Facile and Bioinspired Approach from Gallic Acid for the Synthesis of Biobased Flame Retardant Coatings of Basalt Fibers.

A sustainable, bioinspired approach to functionalize basalt fibers with an innovative gallic acid (GA)-iron phenyl phosphonate complex (BF-GA-FeP), for the purpose of improving the flame retardancy in composite materials, is developed. BFs were at first pretreated with O3, obtaining surface free hydroxyl groups that allowed the subsequent covalent immobilization of biosourced GA units on the fiber through ester linkages. Phenolic -OH groups of the GA units were then exploited for the complexation of iron phenyl phosphonate, resulting in the target-complex-coated BF fiber (BF-GA-FeP). Microwave plasma atomic emission spectroscopy and scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy analyses of BF-GA-FeP highlighted an increase in iron content, modification of fiber morphology, and occurrence of phosphorus, respectively. BFs, modified with a low amount of the developed complex, were used to reinforce a poly(lactic acid) (PLA) matrix in the production of a biocomposite (PLA/BF-FeP). PLA/BF-FeP showed a higher thermal stability than neat PLA and PLA reinforced with untreated BFs (PLA/BF), as confirmed by thermogravimetric analysis. The cone calorimeter test highlighted several advantages for PLA/BF-FeP, including a prolonged time to ignition, a reduced time to flame out, an 8% decrease in the peak heat release rate, and a 15% reduced fire propagating index compared to PLA/BF.

An Event-based Neural Compressive Telemetry with >11× Loss-less Data Reduction for High-bandwidth Intracortical Brain Computer Interfaces.

Intracortical brain-computer interfaces offer superior spatial and temporal resolutions, but face challenges as the increasing number of recording channels introduces high amounts of data to be transferred. This requires power-hungry data serialization and telemetry, leading to potential tissue damage risks. To address this challenge, this paper introduces an event-based neural compressive telemetry (NCT) consisting of 8 channel-rotating Δ-ADCs, an event-driven serializer supporting a proposed ternary address event representation protocol, and an event-based LVDS driver. Leveraging a high sparsity of extracellular spikes and high spatial correlation of the high-density recordings, the proposed NCT achieves a compression ratio of >11.4×, while consumes only 1 µW per channel, which is 127× more efficient than state of the art. The NCT well preserves the spike waveform fidelity, and has a low normalized RMS error <23% even with a spike amplitude down to only 31 µV.

Infrared Imaging Analysis of Green Composite Materials during Inline Quasi-Static Flexural Test: Monitoring by Passive and Active Approaches.

Composite materials have been used for many years in a wide variety of sectors starting from aerospace and nautical up to more commonly used uses such as bicycles, glasses, and so on. The characteristics that have made these materials popular are mainly their low weight, resistance to fatigue, and corrosion. In contrast to the advantages, however, it should be noted that the manufacturing processes of composite materials are not eco-friendly, and their disposal is rather difficult. For these reasons, in recent decades, the use of natural fibers has gained increasing attention, allowing the development of new materials sharing the same advantages with conventional composite systems while respecting the environment. In this work, the behavior of totally eco-friendly composite materials during flexural tests has been studied through infrared (IR) analysis. IR imaging is a well-known non-contact technique and represents a reliable means of providing low-cost in situ analysis. According to this method, the surface of the sample under investigation is monitored, under natural conditions or after heating, by recording thermal images with an appropriate IR camera. Here, the results achieved for jute- and basalt-based eco-friendly composites through the use of both passive and active IR imaging approaches are reported and discussed, showing the possibilities of use also in an industrial environment.

Low Molecular Weight Bio-Polyamide 11 Composites Reinforced with Flax and Intraply Flax/Basalt Hybrid Fabrics for Eco-Friendlier Transportation Components.

The transportation sector is striving to meet the more severe European legislation which encourages all industrial fields to embrace more eco-friendly policies by exploiting constituents from renewable resources. In this framework, the present work assessed the potential of a bio-based, low molecular weight PA11 matrix reinforced with flax and intraply flax/basalt hybrid fabrics. To this aim, both quasi-static and impact performance were addressed through three-point bending and low-velocity impact tests, respectively. For hybrid composites, the effect of stacking sequence, i.e., [0/0] and [0/90], and fiber orientation were considered, while the effect of temperature, i.e., -40 °C, room temperature and +45 °C, was investigated for laminates' impact response. The mechanical experimental campaign was supported by thermal and morphological analyses. The results disclosed an improved processability of the low molecular weight PA11, which ensured a manufacturing temperature of 200 °C, which is fundamental to minimize flax fibers' thermal degradation. Both quasi-static and impact properties demonstrated that hybridization is a good solution for obtaining good mechanical properties while preserving laminates' lightness and biodegradability. The [0/90] configuration proved to be the best solution, providing satisfying flexural performance, with an increase between 62% and 83% in stiffness and between 19.6% and 37.6% in strength compared to flax-based laminates, and the best impact performance, with a reduction in permanent indentation and back crack extent.

Automatic radar-based 2-D localization exploiting vital signs signatures.

In light of the continuously and rapidly growing senior and geriatric population, the research of new technologies enabling long-term remote patient monitoring plays an important role. For this purpose, we propose a single-input-multiple-output (SIMO) frequency-modulated continuous wave (FMCW) radar system and a signal processing technique to automatically detect the number and the 2-D position (azimuth and range information) of stationary people (seated/lying down). This is achieved by extracting the vital signs signatures of each single individual, separating the Doppler shifts caused by the cardiopulmonary activities from the unwanted reflected signals from static reflectors and multipaths. We then determine the number of human subjects present in the monitored environment by counting the number of extracted vital signs signatures while the 2-D localization is performed by measuring the distance from the radar where the vital signs information is sensed (i.e., locating the thoracic region). We reported maximum mean absolute errors (MAEs) of 0.1 m and 2.29[Formula: see text] and maximum root-mean-square errors (RMSEs) of 0.12 m and 3.04[Formula: see text] in measuring respectively the ranges and azimuth angles. The experimental validation demonstrated the ability of the proposed approach in monitoring paired human subjects in a typical office environment.

Thermal and Quasi-Static Mechanical Characterization of Polyamide 6-Graphene Nanoplatelets Composites.

The growing demand for lightweight and multifunctional products in numerous industrial fields has recently fuelled a growing interest in the development of materials based on polymer matrices including graphene-like particles, intrinsically characterized by outstanding mechanical, thermal, and electrical properties. Specifically, with regard to one of the main mass sectors, which is the automotive, there has been a significant increase in the use of reinforced polyamides for underhood applications and fuel systems thanks to their thermal and chemical resistance. In this frame, polyamide 6 (PA6) composites filled with graphene nanoplatelets (GNPs) were obtained by melt-compounding and compared in terms of thermal and mechanical properties with the neat matrix processed under the same condition. The results of the experimental tests have shown that the formulations studied so far offer slight improvements in terms of thermal stability but much more appreciable benefits regarding both tensile and flexural parameters with respect to the reference material. Among these effects, the influence of the filler content on the strength parameter is noteworthy. However, the predictable worsening of the graphene sheet dispersion for GNPs contents greater than 3%, as witnessed by scanning electron images of the tensile fractured sections of specimens, affected the ultimate performance of the more concentrated formulation.

Flexural Properties and Low-Velocity Impact Behavior of Polyamide 11/Basalt Fiber Fabric Laminates.

Environmentally friendly composite plates intended for load-bearing applications were prepared and systematically characterized in terms of mechanical performances and morphological features. Sample plates combining two extrusion grades of bio-polyamide 11, one of which is plasticized, and two basalt fiber fabrics (plain weave and twill architectures) were obtained by film stacking and hot pressing, and their mechanical properties were investigated by quasi-static flexural and low-velocity impact tests. The comparative analysis of the results, also interpreted by the bending damage analysis, through optical microscope observations, and impact damage analysis through visual inspection and indentation measurements demonstrate that, besides interfacial adhesion issues, the mechanical performance of the laminates need to be optimized through a careful selection of the constituents in the light of the final application. In particular, if the goal is a gain in impact strength, the use of the plasticized matrix is beneficial, but it brings about a loss in stiffness and strength that can be partially compensated by properly selecting a more performing fiber fabric architecture. The latter must also be easily permeated by the matrix to enhance the efficiency of stress transfer from the matrix. Overall, our results can be exploited for the development of bio-composites for particularly demanding applications.

Surface Modification of Basalt Fibres with ZnO Nanorods and Its Effect on Thermal and Mechanical Properties of PLA-Based Composites.

The composites based on basalt fibres and poly(lactic acid) (PLA) show promising applications in biomedical and automotive fields, but their mechanical performance is still largely hindered by poor interfacial properties. Zinc oxide nanorods have been successfully used to tune the PLA/basalt fibre interface by growing them on commercially available basalt fabrics. The hierarchical fibres significantly enhanced the mechanical properties of PLA-based composites, especially their flexural strength and stiffness. These values are 26% and 22% higher than those of unmodified basalt/PLA composites, and 24% and 34% higher than those of glass/PLA composites used as a baseline. The increase in tensile and flexural properties hinges on the mechanical interlocking action promoted by ZnO nanorods and on the creation of a compact transcrystallinity structure. A degradation of PLA matrix was detected but it was positively counteracted by the better interfacial stress transfer. This study offers a novel approach for modifying the fibre-matrix interface of biocomposites intended for high-performance applications.

Zinc oxide nanostructures and stearic acid as surface modifiers for flax fabrics in polylactic acid biocomposites.

Different surface treatments including mercerization, stearic acid and growth of zinc oxide nanorods as well as their combinations were exploited to address their effects on the properties of green composites based on polylactic acid (PLA) and flax fabrics. The resulting fabrics were morphologically (SEM), crystallographically (XRD) and thermally (TGA) characterized, showing no significant changes with respect to the untreated samples. In contrast, tensile and flexural properties of composites produced by compression moulding were significantly influenced. A combination of mercerization and environmentally friendly stearic acid treatment turned the character of the flax fabric from hydrophilic to hydrophobic, and led to improved bending and tensile strengths by 20% and 12%, respectively, compared to untreated composites. The presence of ZnO nanorods promoted an increase in flexural and tensile stiffness by 58% and 31%, respectively, but at the expense of strength, with reductions ascribed to the degradation of polylactic acid under high-temperature conditions favoured by ZnO, as confirmed by a reduction in the initial thermal degradation temperature up to 26%. These latter composites can be suggested in those applications where a suitable combination of flexural properties and a shorter persistence in the environment is desired.

A thermoresponsive gel photoreleasing nitric oxide for potential ocular applications.

We report herein the design, preparation, characterization and biological evaluation of a thermoresponsive gel based on binary mixtures of Pluronic® co-polymers F127 and P123, the latter being covalently functionalized with a nitric oxide (NO) photodonor (NOPD). The weight ratio between the two polymeric components is optimized in order to observe gelation of their saline water solution in the range of 32-35 °C, in order to exploit the therapeutic properties of NO for potential ocular applications. Rheological measurements were performed to evaluate the gelation temperature and, hence, to select a co-polymer mixture specifically appropriate for the reference application. Integration of the NOPD into the polymeric scaffold does not affect its rheological and spectroscopic properties, making it a good absorber of visible light both in solution and in the gel phase. Irradiation of the saline solution of the polymeric components with visible light triggers NO release, which occurs with an efficiency of more than one order of magnitude faster than that observed for the isolated NOPD. The polymeric system fully preserves such photobehavior after gelation as demonstrated by the effective NO photorelease from the gel matrix and its diffusion in the supernatant upon illumination. The gel is well-tolerated in both dark and light conditions by corneal cells, while being able to induce growth inhibition towards Staphylococcus aureus under visible light irradiation and has high moduli which can contribute to an adequate retention time within the eyes.

Hybrid Fly Ash-Based Geopolymeric Foams: Microstructural, Thermal and Mechanical Properties.

This research investigates the preparation and characterization of new organic-inorganic geopolymeric foams obtained by simultaneously reacting coal fly ash and an alkali silicate solution with polysiloxane oligomers. Foaming was realized in situ using Si0 as a blowing agent. Samples with density ranging from 0.3 to 0.7 g/cm3 that show good mechanical properties (with compressive strength up to ≈5 MPa for a density of 0.7 g/cm3) along with thermal performances (λ = 0.145 ± 0.001 W/m·K for the foamed sample with density 0.330 g/cm3) comparable to commercial lightweight materials used in the field of thermal insulation were prepared. Since these foams were obtained by valorizing waste byproducts, they could be considered as low environmental impact materials and, hence, with promising perspectives towards the circular economy.

Polypropylene/Basalt Fabric Laminates: Flexural Properties and Impact Damage Behavior.

Recently, the growing interests into the environmental matter are driving the research interest to the development of new eco-sustainable composite materials toward the replacement of synthetic reinforcing fibers with natural ones and exploiting the intrinsic recyclability of thermoplastic resins even for uses in which thermosetting matrices are well consolidated (e.g., naval and aeronautical fields). In this work, polypropylene/basalt fabric composite samples were prepared by film stacking and compression molding procedures. They have been studied in terms of flexural and low-velocity impact behavior. The influence related to the matrix modification with a pre-optimized amount of maleic anhydride grafted PP as coupling agent was studied. The mechanical performances of the composite systems were compared with those of laminates consisting of the pure matrix and obtained by hot-pressing of PP pellets and PP films used in the stacking procedure. Results, on one side, demonstrated a slight reduction of both static and dynamic parameters at the break for specimens from superimposed films to ones prepared from PP pellets. Moreover, an outstanding improvement of mechanical performances was shown in the presence of basalt layers, especially for compatibilized samples.

Effect of Carbon Nanostructures and Fatty Acid Treatment on the Mechanical and Thermal Performances of Flax/Polypropylene Composites.

Four different strategies for mitigating the highly hydrophilic nature of flax fibers were investigated with a view to increase their compatibility with apolar polypropylene. The effects of two carbon nanostructures (graphene nanoplatelets (GNPs) and carbon nanotubes (CNTs)), of a chemical modification with a fatty acid (stearic acid), and of maleated polypropylene on interfacial adhesion, mechanical properties (tensile and flexural), and thermal stability (TGA) were compared. The best performance was achieved by a synergistic combination of GNPs and maleated polypropylene, which resulted in an increase in tensile strength and modulus of 42.46% and 54.96%, respectively, compared to baseline composites. Stearation proved to be an effective strategy for increasing the compatibility with apolar matrices when performed in an ethanol solution with a 0.4 M concentration. The results demonstrate that an adequate selection of surface modification strategies leads to considerable enhancements in targeted properties.

Improving Interaction at Polymer-Filler Interface: The Efficacy of Wrinkle Texture.

One of the main issues in preparing polymer-based nanocomposites with effective properties is to achieve a good dispersion of the nanoparticles into the matrix. Chemical interfacial modifications by specific coupling agents represents a good way to reach this objective. Actually, time consuming compatibilization procedures strongly compromise the sustainability of these strategies. In this study, the role of particles' architectures in their dispersion into a poly-lactic acid matrix and their subsequent influences on physical-chemical properties of the obtained nanocomposites were investigated. Two kinds of silica nanoparticles, "smooth" and "wrinkled," with different surface areas (≈30 and ≈600 m2/g respectively) were synthesized through a modified Stöber method and used, without any chemical surface pre-treatments, as fillers to produce poly-lactic acid based nanocomposites. The key role played by wrinkled texture in modifying the physical interaction at the polymer-filler interface and in driving composite properties, was investigated and reflected in the final bulk properties. Detailed investigations revealed the presence of wrinkled nanoparticles, leading to (i) an enormous increase of the chain relaxation time, by almost 30 times compared to the neat PLA matrix; (ii) intensification of the shear-thinning behavior at low shear-rates; and (iii) slightly slower thermal degradation of polylactic acid.

Morphology, molecular interactions and H2O diffusion in a poly(lactic-acid)/graphene composite: A vibrational spectroscopy study.

A composite system made of poly(l-lactic acid) (PLLA) and graphene nanoplatelets (GNP) was investigated by Raman and FTIR spectroscopy. Two compositions were prepared and characterized in comparison to the pristine polymer: they contained, respectively, 0.25 and 0.75 wt% of the nanofiller. The study was focused on the morphological properties of the system, and, in particular, on the level of dispersion and the homogeneity obtainable with the adopted preparation protocol. Furthermore, the possible molecular interactions taking place between the nanofiller and the polymer matrix were considered. Both the above issues were investigated by confocal Raman spectroscopy, with the aid of first-principle calculations to strengthen the spectral interpretation. Finally, the effect of the nanofiller on water diffusion was investigated by time-resolved FTIR spectroscopy, which provided accurate equilibrium and kinetic data, as well as molecular level information on the penetrant-to-substrate interactions. It was found that, for a 0.25 wt% composition, the adopted preparation protocol allowed us to achieve a dispersion at the level of single nanoplatelets, while for a 0.75 wt% composition, the GNP's aggregate into a co-continuous phase. PLLA/GNP interactions were detected by Raman spectroscopy, producing a detectable perturbation of the PLLA conformational equilibrium. Both the diffusivities and the equilibrium water uptake were found to decrease significantly by increasing the filler content.

Green Composites Based on Blends of Polypropylene with Liquid Wood Reinforced with Hemp Fibers: Thermomechanical Properties and the Effect of Recycling Cycles.

Green composites from polypropylene and lignin-based natural material were manufactured using a melt extrusion process. The lignin-based material used was the so called "liquid wood". The PP/"Liquid Wood" blends were extruded with "liquid wood" content varying from 20 wt % to 80 wt %. The blends were thoroughly characterized by flexural, impact, and dynamic mechanical testing. The addition of the Liquid Wood resulted in a great improvement in terms of both the flexural modulus and strength but, on the other hand, a reduction of the impact strength was observed. For one blend composition, the composites reinforced with hemp fibers were also studied. The addition of hemp allowed us to further improve the mechanical properties. The composite with 20 wt % of hemp, subjected to up to three recycling cycles, showed good mechanical property retention and thermal stability after recycling.

Melt-spun bioactive sutures containing nanohybrids for local delivery of anti-inflammatory drugs.

In this work, a novel concept is introduced in drug-eluting fibres to ensure a good control of drug delivery features and wide applicability to different bioactive compounds. Composite bioactive sutures based on fibre grade poly(ε-caprolactone) (PCL) and loaded with the anti-inflammatory drug Diclofenac (Dic) or a Dic nanohybrid where the drug is intercalated in a synthetic hydrotalcite (Mg/Al hydroxycarbonate) (HT-Dic) were developed. Fibres were prepared by melt-spinning at different PCL/HT-Dic/Dic ratios and analysed in terms of morphology, mechanical properties and drug release features. Results emphasized that tensile properties of fibres are clearly affected by Dic or HT-Dic addition, while the presence of knots has limited influence on the mechanical behaviour of the sutures. Release of Dic strongly depends on how Dic is loaded in the fibre (as free or nanohybrid) whereas the combination of free Dic and HT-Dic can allow a further tuning of release profile. In vivo experiments show a reduction of inflammatory responses associated with Dic-loaded fibers. Thus, a proof of principle is provided for a novel class of bioactive sutures integrating advanced controlled-release technologies.

Analytical innovations in the detection of phenolics in wines.

A liquid chromatographic method with online photometric and luminescent detection for the determination of 18 phenolic compounds in wines is reported. Photometric detection is performed at four wavelengths, namely, 256, 280, 320, and 365 nm, using a diode array detection system. The luminescent detection is achieved by means of a postcolumn derivatization reaction of 10 of these compounds with terbium(III) in the presence of synergistic agents, such as ethylenediaminetetraacetic acid (EDTA) and n-octyltriphosphine oxide (TOPO). A micellar medium provided by the surfactants sodium dodecyl sulfate and Triton X-100 was used for the determination of the luminescent chelates at lambdaex 317 and lambdaem 545 nm. The long wavelength emission of lanthanide chelates can minimize interferences from background sample matrix, which usually emit at shorter wavelengths. The analytical features of the photometric and fluorometric methods, such as dynamic ranges of the calibration graphs, detection limits, and precision data, have been obtained. The practical usefulness of the developed methods is demonstrated by the analysis of Spanish and Italian wine samples (red, rosé, oloroso, and white), which were diluted and directly injected into the chromatographic system. The accuracy of both methods was checked by assaying a recovery study, which was performed at three different analyte levels for each type of sample.

In vitro effects of fluoroquinolone and aminoglycoside antibiotics on human keratocytes.

PURPOSE: The purpose of this study was to assess the cytotoxic effects of the fluoquinolone ofloxacin and the aminoglycoside netilmicin on stromal human keratocytes in vitro. METHODS: Cultured human keratocytes were exposed to various concentrations of ofloxacin or netilmicin (0.16-5.0 mg/mL). Both cell proliferation (MTT assay) and cell morphology (phase-contrast microscopy) were evaluated after 1, 4, 12, and 24 hours of incubation. Measurement of annexin V binding performed in association with the dye exclusion test using propidium iodide (PI) was also performed by FACS analysis after 4 hours of exposure. RESULTS: Both antimicrobials induced dose- and time-dependent morphologic changes in keratocytes, yet the effects of netilmicin were minimal. After 24 hours of exposure, both drugs induced a dose-dependent inhibition of cell proliferation; however, ofloxacin demonstrated significantly more toxic effects than netilmicin (t test for ED50 values, P < 0.0001). Statistical differences between 2 antibiotics start at concentrations above 1.25 mg/mL (ANOVA with post-hoc test, P < 0.01). Expression of the apoptotic marker annexin V was unaffected by antibiotic exposure, whereas the uptake of the necrotic marker PI was increased by ofloxacin (5 mg/mL) but not by netilmicin (ofloxacin versus netilmicin, ANOVA, P < 0.05). CONCLUSIONS: Relative effects of aminoglycosides and fluoroquinolones on stromal keratocytes appear to be different: netilmicin was shown to be significantly less toxic than ofloxacin. This finding is particularly relevant in deciding the optimal antibiotic to be applied in clinical situations in which the epithelium is absent or compromised, as after photorefractive keratectomy, alkali burns, or ulcerative keratitis.

Effect of ofloxacin and netilmicin on human corneal and conjunctival cells in vitro.

The purpose of this study was to compare the cytotoxic effects of the fluoroquinolone ofloxacin with that of the aminoglycoside netilmicin. Human corneal epithelial cells (HCE-T) and human conjunctival epithelial cells (Wong-Kilbourne derivative of Chang conjunctiva) were exposed to antibiotics (0.08-5.0 mg/mL) for 4 or 24 hours. Cell proliferation and viability were assessed with the MTT assay, neutral red uptake, and bromo deoxy uridine incorporation. In both cell lines, ofloxacin inhibited cell proliferation and viability. These effects were time and dose dependent. Concentrations of ofloxacin ranging from 0.4 to 2.4 mg/mL (0.04% to 0.24%) produced a 50% inhibition of proliferation and viability. In contrast, netilmicin induced no toxic effect. The differences between ofloxacin and netilmicin were highly statistically significant (p < 0.001). This finding is particularly relevant in deciding the optimal antibiotic to be applied in clinical situations in which the epithelium is compromised.