Construction of β-cyclodextrin-based supramolecular hyperbranched polymers self-assemblies using AB-type macromonomer and their application in the drug delivery field.

Despite some efforts have been made in the research of supramolecular hyperbranched polymers (SHPs) self-assemblies, the study which has not been consideration to date is the influence of incoming stimuli-responsive polymer chain on their self-assembly property undergo outer stimuli. The introduction of stimuli-responsive segments which could maintain their hydrophilic property are expected to affect the self-assembly behaviour of SHPs and expand their further biomedical application. In this paper, AB-type macromolecular monomer, LA-(CD-PDMA), which consisted one lithocholic acid (LA) and two β-cyclodextrin terminated poly(2-(dimethylamino)ethyl methacrylate) segments (CD-PDMA) was synthesized. LA-(CD-PDMA) based SHP were obtained based on the host-guest inclusion interactions of CD/LA moietes and with PDMA as pH-responsive hydrophilic chains. As a control to study the influence of incoming PDMA chains, both LA-(CD-PDMA) based SHPs-1 and LA-CD based SHPs-2 self-assemblies were comparatively investiged through 2D H NMR ROESY, transmission electron microscopy (TEM) and dynamic light scattering (DLS). The results suggested that except for the higher drug loading efficiency LA-(CD-PDMA) based SHPs-1 pocessing, the release rates of SHPs-1 increased notably at pH 5.0 than that of pH 7.4 due to the repulsion and stretch of protonated PDMA chains while the release rates of SHPs-2 showed no obvious difference. Finally, basic cell experiments demonstrated that the SHPs based self-assemblies can be internalized into cancer cells, indicating their potential application in the drug delivery field.