Stereodivergent Chirality Transfer by Noncovalent Control of Disulfide Bonds

Abstract

Controlling dynamic stereochemistry is an important challenge, as it is not only inherent to protein structure and function but often governs supramolecular systems and selfassembly. Typically, disulfide bonds exhibit stereodivergent behavior in proteins; however, how chiral information is transmitted to disulfide bonds remains unclear. Here, we report that hydrogen bonds are essential in the control of disulfide chirality and enable stereodivergent chirality transfer. The formation of S−S•••H−N hydrogen bonds in solution can drive conformational adaption to allow intramolecular chirality transfer, while the formation of C=O•••H−N hydrogen bonds results in supramolecular chirality transfer to form antiparallel helically selfassembled solid-state architectures. The dependence on the structural information encoded in the homochiral amino acid building blocks reveals the remarkable dynamic stereochemical space accessible through noncovalent chirality transmission.

Tuning the coordination properties of chiral pseudopeptide bis(2-picolyl)amine and iminodiacetamide ligands in Zn(ii) and Cu(ii) complexes

“…An interesting aspect of enzyme function is the chirality transfer from remote chiral centers to the active site by means of non-covalent interactions. [22][23][24][25] This chirality transfer based on the "backdoor induction" principle in phosphine ligands containing chiral centers remote to the active site was studied in our group and enables effective chirality transfer in hydrogenation reactions with selectivity of up to 97%. 26,27 In hexacoordinated ML 2 complexes, such chirality transfer could be achieved by hydrogen bonding interactions between side chains of two ligands in a cis-fac complex (Fig.…”

In Situ Probe Supramolecular Self-Assembly Dynamics and Chirality Transfer Mechanism at Air–Water Interface

“…Endowing achiral molecules with chiral characteristics by coassembly of chiral and achiral molecules is a simple and efficient method to construct chiral supramolecular assemblies with greater complexity and potential function. − Therefore, it has attracted considerable interest in many fields. − The chiral self-assembly process is driven by multiple noncovalent forces and involves multiple assembly steps, which leads to complex chirality transfer, amplification, and dynamics behavior. − The study of molecular assembly dynamics and chirality transfer has always been a critical scientific question. − Prato et al reported the chirality transfer from chiral carbon nanodots to tetra-anionic porphyrins via electrostatic interactions . The Liu group reported the electrostatic force-driven chiral assembly of achiral TPPS molecules and amphiphiles ( l -TyrC18 and d -TyrC18) at the air–water interface.…”

Self-Resetting Bistable Redox Molecular Machines for Fullerene Recognition

“… 10 , 11 The variety of protocols to include the S–S motif, either chemically or electrochemically, in synthetic compounds is widespread 12 , 13 and has been successfully applied in a variety of outstanding concepts. 14 , 15 Corannulene chalcogenides, 16 especially those bearing sulfur as the distinctive heteroatom, have been extensively studied due to their special electronic features when compared to the parent buckybowl, leading to materials with distinctive properties. 17 − 20 One of the most interesting characteristics is their electron donation ability to form stable adducts with fullerenes.…”

“…The model we propose herein, again driven by nature’s inspirational influence, is based on the formation and cleavage of disulfide (S–S) bridges . It is well-known that this motif is present in a vast assortment of biomolecules, especially in proteins, whose function is to provide stability to the molecule favoring the maturation (correct folding) progress toward their native state. , The variety of protocols to include the S–S motif, either chemically or electrochemically, in synthetic compounds is widespread , and has been successfully applied in a variety of outstanding concepts. , Corannulene chalcogenides, especially those bearing sulfur as the distinctive heteroatom, have been extensively studied due to their special electronic features when compared to the parent buckybowl, leading to materials with distinctive properties. − One of the most interesting characteristics is their electron donation ability to form stable adducts with fullerenes. − …”