Polydopamine-Coated Poly-Lactic Acid Aerogels as Scaffolds for Tissue Engineering Applications.

Poly-L-lactic acid (PLLA) aerogel-based scaffolds were obtained from physical PLLA gels containing cyclopentanone (CPO) or methyl benzoate (BzOMe) molecules. An innovative single step method of solvent extraction, using supercritical CO2, was used to achieve cylindrical monolithic aerogels. The pore distribution and size, analyzed by SEM microscopy, were found to be related to the crystalline forms present in the physical nodes that hold the gels together, the stable α'-form and the metastable co-crystalline ε-form, detected in the PLLA/BzOMe and PLLA/CPO aerogels, respectively. A higher mechanical compressive strength was found for the PLLA/CPO aerogels, which exhibit a more homogenous porosity. In vitro biocompatibility tests also indicated that monolithic PLLA/CPO aerogels exhibited greater cell viability than PLLA/BzOMe aerogels. An improved biocompatibility of PLLA/CPO monolithic aerogels was finally observed by coating the surface of the aerogels with polydopamine (PDA) obtained by the in situ polymerization of dopamine (DA). The synergistic effect of biodegradable polyester (PLLA) and the biomimetic interface (PDA) makes this new 3D porous scaffold, with porosity and mechanical properties that are tunable based on the solvent used in the preparation process, attractive for tissue engineering applications.

Liquefied Petroleum Gas Monitoring System Based on Polystyrene Coated Long Period Grating.

In this work, we report the in-field demonstration of a liquefied petroleum gas monitoring system based on optical fiber technology. Long-period grating coated with a thin layer of atactic polystyrene (aPS) was employed as a gas sensor, and an array comprising two different fiber Bragg gratings was set for the monitoring of environmental conditions such as temperature and humidity. A custom package was developed for the sensors, ensuring their suitable installation and operation in harsh conditions. The developed system was installed in a real railway location scenario (i.e., a southern Italian operative railway tunnel), and tests were performed to validate the system performances in operational mode. Daytime normal working operations of the railway line and controlled gas expositions, at very low concentrations, were the searched realistic conditions for an out-of-lab validation of the developed system. Encouraging results were obtained with a precise indication of the gas concentration and external conditioning of the sensor.

The Effect of Carbon-Based Nanofillers on Cryogenic Temperature Mechanical Properties of CFRPs.

In the present work, the effects of carbon-based nanofillers (0.5 wt%), i.e., graphene nanoplatelets (GNPs), carbon nanofibers (CNFs), and carbon nanotubes (CNTs), on the cryogenic temperature (77 K) mechanical properties of carbon fiber reinforced polymers (CFRPs) were investigated. The study utilized an ex situ conditioning method for cryogenic tests. The nanofillers were mixed with the epoxy matrix by a solvent-free fluidized bed mixing technique (FBM), while unidirectional carbon fibers were impregnated with the resulting nanocomposites to manufacture CFRP samples. Optical microscopy was employed to analyze the dispersion of the carbon-based fillers within the matrix, revealing a homogeneous distribution in nanocomposites containing GNPs and CNFs. Fracture toughness tests confirmed the homogeneity of the GNP-loaded systems, showing an improvement in the stress intensity factor (KC) by 13.2% and 14.7% compared to the unmodified matrix at RT (25 °C) and 77 K, respectively; moreover, flexural tests demonstrated a general increase in flexural strength with the presence of carbon-based nanofillers at both temperature levels (RT and 77 K). Additionally, interlaminar shear strength (ILSS) tests were performed and analyzed using the same ex situ conditioning method.

Regiodivergent synthesis of trisubstituted furans through Tf(2)O-catalyzed Friedel-Crafts acylation: a tool for access to tetrahydrofuran lignan analogues.

3- or 4-Aroylfurans have been prepared selectively and in high yields from a common precursor by simple tuning of reaction conditions in Friedel-Crafts acylation promoted by triflic anhydride. The formation of products can be explained on the basis of the ring-chain tautomerism occurring in compounds equipped with two neighbouring carboxylic functions. Since 4-aroylfuran derivatives show a typical lignan backbone, suitable hydrogenation conditions were found out to gain tetrahydrofuran lignans.

Cellulose Amphiphilic Materials: Chemistry, Process and Applications.

In the last decade, amphiphilic cellulose (AC) is emerging as attractive biomaterial for different therapeutic use, due to its unique chemical and physical properties. Using it as alternative to synthetic polymers, AC opens up new avenues to prepare new bio-sustainable materials with low impact in the cellular environment. Herein, most recent methods to synthesize and processing AC materials from different sources-i.e., cellulose nanofibers, bacterial cellulose, cellulose derivatives-will be discussed. By an accurate optimization of morphology and surface chemistry, it is possible to develop innovative amphiphilic platforms, promising for a wide range of biomedical applications, from drug delivery to molecular/particle adsorption.

Effect of the Mixing Technique of Graphene Nanoplatelets and Graphene Nanofibers on Fracture Toughness of Epoxy Based Nanocomposites and Composites.

In this work, the effect of different mixing techniques on thermal and mechanical properties of graphene nanoplatelets (GNPs) and graphene nanofibers (GANFs) loaded epoxy nanocomposites was investigated. Three dispersion methods were employed: a high shear rate (HSR), ultrasonication (US) and the fluidized bed method (FBM). The optical microscopy has revealed that the most suitable dispersion, in terms of homogeneity and cluster size, is achieved by implementing the US and FBM techniques, leading to nanocomposites with the largest increase of glass transition temperature, as supported by the DMA analysis data. The fracture toughness results show a general increase of both the critical stress intensity factor (KIC) and the critical strain energy release rate (GIC), likely due to the homogeneity and the low scale dispersion of the carbonaceous nanostructures. Based on the nanocomposite fracture toughness improvements and also assuming a potential large scale up production of the nanocomposite matrix, a single mixing technique, namely the FBM, was employed to manufacture the carbon fiber reinforced composite (CFRC). This method has resulted in being less time-consuming and is potentially most suitable for the high volume industrial production. The CFRCs were characterized in terms of tensile, flexural and interlaminar fracture toughness properties and the results were analyzed and discussed.

Polydopamine-Coated Alginate Microgels: Process Optimization and In Vitro Validation.

In the last decade, alginate-based microgels have gained relevant interest as three-dimensional analogues of extracellular matrix, being able to support cell growth and functions. In this study, core-shell microgels were fabricated by self-polymerization of dopamine (DA) molecules under mild oxidation and in situ precipitation of polydopamine (PDA) onto alginate microbeads, processed by electro fluid dynamic atomization. Morphological (optical, SEM) and chemical analyses (ATR-FTIR, XPS) confirmed the presence of PDA macromolecules, distributed onto the microgel surface. Nanoindentation tests also indicated that the PDA coating can influence the biomechanical properties of the microgel surfaces-i.e., σmaxALG = 0.45 mN vs. σmaxALG@PDA = 0.30 mN-thus improving the interface with hMSCs as confirmed by in vitro tests; in particular, protein adsorption and viability tests show a significant increase in adhesion and cell proliferation, strictly related to the presence of PDA. Hence, we concluded that PDA coating contributes to the formation of a friendly interface able to efficiently support cells' activities. In this perspective, core-shell microgels may be suggested as a novel symmetric 3D model to study in vitro cell interactions.

Polyaniline nano-needles into electrospun bio active fibres support in vitro astrocyte response.

Recent studies have proposed that the bioelectrical response of glial cells, called astrocytes, currently represents a key target for neuroregenerative purposes. Here, we propose the fabrication of electrospun nanofibres containing gelatin and polyaniline (PANi) synthesized in the form of nano-needles (PnNs) as electrically conductive scaffolds to support the growth and functionalities of primary astrocytes. We report a fine control of the morphological features in terms of fibre size and spatial distribution and fibre patterning, i.e. random or aligned fibre organization, as revealed by SEM- and TEM-supported image analysis. We demonstrate that the peculiar morphological properties of fibres - i.e., the fibre size scale and alignment - drive the adhesion, proliferation, and functional properties of primary cortical astrocytes. In addition, the gradual transmission of biochemical and biophysical signals due to the presence of PnNs combined with the presence of gelatin results in a permissive and guiding environment for astrocytes. Accordingly, the functional properties of astrocytes measured via cell patch-clamp experiments reveal that PnNs do not alter the bioelectrical properties of resting astrocytes, thus setting the scene for the use of PnN-loaded nanofibres as bioconductive platforms for interfacing astrocytes and controlling their bioelectrical properties.

Effect of Strain Rate and Silica Filler Content on the Compressive Behavior of RTM6 Epoxy-Based Nanocomposites.

The aim of this paper is to investigate the effect of strain rate and filler content on the compressive behavior of the aeronautical grade RTM6 epoxy-based nanocomposites. Silica nanoparticles with different sizes, weight concentrations and surface functionalization were used as fillers. Dynamic mechanical analysis was used to study the glass transition temperature and storage modulus of the nanocomposites. Using quasi-static and split Hopkinson bar tests, strain rates of 0.001 s-1 to 1100 s-1 were imposed. Sample deformation was measured using stereo digital image correlation techniques. Results showed a significant increase in the compressive strength with increasing strain rate. The elastic modulus and Poisson's ratio showed strain rate independency. The addition of silica nanoparticles marginally increased the glass transition temperature of the resin, and improved its storage and elastic moduli and peak yield strength for all filler concentrations. Increasing the weight percentage of the filler slightly improved the peak yield strength. Moreover, the filler's size and surface functionalization did not affect the resin's compressive behavior at different strain rates.

Thermal and Mechanical Characterization of an Aeronautical Graded Epoxy Resin Loaded with Hybrid Nanoparticles.

Synthesized silica nanoparticles (SiO2) were coated with a thin polydopamine (PDA) shell by a modified one-step procedure leading to PDA coated silica nanoparticles (SiO2@PDA). Core-shell (CSNPs) characterization revealed 15 nm thickness of PDA shell surrounding the SiO2 core (~270 nm in diameter). Different weight percentages of CSNPs were employed as filler to enhance the final properties of an aeronautical epoxy resin (RTM6) commonly used as matrix to manufacture structural composites. RTM6/SiO2@PDA nanocomposites were experimentally characterized in terms of thermal stability and mechanical performances to assess the induced effects by the synthesized CSNPs on pristine matrix. Thermal stability was investigated by thermogravimetry and data were modelled by the Doyle model and Kissinger methods. An overall enhancement in thermal stability was achieved and clearly highlighted by modelling results. Dynamic Mechanical Analysis has revealed an improvement in the nanocomposite performances compared to the neat matrix, with an increase in the glassy (+9.5%) and rubbery moduli (+32%) as well as glass transition temperature (+10 °C). Fracture Toughness tests confirmed the positive effect in damage resistance compared to unloaded resin with an impressive variation in critical stress intensity factor (KIC) and critical strain energy (GIC) of about 60% and 138%, respectively, with the highest SiO2@PDA content.

Optimization of Polydopamine Coatings onto Poly-ε-Caprolactone Electrospun Fibers for the Fabrication of Bio-Electroconductive Interfaces.

In recent years, mussel adhesive proteins have attracted much attention because they can form strong adhesive interface interactions with various substrates in a wet environment. Inspired by their catechol- and amine-based molecular structure, polydopamine (PDA), a dopamine derived synthetic eumelanin polymer, was recognized as a suitable bio-interface coating. PDA was successfully used to improve adhesion due to the availability of copious functional groups for covalently immobilizing biomolecules and anchoring reactive species and ions. Recently, it has been demonstrated that PDA and its derivatives can be successfully used for the surface modification of implants interfaces to modulate in vitro cellular responses in order to enhance the in vivo functionality of biomedical implants (i.e., prosthesis). Herein, we propose the development of multifunctional scaffolds based on polyε-caprolactone (PCL) electrospun fibers coated with PDA via electro fluid dynamic methods, by optimizing polymerization/oxidation reactions capable of driving PDA self-assembly, and, ultimately, investigating the effects on cell response. Morphological analyses have confirmed the possibility to obtain different surface topographies as a function of the coating process while in vitro studies proved the ability of PDA coating to interact with cells no compromising in vitro viability. In perspective, in vitro conductive properties of fibers will be further investigated in order to validate their promising use as bioconductive interfaces for tissue engineering applications.

Self-associating cellulose-graft-poly(ε-caprolactone) to design nanoparticles for drug release.

The growing interest in the use of polysaccharides nanoparticles for biomedical applications is related to the recent progresses on the synthesis of cellulose-based polymers with the specific functionalities. In particular, cellulose graft copolymers are emerging as amphiphilic materials suitable to fabricate smart nanoparticles for drug delivery applications. In this work, a cellulose-graft-poly(ε-caprolactone) (cell-g-PCL) was synthetized and characterized by FTIR, TGA and DSC in order to validate the synthesis process. We demonstrated that fast evaporation processes promoted cell-g-PCL self-assembly to form nanomicellar structures with hydrodynamic radius ranged from 30 to 60 nm as confirmed by TEM analysis. Moreover, the application of controlled electrostatic forces on solvent evaporation - namely electrospraying - allowed generating round-like nanoscaled particles, as confirmed by SEM supported via image analysis. We demonstrated also that sodium diclofenac (DS) drastically influenced the mechanism of particle formation, favoring the deposition of erythrocyte-like particles with highly concave surfaces, not penalizing the encapsulation efficiency of nanoparticles (>80%). The release profile showed a fast delivery of DS - about 60% during the first 24 h - followed by a sustained release - about 20% during the next 6 days - strictly related to the peculiar weak interactions among amphiphilic polymer segments and water molecules, thus suggesting a successful use of electrosprayed cell-g-PCL nanoparticles for therapeutic treatments in nanomedicine.

Aromatic Hyperbranched Polyester/RTM6 Epoxy Resin for EXTREME Dynamic Loading Aeronautical Applications.

The effects of the addition of an aromatic hyperbranched polyester (AHBP) on thermal, mechanical, and fracture toughness properties of a thermosetting resin system were investigated. AHBP filler, synthesized by using a bulk poly-condensation reaction, reveals a glassy state at room temperature. Indeed, according to differential scanning calorimetry measurements, the glass transition temperature (Tg) of AHBP is 95 °C. Three different adduct weight percentages were employed to manufacture the AHBP/epoxy samples, respectively, 0.1, 1, and 5 wt%. Dynamical Mechanical Analysis tests revealed that the addition of AHBP induces a negligible variation in terms of conservative modulus, whereas a slight Tg reduction of about 4 °C was observed at 5 wt% of filler content. Fracture toughness results showed an improvement of both critical stress intensity factor (+18%) and critical strain energy release rate (+83%) by adding 5 wt% of AHBP compared to the neat epoxy matrix. Static and dynamic compression tests covering strain rates ranging from 0.0008 to 1000 s-1 revealed a pronounced strain rate sensitivity for all AHBP/epoxy systems. The AHBP composites all showed an increase of the true peak yield compressive strength with the best improvement associated with the sample with 0.1 wt% of AHBP.

Survey data on thermal properties of different hyperbranched polymers (HBPs) and on morphological and thermal analysis of the corresponding epoxy matrix nanocomposites.

The following data describe the thermal properties of two different typologies of Hyperbranched Polymers (HBPs): the first one is a polyester (HBPG - Hyperbranched Polymer Glassy) with a glass transition temperature (Tg) higher than room temperature (∼90 °C) whereas the second one is a polyamide ester (HBPR - Hyperbranched Polymer Rubbery) characterized by Tg of about 20 °C. The nanocomposites manufactured using these HBPs as filler were characterized using Optical Microscopy and Differential Scanning Calorimetry. The raw data for the evaluation of fracture toughness properties are reported for the listed materials. This article provides data related to "The effect of Glassy and Rubbery Hyperbranched Polymers as Modifiers in Epoxy Aeronautical Systems" (Zotti et al.).

Thermal Properties and Fracture Toughness of Epoxy Nanocomposites Loaded with Hyperbranched-Polymers-Based Core/Shell Nanoparticles.

Synthesized silicon oxide (silica) nanoparticles were functionalized with a hyperbranched polymer (HBP) achieving a core/shell nanoparticles (CSNPs) morphology. CSNPs were characterized by Fourier Transform Infrared (FTIR) spectroscopy, Transmission Electron Microscopy (TEM), and Thermogravimetric Analysis (TGA). A core diameter of about 250 nm with a 15 nm thick shell was revealed using TEM images. An aeronautical epoxy resin was loaded with the synthesized CSNPs at different percentages and thermal properties, such as thermal stability and dynamic mechanical properties, were investigated with the use of different techniques. Although the incorporation of 2.5 wt% of CSNPs induces a ~4 °C reduction of the hosting matrix glass transition temperature, a slight increase of the storage modulus of about ~10% was also measured. The Kissinger Method was employed in order to study the thermal stability of the nanocomposites; the degradation activation energies that resulted were higher for the sample loaded with low filler content with a maximum increase of both degradation step energies of about ~77% and ~20%, respectively. Finally, fracture toughness analysis revealed that both the critical stress intensity factor (KIC) and critical strain energy release rate (GIC) increased with the CSNPs content, reporting an increase of about 32% and 74%, respectively, for the higher filler loading.

Label-free fiber optic optrode for the detection of class C ß-lactamases expressed by drug resistant bacteria.

This paper reports the experimental assessment of an automated optical assay based on label free optical fiber optrodes for the fast detection of class C ß-lactamases (AmpC BLs), actually considered as one of the most important sources of resistance to ß-lactams antibiotics expressed by resistant bacteria. Reflection-type long period fiber gratings (RT-LPG) have been used as highly sensitive label free optrodes, while a higher affine boronic acid-based ligand was here selected to enhance the overall assay performances compared to those obtained in our first demonstration. In order to prove the feasibility analysis towards a fully automated optical assay, an engineered system was developed to simultaneously manipulate and interrogate multiple fiber optic optrodes in the different phases of the assay. The automated system tested in AmpC solutions at increasing concentrations demonstrated a limit of detection (LOD) of 6 nM, three times better when compared with the results obtained in our previous work. Moreover, the real effectiveness of the proposed optical assay has been also confirmed in complex matrices as the case of lysates of Escherichia coli overexpressing AmpC.

Electro-Active Polymers (EAPs): A Promising Route to Design Bio-Organic/Bioinspired Platforms with on Demand Functionalities.

Through recent discoveries and new knowledge among correlations between molecular biology and materials science, it is a growing interest to design new biomaterials able to interact-i.e., to influence, to guide or to detect-with cells and their surrounding microenvironments, in order to better control biological phenomena. In this context, electro-active polymers (EAPs) are showing great promise as biomaterials acting as an interface between electronics and biology. This is ascribable to the highly tunability of chemical/physical properties which confer them different conductive properties for various applicative uses (i.e., molecular targeting, biosensors, biocompatible scaffolds). This review article is divided into three parts: the first one is an overview on EAPs to introduce basic conductivity mechanisms and their classification. The second one is focused on the description of most common processes used to manipulate EAPs in the form of two-dimensional (2D) and three-dimensional (3D) materials. The last part addresses their use in current applications in different biomedical research areas including tissue engineering, biosensors and molecular delivery.

Long period fiber grating nano-optrode for cancer biomarker detection.

We report an innovative fiber optic nano-optrode based on Long Period Gratings (LPGs) working in reflection mode for the detection of human Thyroglobulin (TG), a protein marker of differentiated thyroid cancer. The reflection-type LPG (RT-LPG) biosensor, coated with a single layer of atactic polystyrene (aPS) onto which a specific, high affinity anti-Tg antibody was adsorbed, allowed the label-free detection of Tg in the needle washouts of fine-needle aspiration biopsies, at concentrations useful for pre- and post-operative assessment of the biomarker levels. Analyte recognition and capture were confirmed with a parallel on fiber ELISA-like assay using, in pilot tests, the biotinylated protein and HRP-labeled streptavidin for its detection. Dose-dependent experiments showed that the detection is linearly dependent on concentration within the range between 0 and 4 ng/mL, while antibody saturation occurs for higher protein levels. The system is characterized by a very high sensitivity and specificity allowing the ex-vivo detection of sub ng/ml concentrations of human Tg from needle washouts of fine-needle aspiration biopsies of thyroid nodule from different patients.