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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
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.

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