Dynamic Metal–Phenolic Coordination Complexes for Versatile Surface Nanopatterning

Abstract

We report a general nanopatterning strategy that takes advantage of the dynamic coordination bonds between polyphenols and metal ions (e.g., Fe 3+ and Cu 2+ ) to create structures on surfaces with a range of properties. With this methodology, under acidic conditions, 29 metal−phenolic complex-based precursors composed of different polyphenols and metal ions are patterned using scanning probe and large-area cantilever free nanolithography techniques, resulting in a library of deposited metal−phenolic nanopatterns. Significantly, post-treatment of the patterns under basic conditions (i.e., ammonia vapor) triggers a change in coordination state and results in the in situ generation of more stable networks firmly attached to the underlying substrates. The methodology provides control over feature size, shape, and composition, almost regardless of substrate (e.g., Si, Au, and silicon nitride). Under reducing conditions (i.e., H 2 ) at elevated temperatures (180−600 °C), the patterned features have been used as nanoreactors to synthesize individual metal nanoparticles. At room temperature, the ammonia-treated features can reduce Ag + to form metal nanostructures and be modified with peptides, proteins, and thiolated DNA via Michael addition and/or Schiff base reaction. The generality of this technique should make it useful for a wide variety of researchers interested in modifying surfaces for catalytic, chemical and biological sensing, and template-directed assembly purposes.

A nature-inspired strategy towards superhydrophobic wood

“…2a2). Secondly, after adding ferric chloride as the chelating agent, Fe( iii ) chelated with the neighboring phenolic hydroxyl groups on the phenyl ring of rutin to form MPNs 53,54 (Fig. 2a3).…”

Peptide-Based Coacervate Protocells with Cytoprotective Metal–Phenolic Network Membranes

“…Reactive oxygen species generated during metabolic processes can cause oxidative damage to cellular molecules, leading to impaired cellular functions and even cell death. MPNs are known to have redox properties as they contain TA, which has abundant phenolic hydroxyl groups and therefore can exhibit antioxidant properties . We validated the antioxidant properties of PC@MPNs using the 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical scavenging assay, where significant DPPH scavenging was seen in the presence of PC@MPNs (89.7%), which was significantly higher than that of PC (8.6%; Figure h).…”

“…MPNs are known to have redox properties as they contain TA, which has abundant phenolic hydroxyl groups and therefore can exhibit antioxidant properties. 41 We validated the antioxidant properties of PC@MPNs using the 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical scavenging assay, where significant DPPH scavenging was seen in the presence of PC@MPNs (89.7%), which was significantly higher than that of PC (8.6%; Figure 2h). Notably, it would be of interest to couple such protocell membranes with redox-dependent processes, particularly when the membrane is required to exhibit scavenging effects analogous to the incorporation of redox-mediating proteins.…”

The controllable patterning of tannic acid on DNA origami

“…[10][11][12][13] Therefore, it is essential to perform TA micropatterning preparation. 14 Present methods for TA patterning mainly include photolithography 11,15 and micro-contact printing. 10 However, these methods usually require complex oper-ation and high-cost instruments, limiting the application and development of TA patterning.…”