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

Abstract

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.

Polyphenol-Mediated Assembly for Particle Engineering

“…We recently developed a protocol for visualizing latent fingerprints (i.e., invisible residual biomolecule patterns) through the formation of Ag nanoparticles on pre-formed MPN films patterned by biomolecules (Figure 6f). 56 (Figure 7a). 58 These polymeric polyphenols then assembled into microspheres with a diameter of 1-3 μm and exhibited green fluorescence under UV irradiation (Figure 7b and 7c).…”

The biomolecule corona of lipid nanoparticles contains circulating cell-free DNA

“…33 In a different study, Yun et al developed a planarsubstrate based protocol in order to investigate the interaction of metal-phenolic network (MPN)-based nanomaterials with multiple biomolecules including synthetic single stranded 40 bp DNA fragments. 31 It is important to note however, that these DNA molecules do not reflect the size and structure of endogenous plasma cfDNA, nor the molecular complexity of blood. 31 Despite the above-mentioned preliminary indications of the interaction of nucleic acids with the surface of NPs, no studies have demonstrated the presence of cfDNA in the biomolecule corona formed when NPs come into contact with human plasma.…”

“…31 It is important to note however, that these DNA molecules do not reflect the size and structure of endogenous plasma cfDNA, nor the molecular complexity of blood. 31 Despite the above-mentioned preliminary indications of the interaction of nucleic acids with the surface of NPs, no studies have demonstrated the presence of cfDNA in the biomolecule corona formed when NPs come into contact with human plasma. The present study aimed to answer this fundamental question and establish whether cfDNA participates in the formation of the biomolecule corona in a non-specific, untargeted manner.…”

“…Scarce speculative statements exist in the literature referencing the presence of nucleic acids in the biomolecule corona. [30][31][32] However, the genomic content of the blood-derived NP corona has never been investigated and there is no experimental evidence to support that the NP corona contains cell-free DNA (cfDNA). This could be partially due to the experimental challenges in identifying minute levels of blood-circulating nucleic acids on the NPs surfaces.…”

“…The very few studies that have tried to investigate any role that nucleic acids may play in the biomolecule corona, focused on miRNAs using rat urine samples, 33 or attempted to understand the interaction of NPs with added synthetic DNA fragments in solution. 31,34 NPs have also been extensively used as biosensors or as nano-carriers to deliver nucleic acids, with positively charged lipid-, polymeric-, gold-and carbon-based (among many other) NPs used to deliver electrostaticallycomplexed nucleic acids for therapeutic applications. [34][35][36][37][38][39][40][41][42] In an alternative approach, Liang et al, intravenously administered cationic polymeric NPs to complex cfDNA in vivo to alleviate the symptoms of inflammation in rheumatoid arthritis (RA).…”