Developing self-complementary macrocycles with ingenious molecules

Developing self-complementary macrocycles with ingenious molecules


Credit: Tokyo Tech

Some organic molecules with environment friendly noncovalent bonding websites can use their bonding properties to create well-defined assemblies from a single class of molecules—i.e., they assemble with one another. These molecules, that are steadily seen in nature, are known as “self-complementary assemblies.” For occasion, the p24 protein hexamer, which is a part of the capsid of the HIV (human immunodeficiency virus), consists of six protein subunits that complementarily self-assemble utilizing many hydrogen bonds.

This phenomenon permits well-designed molecules to kind higher-ordered assemblies with out the steel ions which can be generally used as “joints” between monomer molecules. Indeed, many self-complementary assemblies have been reported on the idea of intrinsic hydrogen bonds, π-interactions, and coordination bonds.
However, self-complementary meeting primarily based on host-guest methods is uncommon and notoriously troublesome to manage. In order to additional our understanding of self-complementary meeting with higher-ordered constructions, many new methods have come to mild lately.
Now, a workforce of researchers from the School of Science at Tokyo Institute of Technology (Tokyo Tech) might need simply cracked the code to creating these progressive methods. The workforce, led by Assistant Professor Masahiro Yamashina and Professor Shinji Toyota, has constructed a novel self-complementary macrocycle meeting utilizing an anthracene-based tweezer-like molecule with a pyridinedicarboxamide (PDA) linker because the monomeric species. Their work is described in Nature Communications.
“The molecule we use has an fascinating property: It can bond with itself in two methods and kind self-complementary constructions. Not solely does it present head-to-tail π-π interactions between the electron-rich tweezer tail (the anthracene teams) and the electron-deficient head, but additionally presents hydrogen bonding by way of the amide (-NH) useful group. By incorporating these two interactions, a preferential course of self-assembly is achieved, and this guides the formation of the macrocycle,” explains Prof. Yamashina.
This sort of twin interplay results in rather more management over the formation of artificial macrocycles, and on this case, provides rise to a secure self-complementary hexameric construction upon crystallization. These hexamers can additional assemble into even larger self-complementary constructions in the best situations.
“When we added trifluoroacetic acid (TFA), we discovered that the cyclic hexamers additional assemble into two predominant, secure supramolecular constructions: rhombohedral grid assemblies and large spherical cuboctahedra, a so-called hierarchical meeting,” Prof. Toyota says. “The latter construction is especially spectacular as it’s shaped from 108 monomeric tweezer items.”
Current strategies to kind supramolecular assemblies require metals that might hurt the surroundings and ecosystems. The metal-free various technique described right here may produce novel supramolecular constructions utilizing a easy anthracene-based tweezer molecule. It opens the door to a brand new vary of supramolecular assemblies with optical and digital capabilities. This work provides a brand new essential device within the chemistry toolbox, one that’s certain to play a giant position within the metal-free supramolecular constructions of the longer term.

Decoding protein meeting dynamics with synthetic protein needles

More data:
Yuta Sawanaka et al, A self-complementary macrocycle by a twin interplay system, Nature Communications (2022). DOI: 10.1038/s41467-022-33357-y

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Tokyo Institute of Technology

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Developing self-complementary macrocycles with ingenious molecules (2022, October 13)
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