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Analytical Chemistry
First semester
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Learning outcomes of the course unit

At the end of the course, the student should have acquired knowledge about the principles and analytical applications of the mass spectrometry-based techniques and methodologies.
In particular, the student should be able to:
- know and describe mass spectrometry potentialities for the development of qualitative and quantitative analytical methods
- know and describe the principles of ionization sources and mass analyzers
- know and describe the acquisition modes and signal elaboration strategies
- evaluate critically the own knowledges and capacities and interpret the obtained results
- connect each other the different topics addressed during the course and connect them with the basic and related disciplines; discuss critically the concepts and consult relevant scientific literature
- apply the acquired knowledge to identify the proper analytical approaches to face a certain analytical issue, considering analyte and matrix nature and investigation type (target or untarget)
- support the own activity on the basis of an autonomous judgment on issues pertinent to the course of study.
- easily retrieve information from scientific literature and databases.
- possess personal logical reasoning and autonomous learning skills, to independently propose solutions for new scientific topics and professional issues.


For the course, it will be fundamental the knowledge of instrumental analytical chemistry and validation of analytical methods

Course contents summary

- Introduction to mass spectrometry techniques and basic concepts
- Principles of ionization sources
- Principles of mass analyzers
- Tandem mass spectrometry and MSn
- Chromatography-mass spectrometry hyphenated techniques
- Ion mobility spectrometry coupled to mass spectrometry
- Qualitative and quantitative analysis. Matrix effect
- Isotope-ratio mass spectrometry (brief mention)
- Discussion of examples from literature
- Applicative exercises and laboratory activities

Course contents

Introduction to mass spectrometry and general principles. Background. Mass spectrum and m/z ratio. Definition of atomic mass unit, average mass, nominal mass and monoisotopic mass. Resolution and accuracy concepts. Isotopic ions and isotopic patterns.

Ionization sources: hard and soft. Gas-phase ionization. Principles and main fragmentation patterns in electronic ionization (EI): simple fragmentation and rearrangements; examples. Principles of chemical ionization (CI) and ionization mechanisms. Condensed-phase ionization. Matrix-assisted laser desorption ionization (MALDI); matrices and sample preparation; MALDI-imaging. Surface-enhanced laser desorption ionization (SELDI). Atmospheric-pressure ionization techniques (API): electrospray (ESI), atmospheric pressure chemical ionization (APCI), atmospheric pressure photoionization (APPI); principles, characteristics and application fields. Multicharged ions and spectra deconvolution in ESI. Nanoelectrospray (nano-ESI). Ambient ionization techniques: desorption electrospray ionization (DESI), direct analysis in real time (DART), paper spray.

Mass analyzers. Parameters and performances. Quadrupolar analyzers. Acquisition modes in a single quadrupole. Triple quadrupole and tandem mass spectrometry (MS/MS) in space. Collision-induced dissociation (CID). Acquisition modes in MS/MS. Ionic traps, 2D (linear ion trap) and 3D (Paul ion trap); Mathieu stability diagrams. Tandem mass spectrometry in time and MSn. Time-of-flight mass analyser (TOF), linear TOF e reflectron TOF; orthogonal acceleration TOF (oaTOF). Magnetic sector analysers. Fourier Transform-mass spectrometry: Orbitrap and Fourier Transform Ion Cycloctron Resonance (FT-ICR). Hybrid mass analyzers (e.g. QqLIT, QTOF, LTQ-Orbitrap)

Ion mobility spectrometry (IMS) and IMS coupled to mass spectrometry (IMS-MS). Q-IMS-TOF instrument. Examples and applications.

Hyphenated techniques. Coupling with separation techniques (LC-MS, GC-MS, CE-MS). Matrix effect and use of stable isotopically labelled standards.


Inorganic mass spectrometry. Inductively Coupled Plasma Mass Spectrometry (ICP-MS).

Isotope-ratio mass spectrometry (IRMS)

Recommended readings

“Mass Spectrometry. A Textbook”, J.H. Gross, Springer

“Mass Spectrometry. Principles and Applications”, E. de Hoffmann, Wiley

Scientific articles and other material necessary for the preparation of the exam, or useful for any further supplementary study, are uploaded on Elly platform and/or indicated in the slides.

Teaching methods

Blended synchronous learning will be adopted: face-to-face course and in real time, simultaneously transmitting it to students who are remotely accessing the same course (via Teams). Video-recording of each lesson will be available, but only within the week during which it has been delivered. Discussion forum in Elly could be used to promote students active participation.
The teaching activities involves frontal lessons supported by examples.
1 CFU (15 hours) will be dedicated to applicative exercises and laboratory activities.
The slides used as lesson support will be available for download on the Elly platform, where are regularly uploaded. It is important to remind that non-attending students have to check the available teaching material and the directions provided by the teacher through the Elly platform.

Assessment methods and criteria

The assessment of the student learning will be carried out through a final oral examination in presence; if due to the persistence of the COVID-19 health emergency it is necessary to integrate examination session with remote modality, remote oral exam will be performed via Teams.
During the oral exam (of about 40 min) the student must demonstrate understanding of the fundamental concepts of each topic, he/she has to be able to discuss in a critical and applicative point of view the issues dealt with and to possess a proper scientific language. No written report is required concerning applicative exercises and laboratory activities; however, the student has to be able to describe and discuss applicative aspects faced during these activities.
The vote will be immediately communicated at the end of the exam and the student’s signature will be required for vote acceptance.