Coassembly of poly(ethylene glycol)-block-poly(glutamate sodium) and gemini surfactants with different spacer lengths

The coassembly of poly(ethylene glycol)-b-poly(glutamate sodium) copolymer (PEG113-PGlu100) with cationic gemini surfactants alkanediyl-α,ω-bis-(dodecyldimethylammonium bromide) [C12H25(CH3)2N(CH2)SN(CH3)2C12H25]Br2 (designated as C12CSC12Br2, S = 3, 6, and 12) have been studied by isothermal titration microcalorimetry, cryogenic transmission electron microscopy, circular dichroism, small-angle X-ray scattering, zeta potential, and size measurement. It has been shown that the electrostatic interaction of C12CSC12Br2 with the anionic carboxylate groups of PEG113-PGlu100 leads to complexation, and the C12CSC12Br2/PEG113-PGlu100 complexes are soluble even at the electroneutral point. The complexes display the feature of superamphiphiles and assemble into ordered nanosheets with a sandwich-like packing. The gemini molecules which were already bound with PGlu chains associate through hydrophobic interaction and constitute the middle part of the nanosheets, whereas the top and bottom of the nanosheets are hydrophilic PEG chains. The size and morphology of the nanosheets are affected by the spacer length of the gemini surfactants. The average sizes of the aggregates at the electroneutral point are 81, 68, and 90 nm for C12C3C12Br2/PEG113-PGlu100, C12C6C12Br2/PEG113-PGlu100, and C12C12C12Br2/PEG113-PGlu100, respectively. Both C12C3C12Br2/PEG113-PGlu100 and C12C12C12Br2/PEG113-PGlu100 mainly generate hexagonal nanosheets, while the C12C6C12Br2/PEG113-PGlu100 system only induces round nanosheets.