RESUMEN
Four aromatic acid compounds: benzoic acid (Bz), 4-hydroxyphenylpropionic acid (HPPA), gallic acid (GA) and 4-aminobenzoic acid (PABA) were covalently bonded to chitosan in order to improve water solubility at neutral pH. The synthesis was performed via a radical redox reaction in heterogeneous phase by employing ascorbic acid and hydrogen peroxide (AA/H2O2) as radical initiators in ethanol. The analysis of chemical structure and conformational changes on acetylated chitosan was also the focus of this research. Grafted samples exhibited as high as 0.46 M degree of substitution (MS) and excellent solubility in water at neutral pH. Results showed a correlation between the disruption of C3-C5 (O3 O5) hydrogen bonds with increasing solubility in grafted samples. Spectroscopic techniques such as FT-IR and 1H and 13C NMR showed modifications in both glucosamine and N-Acetyl-glucosamine units by ester and amide linkage at C2, C3 and C6 position, respectively. Finally, loss of crystalline structure of 2-helical conformation of chitosan after grafting was observed by XRD and correlated with 13C CP-MAS-NMR analyses.
RESUMEN
A commercial ultrafiltration (UF) membrane (HFM-183 de Koch Membrane Systems) made of poly(vinylidene fluoride) (PVDF), was recovered with a negatively-charged polyelectrolyte (poly(sodium 4-styrenesulfonate)) (PSS), and the effects on its electric, chemical, and morphological properties were analyzed. Atomic force microscopy (AFM), liquid-liquid displacement porometry, Electrical Impedance Spectroscopy, X-ray photoelectron spectroscopy, and Raman spectroscopy were used to investigate the modifications induced by the deposition of PSS on the PVDF positively-charged membrane and after its treatment by a radio frequency Ar-plasma. These techniques confirmed a real deposition and posterior compaction of PSS with increasing roughness and decreasing pore sizes. The evolution of the electric resistances of the membranes confirmed crosslinking and compaction with shielding of the sulfonated groups from PSS. In this way, a membrane with a negatively-charged active layer and a pore size which was 60% lower than the original membrane was obtained. The composition of the additive used by manufacturers to modify PVDF to make it positively charged was obtained by different procedures, all of which depended upon the results of X-ray photoelectron spectroscopy, leading to fairly consistent results. This polymer, carrying positive charges, contains quaternary nitrogen, as confirmed by XPS. Moreover, Raman spectroscopy confirmed that PVDF changes from mostly the to the α phase, which is more stable as a substrate for the deposited PSS. The aim of the tested modifications was to increase the retention of divalent anions without reducing permeability.
RESUMEN
Sorption of l- and d-Tyrosine (Tyr) from aqueous solutions on chiral membranes of chitosan (CH) was studied. A high adsorption in the membrane, with a marked enantioselectivity to l-Tyr, was found. Computational calculations carried out by docking and molecular dynamics (MD) showed a difference in the affinity of the enantiomers and two regions of adsorption in the polymer matrix. The interactions of the enantiomers with the polymer matrix were studied by using FTIR, DRx, DSC and TG measurements. These results indicate that adsorption of Tyr reduces the crystallinity of the membrane and generates a rearrangement of the chains, decreasing the intercatenary spacing. Also, it was observed that the hydrated polymorph to anhydrous polymorph ratio has changed during adsorption, that is, water bound to chitosan is also modified. The energy balance of the system hydrogen bonding, desolvation and the conformational changes resulted in a spontaneous and endothermic process.