Rust‐Mediated Continuous Assembly of Metal–Phenolic Networks

Rahim, Md. Arifur; Björnmalm, Mattias; Bertleff‐Zieschang, Nadja; Besford, Quinn A.; Mettu, Srinivas; Suma, Tomoya; Faria, Matthew; Caruso, Frank

doi:10.1002/adma.201606717

Cited by 126 publications

(167 citation statements)

References 30 publications

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“…[11a] The monophasic strategy, based on rapid but rather uncontrollable cohesion of Fe(III)–tannin networks and flocs, inevitably ends up with the undesired termination of film growth, typically after a film thickness of 10 nm . Although this drawback has been tackled elegantly by some modified methods, such as rust‐assisted[14a] and electrochemical depositions,[14b] the film thickness is still limited to be nanometer‐scaled. On the contrary, the biphasic reaction enables the spatioselective layer formation at the fluidic interface, without wasteful, superfluous formation of Fe(III)–tannin complexes, but the continuous layer growth is also technically difficult to achieve because of hampered diffusion and low encounter frequency at the fluidic interface shortly after initial layer formation.…”

Section: Methodsmentioning

confidence: 99%

Iron Gall Ink Revisited: In Situ Oxidation of Fe(II)–Tannin Complex for Fluidic‐Interface Engineering

et al. 2018

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The ancient wisdom found in iron gall ink guides this work to a simple but advanced solution to the molecular engineering of fluidic interfaces. The Fe(II)–tannin coordination complex, a precursor of the iron gall ink, transforms into interface‐active Fe(III)–tannin species, by oxygen molecules, which form a self‐assembled layer at the fluidic interface spontaneously but still controllably. Kinetic studies show that the oxidation rate is directed by the counteranion of Fe(II) precursor salts, and FeCl2 is found to be more effective than FeSO4—an ingredient of iron gall ink—in the interfacial‐film fabrication. The optimized protocol leads to the formation of micrometer‐thick, free‐standing films at the air–water interface by continuously generating Fe(III)–tannic acid complexes in situ. The durable films formed are transferable, self‐healable, pliable, and postfunctionalizable, and are hardened further by transfer to the basic buffer. This O2‐instructed film formation can be applied to other fluidic interfaces that have high O2 level, demonstrated by emulsion stabilization and concurrent capsule formation at the oil–water interface with no aid of surfactants. The system, inspired by the iron gall ink, provides new vistas on interface engineering and related materials science.

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Section: Methodsmentioning

confidence: 99%

Iron Gall Ink Revisited: In Situ Oxidation of Fe(II)–Tannin Complex for Fluidic‐Interface Engineering

et al. 2018

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“…This limitation has been addressed in recent studies where it has been shown that the assembly process for MPNs can be modulated from discrete to continuous by using solid-state metal precursors such as rusted nails (Figure 3g-m). [81] This continuous assembly method has not only yielded the thinnest MPN films (~5 nm) to date, but also produced high-quality multiligand MPN capsules from crude phenolic extracts such as green tea infusions. [82] Another recently demonstrated continuous MPN assembly method used an electro-triggered assembly approach, where a mixture of TA and REVIEW Figure 3.…”

Section: Metal-phenolic Network Assemblymentioning

confidence: 99%

“…[84] Additionally, the redox properties of MPNs have been elucidated in a recent electrochemical study. [82] Though many previous studies have provided useful insights into various aspects of MPN assembly, [16,75,81] more fundamental studies are required to elucidate the kinetic and thermodynamic aspects. The structurefunction relationship of MPNs, when assembled from different REVIEW Figure 4.…”

Section: Metal-phenolic Network Assemblymentioning

confidence: 99%

“…A catechol crosslinking method that has been used is metal complexation, where inorganic ions (e.g., Fe III ) are used to generate desired mechanical properties (e.g., high hardness, extensibility, [205] and gelation). [81] For example, iron-catechol crosslinking can be used to enhance the toughness of elastomers (Figure 11b) [20] owing to the sacrificial, reversible coordination bonds of metal-phenolic chemistry. In another approach, interface-assisted formation of self-healing and self-sealing films was achieved, using a range of phenolic ligands, [206] as polyphenols preferentially form at the air-water interface where phenolic ligands oxidize and polymerize given sufficient oxygen (Figure 11c).…”

Section: Accepted Manuscriptmentioning

confidence: 99%

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Phenolic Building Blocks for the Assembly of Functional Materials

et al. 2018

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Phenolic materials have long been known for their use in inks, wood coatings, and leather tanning. However, recently there has 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. The present review provides an overview of the diverse functional materials that can be prepared from phenolic building blocks, bridging the various fields currently studying and using phenolic compounds. Natural and synthetic phenolic compounds are first discussed, followed by the assembly of functional materials. The engineered phenolic materials are grouped under three broad categories: thin films (e.g., metal-phenolic networks and polydopamine); particles (e.g., metal-organic frameworks and superstructures); and bulk materials (e.g., gels). Applications of phenolic-based materials are then presented, focusing mainly on mechanical (e.g., adhesives), biological (e.g., drug delivery), and environmental and energy (e.g., separation and catalysis) applications. Several examples of their emerging applications are also included. Finally, potential routes for the continued integration of disparate fields using phenolic building blocks and fundamental questions still requiring investigation are highlighted, and an outlook of the field is provided.

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“…Natural biomolecule patterns, e.g., fingerprints, were replicated down to the sweat pore level (on the order of ≈100 µm) upon MPN coating and subsequent AgNP formation on the patterned MPNs for enhanced visualization using reflectance microscopy and fluorescence microscopy. As MPNs are typically on the 10–100 nm scale in thickness, the present high‐fidelity resolution of replication suggests that a similar approach could potentially be used for sub‐micrometer patterns. Still, some limitations could exist for reverse corona experiments, as the biomolecules are first adsorbed onto a substrate and therefore substrate‐effects and reconfiguration are possible.…”

Section: Resultsmentioning

confidence: 97%

The Biomolecular Corona in 2D and Reverse: Patterning Metal–Phenolic Networks on Proteins, Lipids, Nucleic Acids, Polysaccharides, and Fingerprints

Yun

Richardson

Capelli

et al. 2019

Adv Funct Materials

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The adsorption of biomolecules onto nanomaterials can alter the performance of the nanomaterials in vitro and in vivo. Recent studies have primarily focused on the protein "corona", formed upon adsorption of proteins onto nanoparticles in biological fluids, which can change the biological fate of the nanoparticles. Conversely, interactions between nanomaterials and other classes of bio molecules namely, lipids, nucleic acids, and polysaccharides have received less attention despite their important roles in biology.A possible reason is the challenge associated with investigating biomolecule interactions with nanomaterials using current technologies. Herein, a protocol is developed for studying bio-nano interactions by depositing four classes of biomolecules (proteins, lipids, nucleic acids, and polysaccharides) and complex biological media (blood) onto planar substrates, followed by exposure to metal-phenolic network (MPN) complexes. The MPNs preferentially interact with the bio molecule over the inorganic substrate (glass), highlighting that patterned bio molecules can be used to engineer patterned MPNs. Subsequent formation of silver nanoparticles on the MPN films maintains the patterns and endows the films with unique reflectance and fluorescence properties, enabling visualiza tion of latent fingerprints (i.e., invisible residual biomolecule patterns). This study demonstrates the potential complexity of the biomolecule corona as all classes of biomolecules can adsorb onto MPNbased nanomaterials.

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Rust‐Mediated Continuous Assembly of Metal–Phenolic Networks

Cited by 126 publications

References 30 publications

Iron Gall Ink Revisited: In Situ Oxidation of Fe(II)–Tannin Complex for Fluidic‐Interface Engineering

Iron Gall Ink Revisited: In Situ Oxidation of Fe(II)–Tannin Complex for Fluidic‐Interface Engineering

Phenolic Building Blocks for the Assembly of Functional Materials

The Biomolecular Corona in 2D and Reverse: Patterning Metal–Phenolic Networks on Proteins, Lipids, Nucleic Acids, Polysaccharides, and Fingerprints

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