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Temtem M, Casimiro T, Mano JF, Aguiar-Ricardo A. "Preparation of membranes with polysulfone/polycaprolactone blends using a high pressure cell specially designed for a CO2-assisted phase inversion." Journal of Supercritical Fluids. 2008;43(3):542-548. AbstractWebsite
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Temtem M, Barroso T, Casimiro T, Mano JF, Aguiar-Ricardo A. "Dual stimuli responsive poly(N-isopropylacrylamide) coated chitosan scaffolds for controlled release prepared from a non residue technology." Journal of Supercritical Fluids. 2012;66:398-404. AbstractWebsite
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Temtem M, Pompeu D, Jaraquemada G, Cabrita EJ, Casimiro T, Aguiar-Ricardo A. "Development of PMMA membranes functionalized with hydroxypropyl-β-cyclodextrins for controlled drug delivery using a supercritical CO2-assisted technology." International Journal of Pharmaceutics. 2009;376(1-2):110-115. AbstractWebsite
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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, 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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Temtem M, Pompeu D, Casimiro T, Mano JF, Aguiar-Ricardo A. "Supercritical CO 2 generating chitosan membranes and microparticles.". In: 8th World Biomaterials Congress 2008. Vol. 2.; 2008:. Abstract
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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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Temtem M, Casimiro T, Aguiar-Ricardo A. "Solvent power and depressurization rate effects in the formation of polysulfone membranes with CO2-assisted phase inversion method." Journal of Membrane Science. 2006;283(1-2):244-252. AbstractWebsite
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Temtem M, Casimiro T, Mano JF, Aguiar-Ricardo A. "Green synthesis of a temperature sensitive hydrogel." Green Chemistry. 2007;9(1):75-79. AbstractWebsite
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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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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.

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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Ricardo AA, Barreiros SF, Nunes Da Ponte M, Albuquerque GMN, Calado JCG. "(p, Vm, T) of (0.476Ar + 0.524N2)(I) and the calculation of thermodynamic properties of liquid air." The Journal of Chemical Thermodynamics. 1992;24(12):1281-1291. AbstractWebsite
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Ribeiro N, Costa T, Aguiar-Ricardo A, Esperança JMSS, Pires PF, Guedes HJR. "Acoustic determination of thermophysical properties and critical parameters for R410A and critical line of xCO2 + (1 - X)R410A." Journal of Chemical and Engineering Data. 2006;51(5):1906-1914. AbstractWebsite
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Ribeiro N, Casimiro T, Duarte C, Nunes Da Ponte M, Aguiar-Ricardo A, Poliakoff M. "Vapor-Liquid Equilibrium and Critical Line of the CO2 + Xe System. Critical Behavior of CO2 + Xe versus CO2 + n-Alkanes." Journal of Physical Chemistry B. 2000;104(4):791-795. AbstractWebsite
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Ribeiro N, Aguiar-Ricardo A, Kordikowski A, Poliakoff M. "Acoustic determination of the critical surface of {χ1CO2 + χ2C2H6 + (1 - χ1 - χ2)CHF3}." Physical Chemistry Chemical Physics. 2001;3(6):1027-1033. AbstractWebsite
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Ribeiro N, Aguiar-Ricardo A. "A simple acoustic probe for fluid phase equilibria: Application to the CO2 + N(C2H5)3 system." Fluid Phase Equilibria. 2001;185(1-2):295-303. AbstractWebsite
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Restani RB, Correia VG, Bonifácio VDB, Aguiar-Ricardo A. "Development of functional mesoporous microparticles for controlled drug delivery." Journal of Supercritical Fluids. 2010;55(1):333-339. AbstractWebsite
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Restani RB, Morgado PI, Ribeiro MP, Correia IJ, Aguiar-Ricardo A, Bonifácio VDB. "Biocompatible Polyurea Dendrimers with pH-Dependent Fluorescence." Angewandte Chemie International Edition. 2012;51:5162-5165. AbstractWebsite

Biocompatible and biodegradable water-soluble dendrimers comprising ureas within the interior and amino groups on the periphery were synthesized in supercritical carbon dioxide (dendrimer of generation 1 shown in picture). This novel class of dendrimers shows a pH-dependent intrinsic blue fluorescence at very low concentrations, which makes them potential polymeric fluorescent cell markers.

Reis TC, Correia IJ, Aguiar-Ricardo A. "Electrodynamic tailoring of self-assembled three-dimensional electrospun constructs." Nanoscale. 2013;5(16):7528-7536. AbstractWebsite
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Reis JCR, Ribeiro N, Aguiar-Ricardo A. "Can the speed of sound be used for detecting critical states of fluid mixtures?" Journal of Physical Chemistry B. 2006;110(1):478-484. AbstractWebsite
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Raje VP, Morgado PI, Ribeiro MP, Correia IJ, Bonifácio VDB, Branco PS, Aguiar-Ricardo A. "Dual on–off and off–on switchable oligoaziridine biosensor." Biosensors and Bioelectronics. 2013;39:64-69. AbstractWebsite
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