The surface-initiated graft polymerization of polymer brushes attached to an sp3 random carbon network backbone structure is demonstrated. Poly(ethyl acrylate) (PEA), poly(4-fluorostyrene) (PFS) and poly(acrylonitrile) (PAN) brushes were grafted from the network backbone polymer poly(hydridocarbyne), 1, illustrating the breadth of reactivity of the network backbone. Attachment of polymeric/oligomeric chains to the network backbone was observed through two different methods with different polymer systems. First, selective solvent extraction separated a homogeneous mixture of PEA and 1, dissolving PEA in diethyl ether, but leaving 1 behind as a brown precipitate. In contrast, 1 functionalized with PEA brushes completely dissolved, showing that it was not a homogenous mixture of the substrate and free polymeric chains, but a system of covalently bound polymer chains originating from 1. Formation of short chains of PFS at the surface of 1 allowed the use of 19F nuclear magnetic resonance to observe the change in resonance shift and shape for the polymer side chains. Solvent extraction was used to demonstrate that tetrahydrofuran (THF) was able to separate a homogeneous mixture of PAN and 1, dissolving 1 in THF, but leaving PAN behind as a white precipitate.

Nanocrystals of stoichiometry LiNbO3 are produced in a film of poly(4-vinylpyridine) (4-PVP) in a matrix-mediated in situ sol–gel-like synthesis. These crystals are produced at room temperature, and show identical size, morphology, phase, and crystallographic orientation. These features are produced by the application of aspects of biological mineralization to the fabrication of this non-biological composite.

The role of added surfactant in a biomimetic in situ synthesis of inorganic/polymer composites in which the inorganic phase displays uniformity of size, morphology, phase, and crystallographic orientation is discussed. Addition of a surfactant, AOT, to the synthetic system induces nucleation and orientation of CdS crystals within a poly(ethylene oxide) film. Interaction of the AOT with polymer-bound Cd2+ ions determines the nucleation and orientation of the resulting crystals. Other surfactants, with different structures and headgroups, produced different results, ranging from inhibition of mineral growth to extraction of the cations from the film. The use of other metals in place of Cd2+ results in different interactions and produces a change in the order of the product.