Courses

The aim of the course is to provide the basic knowledge and possible applications of EPR spectroscopy to organic radical and paramagnetic metal complexes.
In the first part of the course the Zeeman effect, selection rules, X- and Q-band spectra, nuclear hyperfine interaction, spin Hamiltonian parameters (g and A) will be presented and applied to systems with I = 1/2 and 1. The EPR spectra of organic radicals containing one or more sets of equivalent protons will be discussed.
In the second part, the isotropic and anisotropic spectra of metal complexes will be illustrated, in particular of V(IV), Cr(V) and Cu(II). Next, the zero field splitting and the spectra of metal complexes with more than one unpaired electron (S ³ 1) will be presented with special reference to the paramagnetic dinuclear complexes.
In the third part, some biochemical applications, such the interaction of metal complexes with several bioligands and the antioxidant activity of chemical compounds, will be treated.
Finally, the simulation of EPR spectra and theoretical prediction of the hyperfine coupling constant by DFT methods will be discussed.
Two brief exercitations, one with a computer and one in the laboratory, will also be performed.

Renewable resources, their use and their modification are involved in many important processes that significantly affect the daily life. In particular, renewable resources are crucial in searching for alternatives
to fossil-based raw materials and energy. The concept of biorefinery ‒ which, unlike petrochemical refineries, uses biomass to produce energy and chemicals ‒ fits into this context. Aim of the course is to
deal with:
– the production of chemicals from biomass, whose composition, main uses, pre-treatment and conversion
processes will be illustrated.
– the development of biorefineries, with examples of first generation and advanced biorefineries
(lignocellulosic biorefinery, green biorefinery, fuel-oriented biorefinery, etc.)

Introduction to Molecular Mechanical Force Fields: Inter and intramolecular interactions, Conceptual models to build a force field. Brief historical notes. Force field Parameters. Typical force fields for different chemical systems.
Force field based Methods for studying molecules and matter: The potential energy
surface (PES). Energy Minimization. Conformational analysis. Particle-based simulation methods. Deterministic and stochastic simulations. Monte Carlo simulations (MC). Classic Molecular Dynamics (MD), Classical all-atom MD. Coarse graining simulations. Different
MD techniques.
Analysis of Computer Simulations results: Visualization tools. Introduction to the use of selected softwares (Avogadro, VMD). Structural and dynamical properties. Energy. Radial Distribution Functions (RDFs), Spatial Distribution Functions (SDFs), Time correlation functions. Diffusion. Pros and Cons of MD Building the initial structure. Software to build from scratch, structural data bases.
Solvation: molecules in solution and mixtures, Solubility, preferential solvation.
Tutorial on the use of the amber suite of programs.

The course has the purpose to allow the PhD student to use light scattering techniques autonomously for the characterization of his/her own samples. The course will initially recall the main concepts of colloidal systems and their stability in polar solvents (Brownian motion, electrokinetic theory, DLVO theory) and of light scattering theories (Rayleigh theory, Mie theory). Then, the light scattering techniques will be presented paying attention to the information obtainable by each technique, that is: virial coefficients and average molecular mass (static light scattering); electrophoretic mobility and zeta potential (electrophoretic light scattering); diffusion coefficients and hydrodynamic diameter (dynamic light scattering). In the practical part of the course the students will analyse their own samples with SLS, DLS and ELS techniques. They will be trained to the interpretation of the obtained results like, for example, to understand the difference among different particle size distributions obtained in intensity/volume/number modalities.

The course will focus on the development and use of modern photochemistry and photocatalysis processes (from technological applications to organic synthesis), with particular attention to the use of visible light.
The introductory part of the course will cover the definition of the concept of photochemistry and photocatalysis (both in the homogeneous and heterogeneous phase) and will be accompanied by the definition of the key parameters that characterize these processes. Subsequently, some historical notes will be offered regarding the first works related to the development of photochemical transformation of organic molecules and the recent investigations on photocatalysis. This will be followed by a description of the main types of photocatalysts (complexes based on transition metals, photoorganocatalysts, inorganic derivatives and particles of semiconductor material) and of the reaction mechanisms associated with them.
The central part of the course will cover the applications of the photocatalytic approach, such as the development of systems for the degradation of pollutants (eg treatment of wastewater containing active ingredients of drugs) or for artificial photosynthesis. Particular attention will also be dedicated to the development of eco-sustainable synthetic procedures, giving ample space to the preparation of bioactive molecules and their functionalization. The last part of the course will finally be dedicated to the description of hybrid techniques, where photocatalysis has been coupled with other approaches, both in the synthetic field and in the application field (eg photoelectrochemical approaches for energy storage).

Purposes and utilities. Fundamental principles, ionization methods and sources, analyzers and detectors. Fragmentation pathways. Basic of sample introduction. Hard and soft techniques. Gas/mass. Mass liquid (Electrospray). High resolution mass spectrometry and tandem mass. Hybrid
instruments: Q-Tof, ORBITRAP
Laboratory: practical applications
Suggested books:
Application of Mass Spectrometry to Organic Stereochemisty Edited By J. S, Splittee. F, Turecek
Liquid Chromatography- Mass Spectrometry-Niessen.

Thermal analysis techniques (introduction)
Thermodynamic aspects (with particular reference to micro- and nanostructured materials)
Measurement of the temperature and of the energy developed by the Joule effect
Thermogravimetric analysis, TGA (with examples)
Differential thermal analysis, DTA (with examples)
Differential Scanning Calorimetry, DSC “heat flow” and “power compensation” calorimetry (with examples)
Simultaneous DSC and TG analysis (with examples)
Discussion of case studies
Observation, choice and preparation of a sample for thermal analysis in the Thermal Analysis Laboratory; use of the Pyris software for TGA / DSC measurement, methods of cleaning the sample holder , evaluation of experimental errors.

Chemistry, such as science and industry, has played and still has a key role in the development and
progress of humanity. Since the mid-seventies, humanity has exceeded a critical threshold and the demand for natural resources seems to be growing faster than our planet can regenerate and supply(ecological overshoot). Sustainable chemistry is at the heart of a revolution in the discipline that has the potential to do all of these. Sustainable and environmentally friendly development requires chemistry to play a leading role in transforming old technologies into cleaner processes and in designing new products and new eco-compatible processes. The overarching goals of green chemistry, which is more resource-efficient and inherently safer design of molecules, materials, products, and processes, can be achieved in a wide range of contexts. In this regard, this course intends to analyse in-depth some of the most important topics in green chemistry such as problems caused by volatile organic compounds (VOC), use of environmentally friendly organic reagents,
organic waste management and recycling, microwave reactions, and tribochemistry.

Chimica computazionale. Modellazione e simulazione. Approssimazione orbitalica, di Born-Oppenheimer e LCAO-MO. Metodi di struttura elettronica. Teoria Hartree-Fock. Periodicità, energia di ionizzazione, teorema di Koopmans. Richiami su diagrammi di Orbitali Molecolari per molecole/ioni biatomici mono- ed eteronucleari. Trattazione MO di molecole polinucleari (acqua, ammoniaca, fosfina). Convergenza: Self Consistent Field (SCF). Set di base. Potenziali relativistici (ECP). Metodi semiempirici. Metodi post-HF. Famiglie di metodi convergenti. Metodi basati sulla
teoria del funzionale di densità (DFT). Ottimizzazione di geometria. Sistemi di coordinate Cartesiane, interne, ridondanti. Matrice Z. Gaussian: struttura dei file di ingresso e lettura dei file di uscita. Esempi applicativi. Cenni all’impiego di S.O. Unix e Linux. Protocolli e modalità di gestione remota dei server di calcolo. Utilizzo di Molden, GaussView e Chemissian per l’analisi dei dati computazionali.

The PhD course shall provide the fundamentals of electrochemistry necessary for
investigating the durability of metallic materials in different environments and for the understanding and the application of the electrochemical techniques to characterize
corrosion and durability. The topics for the part “fundamentals” include:
electrochemistry of corrosion processes, thermodynamics and kinetics and mixed
potential theory. The most important corrosion protection methods, the formation
of a protective passive film (passivity) and its destruction by chloride ions leading to
localized corrosion are discussed. The part of “electrochemical techniques” treats
instrumentation (potential meter, potentiostat), the design of electrochemical cells and the requirements for reference electrodes used for all measurements. Among the techniques half-cell potential measurements, polarization resistance method (to
determine corrosion rate) and electrochemical impedance measurements are presented. Part of the course consists in laboratory experiments.

A physical property depends on the size of an object, if its size is comparable to a dimension relevant to that property. In magnetism typical sizes – as for example the dimension of magnetic domains or lengths of
exchange coupling interaction – are in the nanometer range. For this reason, starting some decades ago, great attention has been directed towards nanostructured magnetic materials where constituent phase or
grain structures are modulated on a length scale from 1 to 100 nm. In particular magnetic iron oxide nanoparticles with spinel structure have generated much interest because of their application, ferrofluid
technology, catalysts and biomedicine (drug delivery, contrast enhanced, MRI, Hyperthermia).
This course will discuss magnetic properties and chemical synthesis methods of spherical and Anisometric
iron oxide nanomaterials. After a brief introduction on the fundamental concept of magnetism, a careful description of the magnetism at the nanoscale (i.e. Supermagnetism) will be given. Then, trough several examples, the correlation between crystalline structure, morphology, and magnetic properties relevant to
several applications will be discussed. Particular Attention will also give nanostructured magnetic materials
for biomedical applications.

Surface area and porosity are very important characteristics of solids, especially when used as sorbents or catalysts. Such textural properties can be studied by means of physical adsorption of gases. After an introduction on textural properties of powders and porous solids and on the
principles related to the adsorption phenomenon, the course aims to deepen the application of physical adsorption of gases (mainly N2) for the assessment of the specific surface area and the study of characteristics of the porous system in powders and porous solids. The lectures are complemented by a laboratory session, at the end of which a final test is scheduled.

During the past twenty years, nanotechnologies have been one of the leading topics in advanced research due to the versatility and vast opportunities of application of nanomaterials, going from
space industry to biomedical uses. Metal nanoparticles are particularly interesting for their outstanding properties, that make them suitable tools in catalytic processes, sensing and theranostics, just to quote some. In this course, the synthesis, characterization, properties and
applications of metal (especially silver, gold, iron) nanoparticles will be examined and discussed,
and some time will be dedicated to the experimental work, by carrying out the preparation of silver nanoparticles through the so-called “green synthesis”, and their characterization via spectroscopic
techniques.

From the theoretical standpoint we start with the basics of Crystallography by analyzing and classifying
chemical, geometrical and symmetry of lattices and crystals. Later we examine the associated
reciprocal lattice following diffraction of coherent hard x-rays. The experimental approach will involve sample preparation, patterns collection, results interpretation at varying levels of complexity, by using
software available free-of-charge from the net or specific programs licensed to the department.  

Structure solution from powder diffraction data is closing the remaining gap between indexing and Rietveld refinement. This approach may represent an obliged step when the chemists synthesizes a single phase powdered substance without the possibility to grow a “single crystal” to be submitted to the classical X-ray procedure. With a powder the X-ray experiment supply a one dimensional reciprocal space image of a 3-D representation. The steps back to the 3-D reciprocal space are obtained throughout the indexing approach, for which several programs free-of-charge were made available from literature of powder crystallography.
After determination of the unit cell lattice parameters, the Bravais lattice and space group determination may be surmised from analysis of systematic absences conducting to few candidates.
During the course we will combine the innovative concept of the commercial software Endeavour and its elaborate user interface trying solution of small to medium sized crystal structures from powder at an almost routine process, both for organic and for inorganic materials.
The structure solution is performed using a special variant of the “direct-space” approach, namely a combined global optimization of the difference between experimental and calculated data intensity.

This course introduces concepts from statistical mechanics and quantum electrodynamics that lie behind our understanding of the behaviour of interfaces. We discuss adsorption of ions, origins of the van der Waals force, stabilisation of thin films, and forces between particles and surfaces. Topics covered include the role of the chemical potential of ions
– ion-ion correlations
– the relationship between optical spectra and van der Waals forces
-the impact of surface roughness on surface forces

The lectures and the laboratory exercises will take place either in February 2023 or in
June 2023 according to the students’ registrations.
The objective of this course is the development of the capability of the students in selecting the best analytical strategy for characterizing nanomaterials.
In the first part of the course the classification of the nanomaterials will be
presented together with the problems related to the sampling procedure and sample handling and mounting for the analysis (3 hours).
The second part will be dedicated to the analytical tools available for their
characterization: analytical methods based on relatively low-cost instruments (ATR
FTIR spectroscopy, ellipsometry and contact angle measurements) will be first
presented (3 hours), followed by methods requiring special instruments. Emphasis
will be put on Auger electron spectroscopy (AES) (2 hours), time-of-flight secondary
mass spectrometry (ToF SIMS) (2 hours), and atomic force microscopy (AFM) (2
hours). Methods for measuring nanolayer thicknesses (3 hours).
Visits to the labs will be complementary to the lectures.

The past few years have seen remarkable advances in the development of synthetic
methods that have made possible access to new chemical space and unusual systems that were previously inaccessible. An alternative way to rapidly increase the molecular complexity or to explore unique bond formations could be through the use of strained carbocycles. The use of this synthetic strategy has already been described by several authors as a powerful tool for the modular construction of complex target structures and in the total synthesis of natural products. The course will present the most significant and innovative aspects of the use of strained carbocycles in advanced organic synthesis, highlighting the most relevant information from recent literature and possible future developments in this field of research.

Regarding cancers will be described the tissue tumors, the antineoplastic agents including their chemicalstructures and their mechanism of action and supportive care.
About the rare diseases with CNS involvement and neurological disorders will be described the structure of the drugs and their mechanism of action.Maximum emphasis will be given to the latest approved or PHASE 3 drugs.The chemical synthesis and structure-activity relationships of all the most important drugs described will be illustrated.

This course provides the basics of x-ray photoelectron spectroscopy; special attention will be devoted to and to present the information achievable by this technique, starting by its application for the surface characterization of materials with application in materials science, environmental chemistry and cultural heritage.

If it will be possible, the PhD students will be involved also in laboratory practice: they will deal with the sample preparation for the XPS analyses, with the data recording and with data analysis and interpretation

Introduction to the course. Statistics and errors. Data pretreatment. Optimization methods: OVAT
(one variable at time) and ED (experimental Design). Modelling of the response surfaces and
artificial neural networks. Pattern recognition and analysis of the principal components (PCA).
Clustering techniques for classification. Identification of anomalous data and outliers. Validation
methods. Numerical exercises with PC.
Software
ORIGIN, SIMQA, R, PARVUS, Easy-ANN

The topic of this class will be on different types of soft matter-based nano-structures,possibly useful for nanomedicine applications, with a special emphasis on non-lamellarliquid crystalline nanoparticles. Following an initial discussion on what these kinds of nano-structures are, and with the help of examples taken from the literature, teaching will focuson the ways of preparation and physicochemical characterizations typically adopted forthese formulations, mainly when prepared in the form of nanoparticles. In addition, it willbe described how the use of self-diffusion coefficients extracted by NMR experiments canbe used to clarify the internal structure of several nano-assemblies. These subjects will be discussed from a theoretical and experimental point of view (laboratory)_

Si tratta di un corso di interesse
generico e trasversale. Il corso si
terrà in modalità on-line ed è articolato in tre moduli da quattro
ore ciascuno. I moduli sono così organizzati:
Modulo 1: Corso di formazione generale sulla sicurezza
– Modulo2: Corso di formazione sui rischi specifici
– Modulo 3: Corso di formazione specifico sulle attività di laboratorio scientifico-tecnologico

The course mainly deals with nuclear magnetic resonance in solution. The basic concepts
and fundamentals that are typically provided in the basic courses will be complemented
with more technical details on the signal measurement and about the use of different
weight functions and the Fourier transform for spectra processing. A practical guideline will
be provided in the planning and implementation of real measurements, with particular
emphasis on obtaining geometric information for the definition of the three-dimensional
structure of molecular systems in solution. The main two-dimensional techniques will be
illustrated from a practical point of view, in order to provide a guide to experiments
planning and to understand how to exploit these techniques to determine important
structural parameters at the atomic level. Finally, fundamentals of molecular mechanics will be provided, aimed at introducing the experimentally-derived geometric parameters in a proper computational molecular model.

The aim of the course is to provide students with knowledge on the mainsources of air pollution, the most important analytical techniques aimed atquantifying pollutants and the aspects related to the collection of samples.Topics_ organic pollutants and photochemical smog, air quality, airborneParticulate Matter, analysis and monitoring of air pollutants, indoor andoutdoor pollution, current legislation, methods and tools used in automaticdetection units. During the course, an indoor sample will be collected and all the steps tomeasure the sample amount will be shown. Surface characterization using XPSTechnique will be shown.

The determination of trace elements or ultra-trace elements in agri-food products is relevant to the verification of food safety and authenticity. In this context, ICPMS is the preferred instrumental approach for its analytic performance, versatility and popularity. After a brief presentation of the technique, we will focus on the key points in the development of the ICPMS analytical methods. Applications on some foods produced in Sardinia will therefore be presented.

This course provides a comprehensive overview of the sol-gel process with theoretical lectures and didactic experiments. The course initially introduces the sol-gel process from colloidal suspensions. It then analyzes the so-called alkoxide route and control of reaction kinetics, the effect of pH and H2O/alkoxide ratio, multioxide systems, control of reaction kinetics, thermal drying, and sintering processes. A special section is also devoted to organic-inorganic hybrid systems, polymerization and copolymerization processes. Finally, some basics on mesoporous materials and nanocomposites are provided. After the chemical part, the course focuses on the transformation of sols into thin films (dip- and spin-coating), monoliths (membranes and aerogles) and nanoparticles (aerosols or precipitation).

In addition to lectures, students will be involved in the synthesis of sol-gel materials and will learn about common equipment, working conditions and classical formulations. They will also have the opportunity to get hands-on with a variety of characterization techniques such as FTIR, UV-Visible and Raman spectroscopy, X-ray diffraction, ellipsometry, photoluminescence, dynamic light scattering, etc.

The use of mechanical input to promote chemical transformation dates back to ancient times and it is strictly related to the development of activities of human beens: in prehistorical times this was probably the simplest available way to activate temperature rise and combustion processes.
The born of modern Mechanochemistry is usually considered due to the work of C.Lea and W.Spring at the end of XIX century and to the classification of Ostwald in 1919, who included mechanochemistry in his chemical systematics, considering it as a specific branch of chemistry together with thermochemistry, electro-chemistry, and photochemistry. Since then, much work has been carried out by the scientific community and nowadays mechanical processing techniques are recognized as a powerful tool to synthesize a variety of advanced materials and metastable phases. The effectiveness of the mechanochemical route in the synthesis processes arises from the synergy of mechanical deformation and chemical potential
effects, which reflects in the enhanced reactivity of treated systems. A deepened investigation of transformation paths, and the rationalization of the role of each contribution in activating the systems, require the correlation among mechanical processing parameters, macroscopic kinetics
and local reactivity of materials under shear. Along this line, in this short course some basic aspects and different application will be presented, which will aim to investigate and compare the efficiency of mechanical and thermal activation in several processes through the accurate
evaluation of the conversion kinetics and of the mechanical energy delivered to the reactants. The study of several reacting systems is proposed, concerning solid-solid, solid-liquid and solid-gas interaction, as well as gas phase synthesis over solid catalysts.