An Organometallic Strategy for Assembling Atomically Precise Hybrid Nanomaterials

Abstract

For decades, chemists have strived to mimic the intricate design and diverse functions of naturally occurring systems through the bioinspired synthesis of programmable inorganic nanomaterials. The development of thiol-capped gold nanoparticles (AuNPs) has driven advancement in this area; however, although versatile and readily accessible, hybrid AuNPs are rarely atomically precise, which limits control over their surface topology and therefore the study of complex structure-function relationships. Here, we present a bottom-up approach to the systematic assembly of atomically precise hybrid nanoclusters employing a strategy that mimics the synthetic ease with which thiol-capped AuNPs are normally constructed, while producing welldefined covalent nanoscale assemblies with diverse surface topologies. For the first time, using a structurally characterized cluster-based organometallic building block, we demonstrate the

Sulfoglycodendrimer Therapeutics for HIV‐1 and SARS‐CoV‐2

“…All four of these SGDs are able to bind to the gp120 trimer in a multivalent manner, where the different functional groups of the SGDs interact with gp120 in a correlated manner by the Coulombic and van der Waals (vdW) coupling. [ 20 ] In this multivalent coupling, different branches of SGDs can simultaneously interact with one or two gp120 monomers, as shown in Figures 4B, Figure S40, Supporting Information, for the Lactose‐SGD (15e) compound. On the other hand, the neutral GDs (non‐sulfated, 12d, 15d, 17d, and 18d) are significantly less active in their binding with gp120 (Figures S41 and S42, Supporting Information).…”

“…In our earlier studies of sulfonated gold NPs coupled with Human Papilloma Virus (HPV) capsids, we found that the free energy per one charged interaction (−6 kcal mol −1 ) is 12 times larger than that per one typical hydrophobic group (alkyl, −0.5 kcal mol −1 ). [ 20d ] Coulombic coupling should also dominate the binding of SGDs and gp120. Furthermore, the ranking of SGDs in order of their charged interaction contribution (Figure 4E, left) matches their binding affinities obtained from MST experiments: 15e > 17e > 12e > 18e.…”

“…We conclude that the sulfation level, number of sugars, orientations of polar groups, and overall arrangement of sugars in SGDs determine the strength of their multivalent interactions with target substrates. [ 20a–d,21 ]…”

“…Multivalency plays an important role in the strengthening of binding between protein‐protein or inhibitor‐protein interactions. [ 20d,21,23 ] Here, the oxime‐linked hexavalent scaffold provides the first level contribution to multivalency with additional contributions from the disaccharide or trisaccharide terminus. Orientations of hydroxyl groups and linkage between units are delicate factors determining the multivalency of the designed SGDs.…”

Pt–S Bond‐Mediated Nanoflares for High‐Fidelity Intracellular Applications by Avoiding Thiol Cleavage

“…They have been extensively exploited to construct biosensors by integrating recognition units including molecular beacons, DNAzymes, and aptamers . Among these, Au−S bond‐mediated functionalization of AuNPs is the most important method . However, the Au−S bond is susceptible to harsh conditions, especially thiol compounds, leading to the non‐specific release of surface ligands or signal reporters, and high background signals for cell imaging owing to intracellular biothiols (for example, 1–10 m m glutathione (GSH)) .…”