Reversed Anionic Hofmeister Effect in Metal-Phenolic-Based Film Formation.

Although metal-phenolic species have emerged as one of the versatile material-independent-coating materials, providing attractive tools for interface engineering, mechanistic understanding of their film formation and growth still remains largely unexplored. Especially, the anions have been overlooked despite their high concentration in the coating solution. Considering that the anions are critical in the reactivity of metal-organic complex and the formation and/or property of functional materials, we investigated the anionic effects on the characteristics of film formation, such as film thickness and properties, in the Fe3+-tannic acid coating. We found that the film characteristics were strongly dictated by the counteranions (e.g., SO42-, Cl-, and Br-) of the Fe3+ ion. Specifically, the film thickness and properties (i.e., mechanical modulus, permeability, and stability) followed the reversed anionic Hofmeister series (Br- > Cl- > SO42-). Mechanistic studies suggested that more chaotropic anions, such as Br-, might induce a more widely extended structure of the Fe3+-TA complexes in the coating solution, leading to thicker, harder, but more porous films. The reversed anionic Hofmeister effect was further confirmed by the additive effects of various sodium salts (NaF, NaCl, NaBr, and NaClO4).

Polyphenol-Mediated Assembly of Proteins for Engineering Functional Materials.

Functional materials composed of proteins have attracted much interest owing to the inherent and diverse functionality of proteins. However, establishing general techniques for assembling proteins into nanomaterials is challenging owing to the complex physicochemical nature and potential denaturation of proteins. Here, a simple, versatile strategy is introduced to fabricate functional protein assemblies through the interfacial assembly of proteins and polyphenols (e.g., tannic acid) on various substrates (organic, inorganic, and biological). The dominant interactions (hydrogen-bonding, hydrophobic, and ionic) between the proteins and tannic acid were elucidated; most proteins undergo multiple noncovalent stabilizing interactions with polyphenols, which can be used to engineer responsiveness into the assemblies. The proteins retain their structure and function within the assemblies, thereby enabling their use in various applications (e.g., catalysis, fluorescence imaging, and cell targeting).

Modular Assembly of Host-Guest Metal-Phenolic Networks Using Macrocyclic Building Blocks.

The manipulation of interfacial properties has broad implications for the development of high-performance coatings. Metal-phenolic networks (MPNs) are an emerging class of responsive, adherent materials. Herein, host-guest chemistry is integrated with MPNs to modulate their surface chemistry and interfacial properties. Macrocyclic cyclodextrins (host) are conjugated to catechol or galloyl groups and subsequently used as components for the assembly of functional MPNs. The assembled cyclodextrin-based MPNs are highly permeable (even to high molecular weight polymers: 250-500 kDa), yet they specifically and noncovalently interact with various functional guests (including small molecules, polymers, and carbon nanomaterials), allowing for modular and reversible control over interfacial properties. Specifically, by using either hydrophobic or hydrophilic guest molecules, the wettability of the MPNs can be readily tuned between superrepellency (>150°) and superwetting (ca. 0°).

Smart SERS Hot Spots: Single Molecules Can Be Positioned in a Plasmonic Nanojunction Using Host-Guest Chemistry.

Single-molecule surface-enhanced Raman spectroscopy (SERS) offers new opportunities for exploring the complex chemical and biological processes that cannot be easily probed using ensemble techniques. However, the ability to place the single molecule of interest reliably within a hot spot, to enable its analysis at the single-molecule level, remains challenging. Here we describe a novel strategy for locating and securing a single target analyte in a SERS hot spot at a plasmonic nanojunction. The "smart" hot spot was generated by employing a thiol-functionalized cucurbit[6]uril (CB[6]) as a molecular spacer linking a silver nanoparticle to a metal substrate. This approach also permits one to study molecules chemically reluctant to enter the hot spot, by conjugating them to a moiety, such as spermine, that has a high affinity for CB[6]. The hot spot can accommodate at most a few, and often only a single, analyte molecule. Bianalyte experiments revealed that one can reproducibly treat the SERS substrate such that 96% of the hot spots contain a single analyte molecule. Furthermore, by utilizing a series of molecules each consisting of spermine bound to perylene bisimide, a bright SERS molecule, with polymethylene linkers of varying lengths, the SERS intensity as a function of distance from the center of the hot spot could be measured. The SERS enhancement was found to decrease as 1 over the square of the distance from the center of the hot spot, and the single-molecule SERS cross sections were found to increase with AgNP diameter.

Self-Assembled Metal-Phenolic Networks on Emulsions as Low-Fouling and pH-Responsive Particles.

Interfacial self-assembly is a powerful organizational force for fabricating functional nanomaterials, including nanocarriers, for imaging and drug delivery. Herein, the interfacial self-assembly of pH-responsive metal-phenolic networks (MPNs) on the liquid-liquid interface of oil-in-water emulsions is reported. Oleic acid emulsions of 100-250 nm in diameter are generated by ultrasonication, to which poly(ethylene glycol) (PEG)-based polyphenolic ligands are assembled with simultaneous crosslinking by metal ions, thus forming an interfacial MPN. PEG provides a protective barrier on the emulsion phase and renders the emulsion low fouling. The MPN-coated emulsions have a similar size and dispersity, but an enhanced stability when compared with the uncoated emulsions, and exhibit a low cell association in vitro, a blood circulation half-life of ≈50 min in vivo, and are nontoxic to healthy mice. Furthermore, a model anticancer drug, doxorubicin, can be encapsulated within the emulsion phase at a high loading capacity (≈5 fg of doxorubicin per emulsion particle). The MPN coating imparts pH-responsiveness to the drug-loaded emulsions, leading to drug release at cell internalization pH and a potent cell cytotoxicity. The results highlight a straightforward strategy for the interfacial nanofabrication of pH-responsive emulsion-MPN systems with potential use in biomedical applications.

Covalent Self-Assembly and One-Step Photocrosslinking of Tyrosine-Rich Oligopeptides to Form Diverse Nanostructures.

We present covalently self-assembled peptide hollow nanocapsule and peptide lamella. These biomimetic dityrosine peptide nanostructures are synthesized by one-step photopolymerization of a tyrosine-rich short peptide without the aid of a template. This simple approach offers direct synthesis of fluorescent peptide nanocages and free-standing thin films. The simple crosslinked peptide lamella films provide robust mechanical properties with an elastic modulus of approximately 30 GPa and a hardness of 740 MPa. These nanostructures also allow for the design of peptidosomes. The approach taken here represents a rare example of covalent self-assembly of short peptides into nano-objects, which may be useful as microcompartments and separation membranes.

Hydrolytic Transformation of Microporous Metal-Organic Frameworks to Hierarchical Micro- and Mesoporous MOFs.

A new approach to the synthesis of hierarchical micro- and mesoporous MOFs from microporous MOFs involves a simple hydrolytic post-synthetic procedure. As a proof of concept, a new microporous MOF, POST-66(Y), was synthesized and its transformation into a hierarchical micro- and mesoporous MOF by water treatment was studied. This method produced mesopores in the range of 3 to 20 nm in the MOF while maintaining the original microporous structure, at least in part. The degree of micro- and mesoporosity can be controlled by adjusting the time and temperature of hydrolysis. The resulting hierarchical porous MOF, POST-66(Y)-wt, can be utilized to encapsulate nanometer-sized guests such as proteins, and the enhanced stability and recyclability of an encapsulated enzyme is demonstrated.

Reversible morphological transformation between polymer nanocapsules and thin films through dynamic covalent self-assembly.

A facile method has been developed for synthesizing polymer nanocapsules and thin films using multiple in-plane stitching of monomers by the formation of reversible disulfide linkages. Owing to the reversibility of the disulfide linkages, the nanostructured materials readily transform their structures in response to environmental changes at room temperature. For example, in reducing environments, the polymer nanocapsules release loaded cargo molecules. Moreover, reversible morphological transformations between these structures can be achieved by simple solvent exchanges. This work is a novel approach for the formation of robust nano/microstructured materials that dynamically respond to environmental stimuli.

Highly stable, water-dispersible metal-nanoparticle-decorated polymer nanocapsules and their catalytic applications.

A facile synthesis of highly stable, water-dispersible metal-nanoparticle-decorated polymer nanocapsules (M@CB-PNs: M=Pd, Au, and Pt) was achieved by a simple two-step process employing a polymer nanocapsule (CB-PN) made of cucurbit[6]uril (CB[6]) and metal salts. The CB-PN serves as a versatile platform where various metal nanoparticles with a controlled size can be introduced on the surface and stabilized to prepare new water-dispersible nanostructures useful for many applications. The Pd nanoparticles on CB-PN exhibit high stability and dispersibility in water as well as excellent catalytic activity and recyclability in carbon-carbon and carbon-nitrogen bond-forming reactions in aqueous medium suggesting potential applications as a green catalyst.

Free-standing, single-monomer-thick two-dimensional polymers through covalent self-assembly in solution.

The design and synthesis of two-dimensional (2D) polymers is a challenging task, hitherto achieved in solution only through the aid of a solid surface "template" or preorganization of the building blocks in a 2D confined space. We present a novel approach for synthesizing free-standing, covalently bonded, single-monomer-thick 2D polymers in solution without any preorganization of building blocks on solid surfaces or interfaces by employing shape-directed covalent self-assembly of rigid, disk-shaped building blocks having laterally predisposed reactive groups on their periphery. We demonstrate our strategy through a thiol-ene "click" reaction between (allyloxy)12CB[6], a cucurbit[6]uril (CB[6]) derivative with 12 laterally predisposed reactive alkene groups, and 1,2-ethanedithiol to synthesize a robust and readily transferable 2D polymer. We can take advantage of the high binding affinity of fully protonated spermine (positive charges on both ends) to CB[6] to keep each individual polymer sheet separated from one another by electrostatic repulsion during synthesis, obtaining, for the first-time ever, a single-monomer-thick 2D polymer in solution. The arrangement of CB[6] repeating units in the resulting 2D polymer has been characterized using gold nanoparticle labeling and scanning transmission electron microscopy. Furthermore, we have confirmed the generality of our synthetic approach by applying it to different monomers to generate 2D polymers. Novel 2D polymers, such as our CB[6] derived polymer, may be useful in selective transport, controlled drug delivery, and chemical sensing and may even serve as well-defined 2D scaffolds for ordered functionalization and platforms for bottom-up 3D construction.

Tandem-biocatalysis reactors constructed by topological evolution of CaCO3 particles into hollow metal hydroxide spheres.

Despite remarkable advances in the design and synthesis of hollow inorganic spheres (HISs), the harsh synthetic conditions have precluded the applications of HISs to biochemical and biological fields. Herein we report a biocompatible strategy for synthesizing metal hydroxide HISs (MH-HISs) by simply mixing CaCO3 particles with metal ions in water. The ion-exchange reaction between Ca2+ and metal ions leads to the structural and chemical evolution from solid CaCO3 particles to hollow MH-HISs via core-shell and yolk-shell structures, while enabling the encapsulation of enzymes to the shells without loss of catalytic activities. The biocompatible protocol makes multienzymatic cascade reactions achievable, with great recyclability due to mechanical durability of MH-HISs.

Vortex-assisted, nanoarchitectonic manipulation of microparticles with flavonoid-Fe3+ complex in biphasic water-oil systems.

Coordination-driven self-assembly of metal-ligand complexes is a powerful nanoarchitectonic tool for particle engineering, but its usability is limited when using two immiscible coating components. This paper reports that simple vortexing of a biphasic system of Fe3+ ions in water and flavonoids in oil forms nanoshells on individual particles, thereby enabling the utilization of water-insoluble ligands as coating materials. Mechanistic studies suggest that the biphasic mass-transfer equilibrium of flavonoid-Fe3+ species controls the shell formation, with the oil phase acting as a reservoir of coating precursors for continuous coating. The versatility and convenience of our method expand the chemical toolbox for modulating particle-material interfaces.

A Natural Virucidal and Microbicidal Spray Based on Polyphenol-Iron Sols.

Numerous disinfection methods have been developed to reduce the transmission of infectious diseases that threaten human health. However, it still remains elusively challenging to develop eco-friendly and cost-effective methods that deactivate a wide range of pathogens, from viruses to bacteria and fungi, without doing any harm to humans or the environment. Herein we report a natural spraying protocol, based on a water-dispersible supramolecular sol of nature-derived tannic acid (TA) and Fe3+, which is easy-to-use and low-cost. Our formulation effectively deactivates viruses (influenza A viruses, SARS-CoV-2, and human rhinovirus) as well as suppressing the growth and spread of pathogenic bacteria (Escherichia coli, Salmonella typhimurium, Staphylococcus aureus, and Acinetobacter baumannii) and fungi (Pleurotus ostreatus and Trichophyton rubrum). Its versatile applicability in a real-life setting is also demonstrated against microorganisms present on the surfaces of common household items (e.g., air filter membranes, disposable face masks, kitchen sinks, mobile phones, refrigerators, and toilet seats).

Cell-in-Catalytic-Shell Nanoarchitectonics: Catalytic Empowerment of Individual Living Cells by Single-Cell Nanoencapsulation.

Cell-in-shell biohybrid structures, synthesized by encapsulating individual living cells with exogenous materials, have emerged as exciting functional entities for engineered living materials, with emergent properties outside the scope of biochemical modifications. Artificial exoskeletons have, to date, provided physicochemical shelters to the cells inside in the first stage of technological development, and further advances in the field demand catalytically empowered, cellular hybrid systems that augment the biological functions of cells and even introduce completely new functions to the cells. This work describes a facile and generalizable strategy for empowering living cells with extrinsic catalytic capability through nanoencapsulation of living cells with a supramolecular metal-organic complex of Fe3+ and benzene-1,3,5-tricarboxylic acid (BTC). A series of enzymes are embedded in situ, without loss of catalytic activity, in the Fe3+ -BTC shells, not to mention the superior characteristics of cytocompatible and rapid shell-forming processes. The nanoshell enhances the catalytic efficiency of multienzymatic cascade reactions by confining reaction intermediates to its internal voids and the nanoencapsulated cells acquire exogenous biochemical functions, including enzymatic cleavage of lethal octyl-ß-d-glucopyranoside into d-glucose, with autonomous cytoprotection. The system will provide a versatile, nanoarchitectonic tool for interfacing biological cells with functional materials, especially for catalytic bioempowerment of living cells.

Enzyme-Mediated Kinetic Control of Fe3+-Tannic Acid Complexation for Interface Engineering.

Supramolecular self-assembly of Fe3+ and tannic acid (TA) has received great attention in the fields of materials science and interface engineering because of its exceptional surface coating properties. Although advances in coating strategies often suggest that kinetics in the generation of interface-active Fe3+-TA species is deeply involved in the film formation, there is no acceptable elucidation for the coating process. In this work, we developed the enzyme-mediated kinetic control of Fe2+ oxidation to Fe3+ in a Fe2+-TA complex in the iron-gall-ink-revisited coating method. Specifically, hydrogen peroxide, produced in the glucose oxidase (GOx)-catalyzed reaction of d-glucose, accelerated Fe2+ oxidation, and the optimized kinetics profoundly facilitated the film formation to be about 9 times thicker. We also proposed a perspective considering the coating process as nucleation and growth. From this viewpoint, the kinetics in the generation of interface-active Fe3+-TA species should be optimized because it determines whether the interface-active species forms a film on the substrate (i.e., heterogeneous nucleation and film growth) or flocculates in solution (i.e., homogeneous nucleation and particle growth). Moreover, GOx was concomitantly embedded into the Fe3+-TA films with sustained catalytic activities, and the GOx-mediated coating system was delightfully adapted to catalytic single-cell nanoencapsulation.

Ascorbic acid-mediated reductive disassembly of Fe3+-tannic acid shells in degradable single-cell nanoencapsulation.

Rapid degradation of Fe3+-tannic acid films is achieved under mild conditions via ascorbic acid-mediated Fe3+ reduction, which overcomes the problems in the disassembly of a metal-organic complex including slow reaction rates and reaction incompatibility with living cells. The strategy of reductive disassembly is applied to degradable single-cell nanoencapsulation, providing an advanced tool for tightly controlling and manipulating the cell-material interface.

Engineering of Nebulized Metal-Phenolic Capsules for Controlled Pulmonary Deposition.

Particle-based pulmonary delivery has great potential for delivering inhalable therapeutics for local or systemic applications. The design of particles with enhanced aerodynamic properties can improve lung distribution and deposition, and hence the efficacy of encapsulated inhaled drugs. This study describes the nanoengineering and nebulization of metal-phenolic capsules as pulmonary carriers of small molecule drugs and macromolecular drugs in lung cell lines, a human lung model, and mice. Tuning the aerodynamic diameter by increasing the capsule shell thickness (from ≈100 to 200 nm in increments of ≈50 nm) through repeated film deposition on a sacrificial template allows precise control of capsule deposition in a human lung model, corresponding to a shift from the alveolar region to the bronchi as aerodynamic diameter increases. The capsules are biocompatible and biodegradable, as assessed following intratracheal administration in mice, showing >85% of the capsules in the lung after 20 h, but <4% remaining after 30 days without causing lung inflammation or toxicity. Single-cell analysis from lung digests using mass cytometry shows association primarily with alveolar macrophages, with >90% of capsules remaining nonassociated with cells. The amenability to nebulization, capacity for loading, tunable aerodynamic properties, high biocompatibility, and biodegradability make these capsules attractive for controlled pulmonary delivery.

A new three-way supramolecular switch based on redox-controlled interconversion of hetero- and homo-guest-pair inclusion inside a host molecule.

A novel three-way supramolecular switch based on the interconversion of hetero-guest-pair (D-A) and homo-guest-pair (D(2) or A(2)) inclusion inside cucurbit[8]uril is reported, which can be selectively controlled by chemical or electrochemical stimuli.

Tuning the Mechanical Behavior of Metal-Phenolic Networks through Building Block Composition.

Metal-phenolic networks (MPNs) are an emerging class of functional metal-organic materials with a high degree of modularity in terms of the choice of metal ion, phenolic ligand, and assembly method. Although various applications, including drug delivery, imaging, and catalysis, have been studied with MPNs, in the form of films and capsules, the influence of metals and organic building blocks on their mechanical properties is poorly understood. Herein, we demonstrate that the mechanical properties of MPNs can be tuned through choice of the metal ion and/or phenolic ligand. Specifically, the pH of the metal ion solution and/or size of phenolic ligand influence the Young's modulus ( EY) of MPNs (higher pHs and smaller ligands lead to higher EY). This study systematically investigates the roles of both metal ions and ligands on the mechanical properties of metal-organic materials and provides new insight into engineering the mechanical properties of coordination films.

Ricocheting Droplets Moving on Super-Repellent Surfaces.

Droplet bouncing on repellent solid surfaces (e.g., the lotus leaf effect) is a common phenomenon that has aroused interest in various fields. However, the scenario of a droplet bouncing off another droplet (either identical or distinct chemical composition) while moving on a solid material (i.e., ricocheting droplets, droplet billiards) is scarcely investigated, despite it having fundamental implications in applications including self-cleaning, fluid transport, and heat and mass transfer. Here, the dynamics of bouncing collisions between liquid droplets are investigated using a friction-free platform that ensures ultrahigh locomotion for a wide range of probing liquids. A general prediction on bouncing droplet-droplet contact time is elucidated and bouncing droplet-droplet collision is demonstrated to be an extreme case of droplet bouncing on surfaces. Moreover, the maximum deformation and contact time are highly dependent on the position where the collision occurs (i.e., head-on or off-center collisions), which can now be predicted using parameters (i.e., effective velocity, effective diameter) through the concept of an effective interaction region. The results have potential applications in fields ranging from microfluidics to repellent coatings.