Abstract
This paper reports the synthesis and complex characterization of novel polymeric networks based on the crosslinking of Bombyx mori silk fibroin via poly(N-isopropylacrylamide) bridges generated by an ammonium cerium nitrate redox system. The research study gives an understanding of the polymerization mechanism in terms of the generation of radical sites, radical growth and termination reaction, as well as the involvement of modifications on silk fibroin structure and properties. The physico-chemical characterization was carried out by FTIR-ATR, X-ray photoelectron spectroscopy and RAMAN spectroscopy with unravelling the chemical modification. The structural characterization and spatial arrangement by secondary structure were carried out by X-ray diffraction and circular dichroism. The thermal behavior and thermal stability were evaluated by differential scanning calorimetry and thermogravimetric analysis. The novel complex polymer network is intended to be used in the field of smart drug delivery systems.
Highlights
Grafting reactions carried out in aqueous media by radical mechanisms represent a very useful tool for modifying natural polymers due to the possibility of achieving desired properties
FTIR analysis was carried out in order to reveal the modifications generated by the grafting of poly(N-isopropylacrylamide) (PNIPAM) onto the silk fibroin chain
The chemical structure of silk fibroin is revealed by the main peak at 3286 cm−1, which is specific to the N-H and
Summary
Grafting reactions carried out in aqueous media by radical mechanisms represent a very useful tool for modifying natural polymers due to the possibility of achieving desired properties. This promising technique for the chemical modification of biopolymers through functionalization has gained a lot of attention in recent years due to the ability to tune these polymers by precise approaches for a target application domain [1,2,3,4,5]. ACN has proven to be a very efficient radical generator for the graft polymerization of vinyl monomers [10,11,12] into various substrate polymers such as synthetic polymers [12], proteins [13,14,15]. The reaction mechanism is based on single electron transfer from cerium via the direct generation of radical sites onto polymer backbone
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