Hybrid Polymer Vesicles: Controllable Preparation and Potential Applications.

Hybrid polymer vesicles contain functional nanoparticles (NPs) in their walls, interfaces, coronae, or cavities. NPs render the hybrid vesicles with specific physical properties, while polymers endow them with structural stability and may significantly reduce the high toxicity of NPs. Therefore, hybrid vesicles integrate fascinating multifunctions from both NPs and polymeric vesicles, which have gained tremendous attention because of their diverse promising applications. Various types of delicate hybrid polymeric vesicles with size control and tunable localization of NPs in different parts of vesicles have been constructed via in situ and ex situ strategies, respectively. Their potential applications have been widely explored, as well. This review presents the progress of block copolymer (BCP) vesicle systems containing different types of NPs including metal NPs, magnetic NPs, and semiconducting quantum dots (QDs), etc. The strategies for controlling the location of NPs within hybrid vesicles are discussed. Typical potential applications of the elegant hybrid vesicles are also highlighted.

Porous Polymer Cubosomes with Ordered Single Primitive Bicontinuous Architecture and Their Sodium-Iodine Batteries.

Bicontinuous porous materials, which possess 3D interconnected pore channels facilitating a smooth mass transport, have attracted much interest in the fields of energy and catalysis. However, their synthesis remains very challenging. We report a general approach, using polymer cubosomes as the template, for the controllable synthesis of bicontinuous porous polymers with an ordered single primitive (SP) cubic structure, including polypyrrole (SP-PPy), poly-m-phenylenediamine (SP-PmPD), and polydopamine (SP-PDA). Specifically, the resultant SP-PPy had a unit cell parameter of 99 nm, pore diameter of 45 nm, and specific surface area of approximately 60 m2·g-1. As a proof of concept, the I2-adsorbed SP-PPy was employed as the cathode materials of newly emerged Na-I2 batteries, which delivered a record-high specific capacity (235 mA·h·g-1 at 0.5 C), excellent rate capability, and cycling stability (with a low capacity decay of 0.12% per cycle within 400 cycles at 1 C). The advantageous contributions of the bicontinuous structure and I3- adsorption mechanism of SP-PPy were revealed by a combination of ion diffusion experiments and theoretical calculations. This study opens a new avenue for the synthesis of porous polymers with new topologies, broadens the spectrum of bicontinuous-structured materials, and also develops a novel potential application for porous polymers.

Self-Assembly of Peapod-like Micrometer Tubes from a Planet-Satellite-type Supramolecular Megamer.

This study presents interesting self-assembly of peapod-like micrometer tubes from a planet-satellite-type supramolecular megamer, which was constructed through the specific host-guest molecular recognition between azobenzene (AZO)-functionalized hyperbranched poly(ethyl-3-oxetanemethanol)-star-poly(ethylene oxide) (HSP-AZO) and ß-cyclodextrin(CD)-based hydrophilic hyperbranched polyglycerol (CD-g-HPG). A peapod-like structure with micrometer-sized tube as the pod and vesicles encapsulated inside as the peas was formed through sequential vesicle entosis, linear association, and fusion processes. Dissipative particle dynamics (DPD) simulations support the structural possibility of the supramolecular peapod formation and its mechanism. UV light irradiation could lead to the disassembly of the peapod-like structure. This study expands the family of supramolecular polymers and opens a new avenue to develop bioinspired complex hierarchical nanoarchitectures at the microscopic level.

A Supramolecular-Based Dual-Wavelength Phototherapeutic Agent with Broad-Spectrum Antimicrobial Activity Against Drug-Resistant Bacteria.

With the ever-increasing threat posed by the multi-drug resistance of bacteria, the development of non-antibiotic agents for the broad-spectrum eradication of clinically prevalent superbugs remains a global challenge. Here, we demonstrate the simple supramolecular self-assembly of structurally defined graphene nanoribbons (GNRs) with a cationic porphyrin (Pp4N) to afford unique one-dimensional wire-like GNR superstructures coated with Pp4N nanoparticles. This Pp4N/GNR nanocomposite displays excellent dual-modal properties with significant reactive-oxygen-species (ROS) production (in photodynamic therapy) and temperature elevation (in photothermal therapy) upon light irradiation at 660 and 808 nm, respectively. This combined approach proved synergistic, providing an impressive antimicrobial effect that led to the complete annihilation of a wide spectrum of Gram-positive, Gram-negative, and drug-resistant bacteria both in vitro and in vivo. The study also unveils the promise of GNRs as a new platform to develop dual-modal antimicrobial agents that are able to overcome antibiotic resistance.

Self-assembly of block copolymers.

Block copolymer (BCP) self-assembly has attracted considerable attention for many decades because it can yield ordered structures in a wide range of morphologies, including spheres, cylinders, bicontinuous structures, lamellae, vesicles, and many other complex or hierarchical assemblies. These aggregates provide potential or practical applications in many fields. The present tutorial review introduces the primary principles of BCP self-assembly in bulk and in solution, by describing experiments, theories, accessible morphologies and morphological transitions, factors affecting the morphology, thermodynamics and kinetics, among others. As one specific example at a more advanced level, BCP vesicles (polymersomes) and their potential applications are discussed in some detail.

Hyperbranched polyphthalocyanine micelles with dual PTT/PDT functions for bacteria eradication under an NIR window.

A Zinc phthalocyanine-based (ZnPc-PA) polymeric micelle around 70 nm and with dual-modal PTT/PDT functions for non-antibiotic bacteria eradication was developed. It showed an excellent bacterial killing efficiency of 95.2% and 96.7% in vitro against Methicillin-resistant Staphylococcus aureus (MRSA) and its biofilm, respectively. Furthermore, the in vivo experiments proved its great potential for implant-associated infection (IAI).

A Janus Au-Polymersome Heterostructure with Near-Field Enhancement Effect for Implant-Associated Infection Phototherapy.

Polymer-inorganic hybrid Janus nanoparticles (PI-JNPs) have attracted extensive attention due to their special structures and functions. However, achieving the synergistic enhancement of photochemical activity between polymer and inorganic moieties in PI-JNPs remains challenging. Herein, the construction of a novel Janus Au-porphyrin polymersome (J-AuPPS) heterostructure by a facile one-step photocatalytic synthesis is reported. The near-field enhancement (NFE) effect between porphyrin polymersome (PPS) and Au nanoparticles in J-AuPPS is achieved to enhance its near-infrared (NIR) light absorption and electric/thermal field intensity at their interface, which improves the energy transfer and energetic charge-carrier generation. Therefore, J-AuPPS shows a higher NIR-activated photothermal conversion efficiency (48.4%) and generates more singlet oxygen compared with non-Janus core-particle Au-PPS nanostructure (28.4%). As a result, J-AuPPS exhibits excellent dual-mode (photothermal/photodynamic) antibacterial and anti-biofilm performance, thereby significantly enhancing the in vivo therapeutic effect in an implant-associated-infection rat model. This work is believed to motivate the rational design of advanced hybrid JNPs with desirable NFE effect and further extend their biological applications.

Controlled incorporation of particles into the central portion of vesicle walls.

Vesicles have attracted considerable attention recently because of many potential applications as well as intrinsic interest in the structures. The incorporation of various particles into vesicle walls has also received attention. One of the unsolved problems, in this context, is the controlled incorporation of particles into only the central portion of the vesicle walls, i.e. approximately halfway between the external and internal interfaces. In this paper, we describe a general method for the incorporation of particles into only the central portion, i.e. central 10-20%, of the vesicle walls. The strategy involves the use, as coatings on the particles, of diblock copolymers of a structure similar to that of the vesicle formers, which allows the particles to be preferentially localized in the central portion of the walls.

Polymer-directed synthesis of metal oxide-containing nanomaterials for electrochemical energy storage.

Metal oxide-containing nanomaterials (MOCNMs) of controllable structures at the nano-scale have attracted considerable interest because of their great potential applications in electrochemical energy storage devices, such as lithium-ion batteries (LIBs) and supercapacitors. Among many structure-directing agents, polymers and macromolecules, including block copolymers (BCPs) and graphene, exhibit distinct advantages in the template-assisted synthesis of MOCNMs. In this feature article, we introduce the controlled preparation of MOCNMs employing BCPs and graphene as structure-directing agents. Typical synthetic strategies are presented for the control of structures and sizes as well as the improvement of physical properties and electrochemical performance of MOCNMs in LIBs and supercapacitors.

Multicompartment micelles from hyperbranched star-block copolymers containing polycations and fluoropolymer segment.

In this Article, we have investigated the self-assembly of a series of amphiphilic hyperbranched star-block copolymers to form multicompartment micelles in acidic aqueous solution (pH 3.0) or in a dimethylformamide/water (pH 3.0) mixture. These hyperbranched star-block copolymers were prepared via oxyanion-initiated polymerization process, using hydroxyl-terminated hyperbranched poly[3-ethyl-3-(hydroxymethyl)oxetane] (HP) as a macroinitiator precursor with multi-reactive sites. It was turned into oxyanion end-capped macroinitiator through the reaction with potassium hydride, and followed by a sequential addition of 2-(N,N-dimethylamino)ethyl methacrylate (DMAEMA) and 2,2,3,3,4,4,5,5-octafluoropentyl methacrylate (OFPMA). The resultant HP-star-PDMAEMA-b-POFPMA copolymers were characterized via 1H NMR, 19F NMR, and gel permeation chromatography (GPC). The analyses of transmission electron microscopy (TEM), dynamic light scattering (DLS), and microelectrophoresis confirmed that these copolymers could directly self-organize into supramolecular multicompartment micelles with different diameters, depending on the length of the PDMAEMA segment, which can be protonated in acidic aqueous medium. The measurement of the zeta potential gave further evidence of the aggregating structures for the multicompartment micelles.