Thermoresponsive Complex Coacervate‐Based Underwater Adhesive

Sandcastle worms have developed protein‐based adhesives, which they use to construct protective tubes from sand grains and shell bits. A key element in the adhesive delivery is the formation of a fluidic complex coacervate phase. After delivery, the adhesive transforms into a solid upon an external trigger. In this work, a fully synthetic in situ setting adhesive based on complex coacervation is reported by mimicking the main features of the sandcastle worm's glue. The adhesive consists of oppositely charged polyelectrolytes grafted with thermoresponsive poly(N‐isopropylacrylamide) (PNIPAM) chains and starts out as a fluid complex coacervate that can be injected at room temperature. Upon increasing the temperature above the lower critical solution temperature of PNIPAM, the complex coacervate transitions into a nonflowing hydrogel while preserving its volume—the water content in the material stays constant. The adhesive functions in the presence of water and bonds to different surfaces regardless of their charge. This type of adhesive avoids many of the problems of current underwater adhesives and may be useful to bond biological tissues.     

Rapid Growth and Fusion of Protocells in Surface‐Adhered Membrane Networks

Elevated temperatures might have promoted the nucleation, growth, and replication of protocells on the early Earth. Recent reports have shown evidence that moderately high temperatures not only permit protocell assembly at the origin of life, but can have actively supported it. Here, the fast nucleation and growth of vesicular compartments from autonomously formed lipid networks on solid surfaces, induced by a moderate increase in temperature, are shown. Branches of the networks, initially consisting of self‐assembled interconnected nanotubes, rapidly swell into microcompartments which can spontaneously encapsulate RNA fragments. The increase in temperature further causes fusion of adjacent network‐connected compartments, resulting in the redistribution of the RNA. The experimental observations and the mathematical model indicate that the presence of nanotubular interconnections between protocells facilitates the fusion process.     

Gaseous Nanocarving‐Mediated Carbon Framework with Spontaneous Metal Assembly for Structure‐Tunable Metal/Carbon Nanofibers

Vapor phase carbon (C)‐reduction‐based syntheses of C nanotubes and graphene, which are highly functional solid C nanomaterials, have received extensive attention in the field of materials science. This study suggests a revolutionary method for precisely controlling the C structures by oxidizing solid C nanomaterials into gaseous products in the opposite manner of the conventional approach. This gaseous nanocarving enables the modulation of inherent metal assembly in metal/C hybrid nanomaterials because of the promoted C oxidation at the metal/C interface, which produces inner pores inside C nanomaterials. This phenomenon is revealed by investigating the aspects of structure formation with selective C oxidation in the metal/C nanofibers, and density functional theory calculation. Interestingly, the tendency of C oxidation and calculated oxygen binding energy at the metal surface plane is coincident with the order Co > Ni > Cu > Pt. The customizable control of the structural factors of metal/C nanomaterials through thermodynamic‐calculation‐derived processing parameters is reported for the first time in this work. This approach can open a new class of gas–solid reaction‐based synthetic routes that dramatically broaden the structure‐design range of metal/C hybrid nanomaterials. It represents an advancement toward overcoming the limitations of intrinsic activities in various applications.     

Chemical Signaling and Functional Activation in Colloidosome‐Based Protocells

An aqueous‐based microcompartmentalized model involving the integration of partially hydrophobic Fe(III)‐rich montmorillonite (FeM) clay particles as structural and catalytic building blocks for colloidosome membrane assembly, self‐directed membrane remodeling, and signal‐induced protocell communication is described. The clay colloidosomes exhibit size‐ and charge‐selective permeability, and show dual catalytic functions involving spatially confined enzyme‐mediated dephosphorylation and peroxidase‐like membrane activity. The latter is used for the colloidosome‐mediated synthesis and assembly of a temperature‐responsive poly(N‐isopropylacrylamide)(PNIPAM)/clay‐integrated hybrid membrane. In situ PNIPAM elaboration of the membrane is coupled to a glucose oxidase (GOx)‐mediated signaling pathway to establish a primitive model of chemical communication and functional activation within a synthetic “protocell community” comprising a mixed population of GOx‐containing silica colloidosomes and alkaline phosphatase (ALP)‐containing FeM‐clay colloidosomes. Triggering the enzyme reaction in the silica colloidosomes gives a hydrogen peroxide signal that induces polymer wall formation in a coexistent population of the FeM‐clay colloidosomes, which in turn generates self‐regulated membrane‐gated ALP‐activity within the clay microcompartments. The emergence of new functionalities in inorganic colloidosomes via chemical communication between different protocell populations provides a first step toward the realization of interacting communities of synthetic functional microcompartments.     

Polyoxometalate‐Based Organic–Inorganic Hybrids as Antitumor Drugs

Polyoxometalates (POMs) have shown encouraging antitumor activity. However, their cytotoxicity in normal cells and unspecific interactions with biomolecules are two major obstacles that impede the practical applications of POMs in clinical cancer treatment. Derivatization of POMs with more biocompatible organic ligands is expected to cause a synergetic effect and achieve improved bioactivity and biospecificity. Herein, the synthesis of an amphiphilic organic–inorganic hybrid is reported by grafting a long‐chain organoalkoxysilane lipid onto a POM. The amphiphilic POM hybrid could spontaneously assemble into the vesicles and exhibits enhanced antitumor activity for human colorectal cancer cell lines (HT29) compared to that of parent POMs. This detailed study reveals that the amphiphilic nature of POM hybrids enables the as‐formed vesicles to easily bind to the cell membranes and then be uptaken by the cells, thus leading to a substantial increase in antitumor activity. Such prominent antitumor action is mostly accomplished via cell apoptosis, which ultimately results in cell death. Our finding demonstrates that novel POM hybrids‐based drugs with increased bioactivity could be obtained by decorating POMs with selective organic ligands.     

Rust‐Mediated Continuous Assembly of Metal–Phenolic Networks

The use of natural compounds for preparing hybrid molecular films—such as surface coatings made from metal–phenolic networks (MPNs)—is of interest in areas ranging from catalysis and separations to biomedicine. However, to date, the film growth of MPNs has been observed to proceed in discrete steps (≈10 nm per step) where the coordination‐driven interfacial assembly ceases beyond a finite time (≈1 min). Here, it is demonstrated that the assembly process for MPNs can be modulated from discrete to continuous by utilizing solid‐state reactants (i.e., rusted iron objects). Gallic acid etches iron from rust and produces chelate complexes in solution that continuously assemble at the interface of solid substrates dispersed in the system. The result is stable, continuous growth of MPN films. The presented double dynamic process—that is, etching and self‐assembly—provides new insights into the chemistry of MPN assembly while enabling control over the MPN film thickness by simply varying the reaction time.     

Enzymatically Powered Surface‐Associated Self‐Motile Protocells

Cell motility is central to processes such as wound healing, immune cell surveillance, and embryonic development. Motility requires the conversion of chemical to mechanical energy. An active area of research is to create motile particles, such as microswimmers, using catalytic and enzymatic reactions. Here, autonomous motion is demonstrated in adhesive polymer‐based protocells by incorporating and harnessing the energy production of an enzymatic reaction. Biotinylated polymer vesicles that encapsulate catalase, an enzyme which converts hydrogen peroxide to water and oxygen, are prepared and these vesicles are adhered weakly to avidin‐coated surfaces. Upon addition of hydrogen peroxide, which diffuses across the membrane, catalase activity generates a differential impulsive force that enables the breakage and reformation of biotin–avidin bonds, leading to diffusive vesicle motion resembling random motility. The random motility requires catalase, increases with the concentration of hydrogen peroxide, and needs biotin–avidin adhesion. Thus, a protocellular mimetic of a motile cell.     

Polymer‐Mediated Nanoparticle Assembly: Structural Control and Applications

Nanoparticle–polymer composites are diverse and versatile functional materials, with applications ranging from electronic device fabrication to catalysis. This review focuses on the use of chemical design to control the structural attributes of polymer‐mediated assembly of nanoparticles. We will illustrate the use of designed particles and polymers to create nanocomposites featuring interesting and pragmatic structures and properties. We will also describe applications of these engineered materials.     

Spatial Organization in Proteinaceous Membrane‐Stabilized Coacervate Protocells

As a model protocell, the membrane‐free coacervate microdroplet is widely utilized in functional studies to provide insights into the physicochemical properties of the cell and to engineer cytomimetic soft technologies; however, the lack of a discrete membrane contributes to its instability and limits further application. Herein, a strategy is developed to fabricate a hybrid protocell based on the self‐assembly of a proteinaceous membrane at the surface of coacervate microdroplets driven by a combination of electrostatic adhesion and steric/hydrophilic surface buoyancy. The semipermeable proteinaceous membrane can enhance coacervate stability obviously without compromising sequestration behavior. Significantly, such hybrid protocells demonstrate spatial organization whereby various functional enzymes can be located in discrete regions, which facilitates an on/off modulation for a cascade enzymatic reaction along with enhanced chemical communication between subpopulations.     

Higher Order Assembly of Virus‐like Particles (VLPs) Mediated by Multi‐valent Protein Linkers

Two‐ and three‐dimensional assembly of nanoparticles has generated significant interest because these higher order structures could exhibit collective behaviors/properties beyond those of the individual nanoparticles. Highly specific interactions between molecules, which biology exploits to regulate molecular assemblies such as DNA hybridization, often provide inspiration for the construction of higher order materials using bottom‐up approaches. In this study, higher order assembly of virus‐like particles (VLPs) derived from the bacteriophage P22 is demonstrated by using a small adaptor protein, Dec, which binds to symmetry specific sites on the P22 capsid. Two types of connector proteins, which have different number of P22 binding sites and different geometries (ditopic linker with liner geometry and tetratopic linker with tetrahedral geometry) have been engineered through either a point mutation of Dec or genetic fusion with another protein, respectively. Bulk assembly and layer‐by‐layer deposition of P22 VLPs from solution was successfully achieved using both of the engineered multi‐topic linker molecules, while Dec with only a single binding site does not mediate P22 assembly. Beyond the two types of linkers developed in this study, a wide range of different connector geometries could be envisioned using a similar engineering approach. This is a powerful strategy to construct higher order assemblies of VLP based nanomaterials.