Technological processes study for high value health ingredients and foods production

This PhD thesis describes set up of technological models for obtaining high health value foods and ingredients that preserve the final product characteristics as well as enrich with nutritional components. In particular, the main object of my research has been Virgin Olive Oil (VOO) and its important antioxidant compounds which differentiate it from all other vegetables oils. It is well known how the qualitative and quantitative presence of phenolic molecules extracted from olives during oil production is fundamental for its oxidative and nutritional quality. For this purpose, agronomic and technological conditions of its production have been investigated. It has also been examined how this fraction can be better preserved during storage. Moreover, its relation with VOO sensorial characteristics and its interaction with a protein in emulsion foods have also been studied. Finally, an experimental work was carried out to determine the antioxidative and heat resistance properties of a new antioxidant (EVS-OL) when used for high temperature frying such as is typically employed for the preparation of french fries. Results of the scientific research have been submitted for a publication and some data has already been published in national and international scientific journals.

Materiali Ceramici per Edilizia con Funzionalità Fotocatalitica

This thesis wad aimed at the study and application of titanium dioxide photocatalytic activity on ceramic materials. As a matter of fact, photocatalysis is a very promising method to face most of the problems connected with the increasing environmental pollution. Furthermore, titanium dioxide, in its anatase crystallographic phase, is one of the most investigated photocatalytic material and results to be perfectly compatible with silicate body mixes. That goal was pursued by two different strategies: 1. the addition to a body mix used for heavy clay products of several titania powders, with different mean crystallite size, surface area, morphology and anatase/rutile ratio and a titania nanosuspension as well. The titania addition followed two procedures: bulk and spray addition over the ceramic samples surface. Titania was added in two different percentages: 2.5 and 7.5 wt.% in both of the methods. The ceramic samples were then fired at three maximum temperatures: 900, 950 and 1000 °C. Afterwards, the photocatalytic activity of the prepared ceramic samples was evaluated by following the degradation of an organic compound in aqueous medium, under UV radiation. The influence of titania morphological characteristics on the photoactivity of the fired materials was studied by means of XRD and SEM observations. The ceramic samples, sprayed with a slip containing 7.5 wt.% of titania powder and fired at 900 °C, have the best photoactivity, with a complete photo-decomposition of the organic compound. At 1000 °C no sample acted as a photocatalyst due to the anatase-to-rutile phase transformation and to the reaction between titania and calcium and iron oxides in the raw materials. 2. The second one foresaw the synthesis of TiO2-SiO2 solid solutions, using the following stoichiometry: Ti1-xSixO2 where x = 0, 0.1, 0.3 and 0.5 atoms per formula unit (apfu). The mixtures were then fired following two thermal cycles, each with three maximum temperatures. The effect of SiO2 addition into the TiO2 crystal structure and, consequently, on its photocatalytic activity when fired at high temperature, was thoroughly investigated by means of XRD, XPS, FE-SEM, TEM and BET analysis. The photoactivity of the prepared powders was assessed both in gas and liquid phase. Subsequently, the TiO2-SiO2 solid solutions, previously fired at 900 °C, were sprayed over the ceramic samples surface in the percentage of 7.5 wt.%. The prepared ceramic samples were fired at 900 and 1000 °C. The photocatalytic activity of the ceramic samples was evaluated in liquid phase. Unfortunately, that samples did not show any appreciable photoactivity. In fact, samples fired at 900 °C showed a pretty low photoactivity, while the one fired at 1000 °C showed no photoactivity at all. This was explained by the excessive coarsening of titania particles. To summarise, titania particle size, more than its crystalline phase, seems to have a relevant role in the photocatalytic activity of the ceramic samples.

Sistemi adesivi con applicazioni in campo biomedicale

Polymeric adhesives have been used for many applications like suture and embolization, instead of classic surgical methods or as for dental uses. In this work both subjects have been investigated and the results separated in two parts. In the first, new dentinal adhesives with different polymerizable groups (methacrylic or vinyl-ethereal) were synthesized. A low sensitivity to hydrolysis and equal or enhanced properties, compared to existing commercial products, were considered essentials. Moreover, these monomers need to polymerize by radical photopolymerization and functional groups of different characteristics were tested. All these products were characterized by microtensile bond strength test to determine the bonding strength between the adhesive and tooth. Concerning embolization, cyanoacrylates are nowadays the most-used adhesives in surgery. Thus, they must respond to several requirements. For instance, polymerization time and adhesive strength need to be low, to avoid diffusion of the products in the body and adhesion to the catheter. In order to overcome these problems we developed new cyanoacrylates, which practically instantly polymerize upon contact with blood but do not demonstrate strong adhesion to the catheter, thank to the presence of fluorine atoms, linked to the ester chain. The synthesis of these products was carried out in several steps, such as the depolymerization of the corresponding oligomers at high temperature in acid conditions. Two types of adhesion strengths were determined. Bonding strength between human veins and a microcatheter was determined in vitro by using organic materials as the most realistic model. Another test, on two layers of skin, was conducted to verify the possible use of these new cyanoacrylates as a glue for sutures. As a conclusion, we were able to demonstrate that some of the prepared monomers posses adhesive strength and polymerization time lower than the commercial product Glubran2.

Sustainable inorganic Binders and Their Applications in Building Engineering: A Green Alternative to Ordinary Portland Cement

In the last decades, the building materials and construction industry has been contributing to a great extent to generate a high impact on our environment. As it has been considered one of the key areas in which to operate to significantly reduce our footprint on environment, there has been widespread belief that particular attention now has to be paid and specific measures have to be taken to limit the use of non-renewable resources.The aim of this thesis is therefore to study and evaluate sustainable alternatives to commonly used building materials, mainly based on ordinary Portland Cement, and find a supportable path to reduce CO2 emissions and promote the re-use of waste materials. More specifically, this research explores different solutions for replacing cementitious binders in distinct application fields, particularly where special and more restricting requirements are needed, such as restoration and conservation of architectural heritage. Emphasis was thus placed on aspects and implications more closely related to the concept of non-invasivity and environmental sustainability. A first part of the research was addressed to the study and development of sustainable inorganic matrices, based on lime putty, for the pre-impregnation and on-site binding of continuous carbon fiber fabrics for structural rehabilitation and heritage restoration. Moreover, with the aim to further limit the exploitation of non-renewable resources, the synthesis of chemically activated silico-aluminate materials, as metakaolin, ladle slag or fly ash, was thus successfully achieved. New sustainable binders were hence proposed as novel building materials, suitable to be used as primary component for construction and repair mortars, as bulk materials in high-temperature applications or as matrices for high-toughness fiber reinforced composites.

Effects of Global Warming on Berry Composition of cv. Sangiovese: Biochemical and Molecular Aspects and Agronomical Adaptation Approaches

Wine grape must deal with serious problems due to the unfavorable climatic conditions resulted from global warming. High temperatures result in oxidative damages to grape vines. The excessive elevated temperatures are critical for grapevine productivity and survival and contribute to degradation of grape and wine quality and yield. Elevated temperature can negatively affect anthocyanin accumulation in red grape. Particularly, cv. Sangiovese was identified to be very sensitive to such condition. The quantitative real-time PCR analysis showed that flavonoid biosynthetic genes were slightly repressed by high temperature. Also, the heat stress repressed the expression of the transcription factor “VvMYBA1” that activates the expression of UFGT. Moreover, high temperatures had repressing effects on the activity of the flavonoids biosynthetic enzymes “PAL” and “UFGT”.Anthocyanin accumulation in berry skin is due to the balance between its synthesis and oxidation. In grape cv. Sangiovese, the gene transcription and activity of peroxidases enzyme was elevated by heat stress as a defensive mechanism of ROS-scavenging. Among many isoforms of peroxidases genes, one gene (POD 1) was induced in Sangiovese under thermal stress condition. This gene was isolated and evaluated via the technique of genes transformation from grape to Petunia. Reduction in anthocyanins concentration and higher enzymatic activity of peroxidase was observed in POD 1 transformed Petunia after heat shock compared to untrasformed control. Moreover, in wine producing regions, it is inevitable for the grape growers to adopt some adaptive strategies to alleviate grape damages to abiotic stresses. Therefore, in this thesis, the technique of post veraison trimming was done to improve the coupling of phenolic and sugar ripening in Vitis vinifera L. cultivar Sangiovese. Trimming after veraison showed to be executable to slow down the rate of sugar accumulation in grape (to decrease the alcohol potential in wines) without evolution of the main berry flavonoids compounds.

Effects of temperature and acidity on Mediterranean benthic calcifiers, in the face of globale climate change

The Mediterranean Sea is expected to react faster to global change compared to the ocean and is already showing more pronounced warming and acidification rates. A study performed along the Italian western coast showed that porosity of the skeleton increases with temperature in the zooxanthellate (i.e. symbiotic with unicellular algae named zooxanthellae) solitary scleractinian Balanophyllia europaea while it does not vary with temperature in the solitary non-zooxanthellate Leptopsammia pruvoti. These results were confirmed by another study that indicated that the increase in porosity was accompanied by an increase of the fraction of the largest pores in the pore-space, perhaps due to an inhibition of the photosynthetic process at elevated temperatures, causing an attenuation of calcification. B. europaea, L. pruvoti and the colonial non-zooxanthellate Astroides calycularis, transplanted along a natural pH gradient, showed that high temperature exacerbated the negative effect of lowered pH on their mortality rates. The growth of the zooxanthellate species did not react to reduced pH, while the growth of the two non-zooxanthellate species was negatively affected. Reduced abundance of naturally occurring B. europaea, a mollusk, a calcifying and a non-calcifying macroalgae were observed along the gradient while no variation was seen in the abundance of a calcifying green alga. With decreasing pH, the mineralogy of the coral and mollusk did not change, while the two calcifying algae decreased the content of aragonite in favor of the less soluble calcium sulphates and whewellite (calcium oxalate), possibly as a mechanism of phenotypic plasticity. Increased values of porosity and macroporosity with CO2 were observed in B. europaea specimens, indicating reduces the resistance of its skeletons to mechanical stresses with increasing acidity. These findings, added to the negative effect of temperature on various biological parameters, generate concern on the sensitivity of this zooxanthellate species to the envisaged global climate change scenarios.