Hydrophilic solutes in modified carbon dioxide extraction-prediction of the extractability using molecular dynamic simulation

Super- and subcritical carbon dioxide (CO2) extractions of crude drugs were simulated by molecular modelling to predict the extractability of different hydrophilic plant constituents under various extraction conditions. The CO2 extraction fluids were simulated either with pure CO2 or with solvent modified CO2 at different pressures and temperatures. Molecular modelling resulted in three different solubility parameters: the total solubility parameter δ and the partial solubility parameters δd for the van der Waals and δEL for the polar forces. Thus, δEL enabled the estimation of the polarity of the extraction fluids and the solute molecules. If the value of δEL of the extraction fluid reached the value of the solute molecule in the crude drug, i.e. minimum extraction value, the compound was soluble at the distinct extraction conditions. For a further increase in yield of the hydrophilic solutes, the polarity of the extraction fluid had to be increased, too. That means δEL of the fluid exceeded the minimum extraction value. All simulations were verified by CO2 extractions of the secondary roots of Harpagophytum procumbens (harpagoside, stachyose) and the seeds of Aesculus hippocastanum (aescin). CO2 extractions of the flowers of Matricaria recutita ((−)-α-bisabolol) were obtained from literature data. These four constituents with different properties, like molecular size and the allocation of polar functional groups were extracted, analysed, simulated and the extract content was correlated with the extraction fluid used, respectively.