Retrostructural model to predict biomass formulations for barrier performance.

Barrier performance and retrostructural modeling of the macromolecular components demonstrate new design principles for film formulations based on renewable wood hydrolysates. Hardwood hydrolysates, which contain a fair share of lignin coexisting with poly- and oligosaccharides, offer excellent oxygen-barrier performance. A Hansen solubility parameter (HSP) model has been developed to convert the complex hydrolysate structural compositions into relevant matrix oxygen-permeability data allowing a systematic prediction of how the biomass should be formulated to generate an efficient barrier. HSP modeling suggests that the molecular packing ability plays a key role in the barrier performance. The actual size and distribution of free volume holes in the matrices were quantified in the subnanometer scale with Positron annihilation lifetime spectroscopy (PALS) verifying the affinity-driven assembly of macromolecular segments in a densely packed morphology and regulating the diffusion of small permeants through the matrix. The model is general and can be adapted to determine the macromolecular affinities of any hydrolysate biomass based on chemical composition.

Optimization of subcritical fluid extraction of bioactive compounds using Hansen solubility parameters.

Process engineering operations in food and nutraceutical industries pertaining to the design of extraction of value-added products from biomass using pressurized liquids involve a careful selection of the solvent and optimal temperature conditions to achieve maximum yield. Complex molecular structure and limited physical property data in the literature of biological solutes extracted from biomass compounds have necessitated the process modeling of such operations. In this study, we have applied the Hansen 3-dimensional solubility parameter concept to optimize the extraction of molecularly complex solutes using subcritical fluid solvents. Hansen solubility spheres characterized by the relative energy differences (RED) have been used to characterize and quantify the solute-subcritical solvent interactions as a function of temperature. The solvent power of subcritical water and compressed hydroethanolic mixtures above their boiling points has been characterized using the above-mentioned method. The use of group contribution methods in collaboration with computerized algorithms to plot the Hansen spheres provides a quantitative prediction tool for optimizing the design of extraction conditions. The method can be used to estimate conditions for solute-solvent miscibility, an optimum temperature range for conducting extractions under pressurized conditions, and approximate extraction conditions of solutes from natural matrices.