Exploring shape amphiphiles beyond giant surfactants: molecular design and click synthesis

Rational design of nanomaterials from assembly and reconfigurability of polymer-tethered nanoparticles

“…To precisely control the number of the attached functional groups, one can take advantage of techniques based on "click chemistry" [21,27] and DNA conjugation. [22,23,28,29] In the case of "click chemistry" [21,27] [ Fig. 1(b)], multicomponent building blocks, e.g.…”

“…surfactants and shape amphiphiles, are created through a series of sequential "click reactions", namely the copper-catalyzed azide-alkyne cycloaddition reaction and the thiolene reaction. [21,27] This technique has recently been used to interchange nearly every portion of the building block. [21,[30][31][32] Examples include the ability to interchange head groups from polyhedral oligomeric silsesquioxane (POSS) cages to gold NPs, as well as to exchange polymer types such as polystyrene or poly(methyl methacrylate) (PMMA); additionally, the size, number, and placement of these chemically distinct domains can be controlled, such as tethering a single corner of a POSS molecule with one or more polymer tethers.…”

“…[21,[30][31][32] Examples include the ability to interchange head groups from polyhedral oligomeric silsesquioxane (POSS) cages to gold NPs, as well as to exchange polymer types such as polystyrene or poly(methyl methacrylate) (PMMA); additionally, the size, number, and placement of these chemically distinct domains can be controlled, such as tethering a single corner of a POSS molecule with one or more polymer tethers. [21,27,[30][31][32] Related methods have been used to create additional types of polymer-NP composite blocks. Protein-polymer conjugates, for example, were created using a covalent binding maleimide-thiol coupling reaction to create bioconjugates.…”

“…As mentioned previously, direct realizations of TNP assembly have come from the use of "click chemistry" to attach tethers to NPs directly, creating gram quantities of material. [21,27,30] TNPs created with this method have been used to self-assemble many of the same structures observed in block copolymers, but with the additional benefit of controlling the specific material composition of each domain of the material. By tuning various portions of the block geometry, different types of structures are accessible.…”

“…As another example, the lattice spacing of the superlattices formed by DNA-grafted gold NPs Figure 2. Static assemblies: (a) Nanotubular assemblies from coordination polymers upon addition of divalent metal ions (red circle), [24] (b) assembled structures from shape amphiphiles, including lamellar, gyroid, hexagonal cylinders, and BCC micelle phases, as reported in [21] . (c) Dodecagonal quasicrystal formed in a blend of polyisoprene-polystyrene-poly(2-vinylpyridine) star block copolymers/polysterene homopolymer blend.…”