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Surface chemistry is a major factor that determines the wettability of materials, and devising broadly applicable coating strategies that afford tunable and selective surface properties required for next-generation materials remains a challenge. Herein, we report fluorinated metal-organic coatings that display water-wetting and oil-repelling characteristics, a wetting phenomenon different from responsive wetting induced by external stimuli. We demonstrate this selective wettability with a library of metal-organic coatings using catechol-based coordination and silanization (both fluorinated and fluorine-free), enabling sensing through interfacial reconfigurations in both gaseous and liquid environments, and establish a correlation between the coating wettability and polarity of the liquids. This selective wetting performance is substrate-independent, spontaneous, durable, and reversible and occurs over a range of polar and nonpolar liquids (60 studied). These results provide insight into advanced liquid-solid interactions and a pathway toward tuning interfacial affinities and realizing robust, selective superwettability according to the surrounding conditions.

Supramolecular complexation is a powerful strategy for engineering materials in bulk and at interfaces. Metal-phenolic networks (MPNs), which are assembled through supramolecular complexes, have emerged as suitable candidates for surface and particle engineering owing to their diverse properties. Herein, we examine the supramolecular dynamics of MPNs during thermal transformation processes. Changes in the local supramolecular network including enlarged pores, ordered aromatic packing, and metal relocation arise from thermal treatment in air or an inert atmosphere, enabling the engineering of metal-oxide networks (MONs) and metal-carbon networks, respectively. Furthermore, by integrating photo-responsive motifs (i.e., TiO2 ) and silanization, the MONs are endowed with reversible superhydrophobic (>150°) and superhydrophilic (≈0°) properties. By highlighting the thermodynamics of MPNs and their transformation into diverse materials, this work offers a versatile pathway for advanced materials engineering.

Poly(ethylene glycol) (PEG) is well known to endow nanoparticles (NPs) with low-fouling and stealth-like properties that can reduce immune system clearance in vivo, making PEG-based NPs (particularly sub-100 nm) of interest for diverse biomedical applications. However, the preparation of sub-100 nm PEG NPs with controllable size and morphology is challenging. Herein, we report a strategy based on the noncovalent coordination between PEG-polyphenolic ligands (PEG-gallol) and transition metal ions using a water-in-oil microemulsion phase to synthesize sub-100 nm PEG NPs with tunable size and morphology. The metal-phenolic coordination drives the self-assembly of the PEG-gallol/metal NPs: complexation between MnII and PEG-gallol within the microemulsions yields a series of metal-stabilized PEG NPs, including 30-50 nm solid and hollow NPs, depending on the MnII/gallol feed ratio. Variations in size and morphology are attributed to the changes in hydrophobicity of the PEG-gallol/MnII complexes at varying MnII/gallol ratios based on contact angle measurements. Small-angle X-ray scattering analysis, which is used to monitor the particle size and intermolecular interactions during NP evolution, reveals that ionic interactions are the dominant driving force in the formation of the PEG-gallol/MnII NPs. pH and cytotoxicity studies, and the low-fouling properties of the PEG-gallol/MnII NPs confirm their high biocompatibility and functionality, suggesting that PEG polyphenol-metal NPs are promising systems for biomedical applications.

Engineering coatings with precise physicochemical properties allows for control over the interface of a material and its interactions with the surrounding environment. However, assembling coatings with well-defined properties on different material classes remains a challenge. Herein, we report a co-assembly strategy to precisely control the structure and properties (e.g., thickness, adhesion, wettability, and zeta potential) of coatings on various materials (27 substrates examined) using quinone and polyamine building blocks. By increasing the length of the amine building blocks from small molecule diamines to branched amine polymers, we tune the properties of the films, including the thickness (from ca. 5 to ca. 50 nm), interfacial adhesion (0.05 to 5.54 nN), water contact angle (130 to 40°), and zeta potential (-42 to 28 mV). The films can be post-functionalized through the in situ formation of diverse nanostructures, including nanoparticles, nanorods, and nanocrystals. Our approach provides a platform for the rational design of engineered, substrate-independent coatings for various applications.

Intracellular delivery of proteins is a promising strategy for regulating cellular behavior and therefore has attracted interest for biomedical applications. Despite the emergence of various nanoparticle-based intracellular delivery approaches, it remains challenging to engineer a versatile delivery system capable of responding to various physiological triggers without the need for complex chemical synthesis of the delivery system. Herein, we develop a template-mediated supramolecular assembly strategy to synthesize protein-polyphenol nanoparticles (NPs) capable of endosomal escape and subsequent protein release in the cytosol. These NPs are stable in serum and undergo surface charge reversal from negative to positive in acidic environments, leading to spontaneous endosomal escape. In the cytosol, endogenous small peptides and amino acids with relatively high charge densities, such as glutathione, trigger NP disassembly through competitive supramolecular interactions, thereby releasing functional bioactive proteins, as validated using cytochrome C and β-galactosidase. The versatility of the present strategy in terms of nanoparticle size, protein type, and functional protein delivery makes this a promising platform for potential application in the field of protein therapeutics.

We report a facile strategy for engineering diverse particles based on the supramolecular assembly of natural polyphenols and a self-polymerizable aromatic dithiol. In aqueous conditions, uniform and size-tunable supramolecular particles are assembled through π–π interactions as mediated by polyphenols. Owing to the high binding affinity of phenolic motifs present at the surface, these particles allow for the subsequent deposition of various materials (i.e., organic, inorganic, and hybrid components), producing a variety of monodisperse functional particles. Moreover, the solvent-dependent disassembly of the supramolecular networks enables their removal, generating a wide range of corresponding hollow structures including capsules and yolk–shell structures. The versatility of these supramolecular networks, combined with their negligible cytotoxicity provides a pathway for the rational design of a range of particle systems (including core–shell, hollow, and yolk–shell) with potential in biomedical and environmental applications., Monodisperse colloidal particles with tunable properties show promise for biomedical, energy, and environmental applications and simple routes for fabricating these particles are of interest. Here, the authors report a facile strategy for fabrication of diverse particles based on the supramolecular assembly of phenols and self-polymerizable thiols

Developing materials with programmable permeability for cargo encapsulation and release is challenging but important in a number of fields including drug delivery and sensing. Metal–phenolic networ...

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).

Mesoporous metal-organic networks have attracted widespread interest owing to their potential applications in diverse fields including gas storage, separations, catalysis, and drug delivery. Despite recent advances, the synthesis of metal-organic networks with large and ordered mesochannels (>20 nm), which are important for loading, separating, and releasing macromolecules, remains a challenge. Herein, we report a templating strategy using sacrificial double cubic network polymer cubosomes (Im3m) to synthesize ordered mesoporous metal-phenolic particles (meso-MPN particles) with a large-pore (∼40 nm) single cubic network (Pm3m). We demonstrate that the large-pore network and the phenolic groups in the meso-MPN particles enable high loadings of various proteins (e.g., horseradish peroxidase (HRP), bovine hemoglobin, immunoglobulin G, and glucose oxidase (GOx)), which have different shapes, charges, and sizes (i.e., molecular weights spanning 44-160 kDa). For example, GOx loading in the meso-MPN particles was 362 mg g-1, which is ∼6-fold higher than the amount loaded in commercially available SiO2 particles with an average pore size of 50 nm. Furthermore, we show that HRP, when loaded in the meso-MPN particles (486 mg g-1), retained ∼82% activity of free HRP in solution and can be recycled at least five times with a minimal (∼13%) decrease in HRP activity, which exceeds HRP performance in 50 nm pore SiO2 particles (∼36% retained activity and ∼30% activity loss when recycled five times). Considering the wide selection of naturally abundant polyphenols (>8000 species) and metal ions available, the present cubosome-enabled strategy is expected to provide new avenues for designing a range of meso-MPN particles for various applications.

Functional coatings are of considerable interest because of their fundamental implications for interfacial assembly and promise for numerous applications. Universally adherent materials have recently emerged as versatile functional coatings; however, such coatings are generally limited to catechol, (ortho-diphenol)-containing molecules, as building blocks. Here, we report a facile, biofriendly enzyme-mediated strategy for assembling a wide range of molecules (e.g., 14 representative molecules in this study) that do not natively have catechol moieties, including small molecules, peptides, and proteins, on various surfaces, while preserving the molecule's inherent function, such as catalysis (≈80 % retention of enzymatic activity for trypsin). Assembly is achieved by in situ conversion of monophenols into catechols via tyrosinase, where films form on surfaces via covalent and coordination cross-linking. The resulting coatings are robust, functional (e.g., in protective coatings, biological imaging, and enzymatic catalysis), and versatile for diverse secondary surface-confined reactions (e.g., biomineralization, metal ion chelation, and N-hydroxysuccinimide conjugation).

Background: Porous micro- and nanoparticles have the capacity to encapsulate a large quantity of therapeutics, making them promising delivery vehicles for a variety of applications. This review aims to highlight the latest development of inorganic and hybrid (inorganic/ organic) particles for drug delivery with an additional emphasis on combatting drug resistant cancer. We go one step further and discuss delivery applications beyond medicinal delivery, as there is generally a translation from medicinal delivery to botanic delivery after a short lag time. Methods: We undertook a search of relevant peer-reviewed publications. The quality of the relevant papers was appraised using standard tools. The characteristics of the papers are described herein, and the relevant material and therapeutic properties are discussed. Results: We discuss 4 classes of porous particles in terms of drug delivery and theranostics. We specifically focus on silica, calcium carbonate, metal-phenolic network, and metalorganic framework particles. Other relevant biomedically relevant applications are discussed and we highlight outstanding therapeutic results in the relevant literature. Conclusion: The findings of this review confirm the importance of studying and utilizing porous particles for therapeutic delivery. Moreover, we show that the properties of porous particles that make them promising for medicinal drug delivery also make them promising candidates for agro-industrial applications.

The intracellular delivery of functional nanoparticles (NPs) and the release of therapeutic payloads at a target site are central issues for biomedical applications. However, the endosomal entrapment of NPs typically results in the degradation of active cargo, leading to poor therapeutic outcomes. Current advances to promote the endosomal escape of NPs largely involve the use of polycationic polymers and cell-penetrating peptides (CPPs), which both can suffer from potential toxicity and convoluted synthesis/conjugation processes. Herein, we report the use of metal-phenolic networks (MPNs) as versatile and nontoxic coatings to facilitate the escape of NPs from endo/lysosomal compartments. The MPNs, which were engineered from the polyphenol tannic acid and FeIII or AlIII, enabled the endosomal escape of both inorganic (mesoporous silica) and organic (polystyrene and melamine resin) NPs owing to the "proton-sponge effect" arising from the buffering capacity of MPNs. Postfunctionalization of the MPN-coated NPs with low-fouling polymers did not impair the endosomal escape, indicating the modular and generalizable nature of this approach. We envisage that the ease of fabrication, versatility, low cytotoxicity, and promising endosomal escape performance displayed by the MPN coatings offer opportunities for such coatings to be used for the efficient delivery of cytoplasm-targeted therapeutics using NPs.

Drug carriers typically require both stealth and targeting properties to minimize nonspecific interactions with healthy cells and increase specific interaction with diseased cells. Herein, the assembly of targeted poly(ethylene glycol) (PEG) particles functionalized with cyclic peptides containing Arg-Gly-Asp (RGD) (ligand) using a mesoporous silica templating method is reported. The influence of PEG molecular weight, ligand-to-PEG molecule ratio, and particle size on cancer cell targeting to balance stealth and targeting of the engineered PEG particles is investigated. RGD-functionalized PEG particles (PEG-RGD particles) efficiently target U-87 MG cancer cells under static and flow conditions in vitro, whereas PEG and cyclic peptides containing Arg-Asp-Gly (RDG)-functionalized PEG (PEG-RDG) particles display negligible interaction with the same cells. Increasing the ligand-to-PEG molecule ratio improves cell targeting. In addition, the targeted PEG-RGD particles improve cell uptake via receptor-mediated endocytosis, which is desirable for intracellular drug delivery. The PEG-RGD particles show improved tumor targeting (14% ID g-1) when compared with the PEG (3% ID g-1) and PEG-RDG (7% ID g-1) particles in vivo, although the PEG-RGD particles show comparatively higher spleen and liver accumulation. The targeted PEG particles represent a platform for developing particles aimed at balancing nonspecific and specific interactions in biological systems.

The tunable growth of metal-organic materials has implications for engineering particles and surfaces for diverse applications. Specifically, controlling the self-assembly of metal-phenolic networks (MPNs), an emerging class of metal-organic materials, is challenging, as previous studies suggest that growth often terminates through kinetic trapping. Herein, kinetic strategies were used to temporally and spatially control MPN growth by promoting self-correction of the coordinating building blocks through oxidation-mediated MPN assembly. The formation and growth mechanisms were investigated and used to engineer films with microporous structures and continuous gradients. Moreover, reactive oxygen species generated by ultrasonication expedite oxidation and result in faster (ca. 30 times) film growth than that achieved by other MPN assembly methods. This study expands our understanding of metal-phenolic chemistry towards engineering metal-phenolic materials for various applications.

Extracellular vesicles, including exosomes, shuttle proteins and genetic information between cells and are recently regarded as a promising class of nanoparticles for biomedical applications. Collecting exosomes from patients and amplifying the signal from the exosome cargo could enable new liquid biopsies owing to the exosome’s strong correlation with disease progression. A promising strategy to develop personalized therapeutic carriers is through surface engineering the exosomes and hijacking their inherent messenger system. However, because of the small size and surface complexity, methods to manipulate exosomes are still in their infancy. The purification, preservation, and engineering of exosomes with high scalability and reproducibility is pivotal for practical applications. By regarding exosomes as a bioderived soft nanoparticle, the amassed knowledge and techniques commonly used in materials chemistry and surface science would contribute to exosome development and exploitation. In this perspective...

Metal-phenolic network (MPN) coatings have generated increasing interest owing to their biologically inspired nature, facile fabrication, and near-universal adherence, especially for biomedical applications. However, a key issue in biomedicine is protein fouling, and the adsorption of proteins on tannic acid-based MPNs remains to be comprehensively studied. Herein, we investigate the interaction of specific biomedically relevant proteins in solution (e.g., bovine serum albumin (BSA), immunoglobulin G (IgG), fibrinogen) and complex biological media (serum) using layer-by-layer-assembled tannic acid/FeIII MPN films. When FeIII was the outermost layer, galloyl-modified poly(2-ethyl-2-oxazoline) (P(EtOx)-Gal) could be grafted to the films through coordination bonds. Protein fouling and bacterial adhesion were greatly suppressed after functionalization with P(EtOx)-Gal and the mass of adsorbed protein was reduced by 79%. Interestingly, larger proteins adsorbed more on both the MPNs and P(EtOx)-functionalized MPNs. This study provides fundamental information on the interactions of MPNs with single proteins, mixtures of proteins as encountered in serum, and the noncovalent, coordination-based, functionalization of MPN films.

Growing metal–organic frameworks (MOFs) around biomolecules has recently emerged as a promising method to combine natural and synthetic materials. In parallel, cellulose nanocrystals (CNCs) have fo...

Roughly 4 billion tons of uranium exists in the oceans, which equates to a nearly inexhaustible supply for nuclear power production. However, the extraction of uranium from seawater is highly challenging due the background high salinity and uranium's relatively low concentration (∼3 μg L−1). Current approaches are generally limited by either their selectivity, sustainability, or their economic competitiveness. Here we engineered a biomass-derived microporous membrane, based on the interfacial formation of robust metal–phenolic networks (MPNs), for uranium capture from seawater. These membranes displayed advantages in terms of selectivity, kinetics, capacity, and renewability in both laboratory settings and marine field-testing. The MPN-based membranes showed a greater than ninefold higher uranium extraction capacity (27.81 μg) than conventional methods during a long-term cycling extraction of 10 L of natural seawater from the East China Sea. These results, coupled with our techno-economic analysis, demonstrate that MPN-based membranes are promising economically viable and industrially scalable materials for real-world uranium extraction.

STUDY QUESTION Can vascular endothelial growth factor (VEGF)-loaded silica supraparticles (V-SPs) be used as a novel mode of delivering VEGF to the developing preimplantation embryo in vitro? SUMMARY ANSWER Supplementation of embryo culture media with V-SPs promoted embryonic development in a manner equivalent to media supplemented with free VEGF. WHAT IS KNOWN ALREADY VEGF is a maternally derived growth factor that promotes preimplantation embryonic development in vitro. However, its use in clinical media has limitations due to its low stability in solution. STUDY DESIGN, SIZE, DURATION This study was a laboratory-based analysis utilising a mouse model. V-SPs were prepared in vitro and supplemented to embryonic culture media. The bioactivity of V-SPs was determined by analysis of blastocyst developmental outcomes (blastocyst development rate and total cell number). PARTICIPANTS/MATERIALS, SETTING, METHODS SPs were loaded with fluorescently labelled VEGF and release kinetics were characterised. Bioactivity of unlabelled VEGF released from V-SPs was determined by analysis of embryo developmental outcomes (blastocyst developmental rate and total cell number) following individual mouse embryo culture in 20 µl of G1/G2 media at 5% oxygen, supplemented with 10 ng/ml recombinant mouse VEGF in solution or with V-SPs. The bioactivity of freeze-dried V-SPs was also assessed to determine the efficacy of cryostorage. MAIN RESULTS AND THE ROLE OF CHANCE VEGF release kinetics were characterised by an initial burst of VEGF from loaded spheres followed by a consistent lower level of VEGF release over 48 h. VEGF released from V-SPs resulted in significant increases in total blastocyst cell number relative to the control (P LARGE SCALE DATA N/A. LIMITATIONS, REASONS FOR CAUTION In this proof of principle study, the effects of V-SPs on embryonic development were only analysed in a mouse model. WIDER IMPLICATIONS OF THE FINDINGS These findings suggest that SPs represent a novel method by which a targeted dose of therapeutic agents (e.g. bioactive VEGF) can be delivered to the developing in vitro embryo to promote embryonic development, an approach that negates the breakdown of VEGF associated with storage in solution. As such, V-SPs may be an alternative and effective method of delivering bioactive VEGF to the developing in vitro embryo; however, the potential use of V-SPs in clinical IVF requires further investigation. STUDY FUNDING/COMPETING INTEREST(S) This work was funded by the University of Melbourne. The authors have no conflict of interest to declare.

The buffering effects displayed by pH responsive polymers have recently gained attention in diverse fields such as nanomedicine and water treatment. However, creating libraries of modular and versatile polymers that can be readily integrated within existing materials remains challenging, hence restricting applications inspired by their buffering capacity. Herein, we propose the use of metal phenolic networks MPNs as tunable buffering systems and through mechanistic studies show that their buffering effects are driven by pH responsive, multivalent metal phenolic coordination. Owing to such supramolecular interactions, MPNs exhibit amp; 8764;twofold and fourfold higher buffering capacity than polyelectrolyte complexes and commercial buffer solutions, respectively. We demonstrate that the MPN buffering effects are retained after deposition onto solid supports, thereby allowing stabilization of aqueous environmental pH for 1 week. Moreover, by using different metals and ligands for the films, the endosomal escape capabilities of coated nanoparticles can be tuned, where higher buffering capacity leads to greater endosomal escape. This study forms a fundamental basis for developing future metal organic buffering materials

Polyphenols are naturally occurring compounds that are ubiquitous in plants and display a spectrum of physical, chemical, and biological properties. For example, they are antioxidants, have therapeutic properties, absorb UV radiation, and complex with metal ions. Additionally, polyphenols display high adherence, which has been exploited for assembling nanostructured materials. We previously reviewed the assembly of different phenolic materials and their applications (Angew. Chem. Int. Ed. 2019, 58, 1904-1927); however, there is a need for a summary of the fundamental interactions that govern the assembly, stability, and function of polyphenol-based materials. A detailed understanding of interactions between polyphenols and various other building blocks will facilitate the rational design and assembly of advanced polyphenol particles for specific applications. This Account discusses how different interactions and bonding (i.e., hydrogen, π, hydrophobic, metal coordination, covalent, and electrostatic) can be leveraged to assemble and stabilize polyphenol-based particles for diverse applications. In polyphenol-mediated assembly strategies, the polyphenols typically exert more than one type of stabilizing attractive force. However, one interaction often dominates the assembly process and dictates the physicochemical behavior of the particles, which in turn influences potential applications. This Account is thus divided into sections that each focus on a key interaction with relevant examples of applications to highlight structure-function relationships. For example, metal coordination generally becomes weaker at lower pH, which makes it possible to engineer metal-phenolic materials with a pH-responsive disassembly profile suitable for drug delivery. Engineered particles, such as hollow capsules, mesoporous and core-shell particles, and self-assembled nanoparticles are some of the systems that are covered to highlight how polyphenols interact with other building blocks and therefore make up the major focus of this Account. Some of the applications of these materials exemplified in this Account include drug delivery, catalysis, environmental remediation, and forensics. Finally, a perspective is provided on the current challenges and trends in polyphenol-mediated particle assembly, and viable near-term strategies for further elucidating the interplay of various competing interactions in particle formation are discussed. This Account is also expected to serve as a reference to guide fundamental research and facilitate the rational design of polyphenol-based materials for diverse emerging applications.

We review recent advances and prospects of interfacing functional nanomaterials with biological systems for nanobiohybrids., Nanobiohybrids, synthesized by integrating functional nanomaterials with living systems, have emerged as an exciting branch of research at the interface of materials engineering and biological science. Nanobiohybrids use synthetic nanomaterials to impart organisms with emergent properties outside their scope of evolution. Consequently, they endow new or augmented properties that are either innate or exogenous, such as enhanced tolerance against stress, programmed metabolism and proliferation, artificial photosynthesis, or conductivity. Advances in new materials design and processing technologies made it possible to tailor the physicochemical properties of the nanomaterials coupled with the biological systems. To date, many different types of nanomaterials have been integrated with various biological systems from simple biomolecules to complex multicellular organisms. Here, we provide a critical overview of recent developments of nanobiohybrids that enable new or augmented biological functions that show promise in high-tech applications across many disciplines, including energy harvesting, biocatalysis, biosensing, medicine, and robotics.

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°).

High-performance coatings that durably and fully repel liquids are of interest for fundamental research and practical applications. Such coatings should allow for droplet beading, roll off and bouncing, which is difficult to achieve for ultralow surface tension liquids. Here we report a bottom-up approach to prepare super-repellent coatings using a mixture of fluorosilanes and cyanoacrylate. On application to surfaces, the coatings assemble into thin films of locally multi-re-entrant hierarchical structures with very low surface energies. The resulting materials are super-repellent to solvents, acids and bases, polymer solutions and ultralow surface tension liquids, characterized by ultrahigh liquid contact angles (>150°) and negligible roll-off angles (~0°). Furthermore, the coatings are transparent, durable and demonstrate universal liquid bouncing, tailored responsiveness and anti-freezing properties, and are thus a promising alternative to existing synthetic super-repellent coatings.

Hybrid conformal coatings, such as metal-phenolic networks (MPNs) that are constructed from the coordination-driven assembly of natural phenolic ligands, are of interest in areas including biomedicine, separations, and energy. To date, most MPN coatings have been prepared by immersing substrates in solutions containing the phenolic ligands and metal ions, which is a suitable method for coating small or flexible objects. In contrast, more industrially relevant methods for coating and patterning large substrates, such as spray assembly, have been explored to a lesser extent toward the fabrication of MPNs, particularly regarding the effect of process variables on MPN growth. Herein, a spray assembly method was used to fabricate MPN coatings with various phenolic building blocks and metal ions and their formation and patterning were explored for different applications. Different process parameters including solvent, pH, and metal-ligand pair allowed for control over the film properties such as thickness and roughness. On the basis of these investigations, a potential route for the formation of spray-assembled MPN films was proposed. Conditions favoring the formation of bis complexes could produce thicker coatings than those favoring the formation of mono or tris complexes. Finally, the spray-assembled MPNs were used to generate superhydrophilic membranes for oil-water separation and colorless films for UV shielding. The present study provides insights into the chemistry of MPN assembly and holds promise for advancing the fabrication of multifunctional hybrid materials.

The self-assembly of molecular building blocks into well-defined macroscopic materials is desirable for developing emergent functional materials. However, the self-assembly of molecules into macroscopic materials remains challenging, in part because of limitations in controlling the growth and robustness of the materials. Herein, we report the molecular self-assembly of nano- to macroscopic free-standing materials through the coordination of metals with natural phenolic molecules. Our method involves a simple and scalable solution-based template dipping process in precomplexed metal–phenolic solutions, enabling the fabrication of free-standing macroscopic materials of customized architectures (2D and 3D geometries), thickness (about 10 nm to 5 μm), and chemical composition (different metals and phenolic ligands). Our macroscopic free-standing materials can be physically folded and unfolded like origami, yet are selectively degradable. Furthermore, metal nanoparticles can be grown in the macroscopic free-s...

Biomimetic synthesis merges the unprecedented properties of biominerals with the unique characteristics of synthetic materials to yield hybrid materials with hierarchical morphologies and tunable properties difficult to achieve via traditional physical or chemical synthesis. The biomimetic synthesis of coordination networks, such as metal–organic frameworks and amorphous coordination networks, is a relatively new member in the family of bioinspired or biomimetic materials. There is a growing interest in synthesizing organic–inorganic hybrid materials using biomimetic routes to exploit the synergistic properties of both the synthetic materials and biomaterials. These hybrid biomimetic materials show potential ground-breaking applications in nanotechnology and biomedicine ranging from gas separation to drug delivery and biocatalysis. In this review, we summarize the current state of synthesizing coordination networks using biomimetic routes, utilizing three major classes of materials, including synthetic polymers, biomolecules, and living entities. The biomimetic synthesis of coordination networks from these functional substrates has the potential to address global challenges in energy, healthcare, and environmental sustainability.

Hollow polymeric, submicrometer-scaled capsules show promise in applications ranging from water remediation to drug delivery, and the preferred method for their synthesis includes templating from sacrificial particles. Such particles are typically non-renewable and the process of selective dissolution used to produce the capsules often requires harsh and/or toxic solvents. Thus, there is a critical need to develop inexpensive, sustainable templates that can be dismantled under mild conditions. Lignins have recently been introduced as renewable precursors for the synthesis of solid particles and can favorably substitute solid particles based on petrochemical (such as latex) or mineral (such as silica) precursors. Conveniently, widely available by-product streams of biomass processing can be used for the supramolecular assembly required for lignin particle formation. Herein, we introduce two common lignin sources (kraft and alkali lignins) as renewable and easily degradable particulate templates for the preparation of hollow polymeric capsules. The polymeric nanocoating, or wall of the capsules, was synthesized from renewable tannins, which self-assemble around the lignin particle template in the presence of metal ions, thereby coordinating into metal-phenolic networks (MPNs). The lignin template particles were easily degraded with aqueous or organic solvents under ambient conditions. Thus, the nanocoating assembly and template disassembly processes can be considered to be fully “green”. Finally, the synthesized hollow capsules were successfully utilized for water clean-up through the degradation of an organic dye, exemplifying a cost-effective and facile route for using environmentally friendly nanomaterials for environmental remediation.

Metal–phenolic networks (MPNs) are a versatile class of self-assembled materials that are able to form functional thin films on various substrates with potential applications in areas including drug delivery and catalysis. Different metal ions (e.g., FeIII, CuII) and phenols (e.g., tannic acid, gallic acid) have been investigated for MPN film assembly; however, a mechanistic understanding of the thermodynamics governing MPN formation remains largely unexplored. To date, MPNs have been deposited at low ionic strengths (

A bioactive synthetic porous shell was engineered to enable cells to survive in an oligotrophic environment. Eukaryotic cells (yeast) were firstly coated with a β-galactosidase (β-gal), before crystallization of a metal-organic framework (MOF) film on the enzyme coating; thereby producing a bioactive porous synthetic shell. The β-gal was an essential component of the bioactive shell as it generated nutrients (that is, glucose and galactose) required for cell viability in nutrient-deficient media (lactose-based). Additionally, the porous MOF coating carried out other vital functions, such as 1) shielding the cells from cytotoxic compounds and radiation, 2) protecting the non-native enzymes (β-gal in this instance) from degradation and internalization, and 3) allowing for the diffusion of molecules essential for the survival of the cells. Indeed, this bioactive porous shell enabled the survival of cells in simulated extreme oligotrophic environments for more than 7 days, leading to a decrease in cell viability less than 30 %, versus a 99 % decrease for naked yeast. When returned to optimal growth conditions the bioactive porous exoskeleton could be removed and the cells regained full growth immediately. The construction of bioactive coatings represents a conceptually new and promising approach for the next-generation of cell-based research and application, and is an alternative to synthetic biology or genetic modification.

Surface modification is crucial for conferring novel functionalities to objects and interfaces. However, simple yet versatile strategies for the surface modification of multiple classes of nanomaterials, including biointerfaces, are rare, as the chemical interactions between the surface modifiers and the substrates need to be tailored on a case-by-case basis. Recently, metal-phenolic networks (MPNs) have emerged as a versatile surface modifier based on the universal adherent properties of phenolic molecules, namely the constituent gallol and catechol groups. Additionally, the dynamic interactions between metal ions and phenolic molecules confer additional functionalities to the MPNs, such as stimuli-responsiveness. Given the interest in MPNs for nanomaterial and biointerface engineering, this review aims to provide an overview of the assembly process, physicochemical properties and applications of MPN coatings.

Biomimetic mineralization exploits natural biomineralization processes for the design and fabrication of synthetic functional materials. Here, we report for the first time the use of carbohydrates (polysaccharides) for the biomimetic crystallization of metal-organic frameworks. This discovery greatly expands the potential and diversity of biomimetic approaches for the design, synthesis, and functionalization of new bio-metal-organic framework composite materials.

A faithful reconstruction of the native cellular microenvironment is instrumental for tissue engineering. Macromolecular crowding (MMC) empowers cells to deposit their own extracellular matrix (ECM) in greater amounts, and thus contributes to building tissue-specific complex microenvironments in vitro. Dextran sulfate (DxS, 500 kDa), a semi-synthetic sulfated polyglucose, was shown previously at a fractional volume occupancy (FVO) of 5.2% (v/v; 100 μg/ml) to act as a potent molecular crowding agent in vitro. When added to human mesenchymal stromal cell (MSC) cultures, DxS enhanced fibronectin and collagen I deposition several-fold also at concentrations with negligible FVO (

The targeted therapy of metastatic melanoma is an important yet challenging goal that has received only limited attention to date. Herein, green tea polyphenols, (–)-epigallocatechin-3-gallate (EGCG), and lanthanide metal ions (Sm3+) are used as building blocks to engineer self-assembled SmIII-EGCG nanocomplexes with synergistically enhanced tumor inhibitory properties. These nanocomplexes have negligible systemic toxic effects on healthy cells but cause a significant reduction in the viability of melanoma cells by efficiently regulating their metabolic pathways. Moreover, the wound-induced migration of melanoma cells can be efficiently inhibited by SmIII-EGCG, which is a key criterion for metastatic melanoma therapy. In a mouse melanoma tumor model, SmIII-EGCG is directly compared with a clinical anticancer drug, 5-fluorouracil and shows remarkable tumor inhibition. Moreover, the targeted therapy of SmIII-EGCG is shown to prevent metastatic lung melanoma from spreading to main organs with no adverse side effects on the body weight or organs. These in vivo results demonstrate significant advantages of SmIII-EGCG over its clinical counterpart. The results suggest that these green tea-based, self-assembled nanocomplexes possess all of the key traits of a clinically promising candidate to address the challenges associated with the treatment of advanced stage metastatic melanoma.

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.

Metal-phenolic networks (MPNs) have received widespread interest owing to their modular incorporation of functional metal ions and phenolic ligands. However, the interaction between MPNs and biomolecules is still relatively unexplored. Herein, we studied the effects of MPN-coated gold nanoparticles on amyloid fibril formation (which is associated with Alzheimer's disease) as a function of the metal ion in the MPN systems. All coated particles examined inhibited amyloid formation, with cobalt(ii) MPN-coated particles exhibiting the highest inhibition activity (90%). Molecular dynamics simulations and quantum mechanics calculations suggested that the geometry of the exposed cobalt coordination site in the cobalt-tannic acid networks facilitates its interactions with histidine and methionine residues in the amyloid beta peptides. Furthermore, the unique structure of cobalt MPNs may enable a wider variety of biomedical applications.

Summary Zeolitic imidazolate frameworks (ZIFs) have been widely investigated for their use in separation, gas adsorption, catalysis, and biotechnology. Their practical applications, however, can be hampered by their structural instability in humid acidic conditions. Here, guided by density functional theory calculations, we demonstrate that the acidic stability of two polymorphic ZIFs (i.e., ZIF-8 and ZIF-L) can be enhanced by the incorporation of functional groups on polypeptides or DNA. A range of complementary synchrotron investigations into the local chemical structure and bonding environment suggest that the enhanced acidic stability arises from the newly established coordinative interactions between the Zn centers and the inserted carboxylate (for polypeptides) or phosphate (for DNA) groups, both of which have lower pKas than the imidazolate ligand. With functional biomolecular homologs (i.e., enzymes), we demonstrate a symbiotic stability reinforcement effect, i.e., the encapsulated biomolecules stabilize the ZIF matrix while the ZIF exoskeleton protects the enzyme from denaturation.

Light-driven directional motion is common in nature but remains a challenge for synthetic microparticles, particularly regarding collective motion on a macroscopic scale. Successfully engineering microparticles with light-driven collective motion could lead to breakthroughs in drug delivery, contaminant sensing, environmental remediation, and artificial life. Herein, metal-phenolic particle microswimmers capable of autonomously sensing and swimming toward an external light source are reported, with the speed regulated by the wavelength and intensity of illumination. These microswimmers can travel macroscopic distances (centimeters) and can remain illuminated for hours without degradation of motility. Experimental and theoretical analyses demonstrate that motion is generated through chemical transformations of the organic component of the metal-phenolic complex. Furthermore, cargos with specific spectral absorption profiles can be loaded into the particles and endow the particle microswimmers with activated motion corresponding to these spectral characteristics. The programmable nature of the light navigation, tunable size of the particles, and versatility of cargo loading demonstrate the versatility of these metal-phenolic particle microswimmers.

Methods for depositing thin films are important in generating functional materials for diverse applications in a wide variety of fields. Over the last half-century, the layer-by-layer assembly of nanoscale films has received intense and growing interest. This has been fueled by innovation in the available materials and assembly technologies, as well as the film-characterization techniques. In this Review, we explore, discuss, and detail innovation in layer-by-layer assembly in terms of past and present developments, and we highlight how these might guide future advances. A particular focus is on conventional and early developments that have only recently regained interest in the layer-by-layer assembly field. We then review unconventional assemblies and approaches that have been gaining popularity, which include inorganic/organic hybrid materials, cells and tissues, and the use of stereocomplexation, patterning, and dip-pen lithography, to name a few. A relatively recent development is the use of layer-by-layer assembly materials and techniques to assemble films in a single continuous step. We name this "quasi"-layer-by-layer assembly and discuss the impacts and innovations surrounding this approach. Finally, the application of characterization methods to monitor and evaluate layer-by-layer assembly is discussed, as innovation in this area is often overlooked but is essential for development of the field. While we intend for this Review to be easily accessible and act as a guide to researchers new to layer-by-layer assembly, we also believe it will provide insight to current researchers in the field and help guide future developments and innovation.

Particles adsorb proteins when they enter a physiological environment; this results in a surface coating termed a "protein corona". A protein corona can affect both the properties and functionalities of engineered particles. Here, we prepared hyaluronic acid (HA)-based capsules through the assembly of metal-phenolic networks (MPNs) and engineered their targeting ability in the absence and presence of protein coronas by varying the HA molecular weight. The targeting ability of the capsules was HA molecular weight dependent, and a high HA molecular weight (50 kDa) was required for efficient targeting. The specific interactions between high molecular weight HA capsules and receptor-expressing cancer cells were negligibly affected by the presence of protein coronas, whereas nonspecific capsule-cell interactions were significantly reduced in the presence of a protein corona derived from human serum. Consequently, the targeting specificity of HA-based MPN capsules was enhanced due to the formation of a protein corona. This study highlights the significant and complex roles of a protein corona in biointeractions and demonstrates how protein coronas can be used to improve the targeting specificity of engineered particles.

The biomimetic mineralization of metal-organic framework (MOF) material on living cells is reported. ZIF-8 can be crystallized on a living cell surface as an exoskeleton that offers physical protection while allowing transport of essential nutrients, thus maintaining cell viability. The MOF shell prevents cell division, leading to an artificially induced pseudo-hibernation state. Cellular functions can be fully restored upon MOF removal.

Control over Metal-organic framework (MOF) size and morphology is interesting for both fundamental and applied science. Gravitational force (g) is generally acknowledged as an interesting parameter for controlling crystal size; however, a dedicated study on the effect of g on MOF synthesis is missing. Here, we investigate the effect of varied g (< 1, 1, 20, 50, and 100) during the crystallization of different MOFs [ZIF-8, Tb2(BDC)3 and HKUST-1] in solution. The obtained MOFs were investigated using dynamic light scattering (DLS), X-ray scattering (SAXS and WAXS), and scanning electron and optical microscopy (SEM and OM, respectively). When compared with standard g (g = 1), high g (g = 20) gave rise to the formation of smaller MOF crystals, while low g (g < 1) led to larger crystals likely due to facet-oriented crystal fusion. This demonstrates that gravity and g-force can be used to rationally control the size of different MOFs by increasing or decreasing convection (mass transfer) and sedimentation.

Nano- and microcapsules engineered through layer-by-layer (LbL) assembly are finding an increasingly large number of applications as catalysts, electrochemical biosensors, bioreactors, artificial cells and drug delivery vehicles. While centrifugation-based LbL assembly is the most common method for coating template particles and preparing capsules, it is a batch process and requires frequent intervention that renders the system challenging to automate and scale up. Here, we report the use of a tapered fluidized bed (TFB) for the preparation of multilayered polymer capsules. This is a significant improvement over our recent approach of fluidizing particles in cylindrical fluidized beds (CFB) for LbL assembly. We demonstrate that TFB is compatible with particles

Phenolic materials have long been known for their use in inks, wood coatings, and leather tanning. However, there has recently been a renewed interest in engineering advanced materials from phenolic building blocks. The intrinsic properties of phenolic compounds, such as metal chelation, hydrogen bonding, pH responsiveness, redox potentials, radical scavenging, polymerization, and light absorbance, have made them a distinct class of structural motifs for the synthesis of functional materials. Materials prepared from phenolic compounds often retain many of these useful properties with synergistic effects in applications ranging from catalysis to biomedicine. This Review provides an overview of the diverse functional materials that can be prepared from natural and synthetic phenolic building blocks, as well as their applications.

We report the preparation of polymer particles via convective polymer assembly (CPA). Convection is used to move polymer solutions and cargo through an agarose gel that contains immobilized template particles. This method both coats and washes the particles in a process that is amenable to automation, and does not depend on passive diffusion or electrical currents, thus facilitating incorporation of fragile and nanoscale objects, such as liposomes and gold nanoparticles, into the thin polymer films. Template dissolution leads to the formation of stable polymer particles and capsules.