Expertise

Skills and Competencies
CNR-ICCOM researchers have expertise in many areas of the molecular sciences of which outstanding for quality and diversification of know-how are the following :
o advanced synthetic methods (organic, inorganic and organometallic)
o the design and synthesis of new catalysts (homogeneous, heterogeneous and supported). Photocatalysts and electrocatalysts for use in creating sustainable and efficient processes.
o morphological-structural and functional characterization, with applications ranging from industrial to biomedical
o the application of cutting edge analytical and spectroscopic techniques to the environment, health sciences and the protection of cultural heritage
o computational modeling of complex chemical systems and their physical-chemical and functional properties
o Development of new materials for industrial and biomedical applications
More specifically here we list the competences that each of ICCOMs regional sections have to offer:
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Starting with the headquarters of the CNR-ICCOM housed within the Science and Technology Area of the CNR Sesto Fiorentino, the following operational capabilities and scientific expertise:
o Preparation of chiral and achiral polydentate ligands with various donor atoms
o Synthesis of optically active compounds through innovative enantioselective processes
o Preparation of homogeneous metal nanopowders using the technique referred to as "metal vapor synthesis" and the anchoring of chiral selectors to insoluble matrices with high diffusion for reactants and products.
o Immobilization of catalysts using molecular anchoring either covalent, ionic or through weak interactions.
o Design and optimization of catalytic reactors (bed or flow).
o Synthesis, characterization, and study of the reactivity of metal nanoparticles immobilized on various media (resins, polymeric membranes) for use in selective processes and sustainable production.
o Synthesis, characterization and study of the reactivity of bifunctional catalysts and meso / macroporous support materials.
o Preparation of metallic phases, metal phosphides and metal sulfides dispersed on inorganic / organic supports starting from inorganic and organometallic precursors.
o Synthesis and characterization of complex polymeric systems by reactive blending of polyolefin and / or modified polyolefins with other polymeric materials of synthetic or natural origin.
o Synthesis of nanocomposites.
o Synthesis of conjugated polymers with polyphenylene ethynylene (polyphenylene ethynylene) structures for application in the field of microelectronics and sensors.
o Optimization and scale-up of heterogeneous catalytic processes, such as selective hydrogenation reactions, oxidation and partial oxidation, activation of C-H bonds, C-C bond formation.
o Optimization and scale-up of homogeneous and biphasic catalytic processes and polymerization reactions, oligomerization and copolymerization of olefins and olefins with polar monomers.
o Selective reduction processes (chemo-, regio- and stereoselective) by direct hydrogenation or hydrogen transfer. Selective formation of C-C bonds, CO, CS and C-Si.
o Nuclear magnetic resonance spectroscopy, also in the solid state, and EPR
o FT-IR and UV-VIS spectroscopy
o GC-Mass spectrometry
o Thermogravimetric analysis TGA
o Gas chromatography, gas chromatography with mass detector, high performance liquid chromatography
o Electron Microscopy (TEM, SEM, EDX)
o Porosymetry via physisorption and chemisorption
o Development and study of new energy production systems, such as fuel cells and PEM electrolysers.
o Electrocatalysts based on non-noble metals for direct alcohol fuel cells and PEM electrolyzers.
o Electrochemical study of catalysts derived from complexes deposited on conductive supports, OMFCs (OrganoMetallic Fuel Cells).
o Anodization of titania aimed at the production of photo-active materials (titania nanotubes) and their use in catalysis
o Electrocatalysts and processes for the electroreduction of carbon dioxide, aimed at the production of hydrocarbons and oxygenated products using catalysts based on copper.
o Exploitation of renewable products such as glycerol and ethanol, via partial oxidation in direct alcohol fuel cells.
o Development of systems for the controlled release of hydrogen on-demand through the hydrolysis of metal hydrides
o Study of energy storage systems such as secondary cells and flow batteries.
o Study of environmentally friendly processes for the disposal of lithium ion batteries
o Development of Dye Sensitized Solar Cells (DSSC).
o Catalysts for reforming and partial hydrogenation
o Study, design, modeling and optimization, from an engineering point of view of production facilities and energy conversion, industrial plants (with scales ranging from the prototype to the pilot plant). Study of energy system integration between renewable and non-renewable and smart grids.
o Characterization of compounds and materials in different phases by mass spectrometry and multinuclear NMR spectroscopy.
o Mechanistic studies using magnetic resonance and infrared radiation in the presence of high-pressure gas.
o Resolution of molecular structures from single crystal diffraction data
o Identification of crystalline phases, semi-quantitative and quantitative determination of crystalline phases.
o Variable temperature hot chamber diffractometry under inert gas flow
o Analysis of aqueous and organic solutions by means of gas chromatography coupled with mass spectrometry and HPLC (chiral).
o Functionalization of innovative 1D nanomaterials (nanotubes) and 2D (graphene) by click-chemistry.
o Development of new chiral stationary phases and chiral solvation for the determination of enantiomeric excess by chromatography and NMR.
o Studies of stereochemistry by means of spectroscopic techniques, non-traditional polarized light and high-resolution NMR. Determination of configuration and molecular conformation. Chiral discrimination in chemistry and biochemistry interactions.
o Determination of trace components in complex matrices by mass spectrometry.
o Determination of the magnetic susceptibility of solids and compounds in solution.
o Development and construction of scientific instrumentation for the realization and in situ study of chemical reactions under high pressure gas: autoclaves and devices for NMR and IR.
o Prototyping and design from the mechanical point of view of small instruments and customized systems.
o Kinetic studies of chemical processes in the homogeneous phase
o Test of cytotoxicity and cell viability in relation to treatment with biological substances and / or chemicals (drugs) both in liquid culture or semisolid (agar).
o Tests of the ability of biological substances and / or chemicals to reduce the growth of cancer cells in animal models (xenografts also ortho-topical)
o Computational chemistry aimed at understanding the mechanisms of catalysis and the understanding of interactions between components through biochemical studies of molecular dynamics.
o Synthesis and characterization of magnetic nanoparticles through colloidal techniques for the following applications: magnetic drug delivery, diagnostics and therapy, radio frequency treatment of tumors; hybrid plasmonic-magnetic materials for advanced sensors; electronic switching (high frequency transformers with low losses); Permanent magnets.

Inspiration for much of the scientific research of ICCOM are the multifarious skills acquired in the field of homogeneous and heterogeneous catalysis, expressed in the design and synthesis of mono- and multifunctional ligands (chiral or achiral) with various symmetries, and their coordination compounds with transition metals which are used as catalysts. Such catalysts must be able to combine as much as possible efficiency and selectivity and at the same time be able to meet the increasingly stringent demands of public opinion and legislature regarding the environmental compatibility of processes and the minimization of waste production. Catalysis in aqueous solutions and use of innovative low environmental impact catalytic reactions with metal complexes are two fields of competences already acquired by the researchers of the institute.

An important part of research covers the application of catalysis to renewable energy. ICCOM researchers have acquired know-how in the development of sustainable energy production. Focal points of this work are homogeneous and heterogeneous catalysis, electrocatalysis and photocatalysis, studies of materials for energy, anodic and cathodic catalysts for fuel cells, catalysts for polymer membrane electrolyzers, the electroreduction of CO2 to hydrocarbons, the development of diagnostic tests for fuel cell stacks, the exploitation of renewable resources through electrocatalysis (e.g. glycerol), photo-electrocatalysis, catalysis for the release of hydrogen from hydride materials and metals, operational studies of lithium ion batteries and their disposal and recovery of metals, electrocatalysis under high pressure and temperature. The existence of a number of very diverse lines of research and the presence of excellent expertise in each of these sectors has enabled the institute to establish fruitful relationships both with industry and with other research centers both in Italy and abroad, and have enabled the development of collaborations with industry for the scale up of processes and the creation of prototypes and industrial systems.
In the field of photovoltaics, CNR-ICCOM develops new dyes with high efficiency for DSSC (Dye Sensitized Solar Cell) solar cells and new processes related to the efficient use of solar energy.
Together with the chemical skills described above there is also an engineering department that aims to study and optimize energy conversion systems. The development, the experimental characterization and optimization of pre-industrial prototype systems defines the body of knowledge of this unit, which also has expertise in the field of experimentation, development of descriptive models and analysis of phenomena and systems of machinery, plant energy conversion and storage systems. The topics currently covered include the study and optimization of systems based on renewable energy and fossil fuels, the integration of renewable energy into the existing electricity system and future (smart grid), the development of hydrogen storage systems and technologies.
Among the leading expertise within ICCOM includes the synthesis, functionalization and characterization of of magnetic nanoparticles based on materials such as ferrites, metals and alloys, synthesized by colloidal techniques. In addition to fundamental research, the study of these systems allows the development of numerous applications. For example nanoscale vectors for early diagnosis and treatment of tumor pathologies. In this case, the magnetic component is used for both diagnostic purposes (contrast medium for magnetic resonance imaging) as well as therapeutic, exploiting the heat release induced by the application of an external electromagnetic field. Another application of such systems is the development of hybrid magnetic-plasmonic nanomaterials containing a magnetic component and a plasmon coupled with activities in different geometries with important consequences in the development of new generation sensors with high sensitivity. Finally, these materials may have important applications in power electronics for the reduction of dispersion, and thus energy loss in electronic devices such as, for example, high frequency transformers in switching converters, both for the development of high residual permanent magnets.
Another field of excellence is hydrogenation reactions in heterogeneous phase (conducted with catalysts supported on solid phases or deposited on surfaces such as homogeneous metal nanoparticles by means of metal vapor synthesis (MVS), on different substrates such as cyclic and acyclic unsaturated hydrocarbons, aromatic heterocycles of fossil origin present as minor contaminants of raw petroleum, renewable resources such as polyunsaturated vegetable oils, and polyfunctional intermediates) and in homogeneous phases (the synthesis of optically active compounds with highly enantioselective chiral catalysts).

In recent years ICCOM has accumulated expertise in the field of polymerization, oligomerization and copolymerization of olefins and new macromolecular materials technology. Olefin polymers, stereo-regular copolymers, between carbon monoxide and olefins, including cyclic olefins and alpha-olefins, etc. have been prepared using these skills. Other areas of expertise include the synthesis and characterization of polymeric materials by mixing reactive polyolefin and / or modified polyolefins with polyamides and polyesters, the investigation of the thermo-mechanical properties of polymers and the development of polyolefin or inorganic nanocomposites.
The experience in organometallic chemistry of many ICCOM researchers can be seen in the skills acquired in the design, synthesis and optimization of ligands, homogeneous or heterogeneous catalysts and processes with high selectivity. Important reactions include those that lead to the formation of carbon-carbon bonds and carbon-heteroatom bonds (silicon, oxygen, nitrogen). Specific skills in these reactions and in hydroformylation and, more in general, the carbonylation of olefins are derived from expertise in performing reactions under pressure. The Florence workshop has particular expertise in the design and construction of autoclaves for reactions under pressure and sapphire tubes mounted on titanium for NMR spectroscopy and IR at high pressure.
Numerous advances have been made in the synthesis and functionalization of complex carbon-based nanomaterials, both 1D (nanotubes) and 2D (graphene) through "click-chemistry" and the insertion of heteroatoms into the carbonaceous structure allowing the development of "metal free "catalysts and innovative vectors for drug delivery.
We can imagine, for example, about the use of organometallic complexes in the synthesis and functionalization of compounds with potential biological activity, the development of new synthetic strategies for targeted molecules of pharmacology relevance or as precursors for the fine chemical industry.
These synthetic skills have allowed so many advances in the synthesis of innovative organometallic catalysts both in homogeneous and heterogeneous phases.
As a consequence of the synthetic skills developed at ICCOM, a profound knowledge of materials characterization techniques has also been accumulated. These techniques extend from electromagnetic spectroscopy (IR, NMR), mass spectrometry, to purification by chromatographic techniques and the techniques of X-ray diffraction investigation. Of particular importance in addition to the techniques of HP-NMR previously mentioned are the studies of stereochemistry using spectroscopic techniques in non-traditional polarized light and high-resolution NMR and the development of new chiral stationary phases and chiral solvating for the determination of the enantiomeric excess by chromatography and NMR .
A group of crystallographers within ICCOM have for decades undertaken important research in the field of structural determination by X-ray diffraction, not only at the level of structural characterization, but also the correlation between solid state structure, physico-chemical properties and reactivity.
Regarding morphological investigations, ICCOM researchers are experienced in the techniques of transmission electron microscopy (TEM) and scanning electron microscopy (SEM), also in combination with Energy Dispersive X-ray Analysis (EDX), as well as SPM (scanning probe microscopy), atomic force microscopy (AFM) and scanning tunneling microscopy (STM).
The Institute also has amongst its facilities, various electrochemical techniques, used for the functional characterization of materials for use in renewable energy generation, including diagnostics for fuel cells and electrolyzers. Such studies of energy materials has helped to established numerous working relationships with industry.
The development of new catalytic processes and the optimization of existing ones depends largely upon a robust knowledge of the reactivity of organic and inorganic substrates toward metal complexes. Therefore the study of selective small molecule activation using organometallic complexes combines specific skills that interface with organic chemistry, inorganic and organometallic chemistry, spectroscopy, kinetics and thermodynamics, contributing together to the understanding of the mechanisms of reactions. Such studies provide a natural feedback that can be used for the optimization of the metal complex in terms of chemical reactivity and catalytic stoichiometry.

Studies of reaction mechanisms also benefit from specific expertise gained in the areas of modeling and quantum theory that are not only a way of representing chemical processes and molecular structures, but also provide a precognitive guide to the work of synthetic chemistry. The use of increasingly powerful computational tools and software allows rapid dissemination of the fundamentals of theoretical chemistry and theoretical methods amongst synthetic chemists providing an enormous help in the study of reactivity.
Moreover, the institution possesses an astute understanding of biochemical mechanisms through theoretical studies of molecular interactions, in particular for systems with a high degree of intrinsic disorder and low degree of structure, with the possibility to include also small co-factors (e.g. metal ions ). Time scales and spatial resolution of such models are determined by the properties that you want to study, with the ability to interact between different scales.
The institute has also expertise in the fields of biochemical and biomedical research. The research in the area of the design and use of inorganic, organometallic and organic compounds in medicine and in general as biologically active molecules is another area in which important skills have been developed. This includes research in the field of organometallic compounds potentially employable in therapy (anticancer compounds, antiangiogenic, antiviral etc), of radiopharmaceuticals for biomedical research and clinical applications, the synthesis of receptor ligands or enzyme inhibitors and their applications in medicine, the synthesis of unnatural amino acids, oligopeptides and peptidomimetics as agonists / antagonists, studies of structure-biological activity, determination of configuration and molecular conformation and studies of chiral discrimination in chemistry and biochemistry. Evaluation of the mechanisms of action of substances with cytotoxic action by cell cycle analysis and apoptosis as well as through the analysis of the expression both at the RNA level and at the protein level. Transformation tests, both in vitro (cells) and in vivo (mice), by measuring the neoplastic characteristics of mammalian cells exposed to chemicals.
The study of genetic sequences for highlighting mutations associated with both neoplastic transformation of polymorphisms that can alter the response and / or toxicity of drug treatments.

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The UOS of ICCOM at Pisa, is home to advanced skills in analytical, macromolecular, theoretical and computational chemistry as well as in optical spectroscopy and magnetic resonance imaging. Such complementary and synergistic skills help to support and promote research in the areas of sustainable chemistry, advanced materials, nano-medicine and cultural heritage.

The specific skills that researchers of UOS Pisa are able to offer include:
o The development of new methodologies and tools for the determination and characterization of chemical species at trace level in biological, clinical and environmental matrices.
o The development of analytical instrumentation (atomic spectroscopy) for on-line monitoring of gas emissions (possibly thermal and geothermal).
o The development of new methodologies and tools for the determination and characterization of chemical species at trace levels in biological, clinical and environmental matrices: chemical and photochemical vapor generation coupled with atomic spectrometry / mass spectrometry for the analysis of trace and ultra-trace species; chemical generation of volatile compounds of anionic species using borate salts.
o The study of the mechanisms of generation of volatile hydrides using borane complexes (NaBH4, amminoboranes) and their analytical applications.
o The development of analytical instrumentation (atomic spectroscopy) for the on-line monitoring of gaseous emissions (with particular reference to those that originate from thermal and geothermal plants).
o The study of the processes of photo-degradation of environmental pollutants by combined use of microwave techniques, UV-Vis. and ultrasound.
o The study of surface tension and viscosity of proteins and soluble polymers in aqueous solution by means of detector dynamic surface tension (DSTD).
o The conformational study of proteins by fourier transform infrared spectroscopy (FTIR).
o The study of new experimental procedures for the synthesis of colloidal metal nanoparticles by means of electromagnetic radiation.
o The applications of the LIBS technique (laser induced breakdown spectroscopy) for the on-line analysis of coal for energy production, and the continuous on-line monitoring of the composition of metals and alloys in industrial production lines.
o The development of processing technologies (reactive and reactor blending) of polymer-based materials for recycling and / or polymeric by-products using bio-compatible chemicals and / or from renewable sources.
o The preparation and characterization of photoresponsive (bio)polymeric materials, thermo and photostabilized through reactive functionalization and / or dispersion of nanofillers for multifunctional applications in the areas of packaging, automotive and construction.
o The synthesis of nanofillers for ion exchange reactions with functional properties.
o The study of the dispersion of nanofillers in polymeric matrices
o The study of the post-modification reaction of polymers and the development of the techniques of spectroscopic analysis for the determination of the degree of functionalization.
o The thermal and thermomechanical characterization of polymeric materials.
o The development of state-of-the-art computational methods (and their distribution or open source implementation in commercial codes) for the design of photoelectrochemical solar cells (dye-sensitized solar cells, DSSC), the study of the electronic and energy transfer process, the exploration of potential energy surfaces of complex systems, the study of molecular properties and optical or chiroptical properties, linear and non-linear simulation of vibrational spectra and vibronic systems of large size, the study of the spectroscopic properties of molecular systems of interest to astrochemists and atmospheric chemists and increasingly complex automated parameterization of force fields.
o The development of multi-scale integrated computational protocols for specific advanced devices such as heterogeneous catalysts based on metal nanoparticles for the recycling of CO2, smart polymers and polymers with modulated optical properties, supramolecular aggregates and multi-chromophores, such as 2D interfaces between oxides or ultrathin graphene and metal surfaces.
o The development of computational protocols for the study of the of quantum dynamics of proton/hydrogen transfer and photophysical and photochemical processes in biological systems: models for DNA, GFP and melanins.

o The development of computational methods for the design of organic-inorganic hybrid platforms for the development of innovative biomedical devices: biosensors (DNA-based), surfaces of Si or TiO2 functionalized metal nanoclusters interfaced with biomolecules, luminescent biomarkers and mechanochromic polymers.
o The development and testing of new markers based on nanostructured materials for medical imaging and diagnostics.
o The development of noninvasive and portable instrumentation for the acquisition of chemical and physical parameters useful in the cataloging of artifacts (such as coins, jewelry, figurines) directly in situ, supporting the work of the archaeologist in the field.
o The study of dosimetry using magnetic resonance spectroscopy electronics (EPR) to measure radiation-induced damage (neutrons and gamma radiation).
o Study of the application of EPR spectroscopy to the dynamic and the magnetic properties of free radicals (nitroxide) included in nanostructured matrices.
o The application of EPR spectroscopy to the chemistry of organic and inorganic materials, with particular attention to structure-property relationships.
o The use of EPR spectroscopy with spin trapping techniques to detect and identify the metabolism of free radicals in toxic chemicals, drugs and biochemicals. Unraveling the molecular mechanisms that lead to oxidative stress and the study of antioxidants.
o The development and implementation of EPR and NMR spectroscopic techniques in the analysis of spectroscopic data on the basis of theoretical and / or statistical models.
o The characterization of structural and electronic properties of transition metal compounds using EPR spectroscopic techniques in solution and in the condensed phase and in the study supramolecular organization and the dynamics of biological systems, such as proteins and membranes, using EPR techniques spin labeling and spin probing.
o The application of mono- and bi-dimensional multinuclear NMR techniques in solution, measurement techniques with static or magic angle rotation in the condensed phase, for the structural characterization of polymeric materials, composite materials, liquid crystals and membranes, and systems of environmental interest (soils and carbonaceous materials).
o The measurement and analysis of relaxation times of nuclear spin at different frequencies for the study of molecular dynamics in complex systems in the solid phase or liquid and soft materials, and the relaxometric properties of materials with potential application as contrast agents.

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At the UOS Bari of CNR-ICCOM, competencies have been developed related to numerous processes of asymmetric synthesis, with particular regard to the enantioselective oxidation of sulfides with different types of chiral catalysts, stereo-controlled processing of chiral intermediates and the preparation of new auxiliary chirality. More recently expertise has been developed in the recognition of weak interactions in crystalline phases.
Emphasis must also be given to the existence of comprehensive experience in the design and preparation of both polymeric and small organic compounds, with particular attention to new technologically advanced organic materials, with extended conjugation and semiconducting properties, for application in electronics and photonics. Of equal importance is the existence of a level of experience in the modulation and control of the optoelectronic properties of organic materials through the functionalization of the conjugated skeleton and in the synthesis and characterization of fluoro-functionalized organic materials equipped with special electrical and optical properties, as well as high chemical and thermal resistance.
The synthetic skills relate in particular to the preparation of aromatic thiols with chelating geometry for application in the field of self-assembly of the surface of electrodes based on noble metals in OTFT (organic thin film transistor) type devices. Also of Iridium complexes, suitably functionalized with electron-attractor groups, such as fluorine atoms and sulfonic groups, with emission of light modulated in the entire spectrum of visible light; polymers for solar applications and their interaction with single wall carbon nanotubes to form a hybrid polymer / nanotube materials that form thin films that are used for application in the field of photovoltaic hybrids; oligomer conjugates for solar, properly functionalized these can be linked by a covalent bond to a protein from the photosynthetic bacterium Radobacter sphaeroides R26, for application in the field of organic biological photovoltaics.
Skills are present for the realization of homogeneous thin films with controlled thickness on various types of support, such as quartz, ITO, Si, SiO2, etc., using solution deposition techniques, such as spin coating and casting, controlling the morphology of the thin film through deposition techniques and the functionalization of organic materials.
Methods have also been developed for oxyfunctionalization, selectively targeting both natural and non natural substrates concerning (a) the chemistry of dioxiranes and the process of catalytic transfer of oxygen in particular applied to carbon materials; (B) the selective oxyfunctionalization and spectroscopic characterization of macrocycles of natural origin for the development of new anticancer drugs; (C) the capture and exploitation of CO2 through the study of catalytic systems for the photoconversion with sunlight of CO2 to chemical products with high added value and the development of new absorbers based on nanomaterials and other materials with controlled porosity.
Complementary to these skills are the chemical modification of nano-structured bio-silica surfaces and their applications in nanobiotechnology and in drug delivery.