Conventional methods for controlling self-assembly are generally based on the change in hydrophilic/hydrophobic volume fraction of diblock or triblock copolymers, which suffer from low structural diversity and limited chemical tunability. Inspired by nature, segmented multiblock copolymers (MBCs) offer unparalleled opportunities for engineering of biomimetic nanomaterials with tailored properties. However, the self-assembly of MBCs remains largely unexplored and poorly understood. In this study, we report a segmentation-mediated self-assembly strategy to manipulate the morphology of protein-mimic responsive MBCs by facilely altering the block numbers while holding the amphiphilicity constant. In particular, we found that an increased number of nearly alternating biodegradable poly(ε-caprolactone) and hydrophilic polyethylene glycol segments drives micelle-to-worm-to-vesicle transition. Moreover, the L-cystine residue-enriched interlayer of assemblies enables a depolymerizationinduced morphology reversion, resulting in a redox-hyper-responsive property and ultrafast intracellular drug release. Both experimental and computational results provide a new insight into the self-assembly of macromolecules and propose a convenient approach to the construction of smart nanoassemblies with controlled architectures.
Peptidomimetic polymers have attracted increasing interest because of the advantages of facile synthesis, high molecular tunability, resistance to degradation, and low immunogenicity. However, the presence of non-native linkages compromises their ability to form higher ordered structures and protein-inspired functions. Here we report a class of amino acid-constructed polyureas with molecular weight- and solvent-dependent helical and sheet-like conformations as well as green fluorescent protein-mimic autofluorescence with aggregation-induced emission characteristics. The copolymers self-assemble into vesicles and nanotubes and exhibit H-bonding-mediated metamorphosis and discoloration behaviors. We show that these polymeric vehicles with ultrahigh stability, superfast responsivity and conformation-assisted cell internalization efficiency could act as an “on-off” switchable nanocarrier for specific intracellular drug delivery and effective cancer theranosis in vitro and in vivo. This work provides insights into the folding and hierarchical assembly of biomacromolecules, and a new generation of bioresponsive polymers and nonconventional luminescent aliphatic materials for diverse applications.
Based on disulfide-enriched multiblock copolymer vesicles, we present a straightforward sequential drug delivery system with dual-redox response that releases hydrophilic doxorubicin hydrochloride (DOX·HCl) and hydrophobic paclitaxel (PTX) under oxidative and...
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