91226 - BIOMIMETIC, MOLECULAR AND NANOSTRUCTURED SYSTEMS AND MATERIALS

Course Unit Page

SDGs

This teaching activity contributes to the achievement of the Sustainable Development Goals of the UN 2030 Agenda.

Quality education Sustainable cities

Academic Year 2019/2020

Learning outcomes

At the end of the course the student has acquired: - knowledge useful to design, prepare and characterize molecular materials and coordination networks; - the basic concepts and the main strategies for the bottom-up construction of functional nanostructures, that is, starting from molecules and using the paradigms of Supramolecular Chemistry: molecular devices and machines, dendrimers, nanoparticles, self-assembled monolayers and thin films; - knowledge to design, develop and characterize inorganic and organic-inorganic materials with tailored technological properties, according to the biomimetic principles, such as synthesis in confined reaction spaces, template-directed synthesis, morphosynthesis, crystal tectonics.

Course contents

Module 1. Crystal Engineering (Prof. D. Braga)

Prerequisites: basic knowledge of most relevant techniques for the investigation of the solid state (IR and RAMAN scpetroscopies, solid state NMR, X-ray diffraction, differential scanning calorimetry, TGA) general knowledge of thermodynamic principles

Attendance: the course has no compulsory attendance.

Programme:

1. Introduction. Hystorical background. When crystal engineering was born

2. Introduction. Intermolecular interactions, molecular crystals, amorphous substances

3. Crystal forms. Multeplicity of crystal forms for a same substance, crystal polymorphism, hydrates, solvates, salts, co-crystals and their polymorphs

4. Crystal Polymorphism. The isse of identification, characterization, usage of crystal forms. The impact in the pharmaceutical field. Aspects related to intellectual property issues. Enantiotropic and monotropic poltymorphism. Case studies.

5. Crystallization. Main techniques. From solution, from melt, mechanochemical prep. The kinetic problem and the quest for the most thermodynamically stable form

6. Co-crystals. Preparation of multicomponent molecular crystals, the problem of acid-base crystals, proton transfer. Aspects related to IP issues and patentability. The ionic co-crystals. Case studies.

7. Pigments. The polymorphism of pigments. Stability of pigment properties over time. Case studies.

8. Idrates and solvates. The formation of solvates and hydrates via crystallization. Solvent removal and interconversion. Thermodynamic and calorimetric aspects. Case studies.

9. Chirality. Chiral crystals, relationship between chirality at the molecular level and at crystal level. Racemic mixtures, racemic conglomerates, racemates. The importance of chiral resolution. Case studies.

10. Metal Organic Frameworks. Hystorical background: the relationship between coordination chemistry and coordination networks: spacers and knots. Case studies

11. The properties of MOF. Their industrial utilization: gas storage, catalysis in nanocavities, molecular sieves. Adsorption and desadsorption of molecules in/from MOF.

Module 2. Biomimetic materials (Prof. E. Boanini)

Prerequisites: knowledge of polymorphism and crystals properties (knowledge acquired in the module of Crystal Engineering); general knowledge on self assembled monolayers and Langmuir-Blodgett films (knowledge acquired in the module of Molecular Nanotechnology).

Attendance: the course has no compulsory attendance.

Programme:

1. Introduction. Introduction to biomimetic chemistry. Program outline.

2. Introduction to biomineralization processes. Functions of biomineralized tissues, inorganic and organic components, organic matrix control on inorganic phase deposition.

3. Characterization techniques. General principles of techniques useful to characterize biomimetic materials: wide and small angle X-ray diffraction techniques; Transmission Electron Microscopy (TEM); Scanning Electron Microscopy (SEM).

4. Main inorganic components. Carbonates: chemical and structural properties of calcium carbonate polymorphs, biogenic carbonates. Phosphates: chemical and structural properties of calcium phosphates, biogenic phosphates. Silicates: amorphous and biogenic silicates. Iron oxides: synthetic and biogenic magnetite.

5. Biomineralization processes. Biologically induced mineralization. Biologically controlled mineralization: intercellular, extracellular and intracellular mineralization. Control mechanisms.

6. Chemical control. Classical nucleation theory: homogeneous nucleation, free energy of nucleation and critical nucleus, nucleation rate, heterogeneous nucleation; crystal growth; polymorphism: Ostwald’s law; role of additives on nucleation and growth. Non-classical crystallization: oriented attachment, mesocrystals.

7. Spatial control. Supersaturation control: direct and indirect mechanisms. Phospholipidic vescicles: magnetotactic bacteria. Proteic vesicicles: ferritin. Cellular assembly. Macromolecular frameworks.

8. Structural control. Structural and acidic macromolecules. Organic matrix mediated nucleation. Composition and structure of nacre as a result of structural control.

9. Morphological control. Symmetry breaking. Vectorial regulation. Pattern formation through: organic scaffolds, vescicles grouping, cellular grouping. Silica deposition in diatomee as exemplum of morphological control.

10. Constructional control. Hierarchical organization of bone: bone composition, mineralized collagen fibril, organization levels of bone, osteons.

11. Synthesis in confined reaction spaces. Synthesis into phospholipidic vescicles. Synthesis of metals and metal oxides into apoferritin. Synthesis into polymer sponges.

12. Template-directed material synthesis. Biological matrices. Lipid tubules. Oriented nucleation on Langmuir monolayers. Oriented nucleation on self-assembled monolayers.

13. Morphosynthesis. Physical patterning with supramolecular templates. Physical patterning from reaction field replication. Chemical patterning in unstable reaction fields.

14. Crystal tectonics. Supramolecular assemblies. Complex shapes formation in presence of additives. Nacre inspired layered structural composites.

15. Biomaterials. Synthesis, properties and structure of biocompatible and bioactive materials with potential applications in the field of biomaterials for hard tissues substitution and repair: functionalized calcium phosphates and their uses for the preparation of bone cements, prostheses coatings, scaffolds for regenerative medicine.

Module 3. Molecular nanotechnology (Prof. A. Credi)

Prerequisites: knowledge of the fundamental concepts of spectroscopy, photochemistry and electrochemistry.

Attendance: the course has no compulsory attendance.

Programme: the course deals with the following topics; for each one the general principles and some significant examples are described.

1. Introduction

1.1. Top-down approach to miniaturization: photolithographic techniques

1.2. Bottom-up approach: molecular self-assembly

1.3. Molecular devices

1.4. What is molecular nanotechnology?

2. Self-assembled nanostructures

2.1. Common macrocyclic hosts and their host-guest complexes

2.2. Self-assembled capsules, cages, polymers, vesicles, and other structures

2.3. Self-assembled molecular monolayers on surfaces

3. Multicomponent molecular species

3.1. Nanosystems with complex topologies: rotaxanes, catenanes, knots, and related species

3.2. Dendrimers: synthesis, properties and applications

3.3. Dynamic covalent systems

4. Supramolecular catalysis and nanoreactors

4.1. Catalytic processes in hosts and in molecular and supramolecular containers

4.2. Self-replication, hybridization and mutation in artificial chemical systems

5. Chemical functionalization of surfaces

5.1. The Langmuir-Blodgett methodology

5.2. Functional self-assembled monolayers

5.3. Characterization and imaging of surfaces

6. Nanomaterials

6.1. Size effects and quantum confinement

6.2. Metal nanoparticles

6.3. Semiconductor nanoparticles (quantum dots)

6.4. Carbon-based nanomaterials: fullerenes, nanotubes, graphene

6.5. Nanoporous materials: zeolites, metal-organic and covalent organic frameworks

7. Mechanical molecular machines and motors

7.1. Basic concepts

7.2. Biomolecular machines: motor proteins

7.3. Artificial systems based on topologically complex species

7.4. Artificial systems based on DNA

7.5. Other examples

7.6. Potential applications    

Readings/Bibliography

Module 1. Crystal Engineering (Prof. D. Braga)

Crystal Engineering. A textbook. Gautam Desiraju, Jagadese Vittal, Arunachalam Ramanan. World Scientific Publishing and suitable material provided by the teacher.

Module 2. Biomimetic materials (Prof. E. Boanini)

The use of lecture notes and teaching material (PowerPoint presentations and indications on scientific articles useful for exam preparation) will be fundamental during the course.

Many of the topics covered can be found in the book: S. Mann "Biomineralization" Oxford Chemistry Masters, Oxford University Press 2001

Module 3. Molecular Nanotechnology (Prof. A. Credi)

The course covers advanced topics of great scientific relevance and therefore in continuous evolution. It is essential to use the material made available online by the teacher before the beginning of the course: transparencies used in class, scientific articles to be used both for the study and for the in-depth study of specific topics. There is no textbook covering the whole program; the following texts are recommended for the study and in-depth study of parts of the course:

1) J.-M. Lehn, Supramolecular Chemistry – Concepts and Perspectives, VCH, Weinheim, 1995 (part 1, 2, 4 of the programme).

2) V. Balzani, A. Credi, M. Venturi, Molecular Devices and Machines – Concepts and Perspectives for the Nanoworld, Wiley-VCH, Weinheim, 2008 (parti 1, 3, 7).

3) D. S. Goodsell, Bionanotechnology: Lessons from Nature, Wiley, New York, 2004 (part 1 and 7).

4) C. N. R. Rao, A. Muller, A. K. Cheetham (Eds.), The Chemistry of Nanomaterials, Vol. 1 e 2, Wiley-VCH, Weinheim, 2004 (part 1 and 6).

Teaching methods

The course BIOMIMETIC, MOLECULAR AND NANOSTRUCTURED SYSTEMS AND MATERIALS includes three modules:

Module 1. Crystal Engineering (Prof. D. Braga)

The teaching unit takes place in the first semester and is based on lectures where the principal factors responsible for stability and cohesion of molecular crystals are discussed. Molecular and ionic assembling; relationship between bulk structure and molecular functionality; bottom-up construction of materials for magnetic, optic, photonic and biotechnology applications; supramolecular interactions and solvent-free preparations of crystalline solids; polymorphism and crystal forms.

Module 2. Biomimetic materials (Prof. E. Boanini)

The module is carried out in the second semester. It consists of class lectures on the main properties of biomineralized tissues as model systems for the design and development of synthetic materials with tailored functionalities through the strategies of biomimetic chemistry.

Module 3. Molecular Nanotechnology (Prof. A. Credi)

The module is carried out in the second semester, and consists of class lectures that illustrate the basic principles of supramolecular chemistry and nanosciences; for each specific topic, the introductory concepts as well as some singificant examples taken from the scientific literature are presented.

 

Assessment methods

Module 1. Crystal Engineering (Prof. D. Braga)

The exam is based on the discussion of a scientific paper chosen by the student in order to demonstrate the level of understanding of crystal engineering topics and an oral examination based on the course programme

Module 2. Biomimetic materials (Prof. E. Boanini)

The acquired knowledge and skills will be verified through an oral exam. The theme of the first question is selected by the student. The oral test is aimed to estabilsh the student’s comprehension of the biomimetic chemistry strategies and of their applications to the synthesis of materials with tailored properties.

Module 3. Molecular nanotechnology (Prof. A. Credi)

The learning assessment takes place only with the final exam. The acquisition of the learning outcomes is ascertained by means of an oral exam with an average duration of 20 minutes. The exam consists of two questions on the themes dealt with in the course; the first theme is selected by the student, and the second is chosen by the teacher.

The final evaluation score of BIOMIMETIC, MOLECULAR AND NANOSTRUCTURED SYSTEMS AND MATERIALS is determined as the weighted average of the evaluations obtained in Crystal engineering (5CFU), Biomimetic materials (5CFU), and Molecular nanotechnology (5CFU).

Teaching tools

Overhead projector, PC, video projector, powerpoint presentations, videos.

Office hours

See the website of Elisa Boanini

See the website of Dario Braga

See the website of Alberto Credi