Molecular and Engineering Thermodynamics (MET)

Group Coordinator: Eduardo Filipe

The present MET group congregates 18 members from IST and 9 new members from FCUL. All share the goal of exploring the
links between structure, energetics and interactions at a molecular level, and macroscopic thermodynamic properties. Such
relationships impact different technological areas, with applications ranging from traditional heavy-duty industries (fuel extraction,
cement) to the life sciences (drug development, processing and delivery, respiratory gases, bio-implants).
The group activities can be described by classes of system, properties addressed, and physical conditions considered:

A- The most obvious thermodynamic properties that can be studied are bulk equilibrium or transport properties and the MET
group excels in high-precision experiments and development of theoretical models. Those studies cover pure substances and
mixtures in different phases, under normal pressure-temperature settings and also supercritical domains.

B- One way to modify the relations between structure and molecular interactions is to go from bulk to interface. Such shift has
been explored by relevant works on self-assembly and nano-segregation, diffusion in films, modification of solid substrates, or
crystallization processes.

C- The structure-interaction status-quo can also be changed by introducing ions. This is the realm of ionic liquids (ILs), a recent
class of compounds with unique properties. Contributions in this area include both experimental characterization and modeling of
structural and thermophysical properties.

These research trends converge when applications and relations to CQE TLs are considered: e.g. transport and equilibrium
properties of fluids impact fuel extraction industries (SUSChem); surface and modeling studies are significant for development of
new hydraulic binders (MATSoft), non-equilibrium and supercritical processes are relevant for drug development, optimization and
delivery (MEDLife); ILs can act as reaction or separation media (SYNCat).

There has been a consistent flow of achievements associated with each of the three above-mentioned research trends and their
applications. This can be attested first by more than 300 publications in peer-reviewed ISI-WoK journals in the 2013-
2017 period.

FLUID TECHNOLOGY
Supercritical CO2 can control the crystalline size, morphology, and form of pharmaceutical substances; this led to two
international patents and a national innovation prize. The addition of supercritical CO2 to poly(ethylene) glycols to promote their
process engineering efficiency has been analyzed. A new industrial reference fluid for viscosity was characterized within the
scope of the International Association for Transport Properties.

SURFACE AND NON-EQUILIBRIUM
The relationships between stability, structure, and dynamics of individual molecules, crystals, cell membrane models, and even
living cells have been analyzed. Monolayer studies of copolymers, phospholipids, and hydrophobic ionic liquids at the air-water
interface and surface characterization of films involving copolymers and phospholipids have been carried out. The performance of
antitubercular molecules across cell membranes was accessed. Energy signatures of the effect of exogenous chemical species
on cell metabolism and of cell adaptation have been characterized in real-time. Carbon aggregates (nanotubes, graphene,
fullerenes) have been modeled in the context of their mechanical properties both at a molecular level and in terms of surface
interactions with other molecules. A MET group member acted as PI of the M-ERA.NET PROJECT SurfLenses 2014-2016
involving the University of Iceland and the company PhysIOL from Belgium.

IONIC LIQUIDS AND COMPLEX MIXTURES
Development of different simulation techniques for the study of ionic liquids has been pursued. The articles comprising the corpus
of the CL&P force field for the systematic modeling of ILs have been cited more than 1700 times. Polarizability is now being
introduced in the original force field. The popularity of the force field has been matched by its application to the characterization of
ILs as nano-segregated media and studies related to hydrotrope effects, deep-eutectic solvents, viscosity and surface tension
anomalies, and ionic liquid liquid-crystals. The use of ionic liquids in different applications ranging from Aqueous Biphasic
Systems to separation membranes has also been explored.

SELECTED PUBLICATIONS

Canongia Lopes, J.N.; Pádua, A.A.H.; Shimizu, K.; Molecular Force Field for Ionic Liquids IV: Trialkylimidazolium and Alkoxycarbonyl-Imidazolium Cations; Alkylsulfonate and Alkylsulfate Anions. J. Phys. Chem. B, 112, 5039-5046, 2008. DOI: 10.1021/jp800281e; IF=3.607; CIT=93.

Tariq, M.; Freire, M.G.; Saramago, B.; Coutinho, J.A.P.; Canongia Lopes, J.N.; Rebelo, L.P.N.; Surface tension of ionic liquids and ionic liquid solutions, Chem. Soc. Rev., 41, 829-868, 2012. DOI: 10.1039/c1cs15146k; IF=24.892; CIT=58.

Freire, M. G.; Neves, C. M. S. S.; Marrucho, I. M.; Canongia Lopes, J. N.; Rebelo, L. P. N.; Coutinho, J. A. P.; High-performance extraction of alkaloids using aqueous two-phase systems with ionic liquids, Green Chem. 12; 1715-1718, 2010. DOI: 10.1039/c0gc00179a; IF=6.828; CIT=68

Palavra, A.M.F.; Coelho, J.P.; Barroso, J.G.; Rauter, A. P.; Fareleira J.M.N.A.; Mainar, A.; Urieta, J.S.; Nobre, B.P.; Gouveia, L.; Mendes, R.L.; Cabral, J.M.S.; Novais, J.M.; Supercritical Carbon Dioxide Extraction of Bioactive Compounds from Microalgae and Volatile Oils from Aromatic Plants; J. Supercrit. Fluids 60, 21-27, 2011. DOI: 10.1016/j.supflu.2011.04.017; IF=2,86 ; CIT=11

Grosso, C.; Ferraro, V.; Figueiredo, A. C.; Barroso, J. G.; Coelho, J. A.; Palavra, A. M.; Supercritical Carbon Dioxide Extraction of Volatile Oil from Italian Coriander Seeds; Food Chemistry 111, 197-203, 2008. DOI: 10.1016/j.foodchem.2008.03.031; IF=3,334 ; CIT=56

Koehler, R.; Restolho, J.; Krastev, R.; Shimizu, K.; Canongia Lopes, J.N.; Saramago, B.; Liquid- or Solid-Like Behavior of [omim][BF4] at a Solid Interface?. J. Phys. Chem. Lett. 2, 1551-1555, 2011. DOI: 10.1021/jz2005682; IF=6,586 ; CIT=3

Rodrigues, M.A.; Figueiredo, L.; Padrela, L.; Cadete, A.; Tiago, J.; Matos, H.A.; Gomes de Azevedo, E.; Florindo, H.F.; Gonçalves, L.M.; Almeida, A.J.; Development of a novel mucosal vaccine against strangles by supercritical enhanced suspensions. Eur. J. Pharm. Biopharm. 82, 392-400, 2012. DOI: 10.1016/j.ejpb.2012.07.005; IF=3.826 ; CIT=3

Saramago, B.; Thin liquid wetting films. Curr. Opi. Colloid Interface Sci. 15, 330–340, 2010. DOI: 10.1016/j.cocis.2010.05.005; IF=6.629 ; CIT=6

Caetano, F.J.P.; Fareleira, J.M.N.A.; Fröba, A.P., Harris, K.R.; Leipertz, A.; Oliveira, C.M.B.P.; Trusler, J. P.M.; Wakeham, W.A.; An Industrial Reference Fluid for Moderately High Viscosity, J. Chem. Eng. Data 53, 2003-2011, 2008. DOI: 10.1021/je800059n; IF=2.004 ; CIT=21

Bardin, L.; Fauré, M.C.; Limagne, D.; Chevallard, C.; Konovalov, O.; Filipe, E.F.M.; Waton, G.; Krafft, M.P.; Goldmann, M.; Fontaine, P.; Long Range Nanometer Scale Organization of Semi-Fluorinated Alkane Monolayers at the Air/Water Interface, Langmuir 2, 13497-13505, 2011. DOI: 10.1021/la201802x; IF=4,187 ; CIT=6