Long-term stability of aerophilic metallic surfaces underwater.

Aerophilic surfaces immersed underwater trap films of air known as plastrons. Plastrons have typically been considered impractical for underwater engineering applications due to their metastable performance. Here, we describe aerophilic titanium alloy (Ti) surfaces with extended plastron lifetimes that are conserved for months underwater. Long-term stability is achieved by the formation of highly rough hierarchically structured surfaces via electrochemical anodization combined with a low-surface-energy coating produced by a fluorinated surfactant. Aerophilic Ti surfaces drastically reduce blood adhesion and, when submerged in water, prevent adhesion of bacteria and marine organisms such as barnacles and mussels. Overall, we demonstrate a general strategy to achieve the long-term stability of plastrons on aerophilic surfaces for previously unattainable underwater applications.

Corrosion Resistance of Biodegradable Zinc Surfaces Enhanced by UV-Grafted Polydimethylsiloxane Coating.

Improved living conditions have led to an increase in life expectancy worldwide. However, as people age, the risk of vascular disease tends to increase due to the accumulation and buildup of plaque in arteries. Vascular stents are used to keep blood vessels open. Biodegradable stents are designed to provide a temporary support vessel that gradually degrades and is absorbed by the body, leaving behind healed blood vessels. However, biodegradable metals can suffer from reduced mechanical strength and/or inflammatory response, both of which can affect the rate of corrosion. Therefore, it is essential to achieve a controlled and predictable degradation rate. Here, we demonstrate that the corrosion resistance of biodegradable Zn surfaces is improved by electroless deposition of zinc hydroxystannate followed by UV-grafting with silicone oil (PDMS). Potentiodynamic polarization, electrochemical impedance spectroscopy, respiratory kinetic measurements, and long-term immersion in three simulated body fluids were applied. Although zinc hydroxystannate improves the corrosion resistance of Zn to some extent, it introduces a high surface area with hydroxyl units used to UV-graft PDMS molecules. Our results demonstrate that hydrophobic PDMS causes a 3-fold reduction in corrosion of Zn-based materials in biological environments and reduces cytotoxicity through the uncontrolled release of Zn ions.

Iron oxide nanoparticle-based nanocomposites in biomedical application.

Iron-oxide-based biomagnetic nanocomposites, recognized for their significant properties, have been utilized in MRI and cancer treatment for several decades. The expansion of clinical applications is limited by the occurrence of adverse effects. These limitations are largely attributed to suboptimal material design, resulting in agglomeration, reduced magnetic relaxivity, and inadequate functionality. To address these challenges, various synthesis methods and modification strategies have been used to tailor the size, shape, and properties of iron oxide nanoparticle (FeONP)-based nanocomposites. The resulting modified nanocomposites exhibit significant potential for application in diagnostic, therapeutic, and theranostic contexts, including MRI, drug delivery, and anticancer and antimicrobial activity. Yet, their biosafety profile must be rigorously evaluated. Such efforts will facilitate the broader clinical translation of FeONP-based nanocomposites in biomedical applications.

Silicone-Based Lubricant-Infused Slippery Coating Covalently Bound to Aluminum Substrates for Underwater Applications.

Wetting of solid surfaces is crucial for biological and industrial processes but is also associated with several harmful phenomena such as biofouling and corrosion that limit the effectiveness of various technologies in aquatic environments. Despite extensive research, these challenges remain critical today. Recently, we have developed a facile UV-grafting technique to covalently attach silicone-based coatings to solid substrates. In this study, the grafting process was evaluated as a function of UV exposure time on aluminum substrates. While short-time exposure to UV light results in the formation of lubricant-infused slippery surfaces (LISS), a flat, nonporous variant of slippery liquid-infused porous surfaces, longer exposure leads to the formation of semi-rigid cross-linked polydimethylsiloxane (PDMS) coatings, both covalently bound to the substrate. These coatings were exposed to aquatic media to evaluate their resistance to corrosion and biofouling. While the UV-grafted cross-linked PDMS coating effectively inhibits aluminum corrosion in aquatic environments and allows organisms to grow on the surface, the LISS coating demonstrates improved corrosion resistance but inhibits biofilm adhesion. The synergy between facile and low-cost fabrication, rapid binding kinetics, eco-friendliness, and nontoxicity of the applied materials to aquatic life combined with excellent wetting-repellent characteristics make this technology applicable for implementation in aquatic environments.

Interaction of bovine serum albumin and lysozyme with stainless steel studied by time-of-flight secondary ion mass spectrometry and X-ray photoelectron spectroscopy.

An in-depth mechanistic understanding of the interaction between stainless steel surfaces and proteins is essential from a corrosion and protein-induced metal release perspective when stainless steel is used in surgical implants and in food applications. The interaction between lysozyme (LSZ) from chicken egg white and bovine serum albumin (BSA) and AISI 316L stainless steel surfaces was studied ex situ by means of X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) after different adsorption time periods (0.5, 24, and 168 h). The effect of XPS measurements, storage (aging), sodium dodecyl sulfate (SDS), and elevated temperature (up to 200 °C) on the protein layers, as well as changes in surface oxide composition, were investigated. Both BSA and LSZ adsorption induced an enrichment of chromium in the oxide layer. BSA induced significant changes to the entire oxide, while LSZ only induced a depletion of iron at the utmost layer. SDS was not able to remove preadsorbed proteins completely, despite its high concentration and relatively long treatment time (up to 36.5 h), but induced partial denaturation of the protein coatings. High-temperature treatment (200 °C) and XPS exposure (X-ray irradiation and/or photoelectron emission) induced significant denaturation of both proteins. The heating treatment up to 200 °C removed some proteins, far from all. Amino acid fragment intensities determined from ToF-SIMS are discussed in terms of significant differences with adsorption time, between the proteins, and between freshly adsorbed and aged samples. Stainless steel-protein interactions were shown to be strong and protein-dependent. The findings assist in the understanding of previous studies of metal release and surface changes upon exposure to similar protein solutions.

Influence of bovine serum albumin on biodegradation behavior of pure Zn.

Zinc is emerging as a promising biodegradable metal for temporary implant applications. In this work, we investigate the influence of bovine serum albumin (BSA)-the most abundant blood protein in simulated body fluid (SBF) on degradation of pure Zn via electrochemical measurements and long-term immersion. Electrochemical experiments indicate a decrease of the corrosion rate of bare Zn with increasing BSA concentration in solution for short-term exposures. Samples were characterized with scanning electron microscope (SEM) (including energy dispersive spectroscopy [EDS], X-ray photoelectron spectroscopy [XPS], Fourier transform infrared spectroscopy [FTIR], and time-of-flight secondary ion mass spectrometry [TOF-SIMS]) after immersion up to 21 days. Presence of BSA in the electrolyte, decrease the amount of Ca-phosphate precipitation on Zn surface. However, a more compact surface layer formed in the presence of BSA in solution. Most noteworthy, in long-term exposures, BSA enhances localized corrosion of Zn-such detrimental localized attack was not observed in BSA-free solution. We suggest that a sealed space forming between the Zn substrate and a protein adsorption layer restricts mass transport, thus triggering localized corrosion of Zn.

Nontoxic Liquid-Infused Slippery Coating Prepared on Steel Substrates Inhibits Corrosion and Biofouling Adhesion.

Wetting of surfaces plays a vital role in many biological and industrial processes. There are several phenomena closely related to wetting such as biofouling and corrosion that cause the deterioration of materials, while the efforts to prevent the degradation of surface functionality have spread over several millennia. Antifouling coatings have been developed to prevent/delay both corrosion and biofouling, but the problems remain unsolved, influencing the everyday life of the modern society in terms of safety and expenses. In this study, liquid-infused slippery surfaces (LISSs), a recently developed nontoxic repellent technology, that is, a flat variation of omniphobic slippery liquid-infused porous surfaces (SLIPSs), were studied for their anti-corrosion and marine anti-biofouling characteristics on metallic substrates under damaged and plain undamaged conditions. Austenitic stainless steel was chosen as a model due to its wide application in aquatic environments. Our LISS coating effectively prevents biofouling adhesion and decays corrosion of metallic surfaces even if they are severely damaged. The mechanically robust LISS reported in this study significantly extends the SLIPS technology, prompting their application in the marine environment due to the synergy between the facile fabrication process, rapid binding kinetics, nontoxic, ecofriendly, and low-cost applied materials together with excellent repellent characteristics.

Radiolysis-Driven Evolution of Gold Nanostructures - Model Verification by Scale Bridging In Situ Liquid-Phase Transmission Electron Microscopy and X-Ray Diffraction.

Utilizing ionizing radiation for in situ studies in liquid media enables unique insights into nanostructure formation dynamics. As radiolysis interferes with observations, kinetic simulations are employed to understand and exploit beam-liquid interactions. By introducing an intuitive tool to simulate arbitrary kinetic models for radiation chemistry, it is demonstrated that these models provide a holistic understanding of reaction mechanisms. This is shown for irradiated HAuCl4 solutions allowing for quantitative prediction and tailoring of redox processes in liquid-phase transmission electron microscopy (LP-TEM). Moreover, it is demonstrated that kinetic modeling of radiation chemistry is applicable to investigations utilizing X-rays such as X-ray diffraction (XRD). This emphasizes that beam-sample interactions must be considered during XRD in liquid media and shows that reaction kinetics do not provide a threshold dose rate for gold nucleation relevant to LP-TEM and XRD. Furthermore, it is unveiled that oxidative etching of gold nanoparticles depends on both, precursor concentration, and dose rate. This dependency is exploited to probe the electron beam-induced shift in Gibbs free energy landscape by analyzing critical radii of gold nanoparticles.

Tuning of the Mg Alloy AZ31 Anodizing Process for Biodegradable Implants.

Coatings were grown on the AZ31 Mg alloy by a hard anodizing process in the hot glycerol phosphate-containing electrolyte. Anodizing conditions were optimized, maximizing corrosion resistance estimated by impedance measurements carried out in Hank's solution at 37 °C. A post anodizing annealing treatment (350 °C for 24 h) allowed us to further enhance the corrosion resistance of the coatings mainly containing magnesium phosphate according to energy-dispersive X-ray spectroscopy and Raman analyses. Gravimetric measurements revealed a hydrogen evolution rate within the limits acceptable for application of AZ31 in biomedical devices. In vitro tests demonstrated that the coatings are biocompatible with a preosteoblast cell line.

Functionalization of metallic magnesium with protein layers via linker molecules.

We present an innovative method to cover pure magnesium with protein monolayers by utilizing the OH termination of the oxide surface and silane coupling chemistry. The protein of interest was albumin. Time-of-flight secondary ion mass spectrometry (ToF-SIMS) and X-ray photoelectron spectroscopy (XPS) were used to monitor the success of the treatment. The attachment of proteins via linker groups yielded smoother and more homogeneous surfaces than coatings produced by steeping magnesium in protein solution. A positive effect on the corrosion behavior of pure magnesium was also observed.

Static Wettability of Differently Mechanically Treated and Amphiphobic-Coated Aluminium Surfaces.

Wettability, roughness and surface treatment methods are essential for the majority of practical applications, where liquid-solid surface interactions take place. The present study experimentally investigated the influence of different mechanical surface treatment methods on the static wettability of uncoated and amphiphobic-coated aluminium alloy (AlMg3) samples, specially focusing on the interaction between surface finishing and coating. Five different surfaces were prepared: as-received substrate, polished, sandpapered, fleece-abraded and sandblasted. After characterisation, the samples were spray-coated using an amphiphobic coating. The characterisation of the uncoated and coated samples involved measurements of the roughness parameters and the apparent contact angles of demineralized water and rapeseed oil. The coating was initially characterised regarding its adhesion to the sample and elevated temperature stability. The applied surface treatments resulted in the scattered sample roughness in the range of Sa = 0.3-15.8 µm, water contact angles of θ a p , w = 78°-106° and extremely low oil contact angles. Coating the samples more than doubled the surface roughness to Sa = 13.3-29 µm, whereas the initial surface treatment properties (structure, anisotropy, etc.) were entirely repressed by the coating properties. Coating led the water contact angles to increase to θ a p , w _ c o a t e d = 162°-173° and even more pronounced oil contact angles to increase to θ a p , o _ c o a t e d = 139°-150°, classifying the surfaces as superhydrophobic and oleophobic.

Influence of proteins on the corrosion behavior of a chitosan-bioactive glass coated magnesium alloy.

The current study explored the degradation behavior of a WE43 Mg alloy during immersion tests in Dulbecco's Modified Eagle's Medium (DMEM) for 3d and 7d, for a bare alloy surface as well as for samples with surface pre-treatment, and finally for samples coated with chitosan-bioactive glass. The immersion tests were conducted with and without addition of serum, to study the influence of proteins on the degradation process. Mass-loss was measured to determine the corrosion rate after 3d and 7d of immersion. The samples were analyzed by SEM with respect to their surface morphology and the chemical composition was screened by high-resolution XPS. The results demonstrate not only a significant, time-dependent influence of serum addition on the corrosion behavior of the materials studied, but noteworthy is that depending on the sample type, proteins in solution were observed to either accelerate or inhibit corrosion. These results are discussed in correlation to observed changes in surface chemistry taking place upon immersion in the absence and presence of proteins.

In Vitro Osteocompatibility and Enhanced Biocorrosion Resistance of Diammonium Hydrogen Phosphate-Pretreated/Poly(ether imide) Coatings on Magnesium for Orthopedic Application.

Magnesium, as a biodegradable metal, is a promising candidate for biomedical applications. To modify the degradation behavior of magnesium and improve its osteocompatibility, chemical conversion and spin coating methods were combined to develop a diammonium hydrogen phosphate-pretreated/poly(ether imide) (DAHP/PEI) co-coating system. The diammonium hydrogen phosphate pretreatment was employed to enhance the attachment between PEI coatings and the magnesium substrate; meanwhile, it could serve as another bioactive and anticorrosion layer when PEI coatings break down. Surface characterization, electrochemical tests, and short-term immersion tests in DMEM were performed to evaluate DAHP/PEI coatings. Electrochemical measurements showed that DAHP/PEI coatings significantly improved the corrosion resistance of pure magnesium. No obvious changes of the chemical compositions of DAHP/PEI coatings occurred after 72 h of immersion in DMEM. An in vitro cytocompatibility study confirmed that viability and LDH activity of human osteoblast-like cells on DAHP/PEI coatings showed higher values than those on the DAHP-pretreated layer and pure magnesium. The DAHP-pretreated layer could still enhance the ALP activity of MG-63 cells after the degradation of PEI in DAHP/PEI coatings. Besides that, the in vitro cellular response to the treated magnesium was investigated to gain knowledge on the differentiation and proliferation of human adipose-derived stem cells (hADSCs). Cell distribution and morphology were observed by fluorescence and SEM images, which demonstrated that DAHP/PEI coatings facilitated cell differentiation and proliferation. The high level of C-terminals of collagen type I production of hADSCs on DAHP/PEI coatings indicated the potential of the coating for promoting osteogenic differentiation. Positive results from long-term cytocompatibility and proliferation tests indicate that DAHP/PEI coatings can offer an excellent surface for hADSCs.

Modification of in vitro degradation behavior of pure iron with ultrasonication treatment: Comparison of two different pseudo-physiological solutions.

An ultrasonication treatment is developed as an external method to control the degradation behavior of pure iron. Immersion tests (weight loss measurements) and electrochemical measurements were conducted in two different pseudo-physiological solutions, simulated body fluid (SBF) and Dulbecco's modified Eagle medium (DMEM) solution. By the comparison study in these two different solutions, more information and the mechanism of the degradation process can be revealed. Degradation morphologies (with and without ultrasonication treatment) were observed by scanning electron microscope (SEM), and degradation products on the surface were characterized by Fourier transform infrared (FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS). Moreover, the biocompatibility of iron surfaces after being ultrasonicated was evaluated. Ultrasonication was found to accelerate the degradation rate in DMEM, while it makes no difference in SBF solution; the origin of this different behavior is investigated and discussed. The parameters of the ultrasonication treatment, intensity and frequency, show an influence on the degradation rate. No adverse effects on the proliferation and adhesion of human osteoblast-like cells (MG-63) are observed on surfaces after ultrasonication treatment, as compared to bare iron. Based on these results, ultrasonication treatment is considered to have high potential to control the biodegradation behavior of iron-based materials in an external and flexible manner.

Electrophoretic Deposition of Bioadaptive Drug Delivery Coatings on Magnesium Alloy for Bone Repair.

Biodegradable polymer coatings on magnesium alloys are attractive, as they can provide corrosion resistance as well as additional functions for biomedical applications, e.g., drug delivery. A gelatin nanospheres/chitosan (GNs/CTS) composite coating on WE43 substrate was fabricated by electrophoretic deposition with simvastatin (SIM) loaded into the GNs. Apart from a sustained drug release over 28 days, an anticorrosion behavior of the coated WE43 substrates was confirmed by electrochemical tests. Both the degradation and corrosion rates of the coated substrate were significantly minimized in contrast to bare WE43. The cytocompatibility of the coated samples was analyzed  both quantitatively and qualitatively. Additionally, the osteogenic differentiation of MC3T3-E1 cells on SIM-containing coatings was assessed by measuring the expression of osteogenic genes and related proteins, alkaline phosphatase (ALP) activity, and extracellular matrix mineralization, showing that the SIM-loaded composite coating could upregulate the expression of osteogenic genes and related proteins, promote ALP activity, and enhance extracellular matrix mineralization. In summary, the SIM-loaded GNs/CTS composite coatings were able to enhance the corrosion resistance of the WE43 substrate and promote osteogenic activity, thus demonstrating a promising coating system for modifying the surface of magnesium alloys targeted for orthopedic applications.

Combinatorial Study on Phase Formation and Oxidation in the Thin Film Superalloy Subsystems Co-Al-Cr and Co-Al-Cr-W.

Two Co-based superalloy subsystems, the ternary system Co-Al-Cr and the quasi-ternary system Co-Al-Cr-W with a constant amount of 10 at. % W, were deposited as thin-film materials libraries and analyzed in terms of phase formation and oxidation behavior at 500 °C in air. By combining energy-dispersive X-ray analysis and X-ray photoelectron spectroscopy high-throughput composition measurements, a detailed evaluation of the dependence between the initial multinary metal composition and the oxide scale composition which is forming upon oxidation on the surface of the thin film is established. Phase maps for both materials libraries are provided by high-throughput X-ray diffraction. In addition, the oxidation of a Co-Al-Cr-W bulk sample was analyzed and compared to a corresponding film in the library.

A novel local drug delivery system: Superhydrophobic titanium oxide nanotube arrays serve as the drug reservoir and ultrasonication functions as the drug release trigger.

A local drug delivery system consisting of superhydrophobic titanium oxide nanotube (S-TNTs) arrays and ultrasonic-controlled release trigger was developed in this work. Hydrophilic TNTs arrays are converted into superhydrophobic after being treated by 1H,1H,2H,2H- perfluorooctyl-triethoxysilane (POTS). S-TNTs arrays serving as a drug-carrying vehicle require no extra sealing treatment due to the excellent isolation effect from the trapped air layer on the surface. Different amounts of drugs could be loaded into S-TNTs arrays by control of the structure of arrays (including length and diameter of tubes) and the original amount of drug in the drug-loading solution. The relation between surface morphology of TNTs arrays and superhydrophobicity (isolation effect) was thoroughly investigated. To achieve a stimulus-responsive drug delivery system, ultrasonication was employed as an efficient drug release trigger. Trapped air layer could be selectively removed by ultrasonication, and therefore the loaded drug could be released in a multiple and controlled manner. Any drugs that can dissolve in nonpolar solutions are expected to be suitable for this local drug delivery system.

Electrophoretic deposition of lawsone loaded bioactive glass (BG)/chitosan composite on polyetheretherketone (PEEK)/BG layers as antibacterial and bioactive coating.

In this study, chitosan/bioactive glass (BG)/lawsone coatings were deposited by electrophoretic deposition (EPD) on polyetheretherketone (PEEK)/BG layers (previously deposited by EPD on 316-L stainless steel) to produce bioactive and antibacterial coatings. First, the EPD of chitosan/BG/lawsone was optimized on stainless steel in terms of suspension stability, homogeneity and thickness of coatings. Subsequently, the optimized EPD parameters were used to produce bioresorbable chitosan/bioactive glass (BG)/lawsone coatings on PEEK/BG layers. The produced layered coatings were characterized in terms of composition, microstructure, corrosion resistance, in vitro bioactivity, drug release kinetics and antibacterial activity. Ultraviolet/Visible (UV/VIS) spectroscopic analyses confirmed the release of lawsone from the coatings. Moreover, the deposition of chitosan/BG coatings was confirmed by Scanning Electron Microscopy (SEM) and Fourier Transform Infrared spectroscopy (FTIR). The coated specimens presented higher corrosion resistance (10 times) in comparison to that of bare 316-L stainless steel and showed convenient wettability for initial protein attachment. The presence of lawsone in the top layer provided antibacterial effects against Staphylococcus carnosus. Moreover, the developed coatings formed apatite-like crystals upon immersion in simulated body fluid, indicating the possibility of achieving close interaction between the coating surface and bone. © 2018 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 106A: 3111-3122, 2018.