Blocking of chemical reaction between mefenamic acid and carbon dioxide within pores of nanocrystalline cellulose aerogel

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Abstract
In this work, we investigated how the degree of saturation of a nanocrystalline cellulose (NCC) aerogel with mefenamic acid (MA) affects the chemical reaction between MA and carbon dioxide retained in aerogel pores. A combination of low-temperature nitrogen sorption and IR spectroscopy revealed that with increasing aerogel saturation, the probability of forming an amorphous MA phase inside the aerogel pores increases, while the amount of retained CO2 markedly decreases. Consequently, the probability of initiating a chemical reaction between MA and CO2 is significantly reduced. Furthermore, we found that upon release into the scCO2 phase, the conformer population of MA at low temperatures differs substantially from that in a saturated MA/scCO2 solution at the same state parameters. At elevated temperatures, however, the equilibrium approaches that of a saturated solution. We attributed this effect to the combined influence of the aerogel's confined pore geometry and its ability to form specific interactions with MA molecules, which alters their conformational state.

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