Amino-acid-encoded biocatalytic self-assembly enables the formation of transient conducting nanostructures

Abstract

Aqueous compatible supramolecular materials hold promise for applications in environmental remediation, energy harvesting and biomedicine. One remaining challenge is to actively select a target structure from a multitude of possible options, in response to chemical signals, while maintaining constant, physiological conditions. Here, we demonstrate the use of amino acids to actively decorate a self-assembling core molecule in situ, thereby controlling its amphiphilicity and consequent mode of assembly. The core molecule is the organic semiconductor naphthalene diimide, functionalized with D- and L- tyrosine methyl esters as competing reactive sites. In the presence of α-chymotrypsin and a selected encoding amino acid, kinetic competition between ester hydrolysis and amidation results in covalent or non-covalent amino acid incorporation, and variable supramolecular self-assembly pathways. Taking advantage of the semiconducting nature of the naphthalene diimide core, electronic wires could be formed and subsequently degraded, giving rise to temporally regulated electro-conductivity.

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Fig. 1: Active amino acid encoding of biocatalytic self-assembly pathways.
Fig. 2: Biocatalytic amino acid encoding of transient supramolecular chirality.
Fig. 3: Biocatalytic amino acid encoding of chiral nanotubes.
Fig. 4: Dynamic helix reconfiguration through programmed stereomutation.
Fig. 5: Transient supramolecular conductance in aqueous media.

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Acknowledgements

The authors acknowledge staff at the Biomolecular Spectroscopy Facility for Circular Dichroism, Imaging Suite Facility and Nanofabrication Facility, all of which are part of the Advanced Science Research Center at the Graduate Center, City University of New York. The research leading to these results received funding from the US Air Force (AFOSR, grants FA9550-15-1-0192 and FA9550-014-1-0350), US Army Research Laboratory and US Army Research Office under contract/grant number W911NF-16-1-0113.

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M.K. and R.V.U. conceived the idea, designed and discussed the concepts and experiments, and analysed the data. M.K. performed the experimental work. N.I. and A.H. designed and performed the electronic transport measurements and analysed the data. N.W. performed and analysed the infrared spectroscopy (IR) measurement. V.N. performed the atomic force microscopy experiment. M.K., R.V.U., N.I. and A.H. co-wrote the paper. All authors discussed and commented on the manuscript.

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Correspondence to Rein V. Ulijn.

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Kumar, M., Ing, N.L., Narang, V. et al. Amino-acid-encoded biocatalytic self-assembly enables the formation of transient conducting nanostructures. Nature Chem 10, 696–703 (2018). https://doi.org/10.1038/s41557-018-0047-2

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