Covalently aminated polyimide membranes are prepared by wet chemistry using different amines as modifiers. During this synthesis process carbonyl groups of the imide ring react with amine groups forming amide groups maintaining the macromolecular structure and an additional amide group bearing free amine groups. The reaction sequence was verified by FTIR-ATR and XPS measurements. Using poly(ethylene imine)s, highly aminated polyimide membranes with amine contents higher than 500 nmol/cm2 membrane can be produced which can be used as basic functions for further modification. As a result of amination, the hydrophobic polyimide membranes were strongly hydrophilized. Depending on the process parameters for functionalization and the applied modifier, a symmetric or an asymmetric distribution of amine functions across the membrane was observed. The distributions of amine functions were determined by SEM microscopy (EDX mode) and by AR-XPS (take-off angle resolved XPS). Calculations suggest that in the case of an asymmetric distribution the pores of the surface layer are almost completely filled with a swollen network of the modifier, which allows the covalent binding of second modifiers in order to obtain new types of composite membranes
Membranes for biohybrid organs such as the biohybrid liver support system have to face 2 different environments, namely blood and tissue cells. Accordingly, the respective membrane surfaces must have optimal properties in terms of biocompatibility for blood or tissue. Flat membranes prepared by a phase inversion process from polyetherimide were modified by binding of tris-(hydroxymethyl)-aminomethane to obtain a surface with hydroxyl groups by binding of polyethylene imine to attach a hydrophilic macromolecule with amine groups useful as a spacer for later bonding of further ligands and by attachment of heparin. The binding of the different ligands was successful as monitored by different physicochemical methods. The blood response of plain polyetherimide was comparable to that of polyacrylonitrile, and it could be further improved by the binding of heparin. The tissue compatibility of polyetherimide and its different modifications was compared with commercial cell culture substrate membranes (Millicell) and found to be comparable for polyetherimide and even better after the modification with tris-(hydroxymethyl)-aminomethane. In conclusion, polyetherimide seems to be an interesting material for the production of membranes for application in biohybrid organ systems.
The development of a bioartificial skin is a step toward the treatment of patients with deep burns or nonhealing skin ulcers. One possible approach is based on growing dermal cells on membranes to obtain appropriate living cellular stroma (sheets) to cover the wound. New membrane-forming copolymers were synthesized, based on acrylonitrile (AN) copolymerization with hydrophilic N-vinylpyrrolidone (NVP) monomer, in different percentage ratios, such as 5, 20, and 30% w/w, and with two other relatively high polar comonomers--namely, sodium 2-methyl-2-propene-1-sulfonic acid (NaMAS) and aminoethylmethacrylate (AeMA). All these copolymers were characterized for their bulk composition and number average molecular weight, and used to prepare ultrafiltration membranes. Water contact angles and water uptake were estimated to characterize the wettability and scanning force microscopy to visualize the morphology of the resulting polymer surface. Cytotoxicity was estimated according to the international standard regulations, and the materials were found to be nontoxic. The interaction of the membranes with human skin fibroblasts was investigated considering that these cells are among the first to colonize membranes upon implantation or with prolonged external contact. The overall cell morphology, formation of focal adhesion contacts, and cell proliferation were estimated to characterize the cell material interactions. It was found that the pure polyacrylonitrile homopolymer (PAN) membrane provides excellent conditions for seeding with fibroblasts, comparable only to a copolymer containing AeMA. In contrast, the presence of NaMAS with acidic ionic groups decreased both the attachment and proliferation of fibroblasts. Low content of NVP in the copolymer, up to about 5%, still enabled good attachment and spreading of cells, as well as subsequent proliferation of fibroblasts, but higher ratios of 20 and 30% resulted in a significant decrease of these cellular activities.
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