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SER

Structure, Energetics and Reactivity

Thermodynamics and Solid State Chemistry

Our research is centered in solid state chemistry of organic compounds, aiming at the design, search, and selective preparation of solid forms. Active pharmaceutical ingredients, APIs, are the main targets of research owing to the potential impact of dissimilarities in physico-chemical properties of the different solid forms on API stability and effectiveness.

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Engineering multicomponent pharmaceutical solid samples - co-crystals, salts, solvates, solid solutions, binary eutectics - aiming at biopharmaceutical performance improvement or dual-drug therapy, is one the targets of research. A special emphasis is placed on co-crystals investigation, namely on the effect of co-former structural changes and synthon competition on co-crystal formation capability, and on the potential use of co-crystals for chiral resolution.

Polymorphism of organic APIs and other organic compounds (with emphasis on chiral ones, both enantiomers and racemates) is also being addressed. Solvent effects on polymorph crystallization and rationalization of the ability of molecular compounds to give rise to plastic crystal mesophases are topics being investigated.

Polymorphism of organic APIs and other organic compounds (with emphasis on chiral ones, both enantiomers and racemates) is also being addressed. Solvent effects on polymorph crystallization and rationalization of the ability of molecular compounds to give rise to plastic crystal mesophases are topics being investigated.

Current laboratory members

Integrated

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MarioRosado

M. Ermelinda S. Eusébio,

Department of Chemistry, FCTUC

João Canotilho,

Faculty of Pharmacy, UC

Mário T. S. Rosado,

Department of Chemistry, FCTUC


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Ricardo A. E. Castro,

Faculty of Pharmacy, UC

Teresa M. R. Maria,

Department of Chemistry, FCTUC



Collaborators

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Manuela Ramos Silva,

Department of Physics, FCTUC

Ewa Dryzek,

Henryk Niewodniczański Institute of Nuclear Physics Polish Academy of Sciences, Krakow, Poland

  
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Gilbert Bannach,

UNESP, Universidade Estadual Paulista, Brazil

Glauco Lini Perpétuo,

UNESP, Universidade Estadual Paulista, Brazil

Students

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Mariani Armagni Ciciliati,

PhD student - sandwich, (Universidade de São Paulo, Brazil)

Bruno Barreto da Cunha Holanda,

PhD student – sandwich, (Universidade Estadual Paulista, Brazil)

Joana Silva,

MSc Student



MSc Researcher

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João Agria Baptista,

MSc researcher





Research highlights

  • Synthesis of pharmaceutical co-crystals and identification of pharmaceutical binary eutectic mixtures with API improved intrinsic dissolution rate.
  • Synthesis of dual-drug co-crystals.



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  • Identification of criteria for evaluation of plastic crystal mesophases formation ability
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Recent publications

Machado, S.M.T., Castro, R.A.E., Maria, T.M.R., Canotilho, J., Eusébio, M.E.S., Levetiracetam + nonsteroidal anti-inflammatory drug binary systems: a contribution to the development of new solid dosage forms, Int. J. Pharm., 533, pp. 1-13, 2017. DOI:10.1016/j.ijpharm.2017.09.012

Maria, T.M.R., Marins, F.A., Costa, J.B.S., Ramos Silva, M. Carrilho, R.M.B., Monteiro, C.J.P., Pereira, M.M., Eusébio, M.E.S., Solid state investigation of BINOL and BINOL derivatives: A contribution to enantioselective symmetry breaking by crystallization, Thermochim. Acta, 648, pp. 32-43, 2017.

DOI: 10.1016/j.tca.2016.12.008

 Cortesão, A.M., Henriques, J.G., Castro, R.A.E., Maria, T.M.R., Canotilho, J., Eusébio, M. E.S., Binary phase diagrams of pyridinecarboxamide isomers, J. Therm. Anal. Calorim., 130, pp. 1727–1733, 2017.

DOI: 10.1007/s10973-017-6474-2

 Nogueira, B.A., Ildiz, G.O., Canotilho, J., Eusébio, M.E.S., Henriques, M.S.C., Paixão, J.A., Fausto, R., 5-Methylhydantoin: From Isolated Molecules in a Low-Temperature Argon Matrix to Solid State Polymorphs Characterization, J. Phys. Chem. A, 121, pp. 5267-5279, 2017.

DOI: 10.1021/acs.jpca.7b05030

 Viel, Q., Brandel, C., Cartigny, Y., Eusébio, M.E.S., Canotilho, J., Dupray, V., Dargent, E., Coquerel, G., Petit, S., Crystallization from the Amorphous State of a Pharmaceutical Compound: Impact of Chirality and Chemical Purity, Cryst. Growth Des., 17, pp. 337-346, 2017.

DOI: 10.1021/acs.cgd.6b01566

 Susano, M.T., Martín-Ramos, P., Maria, T.M.R., Folkersma, S., Pereira, L.C.J., Ramos Silva, M., Co-crystal of suberic acid and 1,2-bis(4-pyridyl)ethane: A new case of packing polymorphism, J. Mol. Struct., 1147, pp, 76-83, 2017.

DOI: 10.1016/j.molstruc.2017.06.043

 Martín-Ramos, P., Maria, T.M.R., Guimaraes, A.C., Carrión-Prieto, P., Hernández-Navarro, S., Martín-Gil, J., Crude and refined oils from Elaeis guineensis: Facile characterization by FTIR and thermal analysis techniques, Int. J. Food Prop., 20S3, pp. S2739-S2749, 2017.

DOI: 10.1080/10942912.2017.1372470

 Perpétuo, G.L., Chierice, G.O., Ferreira, L.T., Fraga-Silva, T.F.C., Venturini, J., Arruda, M.S.P., Bannach, G., Castro, R.A.E., A combined approach using differential scanning calorimetry with polarized light thermomicroscopy in the investigation of ketoprofen and nicotinamide cocrystal, J. Therm. Anal. Calorim., 651, pp. 1-10, 2017.

DOI: 10.1016/j.tca.2017.02.014

 Évora, A.O.L., Castro, R.A.E., Maria, T.M.R., Ramos Silva, M., ter Horst, J.H., Canotilho J., Eusébio, M.E.S., Co-crystals of diflunisal and isomeric pyridinecarboxamides - a thermodynamics and crystal engineering contribution, Cryst. Eng.Comm., 18, pp. 4749-4759, 2016.

DOI: 10.1039/c6ce00380j

 Miranda, M.D., Chávez, F.V., Maria, T.M.R., Eusébio, M.E.S., Sebastião, P.J., Martín-Ramos, P., Figueirinhas, J.L., Ramos Silva, M., Synthesis of liquid crystals based on hydrogen-bonding of 4-(Octyloxy)benzoic acid with 4-alkylbenzoic acids, Mol. Cryst. Liq. Cryst., 630, pp. 87-101, 2016.

DOI: 10.1080/15421406.2016.1146881

 Gallo, R.C., Ferreira, A.P.G., Castro, R.A.E., Cavalheiro, E.T.G., Studying the thermal decomposition of carvedilol by coupled TG-FTIR, J. Therm. Anal. Calorim., 123, pp. 2307-2312, 2016.

DOI:10.1007/s10973-015-4931-3

 Sousa, A.F., Gandini, A., Caetano, A., Maria, T.M.R., Freire, C.S.R., Neto, C. P.l, Silvestre, A.J.D., Unravelling the distinct crystallinity and thermal properties of suberin compounds from Quercus suber and Betula pendula outer barks, Int. J. Biol. Macromol. 93, pp. 686-694, 2016.

DOI: 10.1016/j.ijbiomac.2016.09.031

 Brandel, C., Cartigny, Y., Couvrat, N., Eusébio, M.E.S., Canotilho, J., Petit, S., Coquerel, G., Mechanisms of Reversible Phase Transitions in Molecular Crystals: Case of Ciclopirox, Chem. Mater., 27, pp. 6360-6373, 2015.

DOI: 10.1021/acs.chemmater.5b02389

 Silva, P.S.P., Castro, R.A.E., Melro, E., Ramos Silva, M., Maria, T.M.R., Canotilho, J., Eusébio, M.E.S., Structural evidence of polymorphism and conformational isomorphism of a somewhat flexible molecule: m-anisic acid, J. Therm. Anal. Calorim., 120, pp. 667-677, 2015.

DOI: 10.1007/s10973-014-4289-y

 Évora, A.O.L., Castro, R.A.E., Maria, T.M.R., Ramos Silva, M., ter Horst, J.H., Canotilho J., Eusébio, M.E.S., A thermodynamic based approach on the investigation of a diflunisal pharmaceutical co-crystal with improved intrinsic dissolution rate. Int. J. Pharm., 466, pp.67–74, 2014.

DOI: 10.1016/j.ijpharm.2014.02.048

 Bebiano, S.V.S., Rosado, M.T.S., Castro, R.A.E., Ramos Silva, M., Canotilho, J., Maria, T.M.R., Eusébio, M.E.S., Polymorphism of cis-1,4-cyclohexanediol, a new plastic crystal former. Considerations on isomeric cyclohexanediols plastic crystal forming abilities, J. Mol. Struct., Polymorphism and Disorder issue, 1078, pp. 10-19, 2014.

DOI: 10.1016/j.molstruc.2014.02.008

 Rosado, M.T.S., Maria, T.M.R., Castro, R.A.E., Canotilho, J., Ramos Silva, M., Eusébio, M.E.S., Molecular structure and polymorphism of a cyclohexanediol: trans-1,4-cyclohexanedimethanol, Cryst. Eng. Comm., 16, pp. 10977-10986, 2014.

DOI:10.1039/c4ce01211a

 Nogueira, B., Ildiz, G., Canotilho, J., Eusébio, M.E.S., Fausto, R., Molecular Structure, Infrared Spectra, Photochemistry and Thermal Properties of 1-Methylhydantoin, J. Phys. Chem. A, 118, pp. 5994-6008, 2014.

DOI: 10.1021/jp505335c

 Arranja, C.T., Marcos, M., Ramos Silva, M., Eusébio, M.E.S., Castro, R.A.E., Sobral, A.J.F.N., Synthesis and polymorphism evaluation of the 3,5-bis(decyloxy)benzaldehyde, J. Therm. Anal. Calorim., 117, pp. 1375-1383, 2014.

DOI 10.1007/s10973-014-3904-2

 Miranda, M.D., Chávez, F.V., Maria, T.M.R., Eusébio, M.E.S., Sebastião, P.J., Ramos Silva, M., Self-assembled liquid crystals by hydrogen bonding between bipyridyl and alkylbenzoic acids: solvent free synthesis by mechanochemistry, Liq. Cryst., 41, pp. 1743-1751, 2014.

DOI: 10.1080/02678292.2014.950048

 Maria, T.M.R., Castro, R.A.E., Ramos Silva, M., Ramos, M.L., Justino, L.L.G., Burrows, H.D., Canotilho, J., Eusébio, M.E.S., Polymorphism and melt crystallisation of racemic betaxolol, a beta-adrenergic antagonist drug, J. Thermal Anal. Calorim., 111, pp. 2171-2178, 2013.

DOI: 10.1007/s10973-012-2765-9

 Cabral, L.I.L., Maria, T.M.R., Martelo, L., Eusébio, M.E.S., Cristiano, M.L.S., Fausto, R., The Thermal sigmatropic isomerization of pseudosaccharyl crotyl ether, Tetrahedron, 69, pp. 810-815, 2013.

DOI: 10.1016/j.tet.2012.10.100

Polarized-light thermomicroscope
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One of our

DSC systems

Variable temperature FTIR

with interchangeable

ATR accessory

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