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.     

Graphene‐Directed Supramolecular Assembly of Multifunctional Polymer Hydrogel Membranes

Polymer‐based nanoporous hydrogel membranes hold great potential for a range of applications including molecular filtration/separation, controlled drug release, and as sensors and actuators. However, to be of practical utility, polymer membranes generally need to be fabricated as ultrathin yet mechanically robust, have a large‐area yet be defect‐free and in some cases, their structure needs the capability to adapt to certain stimuli. These stringent and sometimes self‐conflicting requirements make it very challenging to manufacture such bulk nanostructures in a controllable, scalable and cost‐effective manner. Here, a versatile approach to the fabrication of multifunctional polymer‐based hydrogel membranes is demonstrated by a single step involving filtration of an aqueous dispersion containing chemically converted graphene (CCG) and a polymer. With CCG uniquely serving as a membrane‐ and pore‐forming directing agent and as a physical cross‐linker, a range of water soluble polymers can be readily processed into nanoporous hydrogel membranes through supramolecular interactions. With the interconnected CCG network as a robust and porous scaffold, the membrane nanostructure can easily be fine‐tuned to suit different applications simply by controlling the chemistry and concentration of the incorporated polymer. This work provides a simple and versatile platform for the design and fabrication of new adaptive supramolecular membranes for a variety of applications.     

High‐Energy Al/CuO Nanocomposites Obtained by DNA‐Directed Assembly

Over the next few years, it is expected that new, energetic, multifunctional materials will be engineered. There is a need for new methods to assemble such materials from manufactured nanopowders. In this article, we demonstrate a DNA‐directed assembly procedure to produce highly energetic nanocomposites by assembling Al and CuO nanoparticles into micrometer‐sized particles of an Al/CuO nanocomposite, which has exquisite energetic performance in comparison with its physically mixed Al/CuO counterparts. Using 80 nm Al nanoparticles, the heat of reaction and the onset temperature are 1.8 kJ g^?1 and 410 °C, respectively. This experimental achievement relies on the development of simple and reliable protocols to disperse and sort metallic and metal oxide nanopowders in aqueous solution and the establishment of specific DNA surface‐modification processes for Al and CuO nanoparticles. Overall, our work, which shows that DNA can be used as a structural material to assemble Al/Al, CuO/CuO and Al/CuO composite materials, opens a route for molecular engineering of the material on the nanoscale.     

Growth‐Factor Free Multicomponent Nanocomposite Hydrogels That Stimulate Bone Formation

Synthetic osteo‐promoting materials that are able to stimulate and accelerate bone formation without the addition of exogenous cells or growth factors represent a major opportunity for an aging world population. A co‐assembling system that integrates hyaluronic acid tyramine ( HA‐Tyr ), bioactive peptide amphiphiles ( GHK‐Cu²⁺ ), and Laponite ( Lap ) to engineer hydrogels with physical, mechanical, and biomolecular signals that can be tuned to enhance bone regeneration is reported. The central design element of the multicomponent hydrogels is the integration of self‐assembly and enzyme‐mediated oxidative coupling to optimize structure and mechanical properties in combination with the incorporation of an osteo‐ and angio‐promoting segments to facilitate signaling. Spectroscopic techniques are used to confirm the interplay of orthogonal covalent and supramolecular interactions in multicomponent hydrogel formation. Furthermore, physico‐mechanical characterizations reveal that the multicomponent hydrogels exhibit improved compressive strength, stress relaxation profile, low swelling ratio, and retarded enzymatic degradation compared to the single component hydrogels. Applicability is validated in vitro using human mesenchymal stem cells and human umbilical vein endothelial cells, and in vivo using a rabbit maxillary sinus floor reconstruction model. Animals treated with the HA‐Tyr‐HA‐Tyr‐GHK‐Cu²⁺ hydrogels exhibit significantly enhanced bone formation relative to controls including the commercially available Bio‐Oss.     

Nanostructured Crystalline Comb Polymer of Perylenebisimide by Directed Self‐Assembly: Poly(4‐vinylpyridine)‐pentadecylphenol Perylenebisimide

Well defined nanostructured polymeric supramolecular assemblies are formed when an asymmetric perylenebisimide substituted with ethylhexyl chains on one end and functionalized with 3‐pentadecylphenol at the other termini ( PDP‐UPBI ) is complexed with poly(4‐vinylpyridine) (P4VP) via a non‐covalent specific interaction such as hydrogen‐bonding. The resulting P4VP(PDP‐UPBI) _n complexes are fully solution processable. The bulk structure and morphologies of the supramolecular film studied using small angle and wide angle X‐ray scattering reveals highly crystalline nature of the complex. Thin film morphology of the 1:1 complex analyzed using transmission electron microscopy shows uniform lamellar structures in the domain range of 5–10 nm. A clear trend of improved electrical parameters in P4VP(PDP‐UPBI) system compared to pristine ( PDP‐UPBI ) is observed from space charge limited current measurements. In short, a simple and facile method to obtain spatially defined organization of n‐type semiconductor perylenebisimide molecules using hydrogen bonding interactions with P4VP as the structural motif is showcased herein.     

Fabrication of Multicomponent Microsystems by Directed Three‐Dimensional Self‐Assembly

We have developed a directed self‐assembly process for the fabrication of three‐dimensional (3D) microsystems that contain non‐identical parts and a statistical model that relates the process yield to the process parameters. The self‐assembly process uses geometric‐shape recognition to identify different components, and surface tension between liquid solder and metal‐coated areas to form mechanical and electrical connections. The concept is used to realize self‐packaging microsystems that contain non‐identical subunits. To enable the realization of microsystems that contain more than two non‐identical subunits, sequential self‐assembly is introduced, a process that is similar to the formation of heterodimers, heterotrimers, and higher aggregates found in nature, chemistry, and chemical biology. The self‐assembly of three‐component assemblies is demonstrated by sequentially adding device segments to the assembly solution including two hundred micrometer‐sized light‐emitting diodes (LEDs) and complementary metal oxide semiconductor (CMOS) integrated circuits. Six hundred AlGaInP/GaAs LED segments self‐assembled onto device carriers in two minutes, without defects, and encapsulation units self‐assembled onto the LED‐carrier assemblies to form a 3D circuit path to operate the final device. The self‐assembly process is a well‐defined statistical process. The process follows a first‐order, non‐linear differential equation. The presented model relates the progression of the self‐assembly and yield with the process parameters—component population and capture probability—that are defined by the agitation and the component design.     

Directed Self‐Assembly of Gradient Concentric Carbon Nanotube Rings

Hundreds of gradient concentric rings of linear conjugated polymer, (poly[2‐methoxy‐5‐(2‐ethylhexyloxy)‐1,4‐ phenylenevinylene], i.e., MEH‐PPV) with remarkable regularity over large areas were produced by controlled “stick‐slip” motions of the contact line in a confined geometry consisting of a sphere on a flat substrate (i.e., sphere‐on‐flat geometry). Subsequently, MEH‐PPV rings were exploited as a template to direct the formation of gradient concentric rings of multiwalled carbon nanotubes (MWNTs) with controlled density. This method is simple, cost effective, and robust, combining two consecutive self‐assembly processes, namely, evaporation‐induced self‐assembly of polymers in a sphere‐on‐flat geometry, followed by subsequent directed self‐assembly of MWNTs on the polymer‐templated surfaces.     

Thermoplastic Elastomer Hydrogels via Self‐Assembly of an Elastin‐Mimetic Triblock Polypeptide

Protein‐based analogues of conventional thermoplastic elastomers can be designed with enhanced properties as a consequence of the precise control of primary structure. Protein 1 undergoes a reversible sol–gel transition, which results in the formation of a well‐defined elastomeric network above a lower critical solution temperature. The morphology of the network is consistent with selective microscopic phase separation of the endblock domains. This genetic engineering approach provides a method for specification of the critical architectural parameters, such as block length and sequence, which define macromolecular properties that are important for downstream applications.     

Hexahistidine‐Tagged Single‐Walled Carbon Nanotubes (His6‐tagSWNTs): A Multifunctional Hard Template for Hierarchical Directed Self‐Assembly and Nanocomposite Construction

While a hexahistidine affinity tag can be introduced at protein termini or internal sites by standard molecular biology procedures for purification, immobilization, or labeling of proteins, here the versatility of this concept is exploited for the chemical preparation of novel hexahistidine‐tagged single‐walled carbon nanotubes (His₆‐tagSWNTs), a novel hard template useful for solubilizing, assembling, processing, and interfacing SWNTs in aqueous conditions. Water‐soluble and exfoliated His₆‐tagSWNTs are prepared and fully characterized. This functional molecular module is able to interact via robust physisorption (π?π stacking) with the sidewall of SWNTs and combines the versatility of small, water‐soluble reporters (His₆) for hierarchical directed self‐assembly (HDSA) and construction of nanocomposites. It is demonstrated that metal coordination bonds with Ni(II) can be used for the supramolecular self assembly of His₆‐tagSWNTs, generating complex reticulated networks and architectures. The His₆‐tagSWNTs hard template nanohybrid is further utilized for directed self‐assembly with silica nanoparticles. The versatility of the novel hybrids opens a new era for the rational design, smart (bio)functionalization, processing, interfacing, and self assembling of carbon nanotubes for the construction of multicomposites and more complex systems with controllable spatial organization and programmable properties for a wide range of applications in biology, nanoelectronics, and catalysis.     

On‐Chip Self‐Assembly of a Smart Hybrid Nanocomposite for Antitumoral Applications

A hybrid nanocomposite comprised by porous silicon nanoparticles and a stimuli responsive polymeric material, polyethylene glycol‐block‐poly(L‐histidine), is spontaneously formed by nanoprecipitation in a flow‐focusing microfluidic chip. The nanocomposite presents a novel hybrid compound micelle structure with a great robustness for therapeutic applications. Therefore, the nanocomposite is developed and tested as a “smart” multistage drug delivery system (MDDS) in response to some of the current problems that cancer treatment presents. Based on the stimuli‐responsive behavior of the nanocomposite, a chemotherapeutic agent is successfully loaded into the nanosystem and released upon changes in the pH‐values. The nanocomposite demonstrates enhanced stability in plasma, narrow size distribution, improved surface smoothness, and high cytocompatibility. Furthermore, the nanocomposite presents reduced nanoparticle internalization by phagocytic macrophage cells and pH‐dependent cell growth inhibition capacity. Overall, the developed hybrid nanocomposite shows very promising features for its further development as a “smart” pH‐responsive MDDS.     

Stimuli‐Responsive Materials Based on Interpenetrating Polymer Liquid Crystal Hydrogels

Stimuli‐responsive materials based on interpenetrating liquid crystal‐hydrogel polymer networks are fabricated. These materials consist of a cholesteric liquid crystalline network that reflects color and an interwoven poly(acrylic acid) network that provides a humidity and pH response. The volume change in the cross‐linked hydrogel polymer results in a dimensional alteration in the cholesteric network as well, which, in turn, leads to a color change yielding a dual‐responsive photonic material. Furthermore a patterned coating having responsive and static interpenetrating polymer network areas is produced that changes both its surface topography and color.     

Temperature‐Switchable Assembly of Supramolecular Virus–Polymer Complexes

Here a method is presented for the temperature‐switchable assembly of viral particles into large hierarchical complexes. Dual‐functional diblock copolymers consisting of poly(diethyleneglycol methyl ether methacry­late) (poly(DEGMA)) and poly((2‐dimethylamino)ethyl methacrylate) (poly(DMAEMA)) blocks self‐assemble electrostatically with cowpea chlorotic mottle virus (CCMV) particles into micrometer‐sized objects as a function of temperature. The poly(DMAEMA) block carries a positive charge, which can interact electrostatically with the negatively charged outer surface of the CCMV capsid. When the solution temperature is increased above 40 °C, to cross the cloud point temperature (T_cp) of the DEGMA block, the polymer chains collapse on the surface of the virus particle, which makes them partially hydrophobic, and consequently causes the formation of large hierarchical assemblies. Disassembly of the virus–polymer complexes can be induced by reducing the solution temperature below the T_cp, which allows the poly(DEGMA) blocks to rehydrate and free virus particles to be released. The assembly process is fully reversible and can sustain several heating–cooling cycles. Importantly, this method relies on reversible supramolecular interactions and therefore avoids the irreversible covalent modification of the particle surface. This study illustrates the potential of temperature‐responsive polymers for controlled binding and releasing of virus particles.     

Hierarchical Directed Self‐Assembly of Diblock Copolymers for Modified Pattern Symmetry

Block copolymer lithography exploiting diblock copolymer thin films is promising for scalable manufacture of device‐oriented nanostructures. Nonetheless, its intrinsic limitation in the degree of freedom for pattern symmetry within hexagonal dot or parallel line array greatly diminishes the potential application fields. Here, we report multi‐level hierarchical self‐assembled nanopatterning of diblock copolymers for modified pattern symmetry. Sequential hierarchical integration of two layers of diblock copolymer films with judiciously chosen molecular weights and chemical composition creates nanopatterned morphology with modified pattern symmetry, including sparse linear cylinder or lamellar arrays. Internal structure of the hierarchically patterned morphology is characterized by grazing‐incidence small‐angle X‐ray scattering throughout the film thickness. Pattern transfer of the modified nanopattern generates linear metal nanodot array with uniform size and regular spacing as a typical example of functional nanopatterned structures.     

Poly(N‐isopropylacrylamide)‐Clay Nanocomposite Hydrogels with Responsive Bending Property as Temperature‐Controlled Manipulators

Novel poly(N‐isopropylacrylamide)‐clay (PNIPAM‐clay) nanocomposite (NC) hydrogels with both excellent responsive bending and elastic properties are developed as temperature‐controlled manipulators. The PNIPAM‐clay NC structure provides the hydrogel with excellent mechanical property, and the thermoresponsive bending property of the PNIPAM‐clay NC hydrogel is achieved by designing an asymmetrical distribution of nanoclays across the hydrogel thickness. The hydrogel is simply fabricated by a two‐step photo polymerization. The thermoresponsive bending property of the PNIPAM‐clay NC hydrogel is resulted from the unequal forces generated by the thermoinduced asynchronous shrinkage of hydrogel layers with different clay contents. The thermoresponsive bending direction and degree of the PNIPAM‐clay NC hydrogel can be adjusted by controlling the thickness ratio of the hydrogel layers with different clay contents. The prepared PNIPAM‐clay NC hydrogels exhibit rapid, reversible, and repeatable thermoresponsive bending/unbending characteristics upon heating and cooling. The proposed PNIPAM‐clay NC hydrogels with excellent responsive bending property are demonstrated as temperature‐controlled manipulators for various applications including encapsulation, capture, and transportation of targeted objects. They are highly attractive material candidates for stimuli‐responsive “smart” soft robots in myriad fields such as manipulators, grippers, and cantilever sensors.     

Micromachining‐Compatible,Facile Fabrication of Polymer Nanocomposite Spin Crossover Actuators

[Fe^II(Htrz)₂(trz)](BF₄) spin crossover particles of 85 nm mean size are dispersed in an SU‐8 polymer matrix and spray‐coated onto silicon microcantilevers. The subsequent photothermal treatment of the polymer resist leads to micrometer thick, smooth, and homogeneous coatings, which exhibit well‐reproducible actuation upon the thermally induced spin transition. The actuation amplitude as a function of temperature is accurately determined by combining integrated piezoresistive detection with external optical interferometry, which allows for the assessment of the associated actuation force (9.4 mN), stress (28 MPa), strain (1.0%), and work density (140 mJ cm^?3) through a stratified beam model. The dynamical mechanical characterization of the films evidences an increase of the resonance frequency and a concomitant decrease of the damping in the high‐temperature phase, which arises due to a combined effect of the thickness and mechanical property changes. The spray‐coating approach is also successfully extended to scale up the actuators for the centimeter range on a polymer substrate providing perspectives for biomimetic soft actuators.     

Surface‐Directed Phase Separation of Conjugated Polymer Blends for Efficient Light‐Emitting Diodes

The ability to control organic‐organic interfaces in conjugated polymer blends is critical for further device improvement. Here, we control the phase separation in blends of poly(9,9‐di‐n‐octylfluorene‐alt‐benzothiadiazole) (F8BT) and poly(9,9‐di‐n‐octylfluorene‐alt‐(1,4‐phenylene‐((4‐sec‐butylphenyl)imino)‐1,4‐phenylene) (TFB) via chemical modification of the substrate by microcontact printing of octenyltrichlorosilane molecules. The lateral phase‐separated structures in the blend film closely replicate the underlying micrometer‐scale chemical pattern. We found nanometer‐scale vertical segregation of the polymers within both lateral domains, with regions closer to the substrate being substantially pure phases of either polymer. Such phase separation has important implications for the performance of light‐emitting diodes fabricated using these patterned blend films. In the absence of a continuous TFB wetting layer at the substrate interface, as typically formed in spin‐coated blend films, charge carrier injection is confined in the well‐defined TFB‐rich domains. This confinement leads to high electroluminescence efficiency, whereas the overall reduction in the roughness of the patterned blend film results in slower decay of device efficiency at high voltages. In addition, the amount of surface out‐coupling of light in the forward direction observed in these blend devices is found to be strongly correlated to the distribution of periodicity of the phase‐separated structures in the active layer.     

Reinforcement of Shear Thinning Protein Hydrogels by Responsive Block Copolymer Self‐Assembly

Shear thinning hydrogels are promising materials that exhibit rapid self‐healing following the cessation of shear, making them attractive for applications including injectable biomaterials. Here, self‐assembly is demonstrated as a strategy to introduce a reinforcing network within shear thinning artificially engineered protein gels, enabling a responsive transition from an injectable state at low temperatures with a low yield stress to a stiffened state at physiological temperatures with resistance to shear thinning, higher toughness, and reduced erosion rates and creep compliance. Protein‐polymer triblock copolymers capable of the responsive self‐assembly of two orthogonal networks are synthesized. Midblock association forms a shear‐thinning network, while endblock aggregation at elevated temperatures introduces a second, independent physical network into the protein hydrogel. These reversible crosslinks introduce extremely long relaxation times and lead to a five‐fold increase in the elastic modulus, significantly larger than is expected from transient network theory. Thermoresponsive reinforcement reduces the high temperature creep compliance by over four orders of magnitude, decreases the erosion rate by at least a factor of five, and increases the yield stress by up to a factor of seven. Combined with the demonstrated potential of shear thinning artificial protein hydrogels for various uses, this reinforcement mechanism broadens the range of applications that can be addressed with shear‐thinning physical gels.     

Vertically Segregated Structure and Properties of Small Molecule–Polymer Blend Semiconductors for Organic Thin‐Film Transistors

A comprehensive structure and performance study of thin blend films of the small‐molecule semiconductor, 2,8‐difluoro‐5,11‐bis(triethylsilylethynyl)anthradithiophene (diF‐TESADT), with various insulating binder polymers in organic thin‐film transistors is reported. The vertically segregated composition profile and nanostructure in the blend films are characterized by a combination of complementary experimental methods including grazing incidence X‐ray diffraction, neutron reflectivity, variable angle spectroscopic ellipsometry, and near edge X‐ray absorption fine structure spectroscopy. Three polymer binders are considered: atactic poly(α‐methylstyrene), atactic poly(methylmethacrylate), and syndiotactic polystyrene. The choice of polymer can strongly affect the vertical composition profile and the extent of crystalline order in blend films due to the competing effects of confinement entropy, interaction energy with substrate surfaces, and solidification kinetics. The variations in the vertically segregated composition profile and crystalline order in thin blend films explain the significant impacts of binder polymer choice on the charge carrier mobility of these films in the solution‐processed bottom‐gate/bottom‐contact thin‐film transistors.     

Sub‐5 nm Dendrimer Directed Self‐Assembly with Large‐Area Uniform Alignment by Graphoepitaxy

Directed self‐assembly (DSA) using soft materials is an important method for producing periodic nanostructures because it is a simple, cost‐effective process for fabricating high‐resolution patterns. Most of the previously reported DSA methods exploit the self‐assembly of block copolymers, which generates a wide range of nanostructures. In this study, cylinders obtained from supramolecular dendrimer films with a high resolution (<5 nm) exhibit planar ordering over a macroscopic area via guiding topographical templates with a high aspect ratio (>10) and high spatial resolution (≈20 nm) of guiding line patterns. Theoretical and experimental studies reveal that this property is related to geometrical anchoring on the meniscus region and physical surface anchoring on the sidewall. Furthermore, this DSA of dendrimer cylinders is demonstrated by the non‐regular geometry of the patterned template. The macroscopic planar alignment of the dendrimer nanostructure reveals an extremely small feature size (≈4.7 nm) on the wafer scale (>16 cm²). This study is expected to open avenues for the production of a large family of supramolecular dendrimers with different phases and feature dimensions oriented by the DSA approach.