhydride) (PSMA) functionalized with amino acids of different hydropathy indices, with the aim of evaluating the effect of the chemical functionality of polyelectrolytes on SH-SY5Y neuroblastoma cell adhesion. Functionalizing PSMA derivatives with L-glutamine, L-methionine, and L-tyrosine yielded PSMA-Gln, PSMA-Met, and PSMA-Tyr polyelectrolytes, respectively. We first studied the adsorption behavior of PSMA functionalized with amino acids on silicon wafer surfaces modified with 3-aminopropyltriethoxysilane at pH 4.0 and 7.0 and at low and high ionic strengths. The highest rate of polyelectrolyte adsorption was at pH 4.0 and high ionic strength and was higher with the glutamine and tyrosine films. The advance contact angles (θ A) of the polyelectrolyte surfaces showed a moderate effect of ionic strength and pH on polyelectrolyte film wettability, with PSMA-Tyr being slightly more hydrophobic. Atomic force microscopy images of the polyelectrolyte surfaces showed two types of morphology: the well-defined globular nanostructure of PSMA-Met and PSMA-Tyr and densely packed nanofibrous-like structure of PSMA-Gln. The highest level of ionic strength caused a slight decrease in the size of the nanostructure that formed the surface domains, which was reflected in the degree of surface roughness. Cell adhesion assays with the polyelectrolyte film showed that SH-SY5Y neuroblastoma cells cultured on PSMA-Met present a well-extended morphology characterized by a stellate shape, with five or more actin-rich thin processes, whereas SH-SY5Y cells that were seeded on PSMA-Gln and PSMA-Tyr have a round morphology, with fewer and shorter processes. These results indicate that it is possible to modulate the surface characteristics of polyelectrolyte films based on their chemical functionality and environmental parameters such as pH and ionic strength in order to evaluate their effect on cell adhesion. Thus, surfaces prepared from polyelectrolytes functionalized with amino acids are an attractive and simple platform for cell adhesion, which can be used in developing biomaterials with modulated surface properties.

Adsorption of As (V) by poly ( N -octyl-4-vinylpyridinium) bromide (P4VPyC8), used as solid phase, was studied. Determination of As (V) was carried out by direct measurement of the fluorescence intensity on the solid phase. Adsorption variables were optimized for obtaining optimum values of pH and agitation time, where pH 9.0 and 60 min were established as optimum values. The adsorption of arsenic (V) was characterized by infrared spectroscopy, thermogravimetric analysis and scanning electron microscopy. It was found that the fluorescence of the solid phase increases as the concentration of arsenic increases. Linearity was observed in the concentration range 6.80 to 90.0 μg L − 1 . The detection limit for determination of As (V) by this method was 2.24 μg L − 1 and the relative standard deviation (RSD) was 1.72%. The amount of retained As (V) was 0.154 mg/g of solid phase. The determination of As (V) in a sample of tap water by this method was well compared with the value reported by an external certified laboratory. Therefore, the method of analysis proposed here could be used as a screening methodology for monitoring the fulfillment of the norm for arsenic concentration in tap water.

An experimental protocol was studied to improve the adhesion of a polymeric poly(methyl methacrylate) coating that was modified with silver nanoparticles to an aluminum alloy, AA2024. The nanoparticles were incorporated into the polymeric matrix to add the property of inhibiting biofilm formation to the anticorrosive characteristics of the film, thus also making the coating antibiocorrosive. The protocol consists of functionalizing the surface through a pseudotransesterification treatment using a methyl methacrylate monomer that bonds covalently to the surface and leaves a terminal double bond that promotes and directs the polymerization reaction that takes place in the process that follows immediately after. This results in more compact and thicker poly(methyl methacrylate) (PMMA) coatings than those obtained without pseudotransesterification. The poly(methyl methacrylate) matrix modified with nanoparticles was obtained by incorporating both the nanoparticles and the methyl methacrylate in the reactor. The in situ polymerization involved combining the pretreated AA2024 specimens combined with the methyl methacrylate monomer and AgNps. The antibiofilm capacity of the coating was evaluated against P. aeruginosa, with an excellent response. Not only did the presence of bacteria decrease, but the formation of the exopolymer subunits was 99.99% lower than on the uncoated aluminum alloy or the alloy coated with unmodified poly(methyl methacrylate). As well and significantly, the potentiodynamic polarization measurements indicate that the PMMA-Ag coating has a good anticorrosive property in a 0.1-M NaCl medium.

A novel method to obtain catalytic bio-nanocomposites based on chitosan containing different amounts of gold nanoparticles generated in situ is reported. The formation of gold nanoparticles takes place in solid phase assisted by a heating induced process. This method only involves the use of chitosan biopolymer and a gold salt precursor. Unlike other methods the addition of external reducing and stabilizing agents to generate gold nanoparticles, is not needed because these roles are played by chitosan. Therefore, the striking properties of chitosan (e.g., high functionality, biodegradability and biocompatibility) are profited, in order to design a facile and green route of synthesis. Additionally, the described method allows to vary the amount and size of the gold nanoparticles contained in the bio-nanocomposite by using different gold ion compositions and temperatures of heating process. Finally, the bio-nanocomposite performance as heterogeneous catalyst on the reduction of p-nitrophenol (4-NP) to p-aminophenol (4-AP) as a model system was assessed. The results showed a significant catalytic effect that increases as the content of gold nanoparticles in the bio-nanocomposite also increases.

The use of implants carries on a series of problems, among them infections, poor biocompatibility, high levels of cytotoxicity, and significant mechanical differences between implants and host organs that promote stress shielding effects. These problems indicate that the materials used to make implants must meet essential requirements and high standards for implantations to be successful. In this work, we present the synthesis, characterization and evaluation of the antibiofilm, mechanical, and thermal properties, and cytotoxic effect of a nanocomposite-based scaffold on polyurethane (PU) and gold nanoparticles (AuNPs) for soft tissue applications. The effect of the quantity of AuNPs on the antibacterial activity of nanocomposite scaffolds was evaluated against Staphylococcus epidermidis and Klebsiella spp., with a resulting 99.99% inhibition of both bacteria using a small quantity of nanoparticles. Cytotoxicity was evaluated with the T10 1/2 test against fibroblast cells. The results demonstrated that porous nanogold/PU scaffolds have no toxic effects on fibroblast cells to the 5 day exposition. With respect to mechanical properties, stress-strain curves showed that the compressive modulus and yield strength of PU scaffolds were significantly enhanced by AuNPs (by at least 10 times). This is due to changes in the arrangement of hard segments of PU, which increase the stiffness of the polymer. Thermogravimetric analysis showed that the degradation onset temperature rises with an increase in the quantity of AuNPs. These properties and characteristics demonstrate that porous nanogold/PU scaffolds are suitable material for use in soft tissue implants.

International audience; Surface based on polyelectrolytes functionalized with amino acids onto amino-terminated solid surfaces of silicon wafers was prepared, with the purpose of evaluate the chemical functionality of the polyelectrolyte films in adsorption and catalytic activity of an enzyme. In this work, the adsorption of the enzyme glucose 6-phosphate dehydrogenase from Leuconostoc mesenteroides (LmG6PD) was studied as model. The polyelectrolytes were obtained from poly (maleic anhydride-alt-vinylpyrrolidone) [poly(MA-alt-VP)] and functionalized with amino acids of different hydropathy index: glutamine (Gln), tyrosine (Tyr) and methionine (Met). The polyelectrolytes were adsorbed onto the amino-terminated silicon wafer at pH 3.5 and 4.5 and at low and high ionic strength. At low ionic strength and pH 3.5, the largest quantity of adsorbed polyelectrolyte was on the films containing glutamine moiety as the most hydrophilic amino acid in the side chain of polymer chain (5.88 mg/m 2), whereas at high ionic strength and pH 4.5, the lowest quantity was in films containing tyrosine moiety in the side chain (1.88 mg/m 2). The films were characterized by ellipsometry, contact angle measurements and atomic force microscopy (AFM). The polyelectrolyte films showed a moderate degree of hydrophobicity, the methionine derivative being the most hydrophobic film. With the aim of evaluate the effect of the amino acid moieties on the ability of the surface to adsorb enzymes, we study the activity of the enzyme on these surfaces. We observed that the polarity of the side chain of the amino acid in the polyelectrolyte affected the quantity of LmG6PD adsorbed, as well as its specific activity, showing that films prepared from poly(MA-alt-VP) functionalized with Met provide the best enzymatic performance. The results obtained demonstrated that the surfaces prepared from polyelectrolytes functionalized with amino acids could be an attractive and simple platform for the im-mobilization of enzymes, which could be of interest for biocatalysis applications.

The intermolecular association of amphipathic polyelectrolytes is studied using fluorescence and conductivity methods. This type of interaction is evidenced by the decrease in the average distances between charges as the polyelectrolyte side chain increases in length. This modify the dissociation degree and consequently, the linear charge density parameter. These distances were calculated with the Manning counterion condensation theory for the conductivity of polyelectrolyte solutions. The determination of the ratio I1/I3 of the fluorescence bands of pyrene with polymer content reveals the formation of hydrophobic microdomains at very low concentrations, smaller than the required concentration to produce a significant change in the average distances between charges. These distances and also the I1/I3 ratio vary with polymer concentration and their values were dependent on the size of the side chain in the polyelectrolyte. Finally, the experimental behavior of the solution viscosity and electrical conductivity of polyelectrolytes, which increase drastically with dilution, can be explained as a continuous change in the average distances between charges which produce conformational changes.