Investigation into the Influence of the Process Parameters on the Stability of a Poly(Vinyl)-Alcohol-Based Coating System.

Most tablets put on the market are coated with polymers soluble in water. The Opadry II 85 series from Colorcon Inc., is a family of PVA-based products marketed since the 1990s. Despite numerous publications on the properties of PVA, to date, limited work has been undertaken to determine the physico-chemical parameters (i.e., UV light, high temperature, and relative humidity) that could affect the performance of PVA-based coatings. To this end, we performed artificial ageing processes on samples made of Opadry Orange II or of some selected components of this coating and analysed them by means of a multidisciplinary approach, using, for example, FTIR, NMR, rheology, and DMTA measurements. In this way, we analysed the influence of the critical components of the Opadry Orange II formula, such as titanium dioxide and aluminium hydroxide, on the coating characteristics under ageing conditions.

Hydrogen Sulfide-Releasing Fibrous Membranes: Potential Patches for Stimulating Human Stem Cells Proliferation and Viability under Oxidative Stress.

The design of biomaterial platforms able to release bioactive molecules is mandatory in tissue repair and regenerative medicine. In this context, electrospinning is a user-friendly, versatile and low-cost technique, able to process different kinds of materials in micro- and nano-fibers with a large surface area-to-volume ratio for an optimal release of gaseous signaling molecules. Recently, the antioxidant and anti-inflammatory properties of the endogenous gasotramsmitter hydrogen sulfide (H2S), as well as its ability to stimulate relevant biochemical processes on the growth of mesenchymal stem cells (MSC), have been investigated. Therefore, in this work, new poly(lactic) acid fibrous membranes (PFM), doped and functionalized with H2S slow-releasing donors extracted from garlic, were synthetized. These innovative H2S-releasing mats were characterized for their morphological, thermal, mechanical, and biological properties. Their antimicrobial activity and effects on the in vitro human cardiac MSC growth, either in the presence or in the absence of oxidative stress, were here assessed. On the basis of the results here presented, these new H2S-releasing PFM could represent promising and low-cost scaffolds or patches for biomedical applications in tissue repair.

Super-hydrophobic multi-walled carbon nanotube coatings for stainless steel.

We have taken advantage of the native surface roughness and the iron content of AISI 316 stainless steel to directly grow multi-walled carbon nanotube (MWCNT) random networks by chemical vapor deposition (CVD) at low-temperature (1000°C) without the addition of any external catalysts or time-consuming pre-treatments. In this way, super-hydrophobic MWCNT films on stainless steel sheets were obtained, exhibiting high contact angle values (154°C) and high adhesion force (high contact angle hysteresis). Furthermore, the investigation of MWCNT films with scanning electron microscopy (SEM) reveals a two-fold hierarchical morphology of the MWCNT random networks made of hydrophilic carbonaceous nanostructures on the tip of hydrophobic MWCNTs. Owing to the Salvinia effect, the hydrophobic and hydrophilic composite surface of the MWCNT films supplies a stationary super-hydrophobic coating for conductive stainless steel. This biomimetical inspired surface not only may prevent corrosion and fouling, but also could provide low friction and drag reduction.

Soybean Oil-Based 3D Printed Mesh Designed for Guided Bone Regeneration (GBR) in Oral Surgery.

This study aims to obtain a cyto-compatible 3D printable bio-resin for the manufacturing of meshes designed from acquired real patients' bone defect to be used in future for guided bone regeneration (GBR), achieving the goal of personalized medicine, decreasing surgical, recovery time, and patient discomfort. To this purpose, a biobased, biocompatible, and photo-curable resin made of acrylated epoxidized soybean oil (AESO) diluted with soybean oil (SO) is developed and 3D printed using a commercial digital light processing (DLP) 3D printer. 3D printed samples show good thermal properties, allowing for thermally-based sterilization process and mechanical properties typical of crosslinked natural oils (i.e., E = 12 MPa, UTS = 1.5 MPa), suitable for the GBR application in the oral surgery. The AESO-SO bio-resin proves to be cytocompatible, allowing for fibroblast cells proliferation (viability at 72 h > 97%), without inducing severe inflammatory response when co-cultured with macrophages, as demonstrated by cytokine antibody arrays, that is anyway resolved in the first 24 h. Moreover, accelerated degradation tests prove that the bio-resin is biodegradable in hydrolytic environments.

New vegetable-waste biomaterials by Lupin albus L. as cellular scaffolds for applications in biomedicine and food.

The reprocessing of vegetal-waste represents a new research field in order to design novel biomaterials for potential biomedical applications and in food industry. Here we obtained a biomaterial from Lupinus albus L. hull (LH) that was characterized micro-structurally by scanning electron microscopy and for its antimicrobial and scaffolding properties. A good adhesion and proliferation of human mesenchymal stem cells (hMSCs) seeded on LH scaffold were observed. Thanks to its high content of cellulose and beneficial phytochemical substances, LH and its derivatives can represent an available source for fabrication of biocompatible and bioactive scaffolds. Therefore, a reprocessing protocol of LH was optimized for producing a new LH bioplastic named BPLH. This new biomaterial was characterized by chemico-physical analyses. The water uptake, degradability and antimicrobial properties of BPLH were evaluated, as well as the mechanical properties. A good adhesion and proliferation of both fibroblasts and hMSCs on BPLH were observed over 2 weeks, and immunofluorescence analysis of hMSCs after 3 weeks indicates an initial commitment toward muscle differentiation. Our work represents a new approach toward the recovery and valorization of the vegetal waste showing the remarkable properties of LH and BPLH as cellular waste-based scaffold with potential applications in cell-based food field as well as in medicine for topical patches in wound healing and bedsores treatment.

Comparative Life Cycle Assessment of SLS and mFFF Additive Manufacturing Techniques for the Production of a Metal Specimen.

This work is part of a research project aimed at developing a bio-based binder, composed mainly of polylactic acid (PLA), to produce Ti6Al4V feedstock suitable for use in MAM (Metal Additive Manufacturing) via mFFF (metal Fused Filament Fabrication), in order to manufacture a titanium alloy specimen. While in Bragaglia et al. the mechanical characteristics of this sample were analyzed, the aim used of this study is to compare the mentioned mFFF process with one of the most used MAM processes in aerospace applications, known as Selective Laser Sintering (SLS), based on the Life Cycle Assessment (LCA) method. Despite the excellent properties of the products manufactured via SLS, this 3D printing technology involves high upfront capital costs while mFFF is a cheaper process. Moreover, the mFFF process has the advantage of potentially being exported for production in microgravity or weightless environments for in-space use. Nevertheless, most scientific literature shows comparisons of the Fused Filament Fabrication (FFF) printing stage with other AM technologies, and there are no comparative LCA "Candle to Gate" studies with mFFF processes to manufacture the same metal sample. Therefore, both MAM processes are analyzed with the LCA "Candle to Gate" method, from the extraction of raw materials to the production of the finished titanium alloy sample. The main results demonstrate a higher impact (+50%) process for mFFF and higher electrical energy consumption (7.31 kWh) compared to SLS (0.32 kWh). After power consumption, the use of titanium becomes the main contributor of Global Warming Potential (GWP) and Abiotic Depletion Potential (ADP) for both processes. Finally, an alternative scenario is evaluated in which the electrical energy is exclusively generated through photovoltaics. In this case, the results show how the mFFF process develops a more sustainable outcome than SLS.

Self-Monitoring Performance of 3D-Printed Poly-Ether-Ether-Ketone Carbon Nanotube Composites.

In this paper, poly-ether-ether-ketone (PEEK) carbon-nanotube (CNT) self-monitoring composites at different levels of filler loading (i.e., 3, 5 and 10% by weight) have been extruded as 3D-printable filaments, showing gauge factor values of 14.5, 3.36 and 1.99, respectively. CNT composite filaments of 3 and 5 wt% were 3D-printed into tensile samples, while the PEEK 10CNT filament was found to be barely printable. The 3D-printed PEEK 3CNT and PEEK 5CNT composites presented piezo-resistive behavior, with an increase in electrical resistance under mechanical stress, and showed an average gauge factor of 4.46 and 2.03, respectively. Mechanical tests highlighted that 3D-printed samples have a laminate-like behavior, presenting ultimate tensile strength that is always higher than 60 MPa, hence they offer the possibility to detect damages in an orthogonal direction to the applied load wit high sensitivity.

Fused Filament Fabrication of Alumina/Polymer Filaments for Obtaining Ceramic Parts after Debinding and Sintering Processes.

In this paper, a hybrid commercially available alumina/polymer filament was 3D printed and thermally treated (debinding and sintering) to obtain ceramic parts. Microscopic and spectroscopic analysis was used to thoroughly characterize the green and sintered parts in terms of their mesostructured, as well as their flexural properties. The sintered samples show an α alumina crystalline phase with a mean density of 3.80 g/cm3, a tensile strength of 232.6 ± 12.3 MPa, and a Vickers hardness of 21 ± 0.7 GPa. The mean thermal conductivity value at room temperature was equal to 21.52 ± 0.02 W/(mK). The values obtained through FFF production are lower than those obtained by conventional processes as the 3D-printed samples exhibited imperfect interlayer bonding and voids similar to those found in the structures of polymeric FFFs. Nonetheless, the highly filled ceramic filament is suitable for use in affordable and easy-to-operate FFF machines, as shown by the cost analysis of a real printed and sintered FFF part.

Influence of Binder Composition and Material Extrusion (MEX) Parameters on the 3D Printing of Highly Filled Copper Feedstocks.

This work aims to better understand the type of thermoplastic binders required to produce highly loaded copper filaments that can be successfully printed via low-cost filament-based material extrusion (MEX). Compounding feedstock material with 55 vol.% of copper and three multi-component binder systems has been performed. The MEX behavior of these feedstocks was evaluated by depositing material at different speeds and appropriately selecting the extrusion temperature depending on the binder composition. The rest of the MEX parameters remained constant to evaluate the printing quality for the different feedstocks. Printable filaments were produced with low ovality and good surface quality. The filaments showed good dispersion of the powder and polymeric binder system in SEM analysis. The feedstock mechanical properties, i.e., the tensile strength of the filament, were sufficient to ensure proper feeding in the MEX machine. The viscosity of the feedstock systems at the adjusted printing temperatures lies in the range of 102-103 Pa·s at the shear rate of 100-1000 s-1, which appears to be sufficient to guarantee the correct flowability and continuous extrusion. The tensile properties vary greatly (e.g., ultimate tensile strength 3-9.8 MPa, elongation at break 1.5-40.5%), and the most fragile filament could not be reliably printed at higher speeds. Micrographs of the cross-section of printed parts revealed that as the printing speed increased, the porosity was minimized because the volumetric flow of the feedstock material increased, which can help to fill pores. This study offers new insights into the feedstock requirements needed to produce low-cost intricate copper components of high quality in a reliable and efficient manner. Such components can find many applications in the electronics, biomedical, and many other industries.

Structural Monitoring of Glass Fiber/Epoxy Laminates by Means of Carbon Nanotubes and Carbon Black Self-Monitoring Plies.

The health monitoring of structures is of great interest in order to check components' structural life and monitor damages during operation. Self-monitoring materials can provide both the structural and monitoring functionality in one component and exploit their piezoresistive behavior, namely, the variation of electrical resistivity with an applied mechanical strain. In this work, self-monitoring plies were developed to be inserted into glass-fiber reinforced epoxy-based laminates in order to achieve structural monitoring. Nanocomposite epoxy-based resins were developed employing different contents of high surface area carbon black (CB, 6 wt%) and multiwall carbon nanotubes (MWCNT, 0.75 and 1 wt%), and rheologically and thermomechanically characterized. Self-monitoring plies were manufactured by impregnating glass woven fabrics with the resins, and were laminated with non-sensing plies via a vacuum-bag process to produce sensored laminates. The self-monitoring performance of the laminates was assessed during monotonic and cyclic three-point bending tests, as well as ball drop impact tests. A higher sensitivity was found for the CB-based systems (Gauge Factor 6.1), while MWCNTs (0.55 and 1.04) ensure electrical percolation at lower filler contents, as expected. The systems also showed the capability of being used to predict residual life and damage occurred under impact.

Additive Manufacturing of Polyether Ether Ketone (PEEK) for Space Applications: A Nanosat Polymeric Structure.

Recent improvements in additive layer manufacturing (ALM) have provided new designs of geometrically complex structures with lighter materials and low processing costs. The use of additive manufacturing in spacecraft production is opening up many new possibilities in both design and fabrication, allowing for the reduction of the weight of the structure subsystems. In this aim, polymeric ALM structures can become a choice, in terms of lightweight and demisability, as far as good thermomechanical properties. Moreover, provided that fused-deposition modeling (FDM) is used, nanosats and other structures could be easily produced in space. However, the choice of the material is a crucial step of the process, as the final performance of the printed parts is strongly dependent on three pillars: design, material, and printing process. As a high-performance technopolymer, polyether ether ketone (PEEK) has been adopted to fabricate parts via ALM; however, the space compatibility of 3D-printed parts remains not demonstrated. This work aimed to realize a nanosat polymeric structure via FDM, including all the phases of the development process: thermomechanical design, raw material selection, printing process tuning, and manufacturing of a proof of concept of a technological model. The design phase includes the application of topology optimization to maximize mass saving and take full advantage of the ALM capability. 3D-printed parts were characterized via thermomechanical tests, outgassing tests of 3D-printed parts are reported confirming the outstanding performance of polyether ether ketone and its potential as a material for structural space application.

Visualizing cell-laden fibrin-based hydrogels using cryogenic scanning electron microscopy and confocal microscopy.

The present investigation explores the microscopic aspects of cell-laden hydrogels at high resolutions, using three-dimensional cell cultures in semi-synthetic constructs that are of very high water content (>98% water). The study aims to provide an imaging strategy for these constructs, while minimizing artefacts. Constructs of poly(ethylene glycol)-fibrinogen and fibrin hydrogels containing embedded mesenchymal cells (human dermal fibroblasts) were first imaged by confocal microscopy. Next, high-resolution scanning electron microscopy (HR-SEM) was used to provide images of the cells within the hydrogels, at submicron resolutions. Because it was not possible to obtain artefact-free images of the hydrogels using room-temperature HR-SEM, a cryogenic HR-SEM imaging methodology was employed to visualize the sample while preserving the natural hydrated state of the hydrogel. The ultrastructural details of the constructs were observed at subcellular resolutions, revealing numerous cellular components, the biomaterial in its native configuration, and the uninterrupted cell membrane as it relates with the biomaterial in the hydrated state of the construct. Constructs containing microscopic albumin microbubbles were also imaged using these methodologies to reveal fine details of the interaction between the cells, the microbubbles, and the hydrogel. Taken together with the confocal microscopy, this imaging strategy provides a more complete picture of the hydrated state of the hydrogel network with cells inside. As such, this methodology addresses some of the challenges of obtaining this information in amorphous hydrogel systems containing a very high water content (>98%) with embedded cells. Such insight may lead to better hydrogel-based strategies for tissue engineering and regeneration.

DOE analysis of the rheological data of shear-thickening fluids for puncture-resistant composite shells.

The dilatancy (Shear-thickening) is a time-independent rheological behaviour exhibited by some non-Newtonian fluids. These fluids manifest a surge in the apparent viscosity with an increase in the shear rate. If these fluids are encapsulated, they can be used to manufacture high-end stab resistance inserts (Cecchini et al., 2018) [1]. In the first part of this work, a comparison between the rheological performance of different shear-thickening fluids (STFs) based on nanosilica dispersed in glycols is presented. This analysis attempts to investigate the combinations of fillers and carriers with the highest energy-absorbing capabilities, among the various glycol-based colloidal STFs. In the second part, the influence of the composition of the STF on its rheological properties is analyzed statistically. The statistical analysis is performed by evaluating the interaction between the main design variables of the fluids (filler dimension, weight-to-weight ratio and molecular weight of the carrier). Finally, the puncture resistance of a composite system obtained by encapsulating the previously manufactured shear-thickening fluids in a polymeric shell is analyzed by means of a high-speed puncture test. This test is performed on the mockup of a tyre tread containing the best performing STF. The results showed that the use of the STF core increased the resistance to puncture by 20% as compared to the same volume of tyre tread material. Furthermore, the STF hermetically sealed the pierced sample, even when the tyre mockup was inflated at high internal pressures.

Eco-sustainable systems based on poly(lactic acid), diatomite and coffee grounds extract for food packaging.

In the food packaging sector many efforts have been (and are) devoted to the development of new materials in order to reply to an urgent market demand for green and eco-sustainable products. Particularly a lot of attention is currently devoted both to the use of compostable and biobased polymers as innovative and promising alternative to the currently used petrochemical derived polymers, and to the re-use of waste materials coming from agriculture and food industry. In this work, multifunctional eco-sustainable systems, based on poly(lactic acid) (PLA) as biopolymeric matrix, diatomaceous earth as reinforcing filler and spent coffee grounds extract as oxygen scavenger, were produced for the first time, in order to provide a simultaneous improvement of mechanical and gas barrier properties. The influence of the diatomite and the spent coffee grounds extract on the microstructural, mechanical and oxygen barrier properties of the produced films was deeply investigated by means of X-Ray diffraction (XRD), infrared spectroscopy (FT-IR, ATR), scanning electron microscopy (SEM), uniaxial tensile tests, O2 permeabilimetry measurements. An improvement of both mechanical and oxygen barrier properties was recorded for systems characterised by the co-presence of diatomite and coffee grounds extract, suggesting a possible synergic effect of the two additives.

H2S-releasing nanoemulsions: a new formulation to inhibit tumor cells proliferation and improve tissue repair.

The improvement of solubility and/or dissolution rate of poorly soluble natural compounds is an ideal strategy to make them optimal candidates as new potential drugs. Accordingly, the allyl sulfur compounds and omega-3 fatty acids are natural hydrophobic compounds that exhibit two important combined properties: cardiovascular protection and antitumor activity. Here, we have synthesized and characterized a novel formulation of diallyl disulfide (DADS) and α-linolenic acid (ALA) as protein-nanoemulsions (BAD-NEs), using ultrasounds. BAD-NEs are stable over time at room temperature and show antioxidant and radical scavenging property. These NEs are also optimal H2S slow-release donors and show a significant anti-proliferative effect on different human cancer cell lines: MCF-7 breast cancer and HuT 78 T-cell lymphoma cells. BAD-NEs are able to regulate the ERK1/2 pathway, inducing apoptosis and cell cycle arrest at the G0/G1 phase. We have also investigated their effect on cell proliferation of human adult stem/progenitor cells. Interestingly, BAD-NEs are able to improve the Lin- Sca1+ human cardiac progenitor cells (hCPC) proliferation. This stem cell growth stimulation is combined with the expression and activation of proteins involved in tissue-repair, such as P-AKT, α-sma and connexin 43. Altogether, our results suggest that these antioxidant nanoemulsions might have potential application in selective cancer therapy and for promoting the muscle tissue repair.

Altered Intracellular ATP Production by Activated CD4+ T-Cells in Very Preterm Infants.

Background. The neonatal immune system is not fully developed at birth; newborns have adequate lymphocytes counts but these cells lack function. Objective. To assess the activity of T-cells and the influence of the main perinatal factors in very preterm infants (birth weight < 1500 g). Design. Blood samples from 59 preterm infants (21/59 were dizygotic twins) were collected at birth and at 30 days of life to measure CD4+ T-cell activity using the ImmuKnow™ assay. Fifteen healthy adults were included as a control group. Results. CD4+ T-cell activity was lower in VLBW infants compared with adults (p < 0.001). Twins showed lower immune activity compared to singletons (p = 0.005). Infants born vaginally showed higher CD4+ T-cell activity compared to those born by C-section (p = 0.031); infants born after prolonged Premature Rupture of Membranes (pPROM) showed higher CD4+ T-cell activity at birth (p = 0.002) compared to infants born without pPROM. Low CD4+ T-cell activity at birth is associated with necrotizing enterocolitis (NEC) in the first week of life (p = 0.049). Conclusions. Preterm infants show a lack in CD4+ T-cell activity at birth. Perinatal factors such as intrauterine inflammation, mode of delivery, and zygosity can influence the adaptive immune activation capacity at birth and can contribute to exposing these infants to serious complications such as NEC.

The Diatom Staurosirella pinnata for Photoactive Material Production.

A native isolate of the colonial benthic diatom Staurosirella pinnata was cultivated for biosilica production. The silicified cell walls (frustules) were used as a source of homogeneous and structurally predictable porous biosilica for dye trapping and random laser applications. This was coupled with the extraction of lipids from biomass showing potential to fabricate photoactive composite materials sustainably. The strain was selected for its ease of growth in culture and harvesting. Biosilica and lipids were obtained at the end of growth in indoor photobioreactors. Frustules were structurally characterized microscopically and their chemistry analyzed with Fourier Transform Infrared Spectroscopy. Frustule capacity of binding laser dyes was evaluated on a set of frustules/Rhodamine B (Rho B) solutions and with respect to silicon dioxide and diatomite by Fluorescence Spectroscopy demonstrating a high affinity for the organic dye. The effect of dye trapping property in conveying Rho B emission to frustules, with enhancement of scattering events, was analyzed on Rho B doped polyacrylamide gels filled or not with frustules. Amplified spontaneous emission was recorded at increasing pump power indicating the onset of a random laser effect in frustule filled gels at lower power threshold compared to unfilled matrices.

Multi-fractal hierarchy of single-walled carbon nanotube hydrophobic coatings.

A hierarchical structure is an assembly with a multi-scale morphology and with a large and accessible surface area. Recent advances in nanomaterial science have made increasingly possible the design of hierarchical surfaces with specific and tunable properties. Here, we report the fractal analysis of hierarchical single-walled carbon nanotube (SWCNT) films realized by a simple, rapid, reproducible, and inexpensive filtration process from an aqueous dispersion, then deposited by drytransfer printing method on several substrates, at room temperature. Furthermore, by varying the thickness of carbon nanotube random networks, it is possible tailoring their wettability due to capillary phenomena in the porous films. Moreover, in order to describe the wetting properties of such surfaces, we introduce a two-dimensional extension of the Wenzel-Cassie-Baxter theory. The hierarchical surface roughness of SWCNT coatings coupled with their exceptional and tunable optical and electrical properties provide an ideal hydrophobic composite surface for a new class of optoelectronic and nanofluidic devices.

Exploiting the hierarchical morphology of single-walled and multi-walled carbon nanotube films for highly hydrophobic coatings.

Self-assembled hierarchical solid surfaces are very interesting for wetting phenomena, as observed in a variety of natural and artificial surfaces. Here, we report single-walled (SWCNT) and multi-walled carbon nanotube (MWCNT) thin films realized by a simple, rapid, reproducible, and inexpensive filtration process from an aqueous dispersion, that was deposited at room temperature by a dry-transfer printing method on glass. Furthermore, the investigation of carbon nanotube films through scanning electron microscopy (SEM) reveals the multi-scale hierarchical morphology of the self-assembled carbon nanotube random networks. Moreover, contact angle measurements show that hierarchical SWCNT/MWCNT composite surfaces exhibit a higher hydrophobicity (contact angles of up to 137°) than bare SWCNT (110°) and MWCNT (97°) coatings, thereby confirming the enhancement produced by the surface hierarchical morphology.

Applications of three-dimensional carbon nanotube networks.

In this paper, we show that it is possible to synthesize carbon-based three-dimensional networks by adding sulfur, as growth enhancer, during the synthesis process. The obtained material is self-supporting and consists of curved and interconnected carbon nanotubes and to lesser extent of carbon fibers. Studies on the microstructure indicate that the assembly presents a marked variability in the tube external diameter and in the inner structure. We study the relationship between the observed microscopic properties and some potential applications. In particular, we show that the porous nature of the network is directly responsible for the hydrophobic and the lipophilic behavior. Moreover, we used a cut piece of the produced carbon material as working electrode in a standard electrochemical cell and, thus, demonstrating the capability of the system to respond to incident light in the visible and near-ultraviolet region and to generate a photocurrent.