Particle engineering enabled by polyphenol-mediated supramolecular networks

Abstract

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.

Polyphenol‐Containing Nanoparticles: Synthesis, Properties, and Therapeutic Delivery

“…Thanks to the antibacterial, antiinflammatory, antioxidant, and anticancer properties as well as the universal adhesion capability of natural tea polyphenols, polyphenols are fast becoming a popular class of molecules that are attracting more researchers to build various materials for bioimaging, therapeutic delivery, and other biomedical applications. [236][237][238][239][240][241][242][243][244][245][246][247][248][249][250][251] Moreover, inspired by the coordination interactions between various metal ions and polyphenols, researchers have also provided a number of functional MPNs to engineer multifunctional nanosystems. [252][253][254][255][256][257][258][259] Here, we have reviewed the structures and classification of natural polyphenols, the synthesis and properties of the polyphenol-containing nanomaterials, and various biomedical applications of polyphenol-based nanosystems.…”

Exploiting Supramolecular Dynamics in Metal–Phenolic Networks to Generate Metal–Oxide and Metal–Carbon Networks

“…Decomposition of the phenolic motifs during the carbonization process in argon to form MCNs led to a positive zeta potential (20 mV). These results show that the surface properties can be reversibly switched by repeating the MPN deposition and thermal decomposition process in air or inert conditions [7b] (Figure S26). Additionally, the permeability of the MPN, MCN, and MON capsules underwent considerable changes owing to the transformation of these networks.…”

Robust and Versatile Coatings Engineered via Simultaneous Covalent and Noncovalent Interactions

“…Self‐assembly processes are widely exploited for constructing structurally tunable and functional ensembles in nature, where the assembly process simultaneously involves covalent and noncovalent interactions among molecular units [24, 25] . Inspired by this, we recently developed size‐tunable nanoparticles (pBDT‐TA) via the assembly of tannic acid (TA) and a self‐polymerizable aromatic dithiol (i.e., benzene‐1,4‐dithiol, BDT), and these nanoparticles served as a generalizable particle template for synthesizing particles with various shell materials [26] . The presence of both covalent and noncovalent interactions in the pBDT‐TA particles underpins their robust stability in various synthetic conditions.…”

“…The interfacial assembly strategy for surface engineering using TA and BDT is shown in Figure 1 a. Specifically, BDT first self‐polymerizes into polybenzene‐1,4‐dithiol (pBDT) via disulfide bridges in aqueous environments and subsequently self‐assembles with TA to form a coating (i.e., pBDT‐TA) on various substrates (across nano‐to‐micrometer‐scales) via the adherent properties of phenolics [26, 28] . In contrast, monothiol‐containing molecules do not result in robust coatings (Figure S1), indicating the importance of disulfide bridges for this coating method.…”