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, separation, 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 2 thickness and roughness. Based on 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.
Demulsification-type Janus membranes are constructed with controllable asymmetric configurations for highly efficient separation of oil-in-water emulsions. A mechanism is proposed as demulsification followed by rapid unidirectional oil transportation.
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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 networks (MPNs) are an emerging class of hybrid coordination materials with pH-responsiveness and modularity that can be engineered into functional thin films for diverse applications. Herein, we engineer MPN-based microcapsules with a dynamic gating mechanism by adjusting the intermolecular interactions in the capsules. Altering the choice of building blocks and precursor ratio provides an intrinsic and modular means of tailoring capsule size and permeability. Alternatively, regulating the pH of the environment, and thereby the protonation states of MPNs, extrinsically enables capsules to switch between highly permeable (>90% of capsules permeable at pH 9) and near-impermeable (<20% at pH 3) states. These findings provide insights into the dynamic nature of MPNs and offer a route to engineer smart delivery systems and selective gating materials.
Skin layers have been fabricated via an enzyme-triggered co-deposition process of natural tea catechins and chitosan for thin film composite nanofiltration membranes with high performance.
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,a sb uilding blocks.H ere,w er eport af acile,b iofriendly enzyme-mediated strategy for assembling aw ide range of molecules (e.g., 14 representative molecules in this study) that do not natively have catechol moieties,i ncluding small molecules,p eptides,a nd proteins,o nv arious surfaces,w hile preserving the molecules inherent function, such as catalysis ( % 80 %r etention 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.T he 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).
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°).
properties and functions. [3] In this field, Therrien et al. presented a series of organometallic cages as anticancer drug delivery vehicles for photodynamic therapy. [4a,b] Lippard and co-workers reported a welldefined metal-organic octahedron that can enhance the delivery of cis-platin prodrugs to cancer cells. [4c] In addition, Isaacs and co-workers highlighted the potential of host-guest interactions, by combining MOP with cucurbituril, for enhanced delivery of chemotherapeutic drugs. [4d,e] Although many MOP-based supramolecular systems have been developed for drug delivery applications, [5] compared to the well-developed NP-based systems such as mesoporous silica NPs, [5d] the use of MOP for drug delivery is still in its infancy. This is especially the case of research concerning targeted drug delivery for cancer therapy. A major limitation of MOP as nanocarriers is their rapid renal clearance and short circulation time owing to their small size, which is typically below the filtration barrier of the glomerulus (i.e., ≈5.5 nm). [4d,e] Furthermore, using coordination complexes for targeted therapy requires their functionalization with various targeting ligands consisting of small molecular moieties or large antibodies. However, the design and synthesis of the required organic linkers are highly challenging.To overcome these limitations, we describe for the first time the superassembly of MOP. The proposed fabrication technique affords a simple synthesis process and the organization Targeted drug delivery remains at the forefront of biomedical research but remains a challenge to date. Herein, the first superassembly of nanosized metal-organic polyhedra (MOP) and their biomimetic coatings of lipid bilayers are described to synergistically combine the advantages of micelles and supramolecular coordination cages for targeted drug delivery. The superassembly technique affords unique hydrophobic features that endow individual MOP to act as nanobuilding blocks and enable their superassembly into larger and well-defined nanocarriers with homogeneous sizes over a broad range of diameters. Various cargos are controllably loaded into the MOP with high payloads, and the nanocages are then superassembled to form multidrug delivery systems. Additionally, functional nanoparticles are introduced into the superassemblies via a one-pot process for versatile bioapplications. The MOP superassemblies are surface-engineered with epidermal growth factor receptors and can be targeted to cancer cells. In vivo studies indicated the assemblies to have a substantial circulation half-life of 5.6 h and to undergo renal clearance-characteristics needed for nanomedicines. Drug Delivery
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