Enhanced corrosion resistance and cytocompatibility of biomimetic hyaluronic acid functionalised silane coating on AZ31 Mg alloy for orthopaedic applications.

This paper reports the corrosion resistant and cytocompatible properties of the hyaluronic acid-silane coating on AZ31 Mg alloy. In this study, the osteoinductive properties of high molecular weight hyaluronic acid (HA, 1-4 MDa) and the corrosion protection of silane coatings were incorporated as a composite coating on biodegradable AZ31 Mg alloy for orthopaedic applications. The multi-step fabrication of coatings first involved dip coating of a passivated AZ31 Mg alloy with a methyltriethoxysilane-tetraethoxysilane sol-gel to deposit a dense, cross-linked and corrosion resistant silane coating (AZ31-MT). The second step was to create an amine-functionalised surface by treating coated alloy with 3-aminopropyl-triethoxy silane (AZ31-MT-A) which facilitated the immobilisation of HA via EDC-NHS coupling reactions at two different concentrations i.e 1 mg.ml-1 (AZ31-MT-A-HA1) and 2 mg.ml-1 (AZ31-MT-A-HA2). These coatings were characterised by Fourier transform infrared spectroscopy, atomic force microscopy and static contact angle measurements which confirmed the successful assembly of the full coatings onto AZ31 Mg alloy. The influence of HA-silane coating on the corrosion of Mg alloy was investigated by electrical impedance spectroscopy and long-term immersion studies measurements in HEPES buffered DMEM. The results showed an enhanced corrosion resistance of HA functionalised silane coated AZ31 substrate over the uncoated equivalent alloy. Furthermore, the cytocompatibility of MC3T3-E1 osteoblasts was evaluated on HA-coated AZ31-MT-A substrates by live-dead staining, quantification of total cellular DNA content, scanning electron microscope and alkaline phosphatase activity. The results showed HA concentration-dependent improvement of osteoblast cellular response in terms of enhanced cell adhesion, proliferation and differentiation. These findings hold great promise in employing such biomimetic multifunctional coatings to improve the corrosion resistance and cytocompatibility of biodegradable Mg-based alloy for orthopaedic applications.

Dual effects of ß-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 ß-cyclodextrin (ß-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 ß-CD improved their efficacy against S. epidermidis CSF 41498, reduced biofilm formation and their cytotoxicity. The study concluded that ß-CD is an effective capping and stabilising agent that reduces toxicity of AgNPs against the mammalian cell while enhancing their antibiofilm activity.

Active film packaging based on bio-nanocomposite TiO2 and cinnamon essential oil for enhanced preservation of cheese quality.

This study involves the preparation of PLA/PBAT composite blend films incorporated with TiO2 and varying concentrations of cinnamon essential oil. The films were characterised for optical and mechanical properties, chemical composition, thermo-stability, surface hydrophobicity, inhibition of biofilm formation, anti-microbial efficiency against S. aureus and E. coli, and application on cheese. The thickness of the films increased with the increase in cinnamon oil concentration along with the water contact angle degree and highest UV-barrier properties with the PLA-PBAT-TiO2-7 %Cinn film. The best anti-bacterial activity was seen in the PLA-PBAT-TiO2-7 %Cinn film against S. aureus and E. coli. The cheese packed in PLA-PBAT-TiO2-7 %Cinn film has shown the least weight loss and enhanced antibacterial activity against E. coli for 12 days of storage. The use of cinnamon oil-loaded TiO2 incorporated in films showed positive effects on the shelf life, quality, and safety of a food product and has a high potential for use commercially.

Extraction, quantification, characterization, and application in food packaging of chitin and chitosan from mushrooms: A review.

The application of chitin in food systems is limited by its insolubility in some common solvents and poor degradability. Hence, it is deacetylated to obtain chitosan, an industrially important derivative with excellent biological properties. Fungal-sourced chitosan is gaining prominence and industrial attraction because of its superior functional and biological properties, and vegan appeal. Further, the absence of such compounds as tropomyosin, myosin light chain, and arginine kinase, which are known to trigger allergic reactions, gives it an edge over marine-sourced chitosan in food and pharmaceutical applications. Mushrooms are macro-fungi with a significant content of chitin, with many authors reporting the highest content to be in the mushroom stalks. This indicates a great potential for the valorisation of a hitherto waste product. Hence, this review was written to provide a global summary of literature reports on the extraction and yield of chitin and chitosan from different fruiting parts of some species of mushrooms, different methods used to quantify extracted chitin, as well as physicochemical properties of chitin and chitosan from some mushroom species are presented. Critical comparisons of reports on chitin and chitosan from mushrooms and other sources are made. This report concludes with an exposition of the potential application of mushroom-sourced chitosan for food packaging application. The reports from this review provide a very positive outlook regarding the use of mushrooms as a sustainable source of chitin and chitosan and the subsequent application of chitosan as a functional component in food packaging.

Advances in emerging technologies for the decontamination of the food contact surfaces.

Foodborne pathogens could be transferred to food from food contact surfaces contaminated by poor hygiene or biofilm formation. The food processing industry has various conditions favouring microbes' adherence, such as moisture, nutrients, and the microbial inoculums obtained from the raw material. The function of the ideal antimicrobial surface is preventing initial attachment of the microbes, killing the microbes or/and removing the dead bacteria. This review article provides detail about the challenges food industries are facing with respect to food contact materials. It also summarises the merits and demerits of several sanitizing methods developed for industrial use. Furthermore, it reviews the new and emerging techniques that enhance the efficiency of reducing microbial contamination. Techniques such as surface functionalisation, high-intensity ultrasound, cold plasma technologies etc. which have high potential to be used for the decontamination of food contact surfaces are discussed. The emerging designs of antibacterial surfaces provide the opportunity to reduce or eradicate the adhesion of microorganisms. The most important purpose of these surfaces is to prevent the attachment of bacteria and to kill the bacteria that come in contact. These emerging technologies have a high potential for developing safe and inert food contact materials for the food industry.

Development and Characterisation of a Whole Hybrid Sol-Gel Optofluidic Platform for Biosensing Applications.

This work outlines, for the first time, the fabrication of a whole hybrid sol-gel optofluidic platform by integrating a microfluidic biosensor platform with optical waveguides employing a standard photolithography process. To demonstrate the suitability of this new hybrid sol-gel optofluidic platform, optical and bio-sensing proof-of-concepts are proposed. A photoreactive hybrid sol-gel material composed of a photopolymerisable organically modified silicon alkoxide and a transition metal complex was prepared and used as the fabrication material for the entire optofluidic platform, including the optical waveguides, the sensing areas, and the microfluidic device. The most suitable sol-gel materials chosen for the fabrication of the cladding and core of the waveguides showed a RIC of 3.5 × 10-3 and gave thicknesses between 5.5 and 7 µm. The material was optimised to simultaneously meet the photoreactive properties required for the photolithography fabrication process and the optical properties needed for the effective optical operability of the microstructured waveguides at 532 and 633 nm with an integrated microfluidic device. The optical proof-of-concept was performed using a fluorescent dye (Atto 633) and recording its optical responses while irradiated with a suitable optical excitation. The biosensing capability of the platform was assessed using a polyclonal primary IgG mouse antibody and a fluorescent labelled secondary IgG anti-mouse antibody. A limit of detection (LOD) of 50 ug/mL was achieved. A correlation between the concentration of the dye and the emission fluorescence was evidenced, thus clearly demonstrating the feasibility of the proposed hybrid sol-gel optofluidic platform concept. The successful integration and operability of optical and microfluidic components in the same optofluidic platform is a novel concept, particularly where the sol-gel fabrication material is concerned.

Characterization and Antimicrobial Activity of Biodegradable Active Packaging Enriched with Clove and Thyme Essential Oil for Food Packaging Application.

Bioactive packaging contains natural antimicrobial agents, which inhibit the growth of microorganisms and increase the food shelf life. Solvent casting method was used to prepare the Poly (lactide)-Poly (butylene adipate-co-terephthalate) (PLA-PBAT) film incorporated with the thyme oil and clove oil in various concentrations (1 wt%, 5 wt% and 10 wt%). The clove oil composite films depicted less green and more yellow as compared to thyme oil composite films. Clove oil composite film has shown an 80% increase in the UV blocking efficiency. The tensile strength (TS) of thyme oil and clove oil composite film decreases from 1.35 MPs (control film) to 0.96 MPa and 0.79, respectively. A complete killing of S. aureus that is a reduction from 6.5 log CFU/mL to 0 log CFU/mL was observed on the 10 wt% clove oil incorporated composite film. Clove oil and thyme oil composite film had inhibited E. coli biofilm by 93.43% and 82.30%, respectively. Clove oil composite film had exhibited UV blocking properties, strong antimicrobial activity and has high potential to be used as an active food packaging.

Nanostructured Materials for Food Applications: Spectroscopy, Microscopy and Physical Properties.

Nanotechnology deals with matter of atomic or molecular scale. Other factors that define the character of a nanoparticle are its physical and chemical properties, such as surface area, surface charge, hydrophobicity of the surface, thermal stability of the nanoparticle and its antimicrobial activity. A nanoparticle is usually characterized by using microscopic and spectroscopic techniques. Microscopic techniques are used to characterise the size, shape and location of the nanoparticle by producing an image of the individual nanoparticle. Several techniques, such as scanning electron microscopy (SEM), transmission electron microscopy/high resolution transmission electron microscopy (TEM/HRTEM), atomic force microscopy (AFM) and scanning tunnelling microscopy (STM) have been developed to observe and characterise the surface and structural properties of nanostructured material. Spectroscopic techniques are used to study the interaction of a nanoparticle with electromagnetic radiations as the function of wavelength, such as Raman spectroscopy, UV⁻Visible spectroscopy, attenuated total reflectance Fourier-transform infrared spectroscopy (ATR-FTIR), dynamic light scattering spectroscopy (DLS), Zeta potential spectroscopy, X-ray photoelectron spectroscopy (XPS) and X-ray photon correlation spectroscopy. Nanostructured materials have a wide application in the food industry as nanofood, nano-encapsulated probiotics, edible nano-coatings and in active and smart packaging.

Prevention of Staphylococcus epidermidis biofilm formation using a low-temperature processed silver-doped phenyltriethoxysilane sol-gel coating.

Sol-gel coatings which elute bioactive silver ions are presented as a potential solution to the problem of biofilm formation on indwelling surfaces. There is evidence that high-temperature processing of such materials can lead to diffusion of silver away from the coating surface, reducing the amount of available silver. In this study, we report the biofilm inhibition of a Staphylococcus epidermidis biofilm using a low-temperature processed silver-doped phenyltriethoxysilane sol-gel coating. The incorporation of a silver salt into a sol-gel matrix resulted in an initial high release of silver in de-ionised water and physiological buffered saline (PBS), followed by a lower sustained release for at least 6 days-as determined by graphite furnace-atomic absorption spectroscopy (GF-AAS). The release of silver ions from the sol-gel coating reduced the adhesion and prevented formation of a S. epidermidis biofilm over a 10-day period. The presence of surface silver before and after 24 h immersion in PBS was confirmed by X-ray photoelectron spectroscopy (XPS). These silver-doped coatings also exhibited significant antibacterial activity against planktonic S. epidermidis. A simple test to visualise the antibacterial effect of silver release coatings on neighbouring bacterial cultures is also reported.

Evidence for magmatic carbon bias in 14C dating of the Taupo and other major eruptions.

Prehistoric timescales, volcanic hazard assessment, and understanding of volcanogenic climate events rely on accurate dating of prehistoric eruptions. Most late Quaternary eruptions are dated by 14C measurements on material from close to the volcano that may be contaminated by geologic-sourced infinite-age carbon. Here we show that 14C ages for the Taupo (New Zealand) First Millennium eruption are geographically arrayed, with oldest ages closer to the vent. The current eruption wiggle match date of 232 ± 5 years CE is amongst the oldest. We present evidence that the older, vent-proximal 14C ages were biased by magmatic CO2 degassed from groundwater, and that the Taupo eruption occurred decades to two centuries after 232 CE. Our reinterpretation implies that ages for other proximally-dated, unobserved, eruptions may also be too old. Plateauing or declining tree ring cellulose δ13C and Δ14C values near a volcano indicate magmatic influence and may allow forecasting of super-eruptions.

Effect of High- and Low-Molecular-Weight Hyaluronic-Acid-Functionalized-AZ31 Mg and Ti Alloys on Proliferation and Differentiation of Osteoblast Cells.

The quality of patient care has increased dramatically in recent years because of the development of lightweight orthopedic metal implants. The success of these orthopedic implants may be compromised by impaired cytocompatibility and osteointegration. Biomimetic surface engineering of metal implants using biomacromolecules including hyaluronic acid (HA) has been used an effective approach to provide conditions favorable for the growth of bone forming cells. To date, there have been limited studies on osteoblasts functions in response to metal substrates modified with the hyaluronic acid of different molecular weight for orthopedic applications. In this study, we evaluated the osteoblasts functions such as adhesion, proliferation, and differentiation in response to high- and low-molecular-weight HA (denoted as h-HA and l-HA, respectively) functionalized on Ti (h-HA-Ti and l-HA-Ti substrates, respectively) and corrosion-resistant silane coated-AZ31 Mg alloys (h-HA-AZ31 and l-HA-AZ31). The DNA quantification study showed that adhesion and proliferation of osteoblasts were significantly decreased by h-HA immobilized on Ti or AZ31 substrates when compared to low-molecular-weight counterpart over a period of 14 days. On the contrary, h-HA significantly increased the osteogenic differentiation of osteoblast over l-HA, as confirmed by the enhanced expression of ALP, total collagen, and mineralization of extracellular matrix. In particular, the h-HA-AZ31 substrates greatly enhanced the osteoblast differentiation among tested samples (l-HA-AZ31, l-HA-Ti, h-HA-Ti, and Ti alone), which is ascribed to the osteoinductive activity of h-HA, relatively up-regulated intracellular Ca2+ ([Ca2+]i) and Mg2+ ([Mg2+]i) concentrations as well as the alkalization of the cell culture medium. This study suggesting that HA of appropriate molecular weight can be successfully used to modify the surface of metal implants for orthopedic applications.

Enhanced Water Barrier Properties of Surfactant-Free Polymer Films Obtained by MacroRAFT-Mediated Emulsion Polymerization.

The presence of low-molar-mass surfactants in latex films results in detrimental effects on their water permeability, gloss, and adhesion. For applications such as coatings, there is a need to develop formulations that do not contain surfactants and have better water barrier properties. Having previously reported the synthesis of surfactant-free latex particles in water using low amounts (<2 wt %) of chains synthesized by controlled radical polymerization (Lesage de la Haye et al. Macromolecules 2017, 50, 9315-9328), here we study the water barrier properties of films made from these particles and their application in anticorrosion coatings. When films cast from aqueous dispersions of acrylate copolymer particles stabilized with poly(sodium 4-styrenesulfonate) (PSSNa) were immersed in water for 3 days, they sorbed only 4 wt % water. This uptake is only slightly higher than the value predicted for the pure copolymer, indicating that the negative effects of any particle boundaries and hydrophilic-stabilizing molecules are minimal. This sorption of liquid water is 5 times lower than what is found in films cast from particles stabilized with the same proportion of poly(methacrylic acid) (PMAA), which is more hydrophilic than PSSNa. In water vapor with 90% relative humidity, the PSSNa-based film had an equilibrium sorption of only 4 wt %. A small increase in the PMAA content has a strong and negative impact on the barrier properties. Nuclear magnetic resonance relaxometry on polymer films after immersion in water shows that water clusters have the smallest size in the films containing PSSNa. Furthermore, these films retain their optical clarity during immersion in liquid water for up to 90 min, whereas all other compositions quickly develop opacity ("water whitening") as a result of light scattering from sorbed water. This implies a remarkably complete coalescence and a very small density of defects, which yields properties matching those of some solvent-borne films. The latex stabilized with PSSNa is implemented as the binder in a paint formulation for application as an anticorrosive barrier coating on steel substrates and evaluated in accelerated weathering and corrosion tests. Our results demonstrate the potential of self-stabilized latex particles for the development of different applications, such as waterborne protective coatings and pressure-sensitive adhesives.

Biomimetic Hyaluronic Acid-Lysozyme Composite Coating on AZ31 Mg Alloy with Combined Antibacterial and Osteoinductive Activities.

This study presents the covalent grafting of a hyaluronic acid-lysozyme (HA-LZ) composite onto corrosion-resistant silane-coated AZ31 Mg alloy via EDC-NHS coupling reactions. The HA-LZ composite coatings created a smooth and hydrophilic surface with the increased concentration of functional lysozyme complexed to the hyaluronic acid. This was confirmed by the measurement of AFM, water contact angle, and quantification of hyaluronic acid and lysozyme. The colonization of S.aureus on HA-LZ composite-coated substrates was significantly reduced as compared to the hyaluronic acid, lysozyme coated and uncoated AZ31 controls. Such activity is due to the enhanced antibacterial activity of lysozyme component as observed from the spread plate assay, propidium iodide staining, and scanning electron microscopy. Furthermore, morphology of the osteoblast cells, alkaline phosphatase activity and DNA quantification studies demonstrated the improved biocompatibility and osteoinductive properties of HA-LZ-coated substrates. This was verified by comparing with the lysozyme coated and uncoated AZ31 substrates in terms of cell adhesion, proliferation, and differentiation of osteoblastic cells. Therefore, such multifunctional composite coatings with antibacterial and osteoinductive properties are promising can be potentially used for the surface modifications of orthopedic implants.

Usefulness of an elevated neutrophil to lymphocyte ratio in predicting long-term mortality after percutaneous coronary intervention.

The neutrophil to lymphocyte (N/L) ratio is a recently described independent predictor of death/myocardial infarction in patients who have undergone coronary angiography. We hypothesized that an elevated N/L ratio would be a predictor of long-term mortality in patients undergoing percutaneous coronary intervention (PCI). A total of 1,046 patients who underwent PCI were divided into tertiles based on their preprocedural N/L ratio (mean N/L ratio, tertile 1, 1.7 +/- 0.5; tertile 2: 3.2 +/- 0.6; tertile 3, 11.2 +/- 12.9). Vital status was assessed using the Social Security Death Index. There were a total of 144 deaths over a mean follow-up of 32 months. The best survival was seen in tertile 1, with an increase in long-term mortality seen in tertiles 2 and 3 (p <0.0001). In multivariable modeling, after adjusting for age, chronic obstructive pulmonary disease, left ventricular ejection fraction, serum hemoglobin, serum creatinine, and lesion severity, the log N/L, but not the white blood cell count, was an independent significant predictor of long-term mortality (hazard ratio 1.85, 95% confidence interval 1.3, to 3.04, p = 0.01). The risk persisted when patients with an acute myocardial infarction were excluded from the analysis (hazard ratio 2.46, 95% confidence interval 1.4 to 4.4, p = 0.002). In conclusion, an elevated preprocedural N/L ratio in patients undergoing PCI is associated with an increased risk of long-term mortality.

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.

Antiplatelet agents in patients undergoing percutaneous coronary intervention: how many and how much?

Antiplatelet agents play a major role in patients undergoing percutaneous coronary intervention (PCI). Stent thrombosis and the demand for improved clinical outcomes have driven the need for aggressive antiplatelet and anticoagulant regimens and newer, more efficacious, therapies. The benefits of intravenous glycoprotein (GP) IIb/IIIa antagonists and clopidogrel in high-risk patients undergoing PCI appear complementary. In low- to intermediate-risk patients, clopidogrel pre-treatment and a maintenance dose of aspirin + clopidogrel for at least 1 year after PCI are supported by the data, although the optimal duration of clopidogrel treatment beyond 1 year remains hotly contested. The next generation of clinical trials will examine the benefits of antiplatelet and antithrombotic agents as adjunctive therapy with drug-eluting stents. A better understanding of our patients' overall risk will add to procedural success and more durable outcomes.

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.

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.