A dynamic mechanical thermal analysis study of the viscoelastic properties and glass transition temperature behaviour of bioresorbable polymer matrix nanocomposites

The application of bioresorbable polymer nanocomposites in orthopaedics offer the potential to address several of the limitations associated with the use of metallic implants. Their enhanced biological performance has been demonstrated recently, but until now relatively little work has been reported on their mechanical properties. To this end, the viscoelastic properties and T_g of bioresorbable polylactide-co-glycolide/α-tricalcium phosphate nanocomposites were investigated by dynamic mechanical thermal analysis. At room temperature of approximately 20°C, the storage moduli of the nanocomposites were generally higher than the storage modulus of the unfilled polymer due to the stiffening effect of the nano-particles. However at physiological temperature of approximately 37°C, the storage moduli of the nanocomposites decreased from 6.2 to 15.4% v/v nano-particle loadings. Similarly the T_g of the nanocomposites also decreased from 6.2 to 15.4% v/v nano-particle loadings. These effects were thought to be due to weak interfacial bonding between the nano-particles and polymer matrix. The storage moduli at 37°C and T_g increased from the minimum value when the particle loading was raised to 25.7 and 34.2% v/v loadings. SEM and particle size distribution histograms showed that at these loadings, there was a broad particle size distribution consisting of nano-particles and micro-particles and that some particle agglomeration was present. The consequent reduction in the interfacial area and the number of weak interfaces presumably accounts for the rise in the storage modulus at 37°C and the T_g.     

Production and characterization of HA and SiHA coatings

Plasma sprayed hydroxyapatite (HA) coatings on metallic prostheses have been used clinically in dentistry and orthopedics since the mid 1980s. The coating properties are dependent on the spraying parameters. Since silicon-substituted hydroxyapatite (SiHA) has been shown to offer improved bioactivity over phase pure HA, SiHA coatings have the potential for enhanced performance in clinical application. In this study, phase pure HA and 0.8 wt% SiHA powders were synthesized with similar particle size distribution and morphology. The powders were plasma sprayed onto Ti–6Al–4V substrates at 37 kW and 40 kW plasma gun input power respectively. Four kinds of samples were prepared, HAC 37, HAC 40, SiHAC 37 and SiHAC 40. Materials characterization showed that the coatings were of relatively high phase purity. In vitro cell culture demonstrated that human osteoblast cells grew well on all samples, with the highest cell growth observed on SiHA coatings produced under the lower plasma gun input power.     

Effect of different land use on soil erosion in the pre-alpine fringe (North-East Italy): Ion budget and sediment yield

Data concerning ion budget from rainfall, runoff and soil loss measurements from two experimental plots located in North-East Italy, under different land cover (beech forest and vineyard, respectively), are reported. The chemical composition of rainfall, soil solution and runoff was determined to study the solute cycle within the soil, and the relationships between water, soil and vegetation. The forest ecosystem is more prone to acidification than the agricultural one; the elemental concentration of runoff water is considerably lower than that of soil solution. Comparing the ion input (rainfall) and output (runoff) at the two sites, it was possible to estimate the ion budget in the two soil-vegetation systems. The runoff amount and the ion balance are related to rainfall volumes and composition; the measured runoff under vineyard is 59% in comparison to the one under beech. The soil loss at the two experimental sites (170 kg/ha and 132 kg/ha, respectively) is quite limited. The measured sediment yield of the two catchments (0.24-0.19 t/ha/year, respectively) is consistent with data reported for native forests of western Europe. Comparing rainfall and soil loss at the two sites proved that maintenance of some form of land cover is advisable if runoff and erosion are to be minimized. In the European context, where the most important consequences of erosion are sedimentation downstream and loss of productivity, this type of data will yield valuable information for the understanding of such processes occurring at catchment scale, and will help policy-makers develop appropriate programs for the territory safeguard.     

Mass spectrometry detection of egg proteins in red wines treated with egg white

The need of label declaration for egg proteins is temporarily suspended when they are used as a processing aid in winemaking, because of a lack of scientific data concerning their actual permanence as residual proteins in fined wines.The possibility to detect residual egg proteins in red wines treated with a commercial egg white preparation was studied. By using an immunochemical method residual egg proteins were detected in the experimental red wines only for doses of fining agent of 50 g/hL or higher, whereas no residual proteins were detected by this system in a commercial red wine.A simple method based on the recovery and identification of the wine fining proteins by liquid chromatography coupled with tandem MS (LC-MS/MS) in a gel-free approach was developed. This allowed the detection of egg proteins in red wines fined down to 5 g/hL of commercial egg white preparation and also in the commercial red wine. These results indicate that the analytical approach here suggested is superior to the immunochemical methods in detecting egg proteins in wines. Therefore hypersensitivity reactions after consumption of wines treated with egg proteins can be a real risk for egg-allergic people.     

Polymer brush coatings for combating marine biofouling

A variety of functional polymer brushes and coatings have been developed for combating marine biofouling and biocorrosion with much less environmental impact than traditional biocides. This review summarizes recent developments in marine antifouling polymer brushes and coatings that are tethered to material surfaces and do not actively release biocides. Polymer brush coatings have been designed to inhibit molecular fouling, microfouling and macrofouling through incorporation or inclusion of multiple functionalities. Hydrophilic polymers, such as poly(ethylene glycol), hydrogels, zwitterionic polymers and polysaccharides, resist attachment of marine organisms effectively due to extensive hydration. Fouling release polymer coatings, based on fluoropolymers and poly(dimethylsiloxane) elastomers, minimize adhesion between marine organisms and material surfaces, leading to easy removal of biofoulants. Polycationic coatings are effective in reducing marine biofouling partly because of their good bactericidal properties. Recent advances in controlled radical polymerization and click chemistry have also allowed better molecular design and engineering of multifunctional brush coatings for improved antifouling efficacies.     

Exploring the Substrate Specificity and Enantioselectivity of a Baeyer–Villiger Monooxygenase from Dietzia sp. D5: Oxidation of Sulfides and Aldehydes

Baeyer–Villiger monooxygenases (BVMOs) are valuable enzymes for specific oxyfunctionalization chemistry. They catalyze the oxidation of ketones to esters, but are also capable of oxidizing other chemical functions, namely aldehydes and heteroatoms such as sulfur, nitrogen, selenium and boron. The oxidation specificity and enantioselectivity of a newly characterized BVMO (BVMO4) from a strain of Dietzia towards sulfide- and aldehyde substrates have been studied. BVMO4 could react with sulfides containing an aromatic group. The presence of a substituent on the aromatic group was tolerated when they were in the meta- and para position and the oxidations yielded predominantly the (R)-sulfoxides. Similarly, BVMO4 displayed a higher activity for aldehydes containing a phenyl group, but long aliphatic aldehydes, namely octanal and decanal, were also accepted as substrate by this enzyme. The major oxidation products of the aldehyde substrates were the respective carboxylic acids in contrast to formate ester that was obtained in most of the previous reports. The Baeyer–Villiger oxidation of the substrate 2-phenylpropionaldehyde was studied in further detail and the corresponding acid product was obtained with good regio- and enantioselectivity. This is a unique feature for BVMO4 and is of great interest for further exploration of an alternative biocatalytic process.     

Electrochemical oxidation of organics in water: Role of operative parameters in the absence and in the presence of NaCl

The electrochemical oxidation of organics in water was investigated theoretically and experimentally to determine the role of several operative parameters on the performances of the process in the presence and in the absence of sodium chloride. Theoretical considerations were used to design the experimental investigation and were confirmed by the results of the electrochemical oxidation of oxalic acid (OA) at boron doped diamond (BDD) or IrO₂-Ta₂O₅ (DSA-O₂) anodes in a continuous batch recirculation reaction system equipped with a parallel plate undivided electrochemical cell. Polarization curves and chronoamperometric measurements indicated that, in the presence of chlorides, the anodic oxidation of OA is partially replaced by an indirect oxidation process. This result was confirmed by electrolyses experiments that show that, in the presence of suitable amount of chlorides, oxidation of OA takes place mainly by a homogeneous process. Interestingly, a very different influence of the nature of the anodic material, the flow rate and the current density on the performances of the process arises in the absence and in the presence of chlorides so that optimization of the two processes requires very different operative conditions. In the absence of chlorides, high current efficiency (CE) is obtained at BDD when most part of the process is under charge transfer controlled kinetics, i.e. when low current densities and high flow rates are imposed. On the other hand, in the presence of NaCl, higher CE are generally obtained at DSA anode when high current densities and low flow rates are imposed, i.e. when a high concentration of chemical oxidants is obtained as a result of the chloride oxidation. The effect of other operative parameters such as the OA concentration and the pH were further investigated.     

Whiteness Constraints in a Unified Variational Framework for Image Restoration

We propose a robust variational model for the restoration of images corrupted by blur and the general class of additive white noises. The key idea behind our proposal relies on a novel hard constraint imposed on the residual of the restoration, namely we characterize a residual whiteness set to which the restored image must belong. As the feasible set is unbounded, solution existence results for the proposed variational model are given. Moreover, based on theoretical derivations as well as on Monte Carlo simulations, we provide well-founded guidelines for setting the whiteness constraint limits. The solution of the non-trivial optimization problem, due to the non-smooth non-convex proposed model, is efficiently obtained by an alternating directions method of multipliers, which in particular reduces the solution to a sequence of convex optimization subproblems. Numerical results show the potentiality of the proposed model for restoring blurred images corrupted by several kinds of additive white noises.     

Additive Manufacturing Approaches for Hydroxyapatite‐Reinforced Composites

Additive manufacturing (AM) techniques have gained interest in the tissue engineering field, thanks to their versatility and unique possibilities of producing constructs with complex macroscopic geometries and defined patterns. Recently, composite materials—namely, heterogeneous biomaterials identified as continuous phase (matrix) and reinforcement (filler)—have been proposed as inks that can be processed by AM to obtain scaffolds with improved biomimetic and bioactive properties. Significant efforts have been dedicated to hydroxyapatite (HA)‐reinforced composites, especially targeting bone tissue engineering, thanks to the chemical similarities of HA with respect to mineral components of native mineralized tissues. Herein, applications of AM techniques to process HA‐reinforced composites and biocomposites for the production of scaffolds with biological matrices, including cellular tissues, are reviewed. The primary outcomes of recent investigations in terms of morphological, structural, and in vitro and in vivo biological properties of the materials are discussed. The approaches based on the nature of the matrices employed to embed the HA reinforcements and produce the tissue substitutes are classified, and a critical discussion is provided on the presented state of the art as well as the future perspectives, to offer a comprehensive picture of the strategies investigated as well as challenges in this emerging field of materiomics.