Publications

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2012
da Silva MS, Viveiros R, Coelho MB, Aguiar-Ricardo A, Casimiro T. "Supercritical CO2-assisted preparation of a PMMA composite membrane for bisphenol A recognition in aqueous environment." Chemical Engineering Science. 2012;68:94-100. AbstractPDFWebsite

This work reports a novel strategy to prepare affinity composite membranes using supercritical fluid technology. By blending molecularly imprinted polymeric particles with PMMA, a porous hybrid structure with affinity to the template molecule, bisphenol A, was prepared using a supercritical carbon dioxide (scCO2)-assisted method. Membranes were characterized in terms of morphology, mechanical performance and transport properties. The ability of the polymers and hybrid membranes to adsorb bisphenol A was tested in aqueous solutions and fitted to a linearized Langmuir equation, showing that adsorption takes place at homogeneous affinity binding sites within the imprinted surface. Filtration experiments showed that the imprinted hybrid membrane was able to adsorb higher amounts of template even in non-equilibrium dynamic binding conditions. The hybridization of the PMMA membrane herein reported conveys two important improvements over neat PMMA membrane: it introduced molecular affinity towards the template molecule and significantly increased the permeability of the porous structures, which are key parameters in processes that involve membranes. This technique could expand the applications of polymeric beads powders and enhance the efficiency of the membrane's transport properties. Our work presents a new method to confer affinity to a porous structure by immobilization of imprinted polymers, combining polymer synthesis and membrane formation using supercritical fluid technology.

da Silva MS, Viveiros R, Aguiar-Ricardo A, Bonifacio VDB, Casimiro T. "Supercritical fluid technology as a new strategy for the development of semi-covalent molecularly imprinted materials." RSC Adv.. 2012;2:5075-5079. AbstractPDFWebsite

Molecularly imprinted polymeric particles with molecular recognition towards Bisphenol A (BPA) were synthesized for the first time using the semi-covalent imprinting approach in supercritical carbon dioxide (scCO2). The material{'}s affinity to BPA was achieved by co-polymerizing ethylene glycol dimethacrylate (EGDMA) with a template-containing monomer{,} Bisphenol A dimethacrylate (BPADM) in scCO2. Bisphenol A is then cleaved from the polymeric matrix by hydrolysis with tetrabutylammonium hydroxide (n-Bu4OH) also in a supercritical environment{,} taking advantage of the high diffusivity of scCO2. The selectivity of the molecular imprinted polymer (MIP) was assessed by evaluating its capability to bind BPA in comparison with progesterone and [small alpha]-ethinylestradiol. In addition{,} the cross-linked particles were used to prepare a PMMA-based hybrid imprinted membrane by a scCO2-assisted phase inversion method. Results show that the incorporation of MIP particles was able to confer molecular affinity to BPA to the membrane and that at dynamic conditions of filtration{,} this imprinted porous structure was able to adsorb a higher amount of BPA than the corresponding non-imprinted hybrid membrane. Our work represents a valuable greener alternative to conventional methods{,} for the synthesis of affinity materials which are able to maintain molecular recognition properties in water.

2011
Correia VG, Bonifácio VD, Raje VP, Casimiro T, Moutinho G, da Silva CL, Pinho MG, Aguiar-Ricardo A. "Oxazoline-Based Antimicrobial Oligomers: Synthesis by CROP Using Supercritical CO 2." Macromolecular Bioscience. 2011;11(8):1128-1137. AbstractWebsite
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Costa E, De-Carvalho J, Casimiro T, da Silva CL, Cidade MT, Aguiar-Ricardo A. "Tailoring thermoresponsive microbeads in supercritical carbon dioxide for biomedical applications." Journal of Supercritical Fluids. 2011;56(3):292-298. AbstractWebsite
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2009
Temtem M, Pompeu D, Barroso T, Fernandes J, Simões PC, Casimiro T, Botelho Do Rego AM, Aguiar-Ricardo A. "Development and characterization of a thermoresponsive polysulfone membrane using an environmental friendly technology." Green Chemistry. 2009;11(5):638-645. AbstractWebsite
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Temtem M, Silva LMC, Andrade PZ, dos Santos F, da Silva CL, Cabral JMS, Abecasis MM, Aguiar-Ricardo A. "Supercritical CO2 generating chitosan devices with controlled morphology. Potential application for drug delivery and mesenchymal stem cell culture." Journal of Supercritical Fluids. 2009;48(3):269-277. AbstractWebsite
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2007
Sousa M, Melo MJ, Casimiro T, Aguiar-Ricardo A. "The art of CO2 for art conservation: A green approach to antique textile cleaning." Green Chemistry. 2007;9(9):943-947. AbstractWebsite
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Brás ARE, Henriques S, Casimiro T, Aguiar-Ricardo A, Sotomayor J, CALDEIRA J, Santos C, Dionísio M. "Characterization of a nematic mixture by reversed-phase HPLC and UV spectroscopy: An application to phase behaviour studies in liquid crystal-CO2 systems." Liquid Crystals. 2007;34(5):591-597. AbstractWebsite
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Temtem M, Casimiro T, Santos AG, Macedo AL, Cabrita EJ, Aguiar-Ricardo A. "Molecular interactions and CO2-philicity in supercritical CO2. A high-pressure NMR and molecular modeling study of a perfluorinated polymer in scCO2." Journal of Physical Chemistry B. 2007;111(6):1318-1326. AbstractWebsite
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2006
Macedo H, Ricardo AA, Sotomayor J. "Construction of a low-cost apparatus for gas adsorption on solids." Journal of Chemical Education. 2006;83(6):915-918. AbstractWebsite
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Duarte ARC, Casimiro T, Aguiar-Ricardo A, Simplício AL, Duarte CMM. "Supercritical fluid polymerisation and impregnation of molecularly imprinted polymers for drug delivery." Journal of Supercritical Fluids. 2006;39(1):102-106. AbstractWebsite
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2005
Casimiro T, Shariati A, Peters CJ, da Ponte MN, Aguiar-Ricardo A. "Phase behavior studies of a perfluoropolyether in high-pressure carbon dioxide." Fluid Phase Equilibria. 2005;228-229:367-371. AbstractWebsite
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2004
Sampaio De Sousa AR, Raeissi S, Aguiar-Ricardo A, Duarte CMM, Peters CJ. "High pressure phase behavior of the system ethane + orange peel oil." Journal of Supercritical Fluids. 2004;29(1-2):59-67. AbstractWebsite
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Casimiro T, Shariati A, Peters CJ, De Ponte MN, Aguiar-Ricardo A. "Phase behavior studies of a perfluoropolyether in high-pressure carbon dioxide." Fluid Phase Equilibria. 2004;224(2):257-261. AbstractWebsite
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Casimiro T, Montilla F, Garcia S, Avilés T, Raeissi S, Shariati A, Peters CJ, Nunes Da Ponte M, Aguiar-Ricardo A. "Phase behaviour of the catalyst dicarbonyl(η5- cyclopentadienyl)-cobalt in carbon dioxide." Journal of Supercritical Fluids. 2004;31(1):1-8. AbstractWebsite
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2003
Aguiar-Ricardo A, Duarte CMM, Ponte MND, Marsh KN, Stølen S. Properties of mixing. Vol. 6.; 2003. AbstractWebsite
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2001
Giles MR, Griffiths RMT, Aguiar-Ricardo A, Silva MMCG, Howdle SM. "Fluorinated graft stabilizers for polymerization in supercritical carbon dioxide: the effect of stabilizer architecture." Macromolecules. 2001;34(1):20-25. AbstractWebsite
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