Grafting direct polymerization, amphiphilic

Oftentimes, the introduction of certain functional moieties into copolymer architectures to drive amphiphile formation, and thus nanoparticle assembly, requires the use of post-polymerization conjugation, or grafting-to a polymer backbone, as depicted in Figure 6.22. Motivation for this approach arises in cases when macromolecules or desired functionalities prove to be unsuitable for direct polymerization because of slow polymerization kinetics, poisoning of the catalyst, or problems with solubility. In these cases, it is possible to... 

Block and graft copolymers as amphiphiles mainly differ from conventional surfactants by the length of hydrophobic and hydrophilic moieties. As a direct consequence the self-assembly of polymeric surfactants, via a so-called closed association process, is characterized by low CMC values. 

Such hydrophilic macromonomers (DPn=7-9) were radically homopolymer-ized and copolymerized with styrene [78] using AIBN as an initiator at 60 °C in deuterated DMSO in order to follow the kinetics directly by NMR analysis. The macromonomer was found to be less reactive than styrene (rM=0.9 for the macromonomer and rs=1.3 for styrene). Polymerization led to amphiphilic graft copolymers with a polystyrene backbone and poly(vinyl alcohol) branches. The hydrophilic macromonomer was also used in emulsion polymerization and copolymerized onto seed polystyrene particles in order to incorporate it at the interface. 

Feng et al. [139] studied the activity of TM reconstituted into the PEM/HBM assembly described in Sect. 2.1. TM is a type ITMP that is a receptor for thrombin and mediates protein C activity in anticoagulant and antiinflammatory pathways. TM functionalization represents a promising strategy to control thrombus formation on the surface of a biomaterial that comes into direct contact with blood, such as the inner surface of an arterial graft. TM was incorporated into vesicles of mono-acrylatePC (Fig. 1) that were then fused onto an amphiphilic terpolymer/PEM/glass coverslip (see Fig. 2). The eosin Y/triethanolamine method [56] was used to polymerize the lipids, after which the supported assembly could be removed from solution for characterization purposes. 

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