Conjugated Polymers and Carbon Nanotube Functionalization
Conjugated polymers have been shown to interact strongly with single-walled carbon nanotubes (SWNTs) via supramolecular π-stacking. This is advantageous because polymer adsorption on the SWNT surface imparts solubility to the complex without adversely affecting the intrinsic properties of the nanotubes. In addition, the polymer structure can be synthetically manipulated to impart functionality and/or reactivity to the overall complex, as well as the ability to differentiate between different nanotube types, such as semiconducting and metallic SWNTs. Recent work in our group has focused on the design of polymers that are uniquely selective toward either semiconducting or metallic SWNTs, which represents an area of active current research (see our review in Chemical Science). We continue to work on the development of new polymer structures, with enhanced selectivity for different SWNT species, that can be prepared and used on large scale.
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New Polymer Structures
Post-polymerization functionalization of conjugated polymer backbones is challenging as it is difficult to introduce reactive functionality within a conjugated system. We have recently focused significant attention on the preparation of polymers that incorporate reactive groups within their backbone, allowing the elaboration of conjugated polymer libraries in which all members of the library have the same average length. For example, we prepared a polyimine structure with cyclooctyne-containing repeat units that can undergo strain-promoted cycloaddition chemistry with azides. This allows investigation of structure-property relationships without the need to consider molecular weight differences of the polymers. This has recently proven valuable in evaluating the ability of different polymer structures to disperse carbon nanotubes. We are currently continuing our efforts to develop and take advantage of new polymer structures with latent reactivity along their backbone, such as the poly(tetrazine) structure illustrated at right. These structures are highly reactive toward trans-cyclooctenes, allowing "plug and play" functionalization.
Dendrimer Synthesis and Applications
Dendrimers are a class of polymers that are precisely synthesized, monodisperse, and can exhibit a large number of functionalizable end-groups. This multivalency of dendrimers makes them attractive scaffolds for drug delivery applications, as a high loading of pharmacophores can be achieved on each structure. In addition, if the pharmacophore is incorporated within the interior of the dendrimer, the periphery of the macromolecule can be tailored for solubility and specific targeting functions. Our work focuses on the preparation and functionalization of aliphatic polyester dendrimers, which are promising for therapeutic applications because they have previously been shown to be water-soluble, biocompatible, non-toxic, and biodegradable. Recently, we have also shown that the branched, globular structure of dendrimers is ideal for protein modification. When high-generation dendrimers are attached to enzymes, they can modify the enzyme's selectivity for specific substrates, allowing control over both function and stability.