Electrostatically Directed Self‐Assembly of Ultrathin Supramolecular Polymer Microcapsules

Supramolecular self‐assembly offers routes to challenging architectures on the molecular and macroscopic scale. Coupled with microfluidics it has been used to make microcapsules—where a 2D sheet is shaped in 3D, encapsulating the volume within. In this paper, a versatile methodology to direct the accumulation of capsule‐forming components to the droplet interface using electrostatic interactions is described. In this approach, charged copolymers are selectively partitioned to the microdroplet interface by a complementary charged surfactant for subsequent supramolecular cross‐linking via cucurbit[8]uril. This dynamic assembly process is employed to selectively form both hollow, ultrathin microcapsules and solid microparticles from a single solution. The ability to dictate the distribution of a mixture of charged copolymers within the microdroplet, as demonstrated by the single‐step fabrication of distinct core–shell microcapsules, gives access to a new generation of innovative self‐assembled constructs.     

Surfactant‐Free One‐Step Synthesis of Dual‐Functional Polyurea Microcapsules: Contact Infection Control and Drug Delivery

Surface functionalized polyurea microcapsules (MCQ) are synthesized in one step. Dimethyl‐dodecyl‐(5‐hydroxy‐pentyl)‐ammonium bromide (DAB), a hydroxyl‐end‐capped quaternary ammonium salt, is synthesized and adopted as a new surfmer for the synthesis of MCQ. It is confirmed by fluorescein adsorption that DAB is covalently bonded to MCQ. The so‐formed MCQ possess dual‐functionality: contact infection control and sustained drug delivery. Agar diffusion antimicrobial tests confirm successful inhibition of multi‐drug‐resistant E. coli by MCQ alone instead of by leaching of free quaternary ammonium salts. Furthermore, few E. coli colonies survive on an agar plate coated with 3–4 layers of MCQ. Dissolution tests show a typical first‐order release profile of courmarin‐1, a model dye, from MCQ.     

Multifunctional Hybrid Polymer‐Based Porous Materials

Polymer‐based porous hybrid materials (PHMs) carrying inorganic nanoparticles on the surface of pores have important applications in chemical and biological sensing, in chromatography, and in heterogeneous catalysis. This Feature Article provides an overview of the recent developments in the synthesis and fabrication of multifunctional PHMs using polymerization‐induced phase separation. Exemplary applications of a PHM coated with gold nanorods were demonstrated for the simultaneous detection of different analytes using surface enhanced Raman scattering (SERS) spectroscopy and fluorescence microscopy.     

All‐Natural Oil‐Filled Microcapsules from Water‐Insoluble Proteins

The formation and characterization of a novel class of all‐natural digestible microcapsules containing a liquid lipid core encapsulated by a water‐insoluble protein shell with tunable thickness is demonstrated. As an example of a water‐insoluble protein, zein is used—the protein of corn—which is an attractive biomaterial from a sustainable source. The microcapsules are prepared by a direct and simple method, based on the precipitation of protein from the continuous phase of an oil‐in‐(water/ethanol) emulsion onto the oil droplets without the need of any surfactant. The shell thickness can be controlled by the amount of precipitated protein. An in vitro digestion assay is performed to study the lipid hydrolysis and biodegradability. The rate of lipid hydrolysis and release of fatty acids are highly dependent on the protein shell thickness. All‐natural edible microcapsules with controlled degradation under gastrointestinal conditions can enable new applications for oral delivery systems. They may further be used as a model system for controlled release studies of lipophilic compounds and could promote the sustainable use of underutilized water insoluble proteins as functional biomaterials.     

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.     

Polymer‐Based Magnetoelectric Materials

Polymer‐based magnetoelectric (ME) materials are an interesting, challenging and innovative research field, that will bridge the gap between fundamental research and applications in the near future. Here, the current state of the art on the different materials, the used configurations for the development of sensors and actuators, as well as the main values of the ME coupling obtained for the different polymer‐based systems are summarized. Further, some of the specific applications that are being developed for those polymer‐based ME materials are addressed as well as the main advantages and remaining challenges in this research field.     

Shape‐Memory Microfluidics

Materials with embedded vascular networks afford rapid and enhanced control over bulk material properties including thermoregulation and distribution of active compounds such as healing agents or stimuli. Vascularized materials have a wide range of potential applications in self‐healing systems and tissue engineering constructs. Here, the application of vascularized materials for accelerated phase transitions in stimuli‐responsive microfluidic networks is reported. Poly(ester amide) elastomers are hygroscopic and exhibit thermo‐mechanical properties (T_g ≈ 37 °C) that enable heating or hydration to be used as stimuli to induce glassy‐rubbery transitions. Hydration‐dependent elasticity serves as the basis for stimuli‐responsive shape‐memory microfluidic networks. Recovery kinetics in shape‐memory microfluidics are measured under several operating modes. Perfusion‐assisted delivery of stimulus to the bulk volume of shape‐memory microfluidics dramatically accelerates shape recovery kinetics compared to devices that are not perfused. The recovery times are 4.2 ± 0.1 h and 8.0 ± 0.3 h in the perfused and non‐perfused cases, respectively. The recovery kinetics of the shape‐memory microfluidic devices operating in various modes of stimuli delivery can be accurately predicted through finite element simulations. This work demonstrates the utility of vascularized materials as a strategy to reduce the characteristic length scale for diffusion, thereby accelerating the actuation of stimuli‐responsive bulk materials.     

Tunable White‐Light Emission from Conjugated Polymer‐Di‐Ureasil Materials

Conjugated polymer (CP)‐di‐ureasil composite materials displaying a tunable emission color from blue to yellow through white have been prepared using a simple sol–gel processing method. The tunability of the emission color arises from a combination of energy transfer between the di‐ureasil and the CP dopant and the excitation wavelength dependence of the di‐ureasil emission. Incorporation of the CP does not adversely affect the bulk or local structure of the di‐ureasil, enabling retention of the structural and mechanical properties of the host. Furthermore, CP‐di‐ureasils display superior thermal and photostability compared to the parent CPs. Thermogravimetric analysis shows that the onset of thermal decomposition can be increased by up to 130 °C for CP‐di‐ureasils, while photostability studies reveal a significant decrease in the extent of photodegradation. Steady‐state photoluminescence spectroscopy and picosecond time‐resolved emission studies indicate that the observed tunable emission arises as a consequence of incomplete energy transfer between the di‐ureasil and the CP dopant, resulting in emission from both species on direct excitation of the di‐ureasil matrix. The facile synthetic approach and tunable emission demonstrate that CP‐di‐ureasils are a highly promising route to white‐light‐emitters that simultaneously improve the stability and reduce the complexity of CP‐based multilayer device architectures.     

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.     

An All Hydrophilic Fluid Diode for Unidirectional Flow in Porous Systems

A fluid diode that allows fluid flow in one direction but blocks fluid flow in the opposite direction has wide applications including oil recovery, drug delivery, and lab‐on‐a‐chip microfluidics. Many studies are conducted to facilitate directional liquid motion on the solid surface or across thin porous layers. However, the self‐driven one‐way flow inside porous systems still remains a significant challenge. Here, a novel all‐hydrophilic fluid diode (AHFD) made of porous materials with asymmetric pores is reported, which allows capillary flow in a chosen direction. The direction‐dependent flow process and the breakthrough pressure are experimentally and theoretically examined. The proposed AHFD can have many potential applications such as functional protective clothing, microfluidic valve, and oil–water separator, and the idea can be extended to develop other all lyophilic fluid diodes such as oleophilic diode.     

Protein/Polymer‐Based Dual‐Responsive Gold Nanoparticles with pH‐Dependent Thermal Sensitivity

This article presents the synthesis and physicochemical behavior of dual‐responsive plasmonic nanoparticles with reversible optical properties based on protein‐coated gold nanoparticles grafted with thermosensitive polymer brushes by means of surface‐initiated atom transfer radical polymerization (SI‐ATRP) that exhibit pH‐dependent thermo‐responsive behavior. Spherical gold NPs of two different sizes (15 nm and 60 nm) and with different stabilizing agents (citrate and cetyltrimethylammonium bromide (CTAB), respectively) were first capped with bovine serum albumin (BSA). The resulting BSA‐capped NPs (Au@BSA NPs) exhibited not only extremely high colloidal stability under physiological conditions, but also a reversible U‐shaped pH‐responsive behavior, similar to pure BSA. The ?‐amine of the L‐lysine in the protein coating was then used to covalently bind an ATRP‐initiator, allowing for the SI‐ATRP of thermosensitive polymer brushes of oligo(ethylene glycol) methacrylates with an LCST of 42 °C in pure water and around 37 °C under physiological conditions. Such protein coated nanoparticles grafted with thermosensitive polymers exhibit a smart pH‐dependent thermosensitive behavior.     

Functionalized‐Silk‐Based Active Optofluidic Devices

Silk protein from the silkworm Bombyx mori has excellent chemical and mechanical stability, biocompatibility, and optical properties. Additionally, when the protein is purified and reformed into materials, the biochemical functions of dopants entrained in the protein matrix are stabilized and retained. This unique combination of properties make silk a useful multifunctional material platform for the development of sensor devices. An approach to increase the functions of silk‐based devices through chemical modifications to demonstrate an active optofluidic device to sense pH is presented. Silk protein is chemically modified with 4‐aminobenzoic acid to add spectral‐color‐responsive pH sensitivity. The functionalized silk is combined with the elastomer poly(dimethyl siloxane) in a single microfluidic device. The microfluidic device allows spatial and temporal control of the delivery of analytic solutions to the system to provide the optical response of the optofluidic device. The modified silk is stable and spectrally responsive over a wide pH range from alkaline to acidic.     

Fabrication of All‐Water‐Based Self‐Repairing Superhydrophobic Coatings Based on UV‐Responsive Microcapsules

Superhydrophobic coatings that are also self‐healing have drawn much attention in recent years for improved durability in practical applications. Typically, the release of the self‐healing agents is triggered by temperature and moisture change. In this study, UV‐responsive microcapsules are successfully synthesized by Pickering emulsion polymerization using titania (TiO₂) and silica (SiO₂) nanoparticles as the Pickering agents to fabricate all‐water‐based self‐repairing, superhydrophobic coatings. These coatings are environmentally friendly and can be readily coated on various substrates. Compared to conventional superhydrophobic coatings, these coatings can regenerate superhydrophobicity and self‐cleaning ability under UV light, mimicking the outdoor environment, after they are mechanically damaged or contaminated with organics. They can maintain the superhydrophobicity after multiple cycles of accelerated weathering tests.     

2D Porous Polymers with sp2‐Carbon Connections and Sole sp2‐Carbon Skeletons

2D porous polymers with a planar architecture and high specific surface area have significant applications potential, such as for photocatalysis, electrochemical catalysis, gas storage and separation, and sensing. Such 2D porous polymers have generally been classified as 2D metal–organic frameworks, 2D covalent organic frameworks, graphitic carbon nitride, graphdiyne, and sandwich‐like porous polymer nanosheets. Among these, 2D porous polymers with sp²‐hybridized carbon ( $C_{s{p}^2}$) bonding are an emerging field of interest. Compared with 2D porous polymers linked by B? O, C?N, or C?C bonds, $C_{s{p}^2}$‐linked 2D porous polymers exhibit extended electron delocalization resulting in unique optical/electrical properties, as well as high chemical/photostability and tunable electrochemical performance. Furthermore, such 2D porous polymers are one of the best precursors for the fabrication of 2D porous carbon materials and carbon skeletons with atomically dispersed transition‐metal active sites. Herein, rational synthetic approaches for 2D porous polymers with $C_{s{p}^2}$ bonding are summarized. Their current practical photoelectric applications, including for gas separation, luminescent sensing and imaging, electrodes for batteries and supercapacitors, and photocatalysis are also discussed.     

Thermo-Responsive Microcapsules with Tunable Molecular Permeability for Controlled Encapsulation and Release

Microcapsules with regulated transmembrane transport are of great importance for various applications. The membranes with a tunable cut-off threshold of permeation provide advanced functionality. Here, thermo-responsive microcapsules are designed, whose hydrogel membrane shows a tunable cut-off threshold of permeation with temperature. To produce the microcapsules, water-in-oil-in-water (W/O/W) double-emulsion droplets are microfluidically produced, whose oil shell contains oil-soluble hydrogel precursor of poly(N, N-diethylacrylamide) copolymerized with benzophenone (PDEAM-BP). The PDEAM hydrogels, crosslinked by BP, show volume-phase transition around 34 °C, which makes the microcapsules with the PDEAM hydrogel membrane thermo-responsive. The microcapsules show temperature-dependent changes in radius and membrane thickness. More importantly, the cut-off threshold of permeation can be reversibly adjusted by temperature control as the degree of swelling decreases with temperature. This enables the molecule-selective encapsulation and the controlled release of the encapsulants in a programmed manner by adjusting the temperature. The microcapsules can be rendered to be photo-responsive by encapsulating photothermal polydopamine nanoparticles during the microfluidic operation, which allows the control of the degree of swelling with near-infrared (NIR) irradiation. The thermo- and photo-responsive microcapsules with a tunable cut-off threshold are appealing as a new platform for drug carriers, microreactors, and microsensors.     

Porous NIR Photoluminescent Silicon Nanocrystals‐POSS Composites

Near infrared photoluminescent porous silicon nanocrystals(ncSi)‐polyhedral oligomeric silsesquioxanes (POSS) polymer composites are synthesized using a combination of thermal hydrosilylation and polymerization between Vinyl‐POSS and hydrogen‐terminated silicon nanocrystals (ncSi:H). The synthesized materials are characterized by IR, powder X‐ray diffraction and solid‐state nuclear magnetic resonance (NMR) (¹³C and ²⁹Si). The results demonstrate that the hydrosilylation–polymerization reaction proceeded to create chemically crosslinked Vinyl‐POSS‐ncSi composites in which the integrity of the POSS cages is maintained intact. Scanning electron microscope (SEM) results demonstrate that morphology of these materials depends on the weight ratio of ncSi:H to Vinyl‐POSS. Brunauer–Emmett–Teller surface area analyses establish that the composites have high surface areas ranging from 290.5 to 1047.2 m² g^?1 and pore volumes from 0.64 to 1.17 cm³ g^?1. The pore sizes range from 6.08 to 3.54 nm and are dependent on the weight ratio of Vinyl‐POSS to ncSi:H. Photoluminescence spectroscopy shows that the absolute quantum yield of the nanocomposites is not affected by the weight ratio of ncSi:H to Vinyl‐POSS. Thermal gravimetric analysis results show that the POSS polymer composites with ncSi have lower thermal stability in nitrogen atmosphere as compared with the pure Vinyl‐POSS polymer. It is envisioned that future applications for these composites will likely be found in the fields of advanced materials, gas adsorption media, and biomedicine.     

Multi‐Stimuli‐Responsive Microcapsules for Adjustable Controlled‐Release

Novel multi‐stimuli‐responsive microcapsules with adjustable controlled‐release characteristics are prepared by a microfluidic technique. The proposed microcapsules are composed of crosslinked chitosan acting as pH‐responsive capsule membrane, embedded magnetic nanoparticles to realize “site‐specific targeting”, and embedded temperature‐responsive sub‐microspheres serving as “micro‐valves”. By applying an external magnetic field, the prepared smart microcapsules can achieve targeting aggregation at specific sites. Due to acid‐induced swelling of the capsule membranes, the microcapsules exhibit higher release rate at specific acidic sites compared to that at normal sites with physiological pH. More importantly, through controlling the hydrodynamic size of sub‐microsphere “micro‐valves” by regulating the environment temperature, the release rate of drug molecules from the microcapsules can be flexibly adjusted. This kind of multi‐stimuli‐responsive microcapsules with site‐specific targeting and adjustable controlled‐release characteristics provides a new mode for designing “intelligent” controlled‐release systems and is expected to realize more rational drug administration.