Morphological and Surface Potential Characterization of Protein Nanobiofilm Formation on Magnesium Alloy Oxide: Their Role in Biodegradation.

The formation of a protein nanobiofilm on the surface of degradable biomaterials such as magnesium (Mg) and its alloys influences metal ion release, cell adhesion/spreading, and biocompatibility. During the early stage of human body implantation, competition and interaction between inorganic species and protein molecules result in a complex film containing Mg oxide and a protein layer. This film affects the electrochemical properties of the metal surface, the protein conformational arrangement, and the electronic properties of the protein/Mg oxide interface. In this study, we discuss the impact of various simulated body fluids, including sodium chloride (NaCl), phosphate-buffered saline (PBS), and Hanks' solutions on protein adsorption, electrochemical interactions, and electrical surface potential (ESP) distribution at the adsorbed protein/Mg oxide interface. After 10 min of immersion in NaCl, atomic force microscopy (AFM) and scanning Kelvin probe force microscopy (SKPFM) showed a higher surface roughness related to enhanced degradation and lower ESP distribution on a Mg-based alloy than those in other solutions. Furthermore, adding bovine serum albumin (BSA) to all solutions caused a decline in the total surface roughness and ESP magnitude on the Mg alloy surface, particularly in the NaCl electrolyte. Using SKPFM surface analysis, we detected a protein nanobiofilm (∼10-20 nm) with an aggregated and/or fibrillary morphology only on the Mg surface exposed in Hanks' and PBS solutions; these surfaces had a lower ESP value than the oxide layer.

Direct microbial electron uptake as a mechanism for stainless steel corrosion in aerobic environments.

Shewanella oneidensis MR-1 is an attractive model microbe for elucidating the biofilm-metal interactions that contribute to the billions of dollars in corrosion damage to industrial applications each year. Multiple mechanisms for S. oneidensis-enhanced corrosion have been proposed, but none of these mechanisms have previously been rigorously investigated with methods that rule out alternative routes for electron transfer. We found that S. oneidensis grown under aerobic conditions formed thick biofilms (∼50 µm) on stainless steel coupons, accelerating corrosion over sterile controls. H2 and flavins were ruled out as intermediary electron carriers because stainless steel did not reduce riboflavin and previous studies have demonstrated stainless does not generate H2. Strain ∆mtrCBA, in which the genes for the most abundant porin-cytochrome conduit in S. oneidensis were deleted, corroded stainless steel substantially less than wild-type in aerobic cultures. Wild-type biofilms readily reduced nitrate with stainless steel as the sole electron donor under anaerobic conditions, but strain ∆mtrCBA did not. These results demonstrate that S. oneidensis can directly consume electrons from iron-containing metals and illustrate how direct metal-to-microbe electron transfer can be an important route for corrosion, even in aerobic environments.

Experimental insights into anodic oxidation of hexafluoropropylene oxide dimer acid (GenX) on boron-doped diamond anodes.

GenX is the trade name of the ammonium salt of hexafluoropropylene oxide dimer acid (HFPO-DA) and is used as a replacement for the banned perfluorooctanoic acid (PFOA). However, recent studies have found GenX to be more toxic than PFOA. This work deals with the electrochemical degradation of HFPO-DA using boron-doped diamond anodes. For the first time, an experimental study was conducted to investigate the influence of sulfate concentration and other operating parameters on HFPO-DA degradation. Results demonstrated that sulfate radicals were ineffective in HFPO-DA degradation due to steric hindrance by -CF3 branch. Direct electron transfer was found as the rate-determining step. By comparing degradation of HFPO-DA with that of PFOA, it was observed that the steric hindrance by -CF3 branch in HFPO-DA decreased the rate of electron transfer from the carboxyl head group even though its defluorination rate was faster. Conclusively, a degradation pathway is proposed in which HFPO-DA mineralizes to CO2 and F- via formation of three intermediates.

Self-Organized Anodic Oxides on Titanium Alloys Prepared from Glycol- and Glycerol-Based Electrolytes.

The anodization of commercially pure Ti alloy (99.5 wt %) and two biomedical titanium alloys, Ti6Al7Nb and Ti6Al4V, was performed, and the resulting anodic oxides were studied. The biomedical alloys were made by Laser Engineered Net Shaping. The glycol-based and glycerol-based electrolytes with 0.3 M ammonium fluoride and 2 wt % of deionized water content were tested. It was found that electrolyte type as well as the chemical composition of the base substrate affected the final morphology and chemical composition of the anodic oxide formed. A higher current density, ionic mobility, and oxide growth rate were obtained in glycol-based electrolyte as compared to those obtained in glycerol-based electrolyte for all tested alloys. A self-organized nanotubular and nanoporous morphology of the anodic oxide in both types of electrolyte was obtained. In each electrolyte, the alloy susceptibility to oxidation increased in the following order: Ti6Al4V < Ti 99.5% < Ti6Al7Nb, which can be correlated to the oxidation susceptibility of the base titanium alloy. It was observed that the more impurities/alloying elements in the substrate, the lower the pore diameters of anodic oxide. There was a higher observed incorporation of electrolyte species into the anodic oxide matrix in the glycerol-based electrolyte compared with that in glycol-based electrolyte.

Triple-Action Self-Healing Protective Coatings Based on Shape Memory Polymers Containing Dual-Function Microspheres.

In this study, a new self-healing shape memory polymer (SMP) coating was prepared to protect the aluminum alloy 2024-T3 from corrosion by the incorporation of dual-function microspheres containing polycaprolactone and the corrosion inhibitor 8-hydroxyquinoline (8HQ). The self-healing properties of the coatings were investigated via scanning electron microscopy, electrochemical impedance spectroscopy, and scanning electrochemical microscopy following the application of different healing conditions. The results demonstrated that the coating possessed a triple-action self-healing ability enabled by the cooperation of the 8HQ inhibitor, the SMP coating matrix, and the melted microspheres. The coating released 8HQ in a pH-dependent fashion and immediately suppressed corrosion within the coating scratch. After heat treatment, the scratched coating exhibited excellent recovery of its anticorrosion performance, which was attributed to the simultaneous initiation of scratch closure by the shape memory effect of the coating matrix, sealing of the scratch by the melted microspheres, and the synergistic effect of corrosion inhibition by 8HQ.

Unravelling the Chemical Influence of Water on the PMMA/Aluminum Oxide Hybrid Interface In Situ.

Understanding the stability of chemical interactions at the polymer/metal oxide interface under humid conditions is vital to understand the long-term durability of hybrid systems. Therefore, the interface of ultrathin PMMA films on native aluminum oxide, deposited by reactive adsorption, was studied. The characterization of the interface of the coated substrates was performed using ambient pressure X-ray photoelectron spectroscopy (APXPS), Fourier transform infrared spectroscopy in the Kretschmann geometry (ATR-FTIR Kretschmann) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). The formation of hydrogen bonds and carboxylate ionic bonds at the interface are observed. The formed ionic bond is stable up to 5 Torr water vapour pressure as shown by APXPS. However, when the coated samples are exposed to an excess of aqueous electrolyte, an increase in the amount of carboxylate bonds at the interface, as a result of hydrolysis of the methoxy group, is observed by ATR-FTIR Kretschmann. These observations, supported by ToF-SIMS spectra, lead to the proposal of an adsorption mechanism of PMMA on aluminum oxide, which shows the formation of methanol at the interface and the effect of water molecules on the different interfacial interactions.

In Situ Characterization of the Initial Effect of Water on Molecular Interactions at the Interface of Organic/Inorganic Hybrid Systems.

Probing initial interactions at the interface of hybrid systems under humid conditions has the potential to reveal the local chemical environment at solid/solid interfaces under real-world, technologically relevant conditions. Here, we show that ambient pressure X-ray photoelectron spectroscopy (APXPS) with a conventional X-ray source can be used to study the effects of water exposure on the interaction of a nanometer-thin polyacrylic acid (PAA) layer with a native aluminum oxide surface. The formation of a carboxylate ionic bond at the interface is characterized both with APXPS and in situ attenuated total reflectance Fourier transform infrared spectroscopy in the Kretschmann geometry (ATR-FTIR Kretschmann). When water is dosed in the APXPS chamber up to 5 Torr (~28% relative humidity), an increase in the amount of ionic bonds at the interface is observed. To confirm our APXPS interpretation, complementary ATR-FTIR Kretschmann experiments on a similar model system, which is exposed to an aqueous electrolyte, are conducted. These spectra demonstrate that water leads to an increased wet adhesion through increased ionic bond formation.