Fabrication of Organized Porphyrin‐Nanotube‐Attached Heat‐Sensitive Polyelectrolyte Capsules

A facile method of connecting fluorescent meso‐tetrakis(4‐sulfonatophenyl)porphine tetranion nanotubes to polyelectrolyte capsules is developed. Heat‐sensitive robust polyelectrolyte capsules consisting of poly(diallyldimethylammonium chloride) and poly(styrene sulfonate) multilayers have been fabricated using the conventional layer‐by‐layer technique. Supramolecular aggregation of porphyrin monomers to nanotubes is induced in the microenvironment of the capsules by sequential addition of salt and acid. Scanning electron microscopy, transmission electron microscopy, and atomic force microscopy images reveal satellite‐like structures consisting of a central capsule core with porphyrin nanotubes emerging radially from the capsule walls. The growth and the distribution of the porphyrin units have been monitored by UV‐vis spectroscopy, fluorescence spectroscopy, and confocal laser scanning microscopy. Changing the temperature alters the dimensions and the arrangement of the nanotubes on the capsule walls. Such an attachment of porphyrin tubes onto robust functional capsules should help in developing an artificial light‐harvesting system.     

Light‐Harvesting Fluorescent Supramolecular Block Copolymers Based on Cyanostilbene Derivatives and Cucurbit[8]urils in Aqueous Solution

A novel system of light‐harvesting supramolecular block copolymers (SBCPs) in water is demonstrated. To realize cucurbit[8]uril (CB[8])‐based SBCPs generating artificial light‐harvesting in water, finely color‐tuned supramolecular homopolymers (SHPs) comprising CB[8] host and different cyanostilbene guests (named as B , G , Y , and R ) emitting blue, green, yellow, and red fluorescence are first synthesized and characterized, respectively. Light‐harvesting SBCPs with mixed guest emitters are then simply produced by mixing blue and red‐emitting SHPs according to the dynamic host–guest exchange interaction. The light‐harvesting SBCPs show highly efficient energy transfer from B (donor D) to R (acceptor A) attributed to the D/A proximity and parallel orientation of their transition dipoles secured in the block copolymer structure. It is comprehensively shown that cyanostilbene/CB[8]‐based fluorescent SBCPs represent a novel and fascinating class of eco‐friendly artificial light‐harvesting system.     

Light‐Switchable Single‐Walled Carbon Nanotubes Based on Host–Guest Chemistry

A new type of light‐switchable “smart” single‐walled carbon nanotube (SWNTs) is developed by the reversible host–guest interaction between azobenzene‐terminal PEO (AzoPEO) and pyrene‐labeled host attached on the sidewalls of nanotubes via π–π stacking. The SWNTs hybrids not only are well dispersed in pure water, but also exhibit switchable dispersion/aggregation states upon the alternate irradiation of UV and visible light. Moreover, the SWNTs hybrids dispersion is preliminarily used as coating fluid to form transparent conductive films. The dispersant AzoPEO is removed by the contamination‐free UV treatment, decreasing the resistance of the films. This kind of light‐switchable SWNTs hybrids, possessing a ‘‘green’’ trigger and intact structure of the nanotube, may find potential applications in sensor of biomedicines, device fabrication, etc. Additionally, such a reversible host–guest interaction system may open up the possibility to control the dispersion state of SWNTs by other common polymers.     

Bio‐inspired Heterostructured Bead‐on‐String Fibers That Respond to Environmental Wetting

Inspired by the geometric structure of ecribellate spider capture silk and its spinning characteristics, we propose a one‐step electrohydrodynamic method to fabricate bead‐on‐string heterostructured fibers (BSHFs). By combining electrospinning and electrospraying strategies using a sprayable outer fluid with low viscosity and a spinnable inner fluid with high viscosity in a coaxial jetting process, hydrophilic poly(ethylene glycol) beads are successfully imprinted on a hydrophobic polystyrene string. It is demonstrated that the BSHFs are capable of intelligently responding to environmental change. With a change in relative humidity, the fibers show a segmented swelling and shrinking behavior in the “bead” parts whereas the “string” parts remain the same. The elastic BSHFs with alternating hydrophilic and hydrophobic surface characteristics represent a type of mesoscale analogues that block copolymers and may bring about new properties and applications. Moreover, the combined electrohydrodynamic approach developed herein should open new routes to multifunctional one‐dimensional heterostructured materials.     

Hierarchically Structured Self‐Healing Actuators with Superfast Light‐ and Magnetic‐Response

Despite the tremendous advancement of intelligent robots, it remains a great challenge to integrate living organisms‐like multistimuli responsive actuation and excellent self‐healing ability into one single material system, which will greatly benefit and broaden the development of smart biomimetic materials. Herein, a novel self‐healable multistimuli responsive actuator is developed based on hierarchical structural design and interfacial supramolecular crosslinking. The resulting biomimetic actuator shows a record high photothermal efficiency (η_PT = 79.1%) and thermal conductivity (31.92 W m^?1 K^?1), and presents a superfast actuating response (near‐infrared light: 0.44 s; magnetic field: 0.36 s). In addition, the supramolecular crosslinking endows excellent self‐healing performance in both mechanical and actuating properties to the material. This biomimetic actuator with its hierarchical structure design provides great potential for various applications, such as artificial muscles, soft robotics, and biomedical microdevices.     

Complex Tuning of Physical Properties of Hyperbranched Polyglycerol‐Based Bioink for Microfabrication of Cell‐Laden Hydrogels

Microfabrication technology has emerged as a valuable tool for fabricating structures with high resolution and complex architecture for tissue engineering applications. For this purpose, it is imperative to develop “bioink” that can be readily converted to a solid structure by the modus operandi of a chosen apparatus, while optimally supporting the biological functions by tuning their physicochemical properties. Herein, a photocrosslinkable hyperbranched polyglycerol (acrylic hyperbranched glycerol (AHPG)) is developed as a crosslinker to fabricate cell‐laden hydrogels. Due to its hydrophilicity as well as numerous hydroxyl groups for the conjugation of reactive functional groups (e.g., acrylate), the mechanical properties of resulting hydrogels could be controlled in a wide range by tuning both molecular weight and degree of acrylate substitution of AHPG. The control of mechanical properties by AHPG is highly dependent on the type of monomer, due to the hydrophilic/hydrophobic balance of polyglycerol backbone and acrylate as well as the dynamic conformational flexibility based on the molecular weight of polyglycerol. The cell encapsulation studies demonstrate the biocompatibility of the AHPG‐linked hydrogels. Eventually, the AHPG‐based hydrogel precursor solution is employed as a bioink for a digital light processing based printing system to generate cell‐laden microgels with various shapes and sizes for tissue engineering applications.     

Drug Delivery: Bio‐inspired Heterostructured Bead‐on‐String Fibers That Respond to Environmental Wetting (Adv. Funct. Mater. 8/2011)

Inspired by the geometric structure of ecribellate spider capture silk and its spinning characteristics, we propose a one‐step electrohydrodynamic method to fabricate bead‐on‐string heterostructured fibers (BSHFs). By combining electrospinning and electrospraying strategies using a sprayable outer fluid with low viscosity and a spinnable inner fluid with high viscosity in a coaxial jetting process, hydrophilic poly(ethylene glycol) beads are successfully imprinted on a hydrophobic polystyrene string. It is demonstrated that the BSHFs are capable of intelligently responding to environmental change. With a change in relative humidity, the fibers show a segmented swelling and shrinking behavior in the “bead” parts whereas the “string” parts remain the same. The elastic BSHFs with alternating hydrophilic and hydrophobic surface characteristics represent a type of mesoscale analogues that block copolymers and may bring about new properties and applications. Moreover, the combined electrohydrodynamic approach developed herein should open new routes to multifunctional one‐dimensional heterostructured materials.     

Versatile Functionalization of the Micropatterned Hydrogel of Hyperbranched Poly(ether amine) Based on “Thiol‐yne” Chemistry

The functionalization of a hydrogel with target molecules is one of the key steps in its various applications. Here, a versatile approach is demonstrated to functionalize a micropatterned hydrogel, which is formed by “thiol‐yne” photo‐click reaction between the yne‐ended hyperbranched poly(ether amine) (hPEA‐yne) and thiol‐containing polyhedral oligomeric silsesquioxane (PEG‐POSS‐SH). By controlling the molar ratio between hPEA‐yne and PEG‐POSS‐SH, patterned hydrogels containing thiol or yne groups are obtained. A series of thiol‐based click chemistry such as “thiol‐epoxy”, “thiol‐halogen”, “thiol‐ene”, and “thiol‐isocyanate” are used to functionalize the thiol‐containing hydrogel (Gel‐1), while the yne‐containing hydrogel (Gel‐2) is functionalized through a typical copper‐catalysed alkyne‐azide reaction (CuAAC). FTIR, UV‐vis spectra and confocal laser scanning microscopy (CLSM) are used to trace these click reactions. Due to the selective adsorption to the hydrophilic dyes, the obtained patterned hydrogel of hPEA modified with fluorescence dye is further demonstrated in application for the recognition of guest molecules.     

Water‐Soluble Triazolium Ionic‐Liquid‐Induced Surface Self‐Assembly to Enhance the Stability and Efficiency of Perovskite Solar Cells

Despite being a promising candidate for next‐generation photovoltaics, perovskite solar cells (PSCs) exhibit limited stability that hinders their practical application. In order to improve the humidity stability of PSCs, herein, a series of ionic liquids (ILs) “1‐alkyl‐4‐amino‐1,2,4‐triazolium” (termed as RATZ; R represents alkyl chain, and ATZ represents 4‐amino‐1,2,4‐triazolium) as cations are designed and used as additives in methylammonium lead iodide (MAPbI₃) perovskite precursor solution, obtaining triazolium ILs‐modified PSCs for the first time (termed as MA/RATZ PSCs). As opposed to from traditional methods that seek to improve the stability of PSCs by functionalizing perovskite film with hydrophobic molecules, humidity‐stable perovskite films are prepared by exploiting the self‐assembled monolayer (SAM) formation of water‐soluble triazolium ILs on a hydrophilic perovskite surface. The mechanism is validated by experimental and theoretical calculation. This strategy means that the MA/RATZ devices exhibit good humidity stability, maintaining around 80% initial efficiency for 3500 h under 40 ± 5% relative humidity. Meanwhile, the MA/RATZ PSCs exhibit enhanced thermal stability and photostability. Tuning the molecule structure of the ILs additives achieves a maximum power conversion efficiency (PCE) of 20.03%. This work demonstrates the potential of using triazolium ILs as additives and SAM and molecular design to achieve high performance PSCs.     

Amino Acid Pairing for De Novo Design of Self‐Assembling Peptides and Their Drug Delivery Potential

Molecular self‐assembly has emerged as the “bottom‐up” engineering route to fabricate functional supramolecules for diverse applications. The design of molecular building units becomes critical in determining the structure, properties, and function of the resulting assemblies. Here, a de novo design principle of amino acid pairing (AAP) to generate new classes of self‐assembling peptides (SAPs) is presented. In this study, the AAP focuses on hydrogen bonding, and ionic and hydrophobic interactions among amino acid pairs. With solely hydrogen bond pairs, SAPs can be constructed with only two amino acids. With all three AAP strategies (hydrogen bonds, ionic and hydrophobic pairs), a short novel SAP is constructed. This peptide can self‐assemble into β‐sheet‐rich nanofibers with a relatively low “critical aggregation concentration (CAC)” of ～10 μM . It also shows the ability to stabilize and deliver the hydrophobic anticancer agent ellipticine in aqueous solution. The peptide‐drug complexes/co‐assemblies exhibit anticancer activity against human lung carcinoma cells A549 and breast cancer cells MCF‐7, and have good dilution stability. The presented AAP design provides a new strategy to fabricate functional supramolecules with potential applications in nanomedicine.     

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.     

Intracellular Fate of Hydrophobic Nanocrystal Self‐Assemblies in Tumor Cells

Control of interactions between nanomaterials and cells remains a biomedical challenge. A strategy is proposed to modulate the intralysosomal distribution of nanoparticles through the design of 3D suprastructures built by hydrophilic nanocrystals (NCs) coated with alkyl chains. The intracellular fate of two water‐dispersible architectures of self‐assembled hydrophobic magnetic NCs: hollow deformable shells (colloidosomes) or solid fcc particles (supraballs) is compared. These two self‐assemblies display increased cellular uptake by tumor cells compared to dispersions of the water‐soluble NC building blocks. Moreover, the self‐assembly structures increase the NCs density in lysosomes and close to the lysosome membrane. Importantly, the structural organization of NCs in colloidosomes and supraballs are maintained in lysosomes up to 8 days after internalization, whereas initially dispersed hydrophilic NCs are randomly aggregated. Supraballs and colloidosomes are differently sensed by cells due to their different architectures and mechanical properties. Flexible and soft colloidosomes deform and spread along the biological membranes. In contrast, the more rigid supraballs remain spherical. By subjecting the internalized suprastructures to a magnetic field, they both align and form long chains. Overall, it is highlighted that the mechanical and topological properties of the self‐assemblies direct their intracellular fate allowing the control intralysosomal density, ordering, and localization of NCs.     

Synthesizing Organo/Hydrogel Hybrids with Diverse Programmable Patterns and Ultrafast Self‐Actuating Ability via a Site‐Specific “In Situ” Transformation Strategy

A simple yet robust strategy called “‘in situ' transformation” is developed to prepare organo/hydro binary gels based on the aminolysis of poly(pentafluorophenyl acrylate) (pPFPA). Treated with desired hydrophilic, oleophilic alkylamines, and their mixtures, pPFPA‐based organogels can be thoroughly transformed to targeted hydrogels, organogels, and even organohydrogels with outstanding mechanical properties. Further, relying on programed aminolysis procedures, site‐specific “in situ” transformation can be realized, giving rise to organo/hydro binary gels with diverse patterns and morphologies, such as macroscopic layered organo/hydrogel with a smooth‐transitioned yet mechanically robust interface, reconfigurable microscale organo/hydrogel hybrids with a high spatial‐resolution pattern capable of reversibly transforming between 2D sheets and 3D helixes with controlled chirality in different solvents, and core–shell structured organo/hydrogel hybrids with readily adjustable core/shell dimensions, tunable internal stress, and transparency. Finally, an oscillator based on a bilayered organo/hydrogel hybrid is developed. Attributing to the synergistic effect of organogel expansion and hydrogel contraction, as well as the robust interfacial mechanical properties, this oscillator is capable of ultrafast self‐actuating through harvesting surrounding chemical and thermal energy. This work provides new design principles and highly efficient synthetic strategy for organo/hydro binary gels, and expands their potential applications in soft robotics.     

Transparent,Mechanically Strong,Extremely Tough,Self‐Recoverable,Healable Supramolecular Elastomers Facilely Fabricated via Dynamic Hard Domains Design for Multifunctional Applications

The design and synthesis of supramolecular self‐healing polymers with high healing efficiency and excellent integrated mechanical properties is challenging due to conflicting attributes of dynamic self‐healing and mechanical properties. Herein, this study introduces a design concept, that is, “dynamic hard domains,” to balance self‐healing performance, mechanical strength, elastic recovery, and at the same time obtain extreme toughness. The essential features of the dynamic hard domains include: (i) a noncrystallized and loose structure, (ii) low binding energy and high mobility, and (iii) sequential dissociation and rapid rearrangement. Based on this strategy, a simple one‐step polycondensation route is reported to synthesize a transparent polyurethane‐urea supramolecular elastomer (PPGTD‐IDA), which successfully combines decent mechanical strength, extreme toughness, outstanding notch‐sensitiveness, self‐recoverability, and room‐temperature self‐healing. Upon rupture, the PPGTD‐IDA completely restores the mechanical properties within 48 h. Furthermore, the results demonstrate repeatable healing of mechanical properties and prominent antiaging healability. Taking advantages of merits of PPGTD‐IDA, it can be utilized for fabricating impact‐resistant materials for protection of aluminum alloys as well as stretchable and self‐healing conductors, which exhibits unique characteristics such as stable conductivity during stretching (even after healing or with notch), and automatic elimination of the notch during stretching/releasing cycles.     

Pseudobilayer Vesicle Formation via Layer‐by‐Layer Assembly of Hydrophobically Modified Polymers on Sacrificial Substrates

A bilayer of a hydrophobically modified polyelectrolyte, octadecyl poly(acrylamide) (PAAm), sandwiched between the layers of a hydrophilic polyelectrolyte, poly(ethyleneimine) (PEI), is prepared by the sequential electrostatic–hydrophobic–electrostatic‐interaction‐driven self‐assembly on planar and colloid substrates. This process results in a PEI/[PAAm]₂/PEI‐multilayer‐coated substrate. The removal of a PAA/PEI/[PAAm]₂/PEI‐multilayer‐coated decomposable colloidal template produces hollow capsules. Irregular hydrophobic domains of the [PAAm]₂ bilayer in the PEI/[PAAm]₂/PEI‐multilayer capsule are infiltrated with a lipid to obtain a uniform, distinct hydrophobic layer, imparting the capsule with a pseudobilayer vesicle structure.     

Self‐Degradable Lipid‐Like Materials Based on “Hydrolysis accelerated by the intra‐Particle Enrichment of Reactant (HyPER)” for Messenger RNA Delivery

RNA‐based therapeutics is a promising approach for curing intractable diseases by manipulating various cellular functions. For eliciting RNA (i.e., mRNA and siRNA) functions successfully, the RNA in the extracellular space must be protected and it must be delivered to the cytoplasm. In this study, the development of a self‐degradable lipid‐like material that functions to accelerate the collapse of lipid nanoparticles (LNPs) and the release of RNA into cytoplasm is reported. The self‐degradability is based on a unique reaction “Hydrolysis accelerated by intra‐Particle Enrichment of Reactant (HyPER).” In this reaction, a disulfide bond and a phenyl ester are essential structural components: concentrated hydrophobic thiols that are produced by the cleavage of the disulfide bonds in the LNPs drive an intraparticle nucleophilic attack to the phenyl ester linker, which results in further degradation. An oleic acid‐scaffold lipid‐like material that mounts all of these units (ssPalmO‐Phe) shows superior transfection efficiency to nondegradable or conventional materials. The insertion of the aromatic ring is unexpectedly revealed to contribute to the enhancement of endosomal escape. Since the intracellular trafficking is a sequential process that includes cellular uptake, endosomal escape, the release of mRNA, and translation, the improvement in each process synergistically enhances the gene expression.     

Smart Supramolecular “Trojan Horse”‐Inspired Nanogels for Realizing Light‐Triggered Nuclear Drug Influx in Drug‐Resistant Cancer Cells

Efficient nuclear delivery of anticancer drugs evading drug efflux transporters (DETs) on the plasma and nuclear membranes of multidrug‐resistant cancer cells is highly challenging. Here, smart nanogels are designed via a one‐step self‐assembly of three functional components including a biocompatible copolymer, a fluorescent organosilica nanodot, and a photodegradable near‐infrared (NIR) dye indocyanine green (ICG). The rationally designed nanogels have high drug encapsulation efficiency (≈99%) for anticancer drug doxorubicin (Dox), self‐traceability for bioimaging, proper size for passive tumor targeting, prolonged blood circulation time for enhanced drug accumulation in tumor, and photocontrolled disassemblability. Moreover, the Dox‐loaded nanogels can effectively kill multidrug‐resistant cells via two steps: 1) They behave like a “Trojan horse” to escape from the DETs on the plasma membrane for efficiently transporting the anticancer “soldier” (Dox) into the cytoplasm and preventing the drugs from being excreted from the cells; 2) Upon NIR light irradiation, the photodegradation of ICG leads to the disassembly of the nanogels to release massive Dox molecules, which can evade the DETs on the nuclear membrane to exert their intranuclear efficacy in multidrug‐resistant cells. Combined with their excellent biocompatibility, the nanogels may provide an alternative solution for overcoming cancer multidrug resistance.     

Solvent‐Controlled Assembly of Aromatic Glutamic Dendrimers for Efficient Luminescent Color Conversion

A binary supramolecular system where self‐sorting and coassembly behavior can be switched by changing the solvent polarity is hereby reported. Glutamic dendron is separately conjugated with pyrene and naphthalimide luminophores through an alkyl spacer. The resulting structurally similar building units can self‐assemble into one‐dimensional micro/nanostructures with hexagonal and lamellar packing, respectively. Varying solvents from polar aqueous solution to nonpolar decane is evidenced to profoundly inverse the superchirality and switch self‐sorted assembly to coassembly of the two building blocks. The moisture sensitivity of the naphthalimide moiety is considered the primary driving force for the self‐sorting phenomenon in aqueous solution, resulting in inevitable hydration to repel its stacking with hydrophobic pyrene moiety. On the other hand, the naphthalimide unit can integrate segmentally with the pyrene unit in decane, greatly facilitating the nanofiber growth and supramolecular gel formation along with improved energy transfer efficiency between luminophores. As a result, the coassembly‐based thin films show efficient luminescent color conversion upon the UV light irradiation. This research presents a useful route for the fabrication of controllable solution‐processed light emitting devices from self‐assembled multicomponent systems.     

A Multifunctional Blue‐Emitting Material Designed via Tuning Distribution of Hybridized Excited‐State for High‐Performance Blue and Host‐Sensitized OLEDs

Actualizing full singlet exciton yield via a reverse intersystem crossing from the high‐lying triplet state to singlet state, namely, “hot exciton” mechanism, holds great potential for high‐performance fluorescent organic light‐emitting diodes (OLEDs). However, incorporating comprehensive insights into the mechanism and effective molecular design strategies still remains challenging. Herein, three blue emitters (CNNPI, 2TriPE‐CNNPI, and 2CzPh‐CNNPI) with a distinct local excited (LE) state and charge‐transfer (CT) state distributions in excited states are designed and synthesized. They show prominent hybridized local and charge‐transfer (HLCT) states and aggregation‐induced emission enhancement properties. The “hot exciton” mechanism based on these emitters reveals that a balanced LE/CT distribution can simultaneously boost photoluminescence efficiency and exciton utilization. In particular, a nearly 100% exciton utilization is achieved in the electroluminescence (EL) process of 2CzPh‐CNNPI. Moreover, employing 2CzPh‐CNNPI as the emitter, emissive dopant, and sensitizing host, respectively, the EL performances of the corresponding nondoped pure‐blue, doped deep‐blue, and HLCT‐sensitized fluorescent OLEDs are among the most efficient OLEDs with a “hot exciton” mechanism to date. These results could shed light on the design principles for “hot exciton” materials and inspire the development of next‐generation high‐performance OLEDs.     

Spherical Triboelectric Nanogenerators Based on Spring‐Assisted Multilayered Structure for Efficient Water Wave Energy Harvesting

Making use of water wave energy at large is one of the most attractive, low‐carbon, and renewable ways to generate electric power. The emergence of triboelectric nanogenerator (TENG) provides a new approach for effectively harvesting such low‐frequency, irregular, and “random” energy. In this work, a TENG array consisting of spherical TENG units based on spring‐assisted multilayered structure is devised to scavenge water wave energy. The introduction of spring structure enhances the output performance of the spherical TENG by transforming low‐frequency water wave motions into high‐frequency vibrations, while the multilayered structure increases the space utilization, leading to a higher output of a spherical unit. Owing to its unique structure, the output current of one spherical TENG unit could reach 120 µA, which is two orders of magnitude larger than that of previous rolling spherical TENG, and a maximum output power up to 7.96 mW is realized as triggered by the water waves. The TENG array fabricated by integrating four units is demonstrated to successfully drive dozens of light‐emitting diodes and power an electronic thermometer. This study provides a new type of TENG device with improved performance toward large‐scale blue energy harvesting from the water waves.