Application of different instrumental techniques to the selective evaluation of bio-sensible compounds in foodstuff of animal and vegetable origin

This PhD thesis describes the application of some instrumental analytical techniques suitable to the study of fundamental food products for the human diet, such as: extra virgin olive oil and dairy products. These products, widely spread in the market and with high nutritional values, are increasingly recognized healthy properties although their lipid fraction might contain some unfavorable components to the human health. The research activity has been structured in the following investigations: “Comparison of different techniques for trans fatty acids analysis” “Fatty acids analysis of outcrop milk cream samples, with particular emphasis on the content of Conjugated Linoleic Acid (CLA) and trans Fatty Acids (TFA), by using 100m high-polarity capillary column” “Evaluation of the oxidited fatty acids (OFA) content during the Parmigiano-Reggiano cheese seasoning” “Direct analysis of 4-desmethyl sterols and two dihydroxy triterpenes in saponified vegetal oils (olive oil and others) using liquid chromatography-mass spectrometry” “Quantitation of long chain poly-unsatured fatty acids (LC-PUFA) in base infant formulas by Gas Chromatography, and evaluation of the blending phases accuracy during their preparation” “Fatty acids composition of Parmigiano Reggiano cheese samples, with emphasis on trans isomers (TFA)”

Liquid crystal polymers: macromolecular design for enhanced performances

During this work, done mainly in the laboratories of the department of Industrial Chemistry and Materials of the University of Bologna but also in the laboratories of the Carnegie Mellon University in collaboration with prof. K. Matyjaszewski and at the university of Zaragoza in collaboration with prof. J. Barberá, was focused mainly on the synthesis and characterization of new functional polymeric materials. In the past years our group gained a deep knowledge about the photomodulation of azobenzene containing polymers. The aim of this thesis is to push forward the performances of these materials by the synthesis of well defined materials, in which, by a precise control over the macromolecular structures, better or even new functionality can be delivered to the synthesized material. For this purpose, besides the rich photochemistry of azoaromatic polymers that brings to the application, the control offered from the recent techniques of controlled radical polymerization, ATRP over all, gives an enormous range of opportunity for the developing of a new generation of functional materials whose properties are determinate not only by the chemical nature of the functional center (e.g. azoaromatic chromophore) but are tuned and even amplified by a synergy with the whole macromolecular structure. Old materials in new structures. In this contest the work of this thesis was focused mainly on the synthesis and characterization of well defined azoaromatic polymers in order to establish, for the first time, precise structure-properties correlation. In fact a series of well defined different azopolymers, chiral and achiral, with different molecular weight and highly monodisperse were synthesized and their properties were studied, in terms of photoexpansion and photomodulation of chirality. We were then able to study the influence of the macromolecular structure in terms of molecular weight and ramification on the studied properties. The huge amount of possibility offered by the tailoring of the macromolecular structure were exploited for the synthesis of new cholesteric photochromic polymers that can be used as a smart label for the certification of the thermal history of any thermosensitive product. Finally the ATRP synthesis allowed us to synthesize a total new class of material, named molecular brushes: a flat surface covered with an ultra thin layer of polymeric chain covalently bond onto the surface from one end. This new class of materials is of extreme interest as they offer the possibility to tune and manage the interaction of the surface with the environment. In this contest we synthesized both azoaromatic surfaces, growing directly the polymer from the surface, and mixed brushes: surfaces covered with incompatible macromolecules. Both type of surfaces acts as “smart” surfaces: the first it is able to move the orientation of a LC cell by simply photomodulation and, thanks to the robustness of the covalent bond, can be used as a command surface overcoming all the limitation due to the dewetting of the active layer. The second type of surface, functionalized by a grafting-to method, can self assemble the topmost layer responding to changed environmental conditions, exposing different functionality according to different environment.

Bioactive and toxic compounds in different foodstuffs: analytical techniques and sensory analysis

Foods that provide medical and health benefits or have a role in disease risk prevention are termed functional foods. The functionality of functional foods is derived from bioactive compounds that are extranutritional constituents present in small quantities in food. Bioactive components include a range of chemical compounds with varying structures such as carotenoids, flavonoids, plant sterols, omega-3 fatty acids (n-3), allyl and diallyl sulfides, indoles (benzopyrroles), and phenolic acids. The increasing consumer interest in natural bioactive compounds has brought about a rise in demand for these kinds of compounds and, in parallel, an increasing number of scientific studies have this type of substance as main topic. The principal aim of this PhD research project was the study of different bioactive and toxic compounds in several natural matrices. To achieve this goal, chromatographic, spectroscopic and sensorial analysis were performed. This manuscript reports the main results obtained in the six activities briefly summarized as follows: • SECTION I: the influence of conventional packaging on lipid oxidation of pasta was evaluated in egg spaghetti. • SECTION II: the effect of the storage at different temperatures of virgin olive oil was monitored by peroxide value, fatty acid activity, OSI test and sensory analysis. • SECTION III: the glucosinolate and phenolic content of 37 rocket salad accessions were evaluated, comparing Eruca sativa and Diplotaxis tenuifolia species. Sensory analysis and the influence of the phenolic and glucosinolate composition on sensory attributes of rocket salads has been also studied. • SECTION IV: ten buckwheat honeys were characterised on the basis of their pollen, physicochemical, phenolic and volatile composition. • SECTION V: the polyphenolic fraction, anthocyanins and other polar compounds, the antioxidant capacity and the anty-hyperlipemic action of the aqueous extract of Hibiscus sabdariffa were achieved. • SECTION VI: the optimization of a normal phase high pressure liquid chromatography–fluorescence detection method for the quantitation of flavanols and procyanidins in cocoa powder and chocolate samples was performed.

Electric techniques for the assessment of quality parameters of foodstuffs

In food industry, quality assurance requires low cost methods for the rapid assessment of the parameters that affect product stability. Foodstuffs are complex in their structure, mainly composed by gaseous, liquid and solid phases which often coexist in the same product. Special attention is given to water, concerned as natural component of the major food product or as added ingredient of a production process. Particularly water is structurally present in the matrix and not completely available. In this way, water can be present in foodstuff in many different states: as water of crystallization, bound to protein or starch molecules, entrapped in biopolymer networks or adsorbed on solid surfaces of porous food particles. The traditional technique for the assessment of food quality give reliable information but are destructive, time consuming and unsuitable for on line application. The techniques proposed answer to the limited disposition of time and could be able to characterize the main compositional parameters. Dielectric interaction response is mainly related to water and could be useful not only to provide information on the total content but also on the degree of mobility of this ubiquitous molecule in different complex food matrix. In this way the proposal of this thesis is to answer at this need. Dielectric and electric tool can be used for the scope and led us to describe the complex food matrix and predict food characteristic. The thesis is structured in three main part, in the first one some theoretical tools are recalled to well assess the food parameter involved in the quality definition and the techniques able to reply at the problem emerged. The second part explains the research conducted and the experimental plans are illustrated in detail. Finally the last section is left for rapid method easily implementable in an industrial process.

Development and optimization of techniques and design parameters for the engineering of atmospheric pressure plasma devices for biomedical applications and plasma medicine

In the last decades, the possibility to generate plasma at atmospheric pressure gave rise to a new emerging field called plasma medicine; it deals with the application of cold atmospheric pressure plasmas (CAPs) or plasma-activated solutions on or in the human body for therapeutic effects. Thanks to a blend of synergic biologically active agents and biocompatible temperatures, different CAP sources were successfully employed in many different biomedical applications such as dentistry, dermatology, wound healing, cancer treatment, blood coagulation, etc.… Despite their effectiveness has been verified in the above-mentioned biomedical applications, over the years, researchers throughout the world described numerous CAP sources which are still laboratory devices not optimized for the specific application. In this perspective, the aim of this dissertation was the development and the optimization of techniques and design parameters for the engineering of CAP sources for different biomedical applications and plasma medicine among which cancer treatment, dentistry and bioaerosol decontamination. In the first section, the discharge electrical parameters, the behavior of the plasma streamers and the liquid and the gas phase chemistry of a multiwire device for the treatment of liquids were performed. Moreover, two different plasma-activated liquids were used for the treatment of Epithelial Ovarian Cancer cells and fibroblasts to assess their selectivity. In the second section, in accordance with the most important standard regulations for medical devices, were reported the realization steps of a Plasma Gun device easy to handle and expected to be mounted on a tabletop device that could be used for dental clinical applications. In the third section, in relation to the current COVID-19 pandemic, were reported the first steps for the design, realization, and optimization of a dielectric barrier discharge source suitable for the treatment of different types of bioaerosol.