Polybutylene terephthalate (PBT) nonwovens were successfully grafted with poly(glycidyl methacrylate) (polyGMA) using a heat induced grafting approach with the thermal initiator benzoyl peroxide (Bz 2 O 2 ). This grafting method resulted in complete, uniform, and conformal grafted layers around the PBT fibers that could be further functionalized as ion exchangers for protein capture. Protein binding capacities as high as 200 mg/g were achieved for ion exchange PBT nonwovens grafted to 20% weight gain using this heat induced grafting method. Compared to UV grafted polyGMA PBT nonwovens, the rates of protein adsorption are several times faster for the heat grafted polyGMA PBT nonwoven, reaching equilibrium within minutes; UV grafted polyGMA ion exchange PBT nonwovens require hours to reach equilibrium. This indicates that polyGMA grafts formed by heat induced grafting are thinner, and therefore more dense, than UV grafted layers with the same % weight gain. To further investigate the structural differences between the two grafting methods, targets of various molecular weights (ATP, lysozyme, BSA, hIgG) were adsorbed to the materials. Increasing the target size resulted in a decrease of target molecules bound for both grafting methods. However, the heat grafted nonwovens exhibited a much stronger dependence of protein molecular weight on protein capture, indicating that heat induced grafting results in a polyGMA layer that has a smaller free volume between chains available for protein binding compared to the UV grafting method. Protein adsorption isotherms for the two grafting methods confirmed that both methods resulted in similar strengths of protein binding, with dissociation constants on the order of K d = 10 −6 M which is consistent with ion exchange binding on polymer brush networks. Heat grafted polyGMA ion exchange PBT nonwovens showed excellent protein binding and elution.
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