RESUMEN
The synthesis of magnetic nanoparticles (MNPs) coated with hydrophilic poly-sodium-acrylate (PSA) ligands was studied to assess PSA-MNP complexes as draw solution (DS) solutes in forward osmosis (FO). For MNP-based DS, the surface modification and the size of the MNPs are two crucial factors to achieve a high osmolality. Superparamagnetic nanoparticles (NP) with functional groups attached may represent the ideal DS where chemical modifications of the NPs can be used in optimizing the DS osmolality and the magnetic properties allows for efficient recovery (DS re-concentration) using an external magnetic field. In this study MNPs with diameters of 4 nm have been prepared by controlled chemical co-precipitation of magnetite phase from aqueous solutions containing suitable salts of Fe2+ and Fe3+ under inert atmosphere and a pure magnetite phase could be verified by X-ray diffraction. Magnetic colloid suspensions containing PSA-coated MNPs with three different molar ratios of PSA:MNP = 1:1, 1:2 and 1:3 were prepared and assessed in terms of osmotic pressure, aggregation propensity and magnetization. Fourier Transform Infrared Spectroscopy (FTIR) confirmed the presence of PSA on coated MNPs and pristine PSA-MNPs with a molar ratio PSA:MNP = 1:1 exhibited an osmotic pressure of 30 bar. Molar ratios of PSA:MNP = 1:2 and 1:3 lead to the formation of less stabile magnetic colloid solutions, which led to the formation of aggregates with larger average hydrodynamic sizes and modest osmotic pressures (5.5 bar and 0.2 bar, respectively). After purification with ultrafiltration, the 1:1 nanoparticles exhibited an osmotic pressure of 9 bar with no aggregation and a sufficient magnetization of 25 emu/g to allow for DS regeneration using an external magnetic field. However, it was observed that the amount of PSA molecules attached to the MNPs decreased during DS recycling steps, leaving only strong chelate-bonded core-shell PSA as coating on the MNPs. This demonstrates the crucial role of MNP coating robustness in designing an efficient MNP-based DS for FO.
RESUMEN
In this contribution, we explore the interaction of lignocellulosics and proteins aiming at a better understanding of their synergistic role in natural systems. In particular, the manufacturing and characterization of amphiphilic bicomponent thin films composed of hydrophilic cellulose and a hydrophobic lignin ester in different ratios is presented which may act as a very simplified model for real systems. Besides detailed characterizations of the films and mechanisms to explain their formation, nonspecific protein adsorption using bovine serum albumin (BSA) onto the films was studied using a quartz crystal microbalance with dissipation (QCM-D). As it turns out, the rather low nonspecific protein adsorption of BSA on cellulose is further reduced when these hydrophobic lignins are incorporated into the films. The lignin ester acts in these blend films as sacrificial component, probably via an emulsification mechanism. Additionally, the amphiphilicity of the films may prevent the adsorption of BSA as well. Although there are some indications, it remains unclear whether any kind of protein interactions in such systems are of specific nature.