Degree: Doctor

Affiliation(s):

FCUP

Bio

Professional career:

(i) 2007 - 2011: Ph.D. in Chemistry
at CIQ-UP - Faculdade de Ciências da Universidade do Porto;
FCT grant SFRH/BD/29394/2006

(ii) 2012 - 2018: Post-doc researcher in Chemistry
at CIQ-UP - Faculdade de Ciências da Universidade do Porto and QOPNA - Universidade de Aveiro;
FCT grant SFRH/BPD/77972/2011

(iii) 2019 - present: Researcher in Chemistry
at CIQ-UP - Faculdade de Ciências da Universidade do Porto


Actual research interests: Molecular structure and energetics; molecular symmetry and entropy; electron correlation in aromatic molecules; aromatic interactions; reactivity of fullerenes; ionic liquids; phase change kinetics and thermodynamics; Suzuki-Miyaura cross-coupling reaction. 

Expertise in the following methodologies: Various types of calorimetric techniques (combustion, DSC, Calvet, Drop); Knudsen effusion methods; Thermogravimetry; 1H, 13C, 2D, and dynamic NMR spectroscopy; UV-Vis spectroscopy; FTIR spectroscopy; GC chromatography; Synthesis of organic compounds by cross-coupling methods; Purification and characterization of organic compounds; Computational thermochemistry. 


Short CV:

- 49 papers in international peer-reviewed journals;

- 1 paper in national peer-reviewed journals;

- Experience as a referee for international peer-reviewed journals;

- Experience as supervisor of undergraduate, Master, and Ph.D. students;

- Academic teaching experience in various Chemistry courses;

- Participation in various initiatives of scientific divulgation (ex. Science Fairs, Open University Days, Winter School, Workshops).


Selected publications:

1 - "Role of the Base and Control of Selectivity in the Suzuki–Miyaura Cross-Coupling Reaction"; Carlos F. R. A. C. Lima, Ana S. M. C. Rodrigues, Vera L. M. Silva, Artur M. S. Silva, Luís M. N. B. F. Santos, ChemCatChem, 2014, 6, 1291;

2 - "Experimental Support for the Role of Dispersion Forces in Aromatic Interactions"; Carlos F. R. A. C. Lima, Marisa A. A. Rocha, Lígia R. Gomes, John N. Low, Artur M. S. Silva, Luís M. N. B. F. Santos, Chem. Eur. J., 2012, 18, 8934 (VIP paper);

3 - "Understanding M-ligand bonding and mer-/fac- isomerism in tris(8-hydroxyquinolinate) metallic complexes"; Carlos F. R. A. C. Lima, Ricardo J. S. Taveira, José C. S. Costa, Ana M. Fernandes, André Melo, Artur M. S. Silva, Luís M. N. B. F. Santos, Phys. Chem. Chem. Phys, 2016, 18, 16555.


Quotes:

"The chemist’s job is to use molecules to understand the laws of Nature, and to use the laws of Nature to understand molecules."

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Publications
Showing 5 latest publications. Total publications: 50
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1. Phase behaviour and heat capacities of DBN and DBU based protic ionic liquids - Insights into the ionic character and nanostructuration, Ribeiro, FMS; Silva, RMA; Santos, LMNBF; Lima, CFRAC in JOURNAL OF MOLECULAR LIQUIDS, 2024, ISSN: 0167-7322,  Volume: 411, 
Article,  Indexed in: crossref, scopus, wos  DOI: 10.1016/j.molliq.2024.125687 P-012-PSA
Abstract Herein, we report the thermal behavior and high-precision heat capacity values, at T = 298.15 K, and in the range from 283 to 363 K, for several protic ionic liquids (PILs), derived from the 1:1 liquid mixtures of the organic superbases 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) with some carboxylic acids (propionic, butyric, hexanoic and octanoic). Glass transition, T g , crystallization, T c , cold- crystallization, T cc , and melting, T m , temperatures were determined for the PILs studied, showing marked differences with the base - T g is lower for all DBN PILs, and no T m , T c , and T cc could be obtained for the DBU PILs. The standard molar heat capacities, C 0 p , m , were obtained with an uncertainty of less than +/- 0.3 % and their dependence on the base and on the acid's chain length was studied in detail. The C 0 p , m of the DBU PILs were found to be significantly higher than those of the corresponding DBN PILs, which corroborates the greater ionic character of DBU PILs. The heat capacity data suggested the existence of a trend-shift with the chain length of the carboxylic acid. Similar to aprotic ionic liquids, the shift occurs around n = 5 (pentanoic acid) and suggests the existence of some degree of nanostructuration into polar and non-polar domains in PILs with larger acids. Moreover, PILs can display abnormally high excess heat capacities, resulting from the formation of an ionic mixture from neutral species. Analysis of the calculated excess heat capacities indicates that PILs tend to become less ionic as the temperature increases, which goes in accordance with the acid-base equilibrium shift.
2. Theoretical Study on the Diels–Alder Reaction of Fullerenes: Analysis of Isomerism, Aromaticity, and Solvation, Rodrigues, DJL; Santos, LMNBF Melo, A; Lima, CFRAC in Organics, 2022, Volume: 3, 
Article,  Indexed in: crossref  DOI: 10.3390/org3040025 P-00X-PAX
Abstract <jats:p>Fullerenes are reactive as dienophiles in Diels–Alder reactions. Their distinctive molecular shape and properties result in interesting and sometimes elusive reaction patterns. Herein, to contribute to the understanding of fullerene reactivity, we evaluate the energies of reactions for Diels–Alder cycloadditions of C60, C70, and IC60MA with anthracene (Ant), by means of DFT computational analysis in vacuum and solution. The methods used showed little differentiation between the reactivity of the different fullerenes. The C70-Ant adducts where addition takes place near the edge of the fullerene were found to be the most stable regioisomers. For the IC60MA-Ant adducts, the calculated energies of reaction increase in the order: equatorial &gt; trans-3 &gt; trans-2 ≈ trans-4 ≈ trans-1 &gt; cis-3 &gt; cis-2. The change in the functional suggests the existence of stabilizing dispersive interactions between the surface of the fullerene and the addends. HOMA (harmonic oscillator model of aromaticity) analysis indicated an increase in aromaticity in the fullerene hexagons adjacent to the bonded addend. This increase is bigger in the rings of bisadduct isomers that are simultaneously adjacent to both addends, which helps explain the extra stability of the equatorial isomers. Solvation by m-xylene decreases the exothermicity of the reactions studied but has little distinguishing effect on the possible isomers. Thermal corrections reduce the exothermicity of the reactions by ~10 kJ∙mol−1.</jats:p>
3. Solid-Liquid-Gas Phase Equilibria for Small Phenylene-Thiophene Co-Oligomers, Lima, CFRAC Costa, JCS Silva, AMS; Mendes, A; Santos, LMNBF in JOURNAL OF CHEMICAL AND ENGINEERING DATA, 2022, ISSN: 0021-9568,  Volume: 67, 
Article,  Indexed in: crossref, scopus, wos  DOI: 10.1021/acs.jced.2c00459 P-00X-9X2
Abstract This work reports a comprehensive experimental evaluation of the solid-liquid-gas phase equilibria for five representative phenylene-thiophene co-oligomers (3-ring aromatic compounds having both phenyl and thienyl units). The melting temperatures and corresponding standard molar enthalpies and entropies of fusion were measured by differential scanning calorimetry. The equilibrium vapor pressures of the crystalline solids as a function of temperature were measured by a combined Knudsen/quartz-crystal effusion method, with the consequent derivation of the standard molar enthalpies, entropies, and Gibbs energies of sublimation. The thermodynamic properties of vaporization were estimated from the fusion and sublimation data. The results were analyzed together with the literature data for the corresponding phenylene and thiophene homo-oligomers. The thermodynamic properties of fusion and sublimation exhibited a dependence on ring identity and position that cannot be adequately described by a simple group additivity reasoning. The plot of the Gibbs energy of sublimation as a function of the number of thienyl rings in the co-oligomer showed the existence of two series. Terminal 3-thienyl rings and a linear molecular shape were found to be consistent factors contributing to the stabilization of the crystal phase. The higher melting temperatures and lower volatilities of crystalline 3-thienyl compounds were tentatively explained by the ability of these rings to maximize intermolecular C-H & BULL;& BULL;& BULL;pi interactions independently of the sulfur position. The optical energy gaps, as measured by UV-vis in solution, were found to lie within the values for typical organic semiconductors (< 4 eV) and to decrease for co-oligomers containing more 2-thienyl units, following the increased ring-ring planarity of the molecules. The surface morphology of vapor-deposited thin films suggests a stronger tendency of the co-oligomers, if compared to their corresponding homo-oligomers p-terphenyl and terthiophene, to form less amorphous films.
4. Thermochemical and structural studies of gallic and ellagic acids, Davalos, JZ; Lima, CFRAC Santos, LMNBF Romero, VL; Liebman, JF in JOURNAL OF CHEMICAL THERMODYNAMICS, 2019, ISSN: 0021-9614,  Volume: 129, 
Article,  Indexed in: crossref, scopus, wos  DOI: 10.1016/j.jct.2018.09.027 P-00P-NQR
Abstract We report a study on the energetics and structural properties of gallic (1) and ellagic (2) acids. The experimental values of standard enthalpy of formation in solid state at 298.15 K, Delta H-f(m)0 (cd) of 1 as (-985.0 +/- 2.9 kJ.mol(-1)) and 2 as (-1377.9 +/- 4.7 kJ.mol(-1)) have been determined. The vapour pressure of 1 have been measure by Knudsen effusion methodology and the derived enthalpy of sublimation, Delta H-g(cd)m(0). was combined with the Delta H-f(m)0 (cd) in order to derive its gas-phase enthalpy of formation, Delta(f) H-m(0)(1,g) = -835.7 +/- 4.0 kJ.mol(-1). Quantum chemical calculations, at DFT (M05-2X) and composite ab initio Gn (n = 3, 4) levels of theory, provided the consistency of the experimental results and a plausible estimation of Delta H-f(m)0 (g) of 2 as (-1128.6 +/- 6.4 kJ.mol(-1)), which was deduced from the isodesmic-reactions methodology. (C) 2018 Published by Elsevier Ltd.
5. Heat Capacity and Phase Behavior of Selected Oligo(ethylene glycol)s, Pokorny, V; Serra, PBP; Fulem, M; Lima, CFRAC Santos, LMNBF Ruzicka, K in JOURNAL OF CHEMICAL AND ENGINEERING DATA, 2019, ISSN: 0021-9568,  Volume: 64, 
Article,  Indexed in: crossref, scopus, wos  DOI: 10.1021/acs.jced.9b00140 P-00Q-QGF
Abstract This work aims to provide reliable heat capacities for ethylene glycol and selected oligo(ethylene glycol)s (diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, and hexaethylene glycol), which are industrially important chemicals produced on a large scale. Besides, new data extend the database needed for a better understanding of complex behavior of compounds capable of forming hydrogen bonds. Isobaric heat capacities of ethylene glycols were measured with a Tian-Calvet-type calorimeter in the temperature range of 260 to 358 K. The phase behavior was investigated with a heat-flux differential scanning calorimeter. A simple additive estimation method for liquid heat capacity of oligo(ethylene glycol)s was developed and tested through comparison with newly measured liquid heat capacities of polyethylene glycols 400 and 600.