Dendronized polymers

Dendronized polymers. (or dendronised polymers) are linear polymers to every repeat unit of which dendrons are attached. Dendrons are regularly branched, tree-like fragments and for larger ones the polymer backbone is wrapped to give sausage-like, cylindrical molecular objects. Figure 1 shows a cartoon representation with the backbone in red and the dendrons like cake slices in green. It also provides a concrete chemical structure showing a polymethylmethacrylate (PMMA) backbone, the methyl group of which is replaced by a dendron of the third generation (three consecutive branching points).

Figure 1. Cartoon representation (left) and a concrete example of a third generation dendronized polymer (right). The peripheral amine groups are modified by a substituent X which often is a protection group. Upon deprotection and modification substantial property changes can be achieved. The subscript n denotes the number of repeat units.

Dendronized polymers can contain several thousands of dendrons in one macromolecule and have a stretched out, anisotropic structure. In this regard they differ from the more or less spherically shaped dendrimers, where a few dendrons are attached to a small, dot-like core resulting in an isotropic structure. Depending on dendron generation, the polymers differ in thickness as the atomic force microscopy image shows (Figure 2). Neutral and charged dendronized polymers are highly soluble in organic solvents and in water, respectively. This is due to their low tendency to entangle. Dendronized polymers have been synthesized with, e.g., polymethylmethacrylate, polystyrene, polyacetylene, polyphenylene, polythiophene, polyfluorene, poly(phenylene vinylene), poly(phenylene acetylene), polysiloxane, polyoxanorbornene, poly(ethylene imine)(PEI) backbones. Molar masses up to 200 Mio g/mol have been obtained. Dendronized polymers have been investigated for/as bulk structure control, responsivity to external stimuli, single molecule chemistry, templates for nanoparticle formation, catalysis, electro-optical devices, and bio-related applications. Particularly attractive is the use of water-soluble dendronized polymers for the immobilization of enzymes on solid surfaces (inside glass tubes or microfluidic devices) and for the preparation of dendronized polymer-enzyme conjugates.

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