Supramolecular polymers as building blocks for the formation of particles

© 2015 Dr. Blaise Leopold TardyOver the last two decades, there has been a growing interest in the development of supramolecular polymers, linear macromolecules whose monomeric components are held together by non-covalent interactions. Such supramolecular assemblies are commonly found in nature and are crucial for the function of living tissues and cells. The recent development of synthetic supramolecular polymers has shown promise for enhancing the properties of polymeric materials. Indeed, studies have shown that such materials have significant benefits when compared to conventional, covalently bound, polymers. These benefits are due to the ability of supramolecular assemblies to respond to stimulus, and to dynamically rearrange their structure in a manner unachievable using conventional, covalently bound polymers. Resemblances between the dynamics of synthetic supramolecular polymers and naturally occurring supramolecular polymers are suggestive of their potential for biomedical applications. In this trend, the most promising supramolecular polymer, cyclodextrin (CD) based polyrotaxanes (PRXs), is now emerging as a potential tool to synthetically form dynamic interfaces for applications in the biomedical field. The recent popularity of these polymers in this field is not only due to their inherent, non-covalent properties but also to the low cost, high engineerability and low toxicity of the components they are made of. In this work, CD-based PRXs have been used as building blocks to form particles that were designed for developments in drug delivery. Specifically, the properties specific to PRXs have been exploited to design particles with degradation or stimuli-based response. The unique characteristics of PRXs were found to translate into similarly unique characteristics of the assembled particles. Different approaches have been studied and their advantages and limitations are highlighted. Initial investigations were aimed at designing particles fitting the requirements in properties and specific characteristics highlighted by recent in vivo and in vitro studies. In this direction, we demonstrated controlled degradation of self-assembled PRX-based structures through stimuli triggered disassembly. Such control was also shown for PRX particles dynamically formed using a templated approach, for which disassembly through judicious selection of specific building blocks is highlighted. The use of the templated approach was shown to be more straightforward and versatile in its applications, laying out a framework to form and engineer particles using PRXs as a building block. Lastly, by using CD’s molecular mobility in the PRX as an additional handle for tuning; a “one block” polymer, able to reversibly segregate into multi-blocks leading to the formation of nanoparticles, was developed. This approach is particularly interesting as many responsive polymeric materials have their response due to a stretched-to-coiled transition of individual chain while we show here a transition between a mono-block like architecture to a multi-block like architecture. The preliminary results highlight the potential of PRXs as building blocks for applications in drug delivery systems