Noemi Baldino

Graphene-Based Nafion Nanocomposite Membranes: Enhanced Proton Transport and Water Retention by Novel Organo-functionalized Graphene Oxide Nanosheets

Novel nanostructured organo-modified layered materials based on graphene oxide carrying various hydrophilic functional groups (-NH(2), -OH, -SO(3)H) are prepared and tested as nanofillers for the creation of innovative graphene-based Nafion nanocomposites. The hybrid membranes are characterized by a combination of analytical techniques, which show that highly homogeneous exfoliated nanocomposites are created. The pulsed field gradient NMR technique is used to measure the water self-diffusion coefficients. Remarkable behavior at temperatures up to 140 °C is observed for some composite membranes, thereby verifying the exceptional water retention property of these materials. Dynamic mechanical analysis shows that hybrid membranes are much stiffer and can withstand higher temperatures than pure Nafion.

Malvidin, a red wine polyphenol, modulates mammalian myocardial and coronary performance and protects the heart against ischemia/reperfusion injury.

A moderate red wine consumption and a colored fruit-rich diet protect the cardiovascular system, thanks to the presence of several polyphenols. Malvidin-3-0-glucoside (malvidin), an anthocyanidine belonging to polyphenols, is highly present in red grape skin and red wine. Its biological activity is poorly characterized, although a role in tumor cell inhibition has been found. To analyze whether and to which extent, like other food-derived polyphenols, malvidin affects the cardiovascular function, in this study, we have performed a quantitative analysis by high-performance liquid chromatography of polyphenolic content of red grape skins extract, showing that it contains a high malvidin amount (63.93 ±12.50 mg/g of fresh grape skin). By using the isolated and Langendorff perfused rat heart, we found that the increasing doses (1-1000 ng/ml) of the extract induced positive inotropic and negative lusitropic effects associated with coronary dilation. On the same cardiac preparations, we observed that malvidin (10(-10)-10(-6) mol/L) elicited negative inotropism and lusitropism and coronary dilation. Analysis of mechanism of action revealed that malvidin-dependent cardiac effects require the activation of the phosphatidylinositol 3-kinase (PI3K)/nitric oxide (NO)/cGMP/PKG pathway and are associated with increased intracellular cGMP and the phosphorylation of endothelial NO synthase (eNOS), PI3K-AKT, ERK1/2, and GSK-3β. AKT and eNOS phosphorylation was confirmed in human umbilical vein endothelial cell. We also found that malvidin act as a postconditioning agent, being able to elicit cardioprotection against ischemia/reperfusion damages. Our results show the cardioactivity of polyphenols-rich red grape extracts and indicate malvidin as a new cardioprotective principle. This is of relevance not only for a better clarification of the beneficial cardiovascular effects of food-derived polyphenols but also for nutraceutical research.

Olive oil/policosanol organogels for nutraceutical and drug delivery purposes

Low molecular weight organogels are semisolid systems structured by the assembly of molecules that crystallise under suitable process conditions. The inner microstructure of organogels is made up of a 3-D network, in which both an organic liquid solvent and other dispersed particles can be entrapped. In this work, olive oil organogels, structured from policosanol (a nutraceutical mixture of fatty alcohols), were studied in order to obtain the best formulation for producing a support for delivery of lipophilic agents (namely ferulic Acid) via oral administration. A rheological optimisation of the olive oil-policosanol organogel was first of all performed with Step Shear Rate Temperature Ramp tests. This provided important information on the policosanol fraction to be added to the system and on the onset of crystallisation temperature, an indirect measurement of the system melting point. It was found that a policosanol weight percentage of 0.03 was suitable to obtain contemporary semisolid organogels, consistent enough and thermally stable for human ingestion. In vitro tests on organogels loaded with ferulic acid were also carried out in order to simulate the oral intake of the nutraceutical compound. This evidenced a release mechanism determined by both erosion and diffusion; a good performance of gels and their ability to control the release rate through the degree of structuration were also observed.

The effects of intermolecular interactions on the physical properties of organogels in edible oils

The microstructure of organogels based on monoglycerides of fatty acids (MAGs) and policosanol and on different edible oils was investigated by using different techniques (calorimetry, nuclear magnetic resonance, infrared spectroscopy, rheology, polarized light microscopy) towards a better understanding and control of the oil gelation phenomena. Dynamic moduli were related via a fractal model to microstructural information such as solid content and fractal dimension. Infrared spectroscopy evidenced that network structure in MAGs gel is mainly due to hydrogen bonding, whereas in policosanol system is mainly given by van der Waals interactions. Because of the different relative contribution of molecular interactions, the investigated organogelators exhibit a distinguished macroscopic behavior. MAGs are sensitive to the utilized oil and structuration occurs quickly, even though at a temperature lower than policosanol. Policosanol organogels exhibit a behavior independent of the used oil and a slower gelation rate, as a result of the weaker van der Waals interactions. Nevertheless, at lower concentration a stronger final gel is obtained, probably due to of the large number of interactions arising among the long alkyl chains of the fatty alcohols. Obtained results evidenced that policosanol is very effective in gelation of different oils and seems promising for potential commercial uses.

Olive oil and hyperthermal water bigels for cosmetic uses.

Bigels are biphasic systems produced with an organogel (or oleogel) and a hydrogel mixed together at high shear rates. These systems are promising for different uses, among them the formulation of new cosmetic matrices for cosmetic agents delivery is under investigation. In the present paper, a common cosmetic formulation for skin care was enriched with increasing fractions of monoglycerides of fatty acids/olive oil organogels, in order to understand the rheology and the microstructure of these systems. Small amplitude oscillation tests, NMR-self diffusion analysis, contrast phase microscopy and electric conductivity confirmed that the addition of the organogel caused a microstructural change of the starting material, which turned from O/W to a more complex system where, probably, a matrix-in-matrix structure is present at the highest fractions of added organogel.

Rheological and 1H-NMR Spin-Spin Relaxation Time for the Evaluation of the Effects of PPA Addition on Bitumen

Bitumens are currently modelled as a colloidal system and are the most used materials for road paving. Despite this large application, asphalts are still affected by some inconveniences that bring to road deterioration. This is prevalently due to temperature cycling which is related to the given local climate conditions and to the incident traffic load. In the last decades bitumen performances have been improved by means of different types of additives in order to match various expectations. This improvement is often the result of the indications given by traditional empirical standardized tests like penetration grade, temperature ductility and Fraas breaking point. The comprehension of the chemical mechanism that regulates the action of the used additives can greatly help in designing new and better performance materials. By means of a Stress Controlled Rheometer we present a laboratory evaluation of the rheological properties of a 70/100 bitumen which has been doped by different percentage of Polyphosphoric acid (PPA). In addition 1H-NMR measurements of proton transverse relaxation time (T2) have been exploited in order to corroborate the rheological data. As a novel approach to the knowledge of bitumen macro-structures, we applied an Inverse Laplace Transform (ILT) to the measured echo decay. The results show the effect of PPA addition on bitumen mechanical behaviour.

Rheological investigation of pectin-based emulsion gels for pharmaceutical and cosmetic uses

Emulsion gels are structured emulsions suitable for different uses for their specific behaviour, which is strongly dependent on the characteristics of the gelled dispersing phase. Therefore, it is important to adopt the specific gelling agent to tune the final emulsion rheological behaviour properly. Pectin is extremely interesting among potential hydrophilic gelling agents owing to its specific characteristics. In the present work, four different low-methoxyl pectins were adopted to prepare gels to be used as the dispersing phase in cosmetic or pharmaceutical emulsion gels. The rheological characterisation of pectin gels, prepared at room temperature to avoid the damage to potential thermolabile components, was carried out with small amplitude oscillations. The obtained gels were used, together with a common non-ionic surfactant (Tween 60), to prepare olive oil emulsion gels suitable to design new cosmetic products. A simple empirical model, proposed to relate the emulsion complex modulus to the oil fraction and properties of the dispersing phase, has shown itself to be a potentially useful tool to design formulations with desired properties.

A rheological and microstructural characterisation of bigels for cosmetic and pharmaceutical uses

Bigels are biphasic systems formed by water-based hydrogels and oil-based organogels, mainly studied, in the last few years, for pharmaceutical and cosmetic application focused on the controlled delivery of both lipophilic and hydrophilic active agents. The rheological properties of bigels depend on both the amount and the rheological characteristics of single structured phases. Moreover, it can be expected that, at large fractions of one of the starting gels, systems more complex than oil-in-water or water-in-oil can be obtained, yielding bicontinuous or matrix-in-matrix arrangement. Model bigels were investigated from a microstructural (i.e. microscopy and electrical conductivity tests) and rheological point of view. The hydrogel was prepared by using a low-methoxyl pectin whereas the organogel was prepared by using olive oil and, as gelator, a mixture of glyceryl stearate and policosanol. Model bigels were obtained by increasing the amount of organogel mixed with the hydrogel, and microstructural characterisation evidenced an organogel-in-hydrogel behaviour for all investigated samples, even though at the highest organogel content a more complex structure seems to arise. A semi-empirical model, based on theoretical equations developed for suspensions of elastic spheres in elastic media, was proposed to relate bigel rheological properties to single phase properties and fractions.

Rheological Characterisation of Dairy Emulsions For Cold Foam Applications

Dairy foams are complex aerated materials where the liquid matrix is an emulsion made by oil droplets dispersed in a water system. An innovative application of these systems leads to an interesting product derived from instant whipped creams that are stored and consumed at low temperatures (typically between −4 and −18°C) like an ice cream. This novel product requires a specific texture due to the particular conditions related to its consumption. In the present work, the effects of some relevant ingredients (emulsifiers, sugars, and fats) on rheological properties and freezing temperature of dairy emulsions were investigated. Samples were prepared on lab scale and it was found that structure extension is affected strongly by stabilizers (carrageenan and guar gum) and in a lower measure by fat content. As far as freezing point is concerned a significant effect only of sugars (type and amount) and fats was measured. A formulation having interesting properties for low temperature applications was obtained and it was prepared on a pilot plant scale to investigate the potential effects of the industrial production. These samples exhibited a relevant reduction in both viscosity and elasticity; it was speculated that this effect could be attributed to the whey protein thermal damage (induced by the UHT treatment) and to the homogenisation conditions, different from those adopted on lab scale.

Influence of Fat Content on Chocolate Rheology

Molten chocolate is a suspension having properties strongly affected by particle characteristics including not only the dispersed particles but also the fat crystals formed during chocolate cooling and solidification. Even though chocolate rheology is extensively studied, mainly viscosity at high temperature was determined and no information on amount and type of fat crystals can be detected in these conditions. However chocolate texture and stability is strongly affected by the presence of specific crystals. In this work a different approach, based on creep test, was proposed to characterize chocolate samples at typical process temperatures (approximately 30 °C). The analysis of compliance, as time function, at short times enable to evaluate a material “elasticity” related to the solid‐like behavior of the material and given by the differential area between the Newtonian and the experimental compliance. Moreover a specific time dependent elasticity was defined as the ratio between the differential area, ...