Shaping Block Copolymer Microparticles by Positively Charged Polymeric Nanoparticles.

Shape-transforming block copolymer (BCP) microparticles have attracted extensive attention due to their promising applications in nanotechnology, biomedicines, interfacial science, and other fields. As their performance is highly associated to their shape and structure, it is very important to realize the precise control of particle shape. In this report, a method is proposed to regulate the shape and structure of polystyrene-b-polydimethoxysiloxane (PS-b-PDMS) microparticles by using positively charged core-crosslinked nanoparticles (CNPs) as a cosurfactant, combining with cationic surfactant cetyltrimethylammonium bromide (CTAB). The electrostatic repulsive interactions between CNPs and CTAB dominate the shape of PS-b-PDMS particles. Upon introducing NaCl, the electrostatic repulsion is reduced, resulting in the reshape of PS-b-PDMS particles from striped Janus ellipsoids to onion-like microspheres at a critical concentration of NaCl (cNaCl ). Interestingly, it is found that the critical cNaCl first increases then reaches a plateau, with the increase in the crosslinking degree of the CNPs. The work provides a simple strategy to tailor the morphology of BCPs by manipulating the electrostatic interaction.

Shaping Block Copolymer Microparticles by pH-Responsive Core-Cross-Linked Polymeric Nanoparticles.

Block copolymer microparticles with controllable morphology have drawn widespread attention owing to their promising applications in photonic materials, energy storage, and other areas. Hence, it is highly desired to achieve a controllable transformation of microparticle morphology. In this work, we report a simple method to shape the morphology of polystyrene-block-poly(dimethylsiloxane) (PS-b-PDMS) microparticles, by employing core-cross-linked polymeric nanoparticles (CNPs) as cosurfactants which are synthesized through cross-linking P4VP segment of PS-block-poly(4-vinylpyridine) (PS-b-P4VP). The addition of pH-responsive CNPs makes the shape of pH-inert PS-b-PDMS microparticles sensitive to pH value. The PS-b-PDMS microparticles transformed from elongated Janus pupa-like particles to onion-like particles by decreasing the pH value of the aqueous phase. The deformation mechanism is investigated by changing pH value, the weight fraction of CNPs, and surfactant property. This study provides a facile strategy to deform microparticles of pH-inert BCPs by tuning pH value, which is anticipated to be applicable to other non-pH-responsive BCP microparticles.

Kinetic Control of Length and Morphology of Segmented Polymeric Nanofibers in Microfluidic Chips.

In this work, we report an approach to prepare segmented polymer nanofibers (SPNFs) composed of rodlike subunits by kinetically controlled self-assembly of polystyrene-b-poly(4-vinylpyridine)-based supramolecules in microfluidic chips. The length and morphology of the SPNFs could be effectively adjusted by changing the total flow rate (Vtotal) and the molar ratio (x) of 4-vinylpyridine (4VP) unit to a hydrogen-bonding molecule, 3-n-pentadecyphenol. Moreover, the subunits of SPNFs could transform from short rods to spheres when the interfacial tension between PS core and solvent increased. On the contrary, the SPNFs elongated along the major axis when the interfacial tension decreased. This work not only offers mechanism insights into the hierarchical self-assembly of block copolymer-based supramolecules but also provides a versatile and effective method for kinetically controlling the hierarchical structures of assemblies.

Flow-Induced Micellar Morphological Transformation in Microfluidic Chips under Nonequilibrium State: From Aggregates to Spherical Micelles.

Self-assembly of block copolymers (BCPs) in microfluidic chips is a versatile yet effective route to produce micellar aggregates with various controllable sizes and morphologies. In this study, the morphological transformation of the BCP of polystyrene-b-poly(4-vinylpyridine) (PS-b-P4VP) assemblies from irregular aggregates to multicompartment micelles and ultimately to ordered spherical micelles is demonstrated in microfluidic chips. Our experimental and computational simulation results indicate that the transverse diffusion of solvents plays an important role in the morphological transformation of PS-b-P4VP assemblies in the confined flow condition. We find that the mixing time (tmix) between a BCP/tetrahydrofuran (THF) solution and water affects the morphological transformation. Micellar morphologies are intended to transform from aggregates to ordered spherical structures under a relatively long mixing time (tmix). In addition, it is observed that the size of the micelles decreases with the increase of the flow velocity ratio by tuning the hydrodynamic conditions of the flows. Moreover, by adjusting the initial polymer solution concentration, temperature, and weight fraction of the introduced homopolystyrene (hPS), which can affect the viscosity of the BCP solution, the flow diffusion in the microfluidic chip and the resulted micellar structures can also be readily adjusted. The current study provides a new flow-driven method to adjust the micellar ordered structural transformation under the nonequilibrium state.

Dynamic Electrostatic Interfacial Engineering for Block Copolymer Microparticles with Reversible Structures.

Responsive nanoparticle surfactants (NPSs) can dynamically and reversibly modulate the interfacial interactions between incompatible components, which are essential in the interfacial catalysis, corrosion, and self-assembly of block copolymers (BCPs). However, NPSs with stimuli-responsive behavior often involve tedious chemical synthesis and surface modifications. Herein, we propose a strategy to in situ construct a kind of dynamic and reversible NPSs by the interfacial electrostatic interaction between the negatively charged nanoparticles (NPs) and the positively charged homopolymers. The NPSs assembled at the oil/water interface reduce the interfacial tension and direct the confined assembly of BCP. Meanwhile, the dynamic NPSs can be disassembled by increasing the pH value or introducing competitive electrostatic attractions, which can dynamically and reversibly change the interfacial properties as well as the alignment of polymer chains, enabling BCP microparticles with reversibly switchable lamellar and cylindrical structures. Furthermore, by the introduction of aggregation-induced emission luminogens as tails to the NPSs, the reversible transformation of BCP microparticles can be visualized by fluorescence emission, which is dependent on the nanostructures of microparticles. This work establishes a concept for dynamically manipulating interfacial interactions and reversibly switching BCP microparticles without time-consuming NPS synthesis, showing promising applications in the fabrication of smart materials with switchable structures and properties.

Dopamine-Substituted Multidomain Peptide Hydrogel with Inherent Antimicrobial Activity and Antioxidant Capability for Infected Wound Healing.

Wound infection can cause a delay in wound healing or even wound deterioration, threatening patients' lives. The excessive accumulation of reactive oxygen species (ROS) in infected wounds activates a strong inflammatory response to delay wound healing. Therefore, it is highly desired to develop hydrogels with inherent antimicrobial activity and antioxidant capability for infected wound healing. Herein, a dopamine-substituted multidomain peptide (DAP) with inherent antimicrobial activity, strong skin adhesion, and ROS scavenging has been developed. DAP can form bilayer ß-sheets with dopamine residues on the surface of nanofibers. The enhanced rheological properties of DAP-based hydrogel can be achieved not only through UV irradiation but also by incorporation of multivalent ions (e.g., PO43-). Furthermore, the DAP hydrogel shows a broad spectrum of antimicrobial activity due to the high positive charges of lysine residues and the ß-sheet formation. When applied to full-thickness dermal wounds in mice, the DAP hydrogel results in a significantly shortened inflammatory stage of the healing process because of its remarkable antimicrobial activity and antioxidant capability. Accelerated wound closure with thick granulation tissue, uniform collagen arrangement, and dense vascularization can be achieved. This work suggests that the DAP hydrogel can serve as antimicrobial coating and ROS-scavenging wound dressing for bacterial-infected wound treatment.

Surface engineering of magnetic iron oxide nanoparticles by polymer grafting: synthesis progress and biomedical applications.

Magnetic iron oxide nanoparticles (IONPs) have wide applications in magnetic resonance imaging (MRI), biomedicine, drug delivery, hyperthermia therapy, catalysis, magnetic separation, and others. However, these applications are usually limited by irreversible agglomeration of IONPs in aqueous media because of their dipole-dipole interactions, and their poor stability. A protecting polymeric shell provides IONPs with not only enhanced long-term stability, but also the functionality of polymer shells. Therefore, polymer-grafted IONPs have recently attracted much attention of scientists. In this tutorial review, we will present the current strategies for grafting polymers onto the surface of IONPs, basically including "grafting from" and "grafting to" methods. Available functional groups and chemical reactions, which could be employed to bind polymers onto the IONP surface, are comprehensively summarized. Moreover, the applications of polymer-grafted IONPs will be briefly discussed. Finally, future challenges and perspectives in the synthesis and application of polymer-grafted IONPs will also be discussed.

Responsive Photonic Crystal Microcapsules of Block Copolymers with Enhanced Monochromaticity.

Self-assembly of block copolymers (BCPs) has been developed as a promising approach for constructing photonic crystal (PC) microspheres for dynamic optical modulation. However, high curvature in the center of microspheres usually distorts the periodic core structure, leading to an inconsistency of photonic bandgap and poor monochromaticity of structural color. Herein, we report a simple yet robust strategy for fabricating responsive PC microcapsules of polystyrene-b-poly(2-vinylpyridine) through self-emulsification strategy. Interestingly, the microcapsules exhibit bright structural color with significantly enhanced monochromaticity, compared to their solid counterpart, since the microcapsules have no irregular cores. The structural colors of the PC microcapsules not only exhibit a variability through binary mixing of BCPs but also show a responsiveness to pH value. As a colored microcarrier, the PC microcapsules show a potential for visualizing the pH-dependent release behavior of encapsulated hydrophilic cargos on account of pH-responsive structural color.

Chemically Responsive Photonic Crystal Hydrogels for Selective and Visual Sensing of Thiol-Containing Biomolecules.

Intracellular thiols (e.g., cysteine, homocysteine, and glutathione) play critical roles in biological functions. Glutathione is the most abundant cellular thiol which is important for preserving redox homeostasis in biosystems. Herein, we demonstrated the fabrication of responsive photonic crystals (RPCs) for selective detection of thiol-containing biomolecules through the combination of self-assembly of monodisperse carbon-encapsulated Fe3O4 nanoparticles (NPs) and in situ photopolymerization. Typically, the polyacrylamide-based PCs were prepared by a cross-linking agent containing disulfide bonds. Interestingly, the specific chemical reaction between the disulfide bonds and thiol-containing biomolecules leads to the decrease of the cross-linking degree for the RPCs, triggering the swelling of the hydrogel and increase of the NP lattice spacing. The reduced glutathione (10-6 to 10-2 mol/L) can be determined by measuring the diffracted wavelength or visually observing the structural color change. Moreover, the RPCs can be used to detect different kinds of thiol-containing biomolecules by a simple color variation due to different reaction rates between disulfide bonds and different thiol-containing biomolecules. This study provides a facile yet effective strategy for visualized determination of the thiol-containing biomolecules.

Segmental Janus nanoparticles of polymer composites.

We demonstrate a facile yet robust "plasma etching and grafting" strategy to prepare Janus nanoparticles (NPs) coated with binary polymer brushes on two different sides. The ratio of the two types of polymer ligands can be tailored by tuning the plasma etching power.

Regulation of Drug Release by Tuning Surface Textures of Biodegradable Polymer Microparticles.

Generally, size, uniformity, shape, and surface chemistry of biodegradable polymer particles will significantly affect the drug-release behavior in vitro and in vivo. In this study, uniform poly(d,l-lactic-co-glycolide) (PLGA) and PLGA-b-poly(ethylene glycol) (PLGA-b-PEG) microparticles with tunable surface textures were generated by combining the interfacial instabilities of emulsion droplet and polymer-blending strategy. Monodisperse emulsion droplets containing polymers were generated through the microfluidic flow-focusing technique. The removal of organic solvent from the droplets triggered the interfacial instabilities (spontaneous increase in interfacial area), leading to the formation of uniform polymer particles with textured surfaces. With the introduction of homopolymer PLGA to PLGA-b-PEG, the hydrophobicity of the polymer system was tailored, and a qualitatively different interfacial behavior of the emulsion droplets during solvent removal was observed. Uniform polymer particles with tunable surface roughness were thus generated by changing the ratio of PLGA-b-PEG in the polymer blends. More interestingly, surface textures of the particles determined the drug-loading efficiency and release kinetics of the encapsulated hydrophobic paclitaxel, which followed a diffusion-directed drug-release pattern. The polymer particles with different surface textures demonstrated good cell viability and biocompatibility, indicating the promising role of the particles in the fields of drug or gene delivery for tumor therapy, vaccines, biodiagnostics, and bioimaging.