A Robust Strategy for Precise Fabrication of Rigid–Flexible Coupling Dendrimers toward Self-Coordinated Hierarchical Assembly

Abstract

Advances in nanotechnology depend upon expanding the ability to create biologically inspired complex materials with well-defined multidimensional structures. Fabrication of hybrid hierarchical structures by combining colloidal organic and inorganic building blocks remains a challenge due to the difficulty in preparing a diverse spectrum of rigid-flexible coupling units of precise shape and size. Herewe report a general strategy for crafting a myriad of uniform aggregates via manipulating self-assembly of distinct dendrimers with precisely controlled polyhedral oligomeric silsesquioxane (POSS)-embedded cores integrating stiffness and ductility. The rigidity of POSS units exerts steric effects on self-amplification of hydrophobic domains while the flexibility from internally ductile linkages provides ideal scenarios in establishing self-adaptive structural optimization, which subsequently drive the assemblies to proceed into hierarchical self-assembly via multiple coordination effects, generating highly complex multicompartment micelles (MCMs) without any preprocessing. Our facile approach enables a robust modular nanofabrication of well-organized dendrimers toward artificial functional systems with defined geometric architectures and intriguing functions for advanced biological applications.

Polyhedral Oligomeric Silsesquioxanes (POSS)‐based Hybrid Materials: Molecular Design, Solution Self‐Assembly and Biomedical Applications

“…Schematic representation of 1→7 divergent approach to precisely tailor rigid‐flexibly coupling POSS dendrimers with well‐defined geometry and customized self‐assembly. [ 96 ] …”

“…modular nanofabrication of well‐organized dendritic polymers towards artificial functional systems with the intriguing properties for the advanced biological applications. [ 96 ]…”

Recent Advances of Chitosan-Based Injectable Hydrogels for Bone and Dental Tissue Regeneration

“…On the one hand, physical crosslinkers mainly include the hydrophobic-hydrophobic, host-guest, ionic or electrostatic, crystallization and stereo complex interactions, which can cause the formation of polymer network in mild conditions ( Hoffman, 2012 ; Sivashanmugam et al, 2015 ; Fan et al, 2019 ; Zhu C.X. et al, 2019 ; Wang et al, 2020a ). Physically crosslinked hydrogels possess great advantages in biological applications because of the absence of chemical crosslinkers that may bring about the unpredictable and potential toxicity for the tissues, but their reversible architectures, poor stability and low mechanics greatly limited the scope of applications ( Zhang et al, 2013 ; Maitra and Shukla, 2014 ; Parhi, 2017 ; Li et al, 2018 ).…”

Molecular Modelling Guided Modulation of Molecular Shape and Charge for Design of Smart Self-Assembled Polymeric Drug Transporters

“…Wang et al [ 153 ] reported a combined experiment–simulation co-study detailing a general strategy to construct uniform aggregates by manipulating self-assembly of dendrimers with precisely controlled polyhedral oligomeric silsesquioxane (POSS)-embedded cores. The authors created different types of amphiphilic dendrimers with rigid–flexible coupling POSS-embedded cores, different PEG chain lengths, and various geometries.…”

“… ( a ) Schematic of self-assembly of nanoarchitectures from Janus dendrimers and the corresponding structure–concentration phase diagram for amphiphilic dendrimer aqueous solutions [ 150 ]. ( b ) Self-assembled morphologies by various C a -POSS b -PEG c polymers observed by microscopy ( top , with zoom-in on nanoscopic feature in the middle panel) and corresponding DPD modelling images of self-assemblies by the amphiphilic polymers at the initial polymer concentration of 1 mg/mL in aqueous solutions ( bottom ) [ 153 ]. ( c ) Typical calculated states of the interactions between a lipid bilayer membrane and a PAMAM dendrimer conjugated with ligands.…”