The principal goal in ILs chemistry is to synthesize low-cost and low-toxicity ionic compounds having specific properties and a melting point near (or below) room temperature to use as solvents, solvent-catalysts or as materials by adsorption on proper supports or through polymerization processes.
In this regard, our research group is involved in design and synthesis of new ILs, to apply as solvents for specific chemical processes or as principal components or additives for the development of smart-materials and electrical devices, possibly starting from cheap chemicals arising from renewable resources.
A relevant part of the research work performed in our laboratories is focused on studying the physico-chemical properties of several classes of ionic liquids, with the goal of connecting macro- (i.e. viscosity and density) and microscopic properties (intrinsic interaction ability of single ionic constituents) to the chemical structure of these systems, taking into account both static and dynamic effects.
To this pourpose physical, transport and electrochemical properties (melting points, phase transitions, glass transition temperature, ionic conductivity, viscosity, density, diffusion coefficients, etc) are measured on pure ILs or ionic mixtures as a function of temperature.
Moreover, spectroscopic and spectrometric measurements (UV, NMR, ESI-MS) are generally performed to evaluate the intermolecular interactions, dynamics, solvation and transport properties.
Kinetic and thermodynamic study of selected reactions are also performed to obtain quantitative information on the solvent properties of ILs.
Finally, FT-IR microscopy is used for the chemical identification of particles and smallest contaminations and the analysis of the distribution of a multitude of different components in complex (bio)materials synthesized in ILs or treated with ILs. These data are used to design and synthesize optimized ILs for specific applications.
Theory - Why theoretical chemistry?
Modeling of solvent effect of molecular liquids has an extensive background; however, the modeling of IL systems is still in its infancy. Recently, we have shown that both the liquid structure and solvation properties of imidazolium based ILs are well reproduced in the framework of RISM integral equation theory. Such approach allows to obtain the liquid structure and the spatial distribution of a ionic solvent around a solute with a very reduced computational cost (minutes) if compared to the one required for molecular dynamics or Monte Carlo simulations (weeks). In this moment, RISM approach is applied to understand the solvation processes of stable compounds and short lived species (intermediates and transition states) in model ionic liquids and how they might differ from the same processes carried out in conventional molecular solvents.
The large unpredictability of ionic liquids properties as solvents, as catalysts, as materials deserve a multidisciplinary approach.
For this reason we combine chemical evidences as reactivity and selectivity and physico-chemical measurements with computational studies.
To explicate the solvent effects of ionic liquids on organic reactivity we use ab-initio calculation on clusters constituted by the reaction actors and one or more ions. This supermolecular approach can explicate specific ion-substrate interactions that are fondamental to understand chemical reactivity in ionic liquids.
Group Pubblications (2014-2019)
Interaction of vanadium species with a functionalized graphite electrode: A combined theoretical and experimental study for flow battery applications, MM Langroudi, CS Pomelli, R Giglioli, C Chiappe, MAC de Oliveira, B Mecheri, S Licoccia, A D’Epifanio, Journal of Power Sources, 2019, 420, 134-142
Investigation of a family of structurally-related guanidinium ionic liquids through XPS and thermal analysis, A Moscardini, A Mezzetta, N Calisi, S Caporali, CS Pomelli, L Guazzelli, C Chiappe, Journal of Molecular Liquids, 2019, 277, 280-289
A family of chiral ionic liquids from the natural pool: Relationships between structure and functional properties and electrochemical enantiodiscrimination tests, M Longhi, S Arnaboldi, E Husanu, S Grecchi, IF Buzzi, R Cirilli, S Rizzo, C Chiappe, PR Mussini, L Guazzelli, Electrochimica Acta, 2019, 298, 194-209
Microheterogeneity in Ionic Liquid Mixtures: Hydrogen Bonding, Dispersed Ions, and Dispersed Ion Clusters, A Mezzetta, MJR Douton, L Guazzelli, CS Pomelli, C Chiappe, Australian Journal of Chemistry, 2019, 72 (2), 106-111
Levulinate amidinium protic ionic liquids (PILs) as suitable media for the dissolution and levulination of cellulose, S Becherini, A Mezzetta, C Chiappe, L Guazzelli, New Journal of Chemistry, 2019, 43 (11), 4554-4561
Design and Synthesis of Ionic Liquid‐Based Matrix Metalloproteinase Inhibitors (MMPIs): A Simple Approach to Increase Hydrophilicity and to Develop MMPI‐Coated Gold Nanoparticles, F D’Andrea, E Nuti, S Becherini, D Cuffaro, E Husanu, C Camodeca, E De Vita, MR Zocchi, A Poggi, C D’Arrigo, V Cappello, M Gemmi, S Nencetti, C Chiappe, A Rossello ChemMedChem, 2019
A computational study of the effect of ionic liquid anions on Reichardt’s dye solvatochromism, CS Pomelli, C Chiappe, Theoretical Chemistry Accounts, 2018, 137 (7), 95
Divergent Syntheses of (Z)-3-Alkylideneisobenzofuran-1(3H)-ones and 1H-Isochromen-1-ones by Copper-Catalyzed Cycloisomerization of 2-Alkynylbenzoic Acids in Ionic Liquids, R Mancuso, CS Pomelli, P Chiappetta, KF Gioia, A Maner, N Marino, L Veltri, C Chiappe, G Bartolo, The Journal of organic chemistry, 2018, 83 (12), 6673-6680
Phosphate and Phosphonate-Based Ionic Liquids as New Additives in Foeniculum vulgare Essential Oil Extraction, L Pistelli, RVB Reidel, P Margari, C Chiappe, Australian Journal of Chemistry, 2018, 71 (3), 127-132
Synthesis of colloidal Ag nanoparticles with citrate based ionic liquids as reducing and capping agents, E Husanu, C Chiappe, A Bernardini, V Cappello, M Gemmi, Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2018, 538, 506-512
Systematic synthesis and properties evaluation of dicationic ionic liquids, and a glance into a potential new field, L Guglielmero, A Mezzetta, L Guazzelli, CS Pomelli, F D’Andrea, C Chiappe, Frontiers in chemistry, 2018, 6
Chiral ionic liquids supported on natural sporopollenin microcapsules,I Palazzo, A Mezzetta, L Guazzelli, S Sartini, CS Pomelli, WO Parker, C Chiappe, RSC Advances, 2018, 8 (38), 21174-21183
Modifying bis (triflimide) ionic liquids by dissolving early transition metal carbamates, L Biancalana, G Bresciani, C Chiappe, F Marchetti, G Pampaloni, CS Pomelli, Physical Chemistry Chemical Physics, 2018, 20 (7), 5057-5066
Exploring and exploiting different catalytic systems for the direct conversion of cellulose into levulinic acid, C Chiappe, MJR Douton, A Mezzetta, L Guazzelli, CS Pomelli, G Assanelli, AR de Angelis, New Journal of Chemistry, 2018, 42 (3), 1845-1852
Recycle and extraction: cornerstones for an efficient conversion of cellulose into 5-hydroxymethylfurfural in ionic liquids, C Chiappe, MJ Rodriguez Douton, A Mezzetta, CS Pomelli, G Assanelli, AR De Angelis, ACS Sustainable Chemistry & Engineering, 2017, 5 (6), 5529-5536
Copper‐Catalyzed Recyclable Synthesis of (Z)‐3‐Alkylideneisoindolinones by Cycloisomerization of 2‐Alkynylbenzamides in Ionic Liquids, R Mancuso, CS Pomelli, DS Raut, N Marino, SV Giofrè, R Romeo, S Sartini, C Chiappe, G Bartolo, ChemistrySelect, 2017, 2 (3), 894-899
Ionic liquids as potential enhancers for transdermal drug delivery, D Monti, E Egiziano, S Burgalassi, P Chetoni, C Chiappe, A Sanzone, S Tampucci, International journal of pharmaceutics, 2017, 516 (1-2), 45-51
Ionic liquids, ultra-sounds and microwaves: an effective combination for a sustainable extraction with higher yields. The cumin essential oil case, R Ascrizzi, J González-Rivera, CS Pomelli, C Chiappe, P Margari, F Costagli, I Longo, MR Tiné, G Flamini, C Duce, Reaction Chemistry & Engineering, 2017, 2 (4), 577-589
A general environmentally friendly access to long chain fatty acid ionic liquids (LCFA-ILs), A Mezzetta, L Guazzelli, M Seggiani, CS Pomelli, M Puccini, C Chiappe, Green Chemistry, 2017, 19 (13), 3103-3111
Divergent syntheses of iodinated isobenzofuranones and isochromenones by iodolactonization of 2-alkynylbenzoic acids in ionic liquids, R Mancuso, CS Pomelli, F Malafronte, A Maner, N Marino, C Chiappe, G Bartolo, Organic & biomolecular chemistry, 2017, 15 (22), 4831-4841
Hydrogen sulfide and ionic liquids: absorption, separation, and oxidation, C Chiappe, CS Pomelli, Ionic Liquids II, 2017, 265-289
Temperature effects on the viscosity and the wavelength-dependent refractive index of imidazolium-based ionic liquids with a phosphorus-containing anion, C Chiappe, P Margari, A Mezzetta, CS Pomelli, S Koutsoumpos, M Papamichael, P Giannios, K Moutzouris, Physical Chemistry Chemical Physics, 2017, 19 (12), 8201-8209
Synthesis and study of the stability of amidinium/guanidinium carbamates of amines and α-amino acids, L Biancalana, G Bresciani, C Chiappe, F Marchetti, G Pampaloni, New Journal of Chemistry, 2017, 41 (4), 1798-1805
Chiral ionic liquid assisted synthesis of some metal oxides, E Husanu, V Cappello, CS Pomelli, J David, M Gemmi, C Chiappe, RSC Advances, 2017, 7 (2), 1154-1160
Access to cross-linked chitosans by exploiting CO2 and the double solvent-catalytic effect of ionic liquids, A Mezzetta, L Guazzelli, C Chiappe, Green Chemistry, 2017, 19 (5), 1235-1239
From pollen grains to functionalized microcapsules: a facile chemical route using ionic liquids, C Chiappe, GC Demontis, V Di Bussolo, MJR Douton, F Rossella, CS Pomelli, S Sartini, S Caporali, Green Chemistry, 2017, 19 (4), 1028-1033
An insight into the molecular mechanism of the masking process in titanium tanning, CS Pomelli, C Chiappe, F Barontini, M Puccini, M Seggiani, S Vitolo, Clean Technologies and Environmental Policy, 2017, 19 (1), 259-267
Formation, Oxidation, and Fate of the Breslow Intermediate in the N-Heterocyclic Carbene-Catalyzed Aerobic Oxidation of Aldehydes, O Bortolini, C Chiappe, M Fogagnolo, A Massi, CS Pomelli, The Journal of organic chemistry, 2016, 82 (1), 302-312
Product as reaction solvent: an unconventional approach for ionic liquid synthesis, C Chiappe, A Mezzetta, CS Pomelli, M Puccini, M Seggiani, Organic Process Research & Development, 2016, 20 (12), 2080-2084
Nanoscale Disassembly and Free Radical Reorganization of Polydopamine in Ionic Liquids, P Manini, P Margari, CS Pomelli, P Franchi, G Gentile, A Napolitano, L Valgimigli, C Chiappe, V Ball, M d’Ischia, The Journal of Physical Chemistry B, 2016, 120 (46), 11942-11950
Ionic liquids and green chemistry, C Chiappe, CS Pomelli, Anal. Appl. Ionic Liq, 2016, 385-404
Surface study of metal-containing ionic liquids by means of photoemission and absorption spectroscopies, S Caporali, M Pedio, C Chiappe, CS Pomelli, RG Acres, U Bardi, Surface Science, 2016, 648, 360-365
Auto-Tandem Catalysis in Ionic Liquids: Synthesis of 2-Oxazolidinones by Palladium-Catalyzed Oxidative Carbonylation of Propargylic Amines in EmimEtSO4, R Mancuso, A Maner, I Ziccarelli, CS Pomelli, C Chiappe, N Della Ca, L Veltri, G Bartolo, Molecules, 2016, 21 (7), 897
Development of cost-effective biodiesel from microalgae using protic ionic liquids, C Chiappe, A Mezzetta, CS Pomelli, G Iaquaniello, A Gentile, B Masciocchi, Green Chemistry, 2016, 18 (18), 4982-4989
Considerable effect of dimethylimidazolium dimethylphosphate in cinnamon essential oil extraction by hydrodistillation, L Pistelli, S Giovanelli, P Margari, C Chiappe, RSC Advances, 2016, 6 (57), 52421-52426
Arrangements of enantiopure and racemic ionic liquids at the liquid/air interface: the role of chirality on self-assembly and layering, S Caporali, C Chiappe, T Ghilardi, A Iuliano, G Longhi, P Margari, CS Pomelli, RSC Advances, 2016, 6 (10), 8053-8060
Ionic liquids can significantly improve textile dyeing: An innovative application assuring economic and environmental benefits, R Bianchini, G Cevasco, C Chiappe, CS Pomelli, MJ Rodrı́guez Douton, ACS Sustainable Chemistry & Engineering, 2015, 3 (9), 2303-2308
Electrodeposition of transition metals from highly concentrated solutions of ionic liquids, S Caporali, P Marcantelli, C Chiappe, CS Pomelli, Surface and Coatings Technology, 2015, 264, 23-31
Alkylation of methyl linoleate with propene in ionic liquids in the presence of metal salts, CS Pomelli, T Ghilardi, C Chiappe, A de Angelis, V Calemma, Molecules, 2015, 20 (12), 21840-21853
How to make a green product greener: use of ionic liquids as additives during essential oil hydrodistillation, G Flamini, B Melai, L Pistelli, C Chiappe, RSC Advances, 2015, 5 (85), 69894-69898
Eco-friendly titanium tanning for the manufacture of bovine upper leathers: pilot-scale studies, M Seggiani, M Puccini, S Vitolo, C Chiappe, CS Pomelli, D Castiello, Clean Technologies and Environmental Policy, 2014, 16 (8), 1795-1803
Dissolution of metal salts in bis (trifluoromethylsulfonyl) imide-based ionic liquids: studying the affinity of metal cations toward a “weakly coordinating” anion, O Bortolini, C Chiappe, T Ghilardi, A Massi, CS Pomelli, The Journal of Physical Chemistry A, 2014, 119 (21), 5078-5087
Point‐Functionalization of Ionic Liquids: An Overview of Synthesis and Applications, C Chiappe, CS Pomelli, European Journal of Organic Chemistry, 2014, (28), 6120-6139
Ecotoxicity of pristine graphene to marine organisms, C Pretti, M Oliva, R Di Pietro, G Monni, G Cevasco, F Chiellini, CS Pomelli, C Chiappe, Ecotoxicology and environmental safety, 2014, 101, 138-145
Functionalized phosphonium based ionic liquids: properties and application in metal extraction, AC Barsanti, C Chiappe, T Ghilardi, CS Pomelli, RSC Advances, 2014, 4 (73), 38848-38854
Tuning of the freezing and melting points of [Hmim][NO 3] by the addition of water and nitrate salts, F Di Francesco, C Ferrari, L Moni, B Melai, L Bernazzani, C Chiappe, RSC Advances, 2014, 4 (76), 40407-40413
An insight into the mechanism of the aerobic oxidation of aldehydes catalyzed by N-heterocyclic carbenes, O Bortolini, C Chiappe, M Fogagnolo, PP Giovannini, A Massi, CS Pomelli, D Ragno, Chemical Communications, 2014, 50 (16), 2008-2011
Are ionic liquids a proper solution to current environmental challenges?, G Cevasco, C Chiappe, Green Chemistry, 2014, 16 (5), 2375-2385
A recyclable and base-free method for the synthesis of 3-iodothiophenes by the iodoheterocyclisation of 1-mercapto-3-alkyn-2-ols in ionic liquids, R Mancuso, CS Pomelli, C Chiappe, RC Larock, B Gabriele, Organic & biomolecular chemistry, 2014, 12 (4), 651-659