Abstract
Giant surfactants refer to a new kind of amphiphile by incorporating functional molecular nanoparticles with polymer tails. As a size-amplified counterpart of small-molecule surfactants, they serve to bridge the gap between small-molecule surfactants and amphiphilic block copolymers. This work reports the design and synthesis of single-tailed giant surfactants carrying a hydrophobic poly(ε-caprolactone) (PCL) as the tail and a hydrophilic cage-like polyhedral oligomeric silsesquioxane (POSS) nanoparticle as the head. The modular synthetic strategy features an efficient “growing-from” and “click-modification” approach. Starting from a monohydroxyl and heptavinyl substituted POSS (VPOSS-OH), a PCL chain with controlled molecular weight and narrow polydispersity was first grown by the ring-opening polymerization (ROP) of ε-CL under the catalysis of stannous octoate, leading to a PCL chain end-capped with heptavinyl substituted POSS (VPOSS-PCL). To endow the POSS head with adjustable polarity and functionality, three kinds of hydrophilic groups, including hydroxyl groups, carboxylic acids, and amine groups, were installed to the periphery of POSS molecule by a high-efficiency thiol-ene “click” reaction. The compounds were fully characterized by NMR, gel permeation chromatography (GPC), MALDI-TOF mass spectrometry, and TGA analysis. In addition, the preliminary self-assembly study of these giant surfactants was also investigated by TEM and dynamic laser light scattering (DLS), which indicated that they can form spherical nanoparticles with different diameters in aqueous solution. This work affords a straightforward and versatile way for synthesizing single-tailed giant surfactants with diverse head surface functionalities.
Highlights
Amphiphiles refer to a kind of molecules containing chemically distinct segments, such as hydrophobic and hydrophilic parts, linked with chemical or supramolecular bonds
Amphiphiles were generally accepted as small-molecule surfactants composed of a hydrophilic polar head and a hydrophobic alkyl chain, which have been broadly used in our daily life, including detergents, dispersants, cosmetics, and pharmaceutical excipients [1]
Afterwards, the region of amphiphiles was extended to amphiphilic block copolymers consisting of hydrophilic and hydrophobic polymeric chains
Summary
Amphiphiles refer to a kind of molecules containing chemically distinct segments, such as hydrophobic and hydrophilic parts, linked with chemical or supramolecular bonds. An emerging category of amphiphiles, named giant surfactants, has been constructed and widely studied through covalently connecting functionalized molecular nanoparticles with polymeric tails [7,8,9,10,11,12,13,14] They have obtained much attention due to their multivalent nature, promising physical/chemical features, and unique self-assembling behaviors, both in bulk and solution states [10,11,15,16]. The polymeric tails can be of different topologies (e.g., linear, cyclic, or branched) or of distinct compositions, while the molecular nanoparticle heads can be modified with various functionalities, such as ionic, non-ionic, bioactive, etc All of these characteristics endow giant surfactants with sophisticated structures and result in more complicated self-assembly behaviors, as well as adjustable functional properties [8]
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