Brendan Duffy

Enhancement of the antibacterial properties of silver nanoparticles using β-cyclodextrin as a capping agent

Silver nanoparticles (AgNPs) were synthesised by reducing silver salts using NaBH(4) followed by capping with varying concentrations of beta-cyclodextrin (beta-CD) and were physically characterised. Antibacterial activity against Escherichia coli, Pseudomonas aeruginosa and Staphylococcus aureus was determined by a microtitre well method. The AgNPs were spherical under transmission electron microscopy, whilst dynamic light scattering showed average diameters of capped particles to be smaller (4-7 nm) than their uncapped equivalents (17 nm). Capped particles demonstrated superior photostability when exposed to intense ultraviolet radiation for 4h as well as significantly (P<0.05) higher (up to 3.5-fold) antibacterial activity. The influence of beta-CD concentration was seen to delay bacterial growth, indicating that a Trojan horse mechanism may be occurring owing to bacterial carbohydrate affinity, thereby enhancing silver ion absorption.

Biodegradable magnesium alloys for orthopaedic applications: A review on corrosion, biocompatibility and surface modifications

Magnesium (Mg) and its alloys have been extensively explored as potential biodegradable implant materials for orthopaedic applications (e.g. Fracture fixation). However, the rapid corrosion of Mg based alloys in physiological conditions has delayed their introduction for therapeutic applications to date. The present review focuses on corrosion, biocompatibility and surface modifications of biodegradable Mg alloys for orthopaedic applications. Initially, the corrosion behaviour of Mg alloys and the effect of alloying elements on corrosion and biocompatibility is discussed. Furthermore, the influence of polymeric deposit coatings, namely sol-gel, synthetic aliphatic polyesters and natural polymers on corrosion and biological performance of Mg and its alloy for orthopaedic applications are presented. It was found that inclusion of alloying elements such as Al, Mn, Ca, Zn and rare earth elements provides improved corrosion resistance to Mg alloys. It has been also observed that sol-gel and synthetic aliphatic polyesters based coatings exhibit improved corrosion resistance as compared to natural polymers, which has higher biocompatibility due to their biomimetic nature. It is concluded that, surface modification is a promising approach to improve the performance of Mg-based biomaterials for orthopaedic applications.

Preparation and rapid analysis of antibacterial silver, copper and zinc doped sol-gel surfaces.

The colonisation of clinical and industrial surfaces with microorganisms, including antibiotic-resistant strains, has promoted increased research into the development of effective antibacterial and antifouling coatings. This study describes the preparation of metal nitrate (Ag, Cu, Zn) doped methyltriethoxysilane (MTEOS) coatings and the rapid assessment of their antibacterial activity using polyproylene microtitre plates. Microtitre plate wells were coated with different volumes of liquid sol-gel and cured under various conditions. Curing parameters were analysed by thermogravimetric analysis (TGA) and visual examination. The optimum curing conditions were determined to be 50-70°C using a volume of 200 μl. The coated wells were challenged with Gram-positive and Gram-negative bacterial cultures, including biofilm-forming and antibiotic-resistant strains. The antibacterial activities of the metal doped sol-gel, at equivalent concentrations, were found to have the following order: silver>zinc>copper. The order is due to several factors, including the increased presence of silver nanoparticles at the sol-gel coating surface, as determined by X-ray photoelectron spectroscopy, leading to higher elution rates as measured by inductively coupled plasma atomic emission spectroscopy (ICP-AES). The use of microtitre plates enabled a variety of sol-gel coatings to be screened for their antibacterial activity against a wide range of bacteria in a relatively short time. The broad-spectrum antibacterial activity of the silver doped sol-gel showed its potential for use as a coating for biomaterials.

Silver doped perfluoropolyether-urethane coatings: Antibacterial activity and surface analysis

The colonisation of clinical and industrial surfaces with pathogenic microorganisms has prompted increased research into the development of effective antibacterial and antifouling coatings. There is evidence that implanted biomedical surfaces coated with metallic silver can be inactivated by physiological fluids, thus reducing the bioactivity of the coating. In this work, we report the biofilm inhibition of Staphylococcus epidermidis using a room temperature processed silver doped perfluoropolyether-urethane coating. The release of silver ions from these fluoropolymers over a six-day period inhibited bacterial encrustation - as observed by scanning electron microscopy (SEM). X-ray photoelectron spectroscopy (XPS) analysis indicated differences in carbon, fluorine and sodium surface composition between silver doped and undoped fluoropolymers after exposure to nutrient rich media. These silver doped perfluoropolyether coatings also exhibited antibacterial activity against methicillin-resistant Staphylococcus aureus (MRSA), Escherichia coli, Pseudomonas aeruginosa and Acinetobacter baumannii; suggesting potential use in preventing transmission of pathogenic and opportunistic microbes on environmental surfaces in healthcare facilities. The broad-spectrum antibacterial activity of these silver release coatings may be exploited on biomaterials surfaces to combat the development of resistant Gram-negative Enterobacteriaceae that can occur during prophylactic treatment for urinary tract infections.

Dual effects of β-cyclodextrin-stabilised silver nanoparticles: enhanced biofilm inhibition and reduced cytotoxicity

The composition and mode of synthesis of nanoparticles (NPs) can affect interaction with bacterial and human cells differently. The present work describes the ability of β-cyclodextrin (β-CD) capped silver nanoparticles (AgNPs) to inhibit biofilm growth and reduce cytotoxicity. Biofilm formation of Staphylococcus epidermidis CSF 41498 was quantified by a crystal violet assay in the presence of native and capped AgNPs (Ag-10CD and Ag-20CD), and the morphology of the biofilm was observed by scanning electron microscope. The cytotoxicity of the AgNPs against HaCat cells was determined by measuring the increase in intracellular reactive oxygen species and change in mitochondrial membrane potential (ΔΨm). Results indicated that capping AgNPs with β-CD improved their efficacy against S. epidermidis CSF 41498, reduced biofilm formation and their cytotoxicity. The study concluded that β-CD is an effective capping and stabilising agent that reduces toxicity of AgNPs against the mammalian cell while enhancing their antibiofilm activity.

Dual-action hygienic coatings: Benefits of hydrophobicity and silver ion release for protection of environmental and clinical surfaces

Coatings that demonstrate reduced attachment of crystalline precipitates and the medical device colonising Staphylococcus epidermidis were prepared by the immobilisation of silver doped perfluoropolyether-urethane siloxane thin films on glass substrates. The presence of stratified hydrophobic perfluoropolyether groups protects the coating surface from the attachment of crystalline hydrophilic species such as chlorides and phosphates, whilst silver ion release inhibited attachment of S. epidermidis and subsequent biofilm formation in vitro. The release of silver ions protects the perfluoro groups from the hydrophobic interactions of S. epidermidis cells, which can reduce the hydrophobicity of the protective coating. These coatings also exhibited significant antibacterial activity against planktonic Acinetobacter baumannii and S. epidermidis bacterial strains. Detailed elemental and chemical surface analysis obtained using X-ray photoelectron spectroscopy (XPS) provided useful information on the effect of bacterial incubation on key indicator hydrophobic and hydrophilic functional groups. XPS analysis indicated preferential adsorption of S. epidermidis cells at the hydrophobic sites along the polymeric chain. These dual-action hygienic coatings can be employed to protect against contamination environmental surfaces and bacterial colonisation on implanted medical devices.

Non-cytotoxic antibacterial silver-coumarin complex doped sol-gel coatings.

Microbial colonisation on clinical and industrial surfaces is currently of global concern and silane based sol-gel coatings are being proposed as potential solutions. Sol-gels are chemically inert, stable and homogeneous and can be designed to act as a reservoir for releasing antimicrobial agents over extended time periods. In the present study, silver nitrate (AgN) and a series of silver coumarin complexes based on coumarin-3-carboxylatosilver (AgC) and it is 6, 7 and 8 hydroxylated analogues (Ag6, Ag7, Ag8) were incorporated into sol-gel coatings. The comparative antibacterial activity of the coatings was determined against meticillin resistant Staphylococcus aureus (MRSA) and multidrug resistance Enterobacter cloacae WT6. The percentage growth inhibitions were found in the range of 9.2 (±2.7)-66.0 (±1.2)% at low silver loadings of 0.3% (w/w) with E. cloacae being the more susceptible. Results showed that among the Ag coumarin complexes, the Ag8 doped coating had the highest antibiofilm property. XPS confirmed the presence of silver in the nanoparticulate state (Ag(0)) at the coating surface where it remained after 4 days of exposure to bacterial culture. Comparative cytotoxicity studies revealed that the Ag-complex coatings were less toxic than the AgN coating. Thus, it can be concluded that a sol-gel matrix with Ag-coumarin complexes may provide non-toxic surfaces with antibacterial properties.

Correlation between the structure and the anticorrosion barrier properties of hybrid sol-gel coatings: application to the protection of AA2024-T3 alloys

Hybrid sol–gel materials have been extensively studied as viable alternatives to toxic chromate (VI)-based coatings for the corrosion protection of AA2024-T3 in the aerospace industry, due to the wide range of available chemistries they offer and the tremendous development potential of innovative functional coatings. However, so far, little work has been performed in identifying the effect of the employed chemistries on the structure and anticorrosion properties of the coatings. This work proposes to contribute to a better understanding of the relationship existing between the structure, morphology and anticorrosion properties of hybrid sol–gel coatings deposited on AA2024-T3 aluminium surfaces, the most widely used alloy in the aerospace industry. The sol–gels are prepared employing two hybrid precursors; an organosilane, 3-trimethoxysilylpropylmethacrylate, and a zirconium complex prepared from the chelation of zirconium n-propoxide, and methacrylic acid. The structure of the hybrid sol–gel formulation is modified by altering the concentration of the transition metal complex. The structure and morphology of the coatings are characterised by dynamic light scattering, fourier transform infrared spectroscopy, silicon nuclear magnetic resonance spectroscopy, differential scanning calorimetry, scanning electron microscopy, atomic-force microscopy and the anticorrosion barrier properties characterised by electrochemical impedance spectroscopy and neutral salt-spray. It is found that the transition metal concentration affected the morphology and structure, as well as the anticorrosion performances of the hybrid sol–gel coatings. A direct correlation between the morphology of the coatings and their final anticorrosion barrier properties is demonstrated, and the optimum material amongst this series is determined to be comprised of a concentration of between 20 and 30% of transition metal.Graphical Abstract

An Investigation of the Biochemical Properties Of Tetrazines as Potential Coating Additives

1,2,4,5-Tetrazine and its 3,6-disubstituted derivatives are currently used for a range of industrial and medical applications as they exhibit particular coordination chemistries, characterised by electron and charge transfer phenomena. The aim of the present work is to synthesise two tetrazine derivatives, namely 3,6-dihydrazino-1,2,4,5-tetrazine (DHDTZ) and 1,2,4,5-tetrazine dicarboxylic acid (DCTZ), and determine their antibacterial, antioxidant and anticorrosion characteristics as additives in a sol-gel coating on SS316L steel. The structure of the tetrazines was confirmed by NMR and FTIR while the surface morphology of bacterial cells in their presence was observed by AFM. Their ability to inhibit corrosion on 316L stainless steel was electrochemically determined using a potentiodynamic scanning (PDS) technique. The corrosion inhibition results showed that the acidic DCTZ provided the best corrosion protection. The concentration-dependent antioxidant capacity of the tetrazines was confirmed by both DPPH radical scavenging activity and FRAP assays, showing higher activity for DHDTZ than DCTZ. Furthermore, a DHDTZ doped sol-gel solution was prepared and curing parameter (temperature and time) was optimised for coating on microtitre wells and stainless steel panel. The antibacterial activity of the coated surfaces against Pseudomonas aeruginosa ATCC 27853 and the biofilm forming bacteria Staphylococcus epidermidis CSF 41498 was determined. DHDTZ showed significantly higher antibacterial activities with MIC as low as 31 ppm compared to 250 ppm for DCTZ.

Enhanced corrosion protection and biocompatibility of a PLGA–silane coating on AZ31 Mg alloy for orthopaedic applications

This paper reports a multi-step procedure to fabricate a novel corrosion resistant and biocompatible PLGA–silane coating on the magnesium (Mg) alloy AZ31. The first step involves alkaline passivation followed by dip coating in a methyltriethoxysilane (MTES) and tetraethoxysilane (TEOS) mixture to produce a cross-linked siloxane coating. The second step is to impart an amine functionalization to the silane modified surface by using 3-aminopropyl-triethoxy silane (APTES) for promoting adhesion of the acid terminated poly-(lactic-co-glycolic) acid (PLGA) as a final coating step. Static contact angle measurements, Fourier transform infrared spectroscopy and scanning electron microscopy analysis confirmed the successful assembly of coatings on the AZ31 Mg alloy. Potentiodynamic polarization and impedance spectroscopy studies showed the improved initial corrosion resistance of the coated AZ31 substrate. Measurements of magnesium ion release, pH changes and hydrogen evolution showed enhanced corrosion protection of coated substrate over uncoated AZ31 alloy for 21 and 14 days respectively. The MTT assay, live–dead cells staining, DNA quantification and alkaline phosphatase activity assay were used to measure the biocompatibility, proliferation and differentiation of MC3T3-E1 osteoblast cells. Scanning electron microscopy was used to observe cell morphology and integration with the coated surface. The coated substrate showed improved cytocompatibility as compared to the uncoated AZ31 alloy surface. The application of such coatings on biodegradable Mg alloys enhanced their corrosion resistance and biocompatibility. An additional advantage is that the coating also served as a potential delivery vehicle for specific drugs and bio-active molecules releasing from an implant surface as the coatings, such as PLGA, adapt during the corrosion process, thereby enhancing bone regeneration.