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BIOINORGANIC CHEMISTRY AND CATALYSIS

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Versione italiana
Academic year
2022/2023
Teacher
ALESSANDRA MOLINARI
Credits
6
Didactic period
Primo Semestre
SSD
CHIM/03

Training objectives

The course aims to provide the tools and knowledge to understand how chemistry is also a fundamental discipline for medicine, biology, etc. By the end of the course, the student will have understood the role of metals in many biological systems and will be able to understand the strong affinities between enzymatic and purely inorganic heterogeneous catalysts.
Main acquired abilities will be:
- connect properties of a bioinorganic catalyst with the reaction type that it catalyzes
- choose the correct type of catalyst for a given chemical reaction
- show common aspects between enzymatic catalytic sites and heterogeneous catalysts
- apply previous knowledges about coordination chemistry, surface characterization techniques, spectroscopic methods to (bio)inorganic catalytic systems.

Prerequisites

A good knowledge of coordination chemistry, of biochemistry and of kinetics is mandatory for a full comprehension of the contents. Basic concepts of the main spectroscopic techniques is also necessary.

Course programme

The course is of 36 hours of lessons provided in classroom. The main subjects will be:
BIOINORGANIC CHEMISTRY AND BIOCATALYSIS (18 hrs)
• fundamental concepts of kinetics and of enzymatic kinetic.
• Coordination chemistry in biological systems: ligands of biological interest, thermodynamic and kinetic aspects, spectroscopic and magnetic properties. Effects of the polipeptidic chain: control of the geometry, of the potential redox and of the reaction environment.
• Acid-base catalysis: zinc enzymes
• Catalysis involving O2: Cu-Zn superoxide dismutase, prosthetic groups with catalytic activity and their model systems. Metal-porphyirins and analogues, biomimetic catalysis, catalase, peroxidase, cytochrome P450.
• Oxidative phosphorilation: centres of electron transfer processes. Cytochrome c, iron-sulfur proteins, cytochrome c oxidase.
• Clorophyills, vitamine B12, cianocobalamine
• Biocatalysis: general principles and analysis of the processes for the production of acrylamide, penicillines and of an antitumoral drug.
HETEROGENEOUS CATALYSIS (15 hrs)
• Heterogeneous catalysis: concepts and general principles. Most important techniques for the characterization of a solid surface. Allumina, silica, mesoporous silica.
• Zeolites: synthesis, structure and applications. Zeolites as acid catalysts (electrophilic substitution reactions) and base catalysts (aldol condensation, Knoevenagel reaction). Zeolites containing transition metal ions (Sn e Ti)
• Clays, silica and sulfonated Nafion as acid catalysts: preparation, properties and applications.
• Layered double hydroxides as base catalysts: preparation, properties and applications
• Biphasic catalysis: fluorurated solvents.
ELECTRON PARAMAGNETIC RESONANCE (3 h)
basic theory concepts, relevance of this spectroscopic technique in the study of coordination compounds with metal ions presenting unpaired electrons and in the study of formation of radical species during reaction mechanisms.

Didactic methods

Teaching will be delivered in video recorded mode. Video lectures are uploaded to the dedicated Classroom.
In-person meetings or via Meet will be scheduled in September-December for focus group activities. These are meetings to explain and deepen the content of the video lectures.
The student who chooses this teaching must register for the Classroom stream using the code bgatgcb
The Classroom stream is also used for information exchange between the lecturer and all registered students.

Learning assessment procedures

The exam is oral and it is made of a series of questions concerning course contents and belonging to the area of bioinorganic chemistry/biocatalysis and of heterogeneous catalysis. Once the knowledge of an argument has been verified, the teacher will pass to the evaluation of the student ability in applying knowledges to cases of interest or to practical examples.
The exam is passed if the student has knowledge of almost 50% of the questions arguments. The evaluation level depends on knowledge degree and on the ability acquired in the application of knowledge and it is based on whether the student demonstrates to be master of the subject and to be able to place the acquired knowledges in a wider view of chemistry.

Reference texts

The following are some texts that were used for the video lectures and are useful study aids. The books below are present at the Universitary library or are suitable at the Professor office:
- Bioinorganic chemistry: Bertini, Gray, Lippard, Valentine, “Bioinorganic Chemistry”, University Science Books, 1995
- Heterogeneous catalysis and biphasic systems: Rothenberg, “Catalysis”, Wiley VCH 2008
- Zeolites: Sheldon, Arends, Hanefeld, “Green chemistry and catalysis”, Wiley-VCH
- Sn- e Ti-silicalites: Clerici, Kholdeeva, “Liquid phase oxidation via heterogeneous catalysis”, Wiley-VCH 2013