The paper presents the contribution of the cocrystallization method in the physicochemical modification of catechins that exhibit low oral bioavailability. This was done to obtain cocrystals for two naturally occurring polyphenolic diastereoisomers (+)-catechin and (−)-epicatechin with commonly used coformers. Due to distinct crystallization behavior, only the (−)-epicatechin cocrystal with barbituric acid in a 1:1 stoichiometry was obtained. The cocrystal of (−)-epicatechin (EC) with barbituric acid (BTA) was prepared by the slow solvent-evaporation technique. The structure and intermolecular interactions were determined by X-ray crystallographic techniques. The analysis of packing and interactions in the crystal lattice revealed that molecules in the target cocrystal were packed into tapes, formed by the O–H···O type contacts between the (−)-epicatechin and coformer molecules. The EC molecules interact with the carboxyl group in the BTA coformer mainly by −OH groups from the benzene ring A. The cocrystalline phase constituents were also investigated in terms of Hirshfeld surfaces. The application of Raman spectroscopy confirmed the involvement of the C═O group in the formation of hydrogen bonds between the (−)-epicatechin and barbituric acid molecules. Additionally, the solubility studies of pure EC and the EC-BTA cocrystal exhibited minor enhancement of EC solubility in the buffer solution, and pH measurements confirmed a stable level of solubility for EC and its cocrystal.

The main purpose of the research was to obtain and study hybrid materials based on three different nano-oxides commonly used in the cosmetic and pharmaceutical industries: Al₂O₃, TiO₂, and ZnO, with the natural bioactive polysaccharide fucoidan. Since the mentioned oxides are largely utilized by industry, there is no doubt that the presented studies are important from an environmental point of view. On the basis of the textural studies (dynamic light scattering DLS, low temperature nitrogen adsorption, X-ray diffraction analysis XRD, scanning electron microscopy SEM) it was proved that the properties of the hybrid materials differ from the pure components of the system. Moreover, the advanced thermal analysis (TG-DTG-DSC) combined with the evolved gas analysis using Fourier transformed infrared spectroscopy (FTIR) and mass spectrometry were applied to describe the thermal decomposition of fucoidan, oxides and hybrid materials. It was found that the interactions between the polymer and the oxides results in the formation of the hybrid materials due to the functionalization of the nanoparticles surface, and that their thermal stability increased when compared to the pure substrates. Such findings definitely fill the literature void regarding the fucoidan based hybrid materials and help the industrial formulators in the preparation of new products.