Haibao Jin

A Supramolecular Janus Hyperbranched Polymer and Its Photoresponsive Self-Assembly of Vesicles with Narrow Size Distribution

Herein, we report a novel Janus particle and supramolecular block copolymer consisting of two chemically distinct hyperbranched polymers, which is coined as Janus hyperbranched polymer. It is constructed by the noncovalent coupling between a hydrophobic hyperbranched poly(3-ethyl-3-oxetanemethanol) with an apex of an azobenzene (AZO) group and a hydrophilic hyperbranched polyglycerol with an apex of a β-cyclodextrin (CD) group through the specific AZO/CD host-guest interactions. Such an amphiphilic supramolecular polymer resembles a tree together with its root very well in the architecture and can further self-assemble into unilamellar bilayer vesicles with narrow size distribution, which disassembles reversibly under the irradiation of UV light due to the trans-to-cis isomerization of the AZO groups. In addition, the obtained vesicles could further aggregate into colloidal crystal-like close-packed arrays under freeze-drying conditions. The dynamics and mechanism for the self-assembly of vesicles as well as the bilayer structure have been disclosed by a dissipative particle dynamics simulation.

A POSS-based supramolecular amphiphile and its hierarchical self-assembly behaviors.

A polyhedral oligomeric silsesquioxane (POSS)-based supramolecular amphiphile is prepared from the host-guest inclusion complexation between a mono adamantane-functionalized POSS (AD-POSS) and a β-cyclodextrin oligomer (P(β-CD)). Assisted by the interface of H(2)O/toluene, the obtained supramolecular hybrids self-assemble into stable hollow nanospheres with thick walls. These hollow nanospheres aggregate together into a sphere layer through a spin coating technique, which then further transforms into a thin porous film containing nanometer-scale holes. The hollow nanospheres have a low cytotoxicity. The in vitro cell culture indicates the nanoporous films promote adhesion and proliferation of cells. The self-assembly morphologies and structures have been carefully characterized by SEM, TEM, AFM, DLS, XPS and water-contact angle measurements, and the self-assembly mechanism has also been discussed.

Cytomimetic Large-Scale Vesicle Aggregation and Fusion Based on Host–Guest Interaction

Herein, we have shown a large-scale cell-mimetic (cytomimetic) aggregation process by using cell-sized polymer vesicles as the building blocks and intervesicular host-guest molecular recognition interactions as the driving force. We first prepared the hyperbranched polymer vesicles named branched polymersomes (BPs) around 5-10 μm through the aqueous self-assembly of a hyperbranched multiarm copolymer of HBPO-star-PEO [HBPO = hyperbranched poly(3-ethyl-3-oxetanemethanol); PEO = poly(ethylene oxide)]. Subsequently, adamantane-functionalized BPs (Ada-BPs) or β-cyclodextrin-functionalized BPs (CD-BPs) were prepared through the coassembly of HBPO-star-PEO and Ada-modified HBPO-star-PEO (HBPO-star-PEO-Ada), or of HBPO-star-PEO and CD-modified HBPO-star-PEO (HBPO-star-PEO-CD), respectively. Macroscopic vesicle aggregates were obtained by mixing CD-BPs and Ada-BPs. The intervesicular host-guest recognition interactions between β-CD units in CD-BPs and Ada units in Ada-BPs, which were proved by (1)H nuclear Overhauser effect spectroscopy (NOESY) spectrum and the fluorescence probe method, are responsible for the vesicle aggregation. Additionally, the vesicle fusion events happened frequently in the process of vesicle aggregation, which were certified by double-labeling fluorescent assay, real-time observation, content mixing assay, and component mixing assay.

A facile method for fabricating TiO2@mesoporous carbon and three-layered nanocomposites

Herein, we report a new and facile method for fabricating TiO(2)@mesoporous carbon hybrid materials. Uniform polydopamine (PDA) layers were coated onto the surface of titanate nanotubes (TNTs) and TiO(2) nanorods (TNDs) through the spontaneous adhesion and self-polymerization of dopamine during the dipping process. Core-shell mesoporous carbon nanotubes with TiO(2) nanorods or nanoparticles encapsulated inside (TiO(2)@MC) were then obtained by transforming PDA layers into carbonaceous ones through calcination in nitrogen at 800 °C. The thickness of the mesoporous carbon layers is tens of nanometers and can be controlled by adjusting the coated PDA layers through the self-polymerization reaction time. In addition, three-layered nanocomposites of TiO(2)@MC@MO (MO, metal oxide) can be readily prepared by utilizing PDA layers in TNTs@PDA or TNDs@PDA to adsorb the metal ions, followed by the calcination process.

Construction of Macroscopic Cytomimetic Vesicle Aggregates Based on Click Chemistry: Controllable Vesicle Fusion and Phase Separation

Vesicle-vesicle aggregation to mimic cell-cell aggregation has attracted much attention. Here, hyperbranched polymer vesicles (branched-polymersomes, BPs) with a cell-like size were selected as model membranes, and the vesicle aggregation process, triggered by click chemistry of the copper-catalysed azide-alkyne cycloaddition reaction, was systematically studied. For this purpose, azide and alkynyl groups were loaded on the membranes of BPs through the co-assembly method to obtain N(3)-BPs and Alk-BPs, respectively. Subsequently, macroscopic vesicle aggregates were obtained when these two kinds of functional BPs were mixed together with the ratio of azide to alkynyl groups of about 1:1. Both the vesicle fusion events and lateral phase separation on the vesicle membrane occurred during such a vesicle aggregation process, and the fusion rate and phase-separation degree could be controlled by adjusting the clickable group content. The vesicle aggregation process with N(3) -micelles as desmosome mimics to connect with Alk-BPs through click-chemistry reaction was also studied, and large-scale vesicle aggregates without vesicle fusion were obtained in this process. The present work has extended the controllable cytomimetic vesicle aggregation process with the use of covalent bonds, instead of noncovalent bonds, as the driving force.

Dissipative Particle Dynamics Simulation Study on Vesicles Self‐Assembled from Amphiphilic Hyperbranched Multiarm Copolymers

Hyperbranched multiarm copolymers (HMCs) have been shown to hold great potential as precursors in self-assembly, and many impressive supramolecular structures have been prepared through the self-assembly of HMCs in solution. However, theoretical studies on the corresponding self-assembly mechanism have been greatly lagging behind. Herein, we report the self-assembly of normal or reverse vesicles from amphiphilic HMCs by dissipative particle dynamics (DPD) simulation. The simulation disclosed both the self-assembly mechanisms and dynamics of vesicles. It indicates that the self-assembly of HMCs involves several steps, from randomly distributed unimolecular micelles to small spherical micelles, to membrane-like micelles, to finally small vesicles. The membranes are formed through the direct aggregation and lateral fusion of small micelles, and the bending and closing of the membranes give rise to small vesicles. Finally, large and steady vesicles are formed through the fusion of small vesicles. In addition, the bilayer or monolayer molecular packing modes as well as the mircrophase separation behaviors of HMCs in normal or reverse vesicles have also been studied. These simulation results explore details that cannot be observed in the experiments to a certain degree, and have extended the understanding of the vesicular self-assembly process of HMCs.