ANALYTICAL CHEMISTRY
2 CFU: Aims of Analytical Chemistry. Phases of the chemical-analytical process. Classification of methods of analysis. Processing of experimental data. Mean value of a data series, mode and median. Standard deviation and relative standard deviation. Systematic, random and gross errors. Absolute error and relative error. Source and treatment of systematic errors in analytical chemistry. Statistical treatment of random error. Gaussian probability distributions and Student's t. Average confidence intervals. Accuracy and precision. Exercises.
4 CFU: Sample preparation techniques for the determination of inorganic and organic analytes, of pollutants in the determination of heavy metals, pesticides, aromatic compounds, organic solvents. Air pollutants. Emerging pollutants, drugs (antibiotics, anticancer, antidepressants, hormones) and their metabolites. Endocrine modulators, plasticizers, PCBs. Personal care products. Fragrances, insecticides, glyphosate. Microplastics, metal nanoparticles. Polluting mixtures. Electromagnetic radiation. Origin of the emission and absorption spectra. Radiation sources, monochromators and detectors. Molecular absorption spectrophotometry in the Visible / UV. Absorption spectra of molecules. Relationship between absorption and molecular structure. Lambert-Beer law. Spectrophotometers and their calibration. Spectrophotometric analysis of a single substance. Analysis of mixtures. Spectrophotometric titrations. Luminescence and Chemiluminescence. Fluorescence and phosphorescence. Fluorimetry. Exercises. Atomic spectroscopy: general aspects. Atomization systems. Quantitative relationships and calibration lines. Emission spectroscopy. Atomic absorption spectroscopy (AA) on flame and electroatomizer. Atomic emission with plasma atomizers. Mass spectrometry and its applications in the environmental field in the determination of xenobiotics (LC-MS, LC-MS / MS). ICP-MS. Introduction to chromatographic separations: general principles. Classification of chromatographic methods. Chromatographic parameters: retention time, retention and selectivity factor, resolution. Efficiency of a chromatographic column: number of theoretical plates, equivalent height of a theoretical plate. Van Deemter equation. Bandwidth. Variables that affect the chromatographic efficiency. Qualitative and quantitative analysis by chromatography. Exercises. Principles of gas chromatography (GC). Isocratic and gradient chromatography. High and ultra-performance liquid chromatography (HPLC, UPLC), instrumentation and detectors.
ORGANIC CHEMISTRY
• Introduction: Organic compounds and life - The chemistry of carbon –
• Chemical bonding and isomerism: Molecular formula - Ionic and covalent bond – Structural formulas – Resonance – Hybridization and Molecular Structure
• Alkanes and cycloalkanes - Conformational and geometric isomerism: Structure of alkanes - IUPAC rules of nomenclature - Alkyl groups - Sources of alkanes - Physical Properties - Reactions of alkanes – Radical halogenation
• Stereoisomers: Chirality and optical activity - Enantiomers and racemates - Properties of enantiomers – Absolute and relative configuration - Compounds with more than one chiral center - Diastereomers - Meso forms - Resolution of racemic mixtures
• Alkyl halides: Preparation of alkyl halides - Nucleophilic substitution and elimination reactions: mechanisms of nucleophilic substitution SN1 and SN2; mechanisms of elimination: E1 and E2
• Organometallic compounds: Generality - Grignard reagents: use in the organic synthesis - Cadmium organic reagents
• Alcohols and thiols: Nomenclature and physical properties - Acidity - Synthesis of alcohols and thiols - Dehydration of alcohols - Reactions of alcohols with hydrogen halides - Oxidation of alcohols
• Ethers and Epoxides: Physical properties and structure - Synthesis and reactivity
• Alkenes and alkynes: bond - Nomenclature and physical properties - Addition of halogen, hydrogen, acids and water - Electrophilic addition to asymmetrical alkenes of asymmetric reagents: the Markovnikov rule – Radical addition - Radical and cationic polymerization – Oxidation reaction of alkenes Acidity of alkynes - Stereospecific reductions of alkynes
• Conjugated dienes: Structure, conformations and reactivity - 1,4 addition reaction of conjugated dienes) - The Diels-Alder reaction
• Aromatic compounds: Structure and Kekule’ resonance – Aromaticity - - Nomenclature – Electrofilic aromatic substitutions: nitration, sulfonation, halogenation, Friedel-Crafts’ alkylation and acylation - Effect of the substituent in disubstitution reactions (reactivity and orientation) - Nucleophilic aromatic substitution reactions - Aryne intermediates - Heterocyclic aromatic compounds
• Phenol and derivatives: Structure, acidity and reactivity
• Aldehydes and ketones: Nomenclature - Features of the carbonyl group - Nucleophilic Addition Reactions: addition of alcohols, water, hydrogen cyanide, ammonia and its derivatives, Grignard reagents – Wittig reaction -Oxidation-reduction reactions - Acidity of the alpha hydrogens - Keto-enol tautomerism – alpha halogenation - Aldol condensation
• Carboxylic acids and their derivatives: Nomenclature and physical properties - Acidity: correlation between structure and acidity - Methods of preparation - Mechanisms of Nucleophilic acyl substitution - Esters - Fischer Esterification - Claisen Condensation – Acetoacetic synthesis and malonic synthesis - Saponification - Acyl halides, amides and anhydrides – Reactivity of acyl compounds
• Amines: Structure, nomenclature and physical properties of amines - Basicity and formation of ammonium salts - Preparations from alkylation of ammonia and reduction of other nitrogen compounds – Hofmann rearrangement - Gabriel reaction – Ammines as nucleophiles - Diazonium salts and Sandmeyer reactions
• Carbohydrates: Classification - Monosaccharides and their chirality - Fischer Projections - Cyclic structures of monosaccharides - Anomers and mutarotation - Pyranose and furanose forms - Reactions of monosaccharides: oxidation, reduction, formation of ethers, esters and glycosides - Disaccharides: maltose, lactose and sucrose - Polysaccharides: starch, cellulose and glycogen - Deoxy sugars
• Amino acids, peptides and proteins: The natural amino acids - Acid-base properties - Isoelectric point - Chirality - Reactions of amino acids - The disulfide bond - Primary structure of proteins - Determination of the sequence structure - Secondary structure of proteins - Tertiary structure of proteins: fibrous and globular proteins - Quaternary structure of proteins
• Nucleotides and Nucleic Acids: Primary structure of DNA - Double Helix - Notes on the function of nucleic acids.
