RESUMO
We report the design of slippery liquid-infused porous surfaces (SLIPS) fabricated from building blocks that are biodegradable, edible, or generally regarded to be biocompatible. Our approach involves infusion of lubricating oils, including food oils, into nanofiber-based mats fabricated by electrospinning or blow spinning of poly(ε-caprolactone), a hydrophobic biodegradable polymer used widely in medical implants and drug delivery devices. This approach leads to durable and biodegradable SLIPS that prevent fouling by liquids and other materials, including microbial pathogens, on objects of arbitrary shape, size, and topography. This degradable polymer approach also provides practical means to design "controlled-release" SLIPS that release molecular cargo at rates that can be manipulated by the properties of the infused oils (e.g., viscosity or chemical structure). Together, our results provide new designs and introduce useful properties and behaviors to antifouling SLIPS, address important issues related to biocompatibility and environmental persistence, and thus advance new potential applications, including the use of slippery materials for food packaging, industrial and marine coatings, and biomedical implants.
Assuntos
Incrustação Biológica , Polímeros , Incrustação Biológica/prevenção & controle , Excipientes , Lubrificantes , Óleos de Plantas , Polímeros/química , PorosidadeRESUMO
An extensive correlated molecular orbital theory study of the reactions of CO2 with a range of substituted amines and H2O in the gas phase and aqueous solution was performed at the G3(MP2) level with a self-consistent reaction field approach. The G3(MP2) calculations were benchmarked at the CCSD(T)/CBS level for NH3 reactions. A catalytic NH3 reduces the energy barrier more than a catalytic H2O for the formation of H2NCOOH and H2CO3. In aqueous solution, the barriers to form both H2NCOOH and H2CO3 are reduced, with HCO3- formation possible with one amine present and H2NCOO- formation possible only with two amines. Further reactions of H2NCOOH to form HNCO and urea via the Bazarov reaction have high barriers and are unlikely in both the gas phase and aqueous solution. Reaction coordinates for CH3NH2, CH3CH2NH2, (CH3)2NH, CH3CH2CH2NH2, (CH3)3N, and DMAP were also calculated. The barrier for proton transfer correlates with amine basicity for alkylammonium carbamate (ΔGaq < 15 kcal/mol) and alkylammonium bicarbonate (ΔGaq < 30 kcal/mol) formation. In aqueous solution, carbamic acids, carbamates, and bicarbonates can all form in small amounts with ammonium carbamates dominating for primary and secondary alkylamines. These results have implications for CO2 capture by amines in both the gas phase and aqueous solution as well as in the solid state, if enough water is present.