Polymer Microparticles with Controllable Surface Textures Generated through Interfacial Instabilities of Emulsion Droplets

A general and versatile route to prepare hierarchical polymer microparticles via interfacial instabilities of emulsion droplets is demonstrated. Uniform emulsion droplets containing hydrophobic polymers and n‐hexadecanol (HD) are generated through microfluidic devices. When organic solvent diffuses through the aqueous phase and evaporates, shrinking emulsion droplets containing HD and polystyrene (PS) will trigger interfacial instabilities to form microparticles with wrinkled surfaces. Interestingly, surface‐textures of the particles can be accurately tailored from smooth to high textures by varying the HD concentration and/or the rate of solvent evaporation. Moreover, composite particles can be generated by suspending different hydrophobic species to the initial polymer solutions. This versatile approach for preparing particles with highly textured surfaces can be extended to other type of hydrophobic polymers which will find potential applications in the fields of drug delivery, tissue engineering, catalysis, coating, and device fabrication.     

Polyaniline–Silica Composite Conductive Capsules and Hollow Spheres

In this paper, we report on the preparation of monodisperse polyaniline (PANi)–silica composite capsules and hollow spheres on monodisperse core–gel‐shell template particles. An extension of the previously reported inward growth method was used. The samples were self‐stabilized without external additives. The core–gel‐shell particles were prepared by the inward sulfonation of monodisperse polystyrene particles. The introduced sulfonic acid and sulfone groups are responsible for the gel properties. The gel‐shell thickness and core size were synchronously controlled over the whole particle radius range. After aniline (ANi) monomer was preferentially absorbed in the sulfonated polystyrene shell, PANi was formed by polymerization. PANi was doped in situ with a sulfonic acid group to give the capsules a high conductivity. PANi hollow spheres were derived after the polystyrene cores were dissolved: their cavity size and shell thickness were synchronously controlled by using different core–gel‐shell particles. The PANi–silica composite capsules and hollow spheres were therefore prepared by a sol–gel process using tetraethylorthosilicate in the conducting shell. The PANi shell became more robust while maintaining the same conductivity level. Morphological results indicate that the PANi and silica formed a bicontinuous network. Fourier‐transform infrared (FTIR) spectra revealed that the hydrogen bonding in the PANi–gel shell was enhanced after the silica phase was incorporated, which could explain the high conductivity level after the silica phase was added. In a converse procedure, silica capsules and hollow spheres were prepared by a sol–gel process that incorporated tetraethylorthosilicate into the core–gel‐shell templates, which was followed by the absorption and polymerization of aniline in the silica shell thus forming PANi–silica composite capsules and hollow spheres. The silica capsules and hollow spheres thereby became conductive.     

Positively Thermo‐Sensitive Monodisperse Core–Shell Microspheres

In this paper, we report on a novel family of monodisperse thermo‐sensitive core–shell hydrogel microspheres that is featured with high monodispersity and positively thermo‐responsive volume phase transition characteristics with tunable swelling kinetics, i.e., the particle swelling is induced by an increase rather than a decrease in temperature. The microspheres were fabricated in a three‐step process. In the first step, monodisperse poly(acrylamide‐co‐styrene) seeds were prepared by emulsifier‐free emulsion polymerization. In the second step, poly(acrylamide) or poly[acrylamide‐co‐(butyl methacrylate)] shells were fabricated on the microsphere seeds by free radical polymerization. In the third step, the core–shell microspheres with poly‐ (acrylamide)/poly(acrylic acid) based interpenetrating polymer network (IPN) shells were finished by a method of sequential IPN synthesis. The proposed monodisperse core–shell microspheres provide a new mode of the phase transition behavior for thermo‐sensitive “smart” or “intelligent” monodisperse micro‐actuators that is highly attractive for targeting drug delivery systems, chemical separations, sensors, and so on.     

Polydopamine‐Graphene Oxide Flame Retardant Nanocoatings Applied via an Aqueous Liquid Crystalline Scaffold

A highly effective flame retardant (FR) nanocoating was developed by conducting oxidative polymerization of dopamine monomer within an aqueous liquid crystalline (LC) graphene oxide (GO) scaffold coating. Due to its high water content, the LC scaffold coating approach facilitated fast transport and polymerization of dopamine precursors into polydopamine (PDA) within the water swollen interlayer galleries. Uniform and periodically stacked (14.5 Å d‐spacing) PDA/GO nanocoatings could be universally applied on different surfaces, including macroporous flexible polyurethane (PU) foam and flat substrates such as silicon wafers. Remarkably, PDA/GO coated PU foam exhibited highly efficient flame retardant performance reflected by a 65% reduction in peak heat release rate at 5 wt% PDA/GO loading in an 80 nm thick coating. While many physically mixed flame retardants are usually detrimental to the mechanical properties of the foam, the PDA/GO coating did not affect mechanical properties substantially. In addition, the PDA/GO coatings were stable in water due to the intrinsic adhesion capability of PDA and the transformation of GO to the more hydrophobic reduced GO form. Given that PDA is produced from dopamine, a molecule prevalent in nature, these findings suggest that significant opportunities exist for new polymeric FRs derived from other natural catechols.     

Hybrid Capsules via Self‐Assembly of Thermoresponsive and Interfacially Active Bionanoparticle–Polymer Conjugates

New bionanoparticles have been prepared from horse spleen ferritin by grafting thermoresponsive poly(N‐isopropyl acrylamide) (PNIPAAm) and photo‐crosslinkable 2‐(dimethyl maleinimido)‐N‐ethyl‐acrylamide (DMIAAm) from the protein surface. The 72 addressable amino groups on the exterior of HSF were modified with N‐hydroxysuccinimide‐activated 2‐bromo‐isobutyrate to form a macro‐initiator for atom transfer radical polymerization, which was performed in water/DMF solutions at low temperature. The modification of the HSF and the presence of the polymer shell were confirmed by size exclusion chromatography (SEC), sodium dodecyl sulfate‐polyacrylamide gel‐electrophoresis, transmission electron microscopy, and scanning force microscopy. The thermoresponsive behavior of the ferritin‐PNIPAAm conjugates was investigated in solution by UV–vis spectroscopy showing a phase transition in the form of a cloud point around 32 °C. Further, dynamic light scattering revealed an increasing hydrodynamic radius around this transition, indicating aggregation of the particles at elevated temperatures which was confirmed by transmission electron microscopy. Initial experiments show that the particles are highly surface active, much more than the individual components alone, which was demonstrated by pendant‐drop interfacial tension measurements. This leads to the fact that they form stable Pickering emulsions, i.e., emulsion droplets decorated with polymer‐modified bionanoparticles which can be cross‐linked successively. This allows the formation of capsules with thermoresponsiveness for controlled release purposes, e.g., in drug delivery.     

Osmotic Pressure Triggered Rapid Release of Encapsulated Enzymes with Enhanced Activity

In this study, a single‐step microfluidic approach is reported for encapsulation of enzymes within microcapsules with ultrathin polymeric shell for controlled release triggered by an osmotic shock. Using a glass capillary microfluidic device, monodisperse water‐in‐oil‐in‐water double emulsion droplets are fabricated with enzymes in the core and an ultrathin middle oil layer that solidifies to produce a consolidated inert polymeric shell with a thickness of a few tens to hundreds of nanometers. Through careful design of microcapsule membranes, a high percentage of cargo release, over 90%, is achieved, which is triggered by osmotic shock when using poly(methyl methacrylate) as the shell material. Moreover, it is demonstrated that compared to free enzymes, the encapsulated enzyme activity is maintained well for as long as 47 days at room temperature. This study not only extends industrial applications of enzymes, but also offers new opportunities for encapsulation of a wide range of sensitive molecules and biomolecules that can be controllably released upon applying osmotic shock.     

Microgel‐Based Stimuli‐Responsive Capsules

In this paper, a preparation of stimuli‐responsive capsules based on aqueous microgels is described. Microgel particles act as stabilizers for oil‐in‐water emulsion and organize themselves on the surface of chloroform droplets containing the biodegradable polymer poly(4‐hydroxybutyrate‐co‐4‐hydroxyvalerate) (PHBV). After chloroform evaporation, composite capsules consisting of a thin PHBV wall with integrated microgels are obtained. Due to the presence of microgels acting as sensitive building blocks, the capsules respond to different stimuli (temperature, solvent concentration). Preliminary results indicate that the capsule dimensions and morphology can be tuned by microgel and PHBV concentration in water and chloroform, respectively.     

Fabrication and Dielectric Characterization of Advanced BaTiO3/Polyimide Nanocomposite Films with High Thermal Stability

Barium titanate/polyimide (BaTiO₃/PI) nanocomposite films with high dielectric permittivity (20), high breakdown strength (67 MV m^?1), and high thermal stability are prepared by an in‐situ polymerization process. A very thin polymer layer (about 5 nm) is coated on the surface of nanosized BaTiO₃ particles to form a core–shell‐like structure, which can guarantee homogeneous dispersion of the BaTiO₃ particles in the PI matrix. It is confirmed that the core–shell‐like structure originates from both the electrostatic attraction between the precursor poly(amic acid) (PAA) and the BaTiO₃ particles and the hydrogen bond interaction between PI and the BaTiO₃ particles. Such a structure also has some influence on the dielectric properties and breakdown strength of films. After casting and degassing of the sticky film, the dielectric permittivity of the nanocomposite film is close to or even higher than that of submicrocomposite films, which is attributed to the advanced interfacial structure between the BaTiO₃ and PI phases.     

Highly Stable Colloidal “Giant” Quantum Dots Sensitized Solar Cells

Colloidal quantum dots (QDs) are widely studied due to their promising optoelectronic properties. This study explores the application of specially designed and synthesized “giant” core/shell CdSe/(CdS)_x QDs with variable CdS shell thickness, while keeping the core size at 1.65 nm, as a highly efficient and stable light harvester for QD sensitized solar cells (QDSCs). The comparative study demonstrates that the photovoltaic performance of QDSCs can be significantly enhanced by optimizing the CdS shell thickness. The highest photoconversion efficiency (PCE) of 3.01% is obtained at optimum CdS shell thickness ≈1.96 nm. To further improve the PCE and fully highlight the effect of core/shell QDs interface engineering, a CdSe_x S_1?x interfacial alloyed layer is introduced between CdSe core and CdS shell. The resulting alloyed CdSe/(CdSe_x S_1?x )₅/(CdS)₁ core/shell QD‐based QDSCs yield a maximum PCE of 6.86%, thanks to favorable stepwise electronic band alignment and improved electron transfer rate with the incorporation of CdSe_x S_1?x interfacial layer with respect to CdSe/(CdS)₆ core/shell. In addition, QDSCs based on “giant” core/CdS‐shell or alloyed core/shell QDs exhibit excellent long‐term stability with respect to bare CdSe‐based QDSCs. The giant core/shell QDs interface engineering methodology offers a new path to improve PCE and the long‐term stability of liquid junction QDSCs.     

Biocompatible,Luminescent Silver@Phenol Formaldehyde Resin Core/Shell Nanospheres: Large‐Scale Synthesis and Application for In Vivo Bioimaging

Biocompatible and green luminescent monodisperse silver/phenol formaldehyde resin core/shell spheres with controllable sizes, in the range of 180 to 1000 nm, and interesting architectures (centric, eccentric, and coenocytic core/shell spheres) have been synthesized by a facile one‐step hydrothermal approach. These spheres can be used as bioimaging labels for human lung cancer H1299 cells. The results demonstrate that the nanoparticles can be internalized into cells and exhibit no cytotoxic effects, showing that such novel biocompatible core/shell structures can potentially be used as in vivo bioimaging labels. This facile one‐pot polymerization and encapsulation technique may provide a useful tool to synthesize other core/shell particles that have potential application in biotechnology.     

Nonflammable and Magnetic Sponge Decorated with Polydimethylsiloxane Brush for Multitasking and Highly Efficient Oil–Water Separation

Developing sponge materials integrating excellent flame retardancy, multitasking separation performance, and efficient emulsion‐breaking ability is significant but challenging for the remediation of oil spills causing fires and environmental damages. Herein, a superhydrophobic oil–water separation sponge material, containing a melamine‐formaldehyde (MF) sponge substrate, magnetic polydopamine (PDA) coating, and branched polydimethylsiloxane (PDMS) brush, through dopamine‐mediated surface initiated atom transfer radical polymerization (SI‐ATRP) is fabricated. The synergistic flame resistance of the MF substrate and PDMS brush significantly improves its adaptability in fire. More importantly, the decorated PDMS brushes can effectively overcome the size mismatch between sponge macropores and tiny emulsified droplets, while remaining the intrinsic macroporous characteristic. When treating W/O emulsions, the PDMS brushes stretch up to act as “interface‐breaking blades” to accelerate the coalescence of emulsified water droplets. Meanwhile, such PDMS brushes can serve as “oil‐trapping tentacles” to efficiently capture oil droplets when treating O/W emulsions. Such material design synergistically contributes to satisfactory separation efficiency (98.7%) and ultrahigh permeation flux (up to 1.35 × 10⁵ L m^?2 h^?1), even for treating high viscosity emulsions. Besides, the reported sponge also inherits robust durability, superior recyclability, and convenient magnetic collection. These features make the sponge promising for multitasking and highly efficient oil–water separation.     

Polymer–Aptamer Hybrid Emulsion Templating Yields Bioresponsive Nanocapsules

This article describes the synthesis of a DNA–polymer, being the nucleotide sequence an aptamer selected in vitro to target specifically the immunoglobulin E (IgE) protein, an allergy biomarker. Subsequent to coupling to poly(2‐alkyl‐2‐oxazoline) with N‐Boc protected amino acid side chains, the resulting amphiphilic DNA–polymer hybrid composed of the water‐soluble DNA fragment grafted to the hydrophobic polymer segment can be regarded as a high molecular weight analogue of a surfactant. It is demonstrated that the copolymer–aptamer stabilizes efficiently submicrometer size oil‐in‐water and water‐in‐oil emulsions, by dynamic light scattering, microscopy, and reflectometry. Particularly interesting is that the aptamer remains functional after coupling to a polymer backbone, stabilization of the emulsion droplets, and locking of the structure subsequent to cross‐linking polymerization. The resulting nanocapsules still target specifically the IgE protein. The biological‐stimulus responsiveness of the structures is of high potential for future developments of carriers for sustained and targeted delivery.     

Microcapsules: Packing of Emulsion Droplets: Structural and Functional Motifs for Multi‐Cored Microcapsules (Adv. Funct. Mater. 9/2011)

Advances in microfluidic emulsification have enabled the creation of multiphase emulsion drops, which have emerged as promising templates for producing functional microcapsules. However, most previous micro‐encapsulation methods have limitations in terms of capsule stability, functionality, and simplicity of fabrication procedures. Here, we report a simple single‐step encapsulation technique that uses an optofluidic platform to efficiently and precisely encapsulate a specific number of emulsion droplets in photocurable shell droplets. In particular, we show, for the first time, that densely confined core droplets within an oily shell droplet rearrange into a unique configuration that minimizes the interfacial energy, as confirmed here from theory. These structures are then consolidated into multi‐cored microcapsules with structural and mechanical stability through in situ photopolymerization of the shell in a continuous mode, which are capable of isolating active materials and releasing them in a controlled manner using well‐defined nanohole arrays or nanoscopic silver architectures on thin membranes.     

Packing of Emulsion Droplets: Structural and Functional Motifs for Multi‐Cored Microcapsules

Advances in microfluidic emulsification have enabled the creation of multiphase emulsion drops, which have emerged as promising templates for producing functional microcapsules. However, most previous micro‐encapsulation methods have limitations in terms of capsule stability, functionality, and simplicity of fabrication procedures. Here, we report a simple single‐step encapsulation technique that uses an optofluidic platform to efficiently and precisely encapsulate a specific number of emulsion droplets in photocurable shell droplets. In particular, we show, for the first time, that densely confined core droplets within an oily shell droplet rearrange into a unique configuration that minimizes the interfacial energy, as confirmed here from theory. These structures are then consolidated into multi‐cored microcapsules with structural and mechanical stability through in situ photopolymerization of the shell in a continuous mode, which are capable of isolating active materials and releasing them in a controlled manner using well‐defined nanohole arrays or nanoscopic silver architectures on thin membranes.     

Photo‐Induced Functionalization of Spherical and Planar Surfaces via Caged Thioaldehyde End‐Functional Polymers

The synthesis and application of a novel reversible addition‐fragmentation chain transfer (RAFT) agent carrying a photocaged thioaldehyde moiety is described (λ_max = 355 nm). RAFT polymerization of styrene, dimethylacrylamide and a glycomonomer is evidenced (3600 g mol^?1 ≤ M_n ≤ 15 000 g mol^?1; 1.07 ≤ ? ≤ 1.20) with excellent end‐group fidelity. The photogenerated thioaldehyde on the chain ends can undergo hetero Diels–Alder reactions with dienes as well as reactions with nucleophiles. The terminal photoreactive polymers are photografted to porous diene‐reactive polymeric microspheres. The grafted particles are in‐depth characterized via scanning electron microscopy, elemental analysis, X‐ray photoelectron spectroscopy, and high resolution FT‐IR microscopy, leading to a qualitative as well as quantitative image of the core–shell objects. Grafting densities up to 0.10 molecules nm^?2 are reached. The versatility of the thioaldehyde ligation is evidenced by spatially resolved grafting of polystyrene onto nucleophilic groups present in poly (dopamine) (PDA)‐coated glass slides and silicon wafers via two‐photon direct laser writing (DLW) imaged by ToF‐SIMS. The combination of thioaldehyde ligation, RAFT polymerization, and DLW allows for the spatially resolved grafting of a vast range of polymers onto various substrates in any desired pattern with sub‐micrometer resolution.     

聚苯乙烯-丙烯酸共聚物胶体纳米球核壳结构及其选择性溶解过程的表征

本文对采用自由基乳液聚合法制备的聚苯乙烯-丙烯酸(polystyrene-acrylic acid,PS-AA)共聚物胶体纳米球进行了微结构表征.发现原始合成的聚苯乙烯胶体球具有典型的核壳结构,磷钨酸(phosphotungstic acid,PTA)优先在核壳界面聚集.中心核主要由疏水性的苯乙烯组成,外壳主要由亲水性的丙烯酸组成.甲苯能对PS-AA胶体球进行原位选择性溶解.溶解过程中,胶体球发生溶胀破裂,中心聚苯乙烯初步溶解,孔结构经历了内径由小到大,孔边缘由粗糙不规则到光滑的变化过程.胶体球形成高分子孔结构,圆孔发生了一定程度的变形.     

Preparation of Hollow Silica Nanospheres by Surface‐Initiated Atom Transfer Radical Polymerization on Polymer Latex Templates

Poly(vinylbenzyl chloride), (PVBC) latex particles of about 100 nm in size are prepared by emulsion polymerization. Silyl functional groups are introduced onto the PVBC‐nanoparticle templates via surface‐initiated atom transfer radical polymerization of 3‐(trimethoxysilyl)propyl methacrylate. The silyl groups are then converted into a silica shell, approximately 20 nm thick, via a reaction with tetraethoxysilane in ethanolic ammonia. Hollow silica nanospheres are finally generated by thermal decomposition of the PVBC template cores. Field‐emission scanning electron microscopy and field‐emission transmission electron microscopy are used to characterize the intermediate products and the hollow nanospheres. Fourier‐transform infrared spectroscopy results indicate that the polymer cores are completely decomposed.     

Hydrophilic/Oleophilic Magnetic Janus Particles for the Rapid and Efficient Oil–Water Separation

The separation of microsized oil droplets from water is strongly required by the environmental protection and petroleum industry. However, the separation of microsized oil droplets from water is often ignored. Herein, magnetic Janus particles are reported with a convex hydrophilic surface/concave oleophilic surface by emulsion interfacial polymerization and selective surface assembly, realizing the rapid and efficient separation of microscaled tiny oil droplets from water. These magnetic Janus particles exhibit significant abilities to separate microscaled oil droplets from water, which usually occurs within 120 s with a separation efficiency >99%. Theoretical and experimental results demonstrate that these magnetic Janus particles can capture tiny oil droplets to make them coalesce into larger ones during the process of separation. Further studies reveal that these Janus particles can self‐assemble and closely pack onto the interface of larger oil droplets, acting as surfactants to stabilize them. Moreover, the shape effect of the Janus particle is demonstrated on the coalescence of the oil droplets.     

Monodisperse Hollow Supraparticles via Selective Oxidation

A novel and general strategy to fabricate monodisperse hollow supraparticles (SPs) via selective chemical oxidation is developed. Core‐shell SPs made of semiconductor nanocrystals (NCs) are first obtained by an in situ assembly method. Subsequently, the cores can be selectively removed by preferential oxidation with dilute H₂O₂, resulting in formation of monodisperse hollow SPs. The structural parameters of the products, such as size, shell thickness, and composition, are tailored easily. The hollow structures achieved from CdSe/CdS core‐shell SPs possess high fluorescence quantum yields and a large Stokes shift, the latter is remarkably different from that of conventional organic dyes and quantum dots. In addition to simple hollow structures, rattle‐type nanostructures composed of semiconductor SPs or noble metal‐semiconductor hybrids are also prepared, exemplifying the versatility of the proposed strategy.     

Gas Pickering Emulsion Templated Hollow Carbon for High Rate Performance Lithium Sulfur Batteries

A CO₂ in water nanoparticle stabilized Pickering emulsion is used to template micrometer sized hollow porous nitrogen doped carbon particles for high rate performance lithium sulfur battery. For the first time, nanoparticles serve the dual role of an emulsion stabilizer and a pore template for the shell, directly utilizing in situ generated CO₂ bubbles as template for the core. The minimalistic nature of this method does not require expensive surfactants or additional core templates. Upon polymerization of melamine formaldehyde onto CO₂, a robust polymer/silica composite shell is formed and transformed into a porous shell upon washing. The micrometer‐sized hollow morphology in combination with its nitrogen rich porous shell demonstrates impressive rate capabilities of 670 and 500 mAh g^?1 even at a high rate of 7C and 9C, respectively. This material also possesses excellent cycle durability, exhibiting a low capacity decay of 0.088%/cycle over 300 cycles. Measurement of the shuttle current and impedance provides interesting insight into the polysulfide mass transfer mechanism of hollow structured sulfur hosts.