Mucus Structure, Viscoelastic Properties, and Composition in Chronic Respiratory Diseases.

The respiratory mucus, a viscoelastic gel, effectuates a primary line of the airway defense when operated by the mucociliary clearance. In chronic respiratory diseases (CRDs), such as asthma, chronic obstructive pulmonary disease (COPD), and cystic fibrosis (CF), the mucus is overproduced and its solid content augments, changing its structure and viscoelastic properties and determining a derangement of essential defense mechanisms against opportunistic microbial (virus and bacteria) pathogens. This ensues in damaging of the airways, leading to a vicious cycle of obstruction and infection responsible for the harsh clinical evolution of these CRDs. Here, we review the essential features of normal and pathological mucus (i.e., sputum in CF, COPD, and asthma), i.e., mucin content, structure (mesh size), micro/macro-rheology, pH, and osmotic pressure, ending with the awareness that sputum biomarkers (mucins, inflammatory proteins and peptides, and metabolites) might serve to indicate acute exacerbation and response to therapies. There are some indications that old and novel treatments may change the structure, viscoelastic properties, and biomarker content of sputum; however, a wealth of work is still needed to embrace these measures as correlates of disease severity in association with (or even as substitutes of) pulmonary functional tests.

Shall We Tune? From Core-Shell to Cloud Type Nanostructures in Heparin/Silica Hybrids.

Heparin plays multiple biological roles depending on the availability of active sites strongly influenced by the conformation and the structure of polysaccharide chains. Combining different components at the molecular scale offers an extraordinary chance to easily tune the structural organization of heparin required for exploring new potential applications. In fact, the combination of different material types leads to challenges that cannot be achieved by each single component. In this study, hybrid heparin/silica nanoparticles were synthesized, and the role of silica as a templating agent for heparin supramolecular organization was investigated. The effect of synthesis parameters on particles compositions was deeply investigated by Fourier Transform Infrared Spectroscopy (FTIR) and Thermogravimetric Analysis (TGA). Transmission Electron Microscopy (TEM) reveals a different supramolecular organization of both components, leading to amazing organic-inorganic nanoparticles with different behavior in drug encapsulation and release. Furthermore, favorable biocompatibility for healthy human dermal fibroblasts (HDF) and tumor HS578T cells has been assessed, and a different biological behavior was observed, ascribed to different surface charge and morphology of synthesized nanoparticles.

Silica Meets Tannic Acid: Designing Green Nanoplatforms for Environment Preservation.

Hybrid tannic acid-silica-based porous nanoparticles, TA-SiO2 NPs, have been synthesized under mild conditions in the presence of green and renewable tannic acid biopolymer, a glycoside polymer of gallic acid present in a large part of plants. Tannic acid (TA) was exploited as both a structuring directing agent and green chelating site for heavy metal ions recovery from aqueous solutions. Particles morphologies and porosity were easily tuned by varying the TA initial amount. The sample produced with the largest TA amount showed a specific surface area an order of magnitude larger than silica nanoparticles. The adsorption performance was investigated by using TA-SiO2 NPs as adsorbents for copper (II) ions from an aqueous solution. The effects of the initial Cu2+ ions concentration and the pH values on the adsorption capability were also investigated. The resulting TA-SiO2 NPs exhibited a different adsorption behaviour towards Cu2+, which was demonstrated through different tests. The largest adsorption (i.e., ~50 wt% of the initial Cu2+ amount) was obtained with the more porous nanoplatforms bearing a higher final TA content. The TA-nanoplatforms, stable in pH value around neutral conditions, can be easily produced and their use would well comply with a green strategy to reduce wastewater pollution.

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.

Borate cross-linked graphene oxide-chitosan as robust and high gas barrier films.

Chitosan (CS) is one of the most promising polymers due to its biocompatibility, biodegradability, and natural abundance. However, its poor mechanical and barrier properties make it difficult to satisfy a wide range of applications. Herein, borate ions, originating from the hydrolysis of sodium tetraborate decahydrate (borax), have been used to crosslink chitosan and graphene oxide (GO) nanocomposites. Chitosan films consisting of 1.0 wt% boron and 1.0 wt% GO exhibit a significant improvement in both the toughness and oxygen barrier properties compared to pristine chitosan. In particular the tensile strength of the samples after thermal treatment increases by ∼160% compared to pristine chitosan, whereas their oxygen permeability reduces by ∼90%. This is ascribed to the chemical crosslinking between chitosan and GO nanoplatelets through borate ions, as well as the formation of a layered morphology with graphene nanoplatelets oriented parallel to the sample surface. The exceptional robust and high gas barrier film has promising application in the packaging industry. The borate-crosslinking chemistry represents the potential strategy for improving properties of other polymer nanocomposites.

Towards the development of a novel bioinspired functional material: synthesis and characterization of hybrid TiO2/DHICA-melanin nanoparticles.

A large number of recent literature data focus on modification/modulation of surface chemistry of inorganic materials in order to improve their functional properties. Melanins, a wide class of natural pigments, are recently emerging as a powerful organic component for developing bioinspired active material for a large number of applications from organoelectronics to bioactive compounds. Here we report the use of the approach referred as "chimie douce", involving in situ formation of the hybrids through reactions of precursors under mild conditions, to prepare novel hybrid functional architectures based on eumelanin like 5,6 dihydroxyindole-2-carboxylic acid (DHICA) polymer and TiO2. Two synthesis procedures were carried out to get DHICA-melanin coated TiO2 nanoparticles as well as mixed DHICA/TiO2 hybrid nanostructures. Such systems were characterized through EPR, FT-IR and fluorescence spectroscopy, thermogravimetric analysis (TGA), X-ray diffraction (XRD), and TEM microscopy in order to assess the effect of synthesis path as well as of DHICA content on structural, morphological and optical properties of TiO2 nanostructures. In particular, EPR, FT-IR spectra and TGA analysis confirmed the presence of DHICA-melanin in these samples. TEM measurements indicated the formation of the nanoparticles having relatively narrow size distribution with average particle size of about 10nm. DHICA-melanin does act as a morphological agent affecting morphology of hybrid nanostructures. XRD analysis proved that TiO2 hybrid nanoparticles kept anatase structures for DHICA-melanin contents within the range of investigated compositions, i.e. up to 50% wt/wt.

Heparin conjugated silica nanoparticle synthesis.

We report on a facile method towards a synthesis of novel hybrid heparin silica nanoparticles involving a modification of the Stober method. Tetrapropyl orthosilicate (TPOS) was used instead of the traditional TEOS or TMOS; by this way we could overcome the solubility problems of heparin in ethanol and exploit the good solubility of heparin in proper isopropanol-water mixtures. Aminopropyl triethoxysilane (APTS) was also used to have a good link of heparin to silica particles. SEM, DLS, FTIR and NMR proved that we did find conditions in which heparin conjugated silica particles were produced. Thermogravimetry allowed to evaluate the heparin/silica weight ratio to be 0.61. The efficiency of heparin binding to the particles was appreciated to be 35wt.%.