Synthesis of Cellulose-graft-Polypropionic Acid Nanofiber Cation-Exchange Membrane Adsorbers for High-Efficiency Separations

Fabrication of membrane adsorbers with elevated binding capacity and high throughput is highly desired for simplifying and improving purification efficiencies of bioproducts (biotherapeutics, vaccines, etc.) in the biotechnological and biopharmaceutical industries. Here we demonstrate the preparation of a novel class of self-supported, cellulose-graft-polypropionic acid (CL-g-PPA) cation-exchange nanofiber membrane adsorbers under mild reaction conditions for the purification of positively charged therapeutic proteins. In our fabrication method, acrylonitrile was first polymerized and surface grafted onto cellulose nanofibers using cerium ammonium nitrate as a redox initiator to form cellulose-g-polyacrylonitrile (CL-g-PAN). CL-g-PAN was then submitted to a hydrolyzation reaction to form CL-g-PPA cationic membrane adsorbers. Morphology and structural characterization illustrated the formation of CL-g-PPA membranes with uniform coating of polyacid nanolayers along the individual nanofibers without disturbing the nanofiber structure. Benefiting from these numerous cationic polyacid binding sites and inherent large surface area and open porous structure, CL-g-PPA nanofiber membrane adsorbers showed a lysozyme static adsorption capacity of 1664 mg/g of nanofibers. These membranes showed a lysozyme dynamic binding capacity of 508 mg/g of nanofibers at 10% breakthrough (equivalent to 206 g/L capacity), with a residence time of less than 6 s. Moreover, CL-g-PPA self-supported nanofibers displayed excellent structural stability and reversibility after several cycles of protein binding studies. This dynamic binding capacity of the CL-g-PPA nanofiber membranes was 3.2 times higher than that of macroporous cellulose membranes and 8.5 times higher than that of the Sartobind S commercial membrane adsorber. Considering the simple fabrication method employed, excellent protein adsorption capacity, remarkable structural stability, and reusability, CL-g-PPA nanofiber membranes provided a versatile platform for the chromatographic separations of biomolecules (e.g., proteins, nucleic acids, and viral vaccines) as well as water purification and similar ion-exchange applications.