On-off transition and ultrafast decay of amino acid luminescence driven by modulation of supramolecular packing

Zohar A. Arnon; Topaz Kreiser; Boris Yakimov; Noam Brown; Ruth Aizen; Shira Shaham-Niv; Pandeeswar Makam; Muhammad Nawaz Qaisrani; Emiliano Poli; Antonella Ruggiero; Inna Slutsky; Ali Hassanali; Evgeny Shirshin; Davide Levy; Ehud Gazit

doi:10.1016/j.isci.2021.102695

On-off transition and ultrafast decay of amino acid luminescence driven by modulation of supramolecular packing

Zohar A. Arnon, Topaz Kreiser, Boris Yakimov, Noam Brown, Ruth Aizen, Shira Shaham-Niv, Pandeeswar Makam, Muhammad Nawaz Qaisrani, Emiliano Poli, Antonella Ruggiero, Inna Slutsky, Ali Hassanali, Evgeny Shirshin, Davide Levy, Ehud Gazit

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23 Scopus citations

Abstract

Luminescence of biomolecules in the visible range of the spectrum has been experimentally observed upon aggregation, contrary to their monomeric state. However, the physical basis for this phenomenon is still elusive. Here, we systematically examine all coded amino acids to provide non-biased empirical insights. Several amino acids, including non-aromatic, show intense visible luminescence. Lysine crystals display the highest signal, whereas the very chemically similar non-coded ornithine does not, implying a role for molecular packing rather than the chemical characteristics. Furthermore, cysteine shows luminescence that is indeed crystal packing dependent as repeated rearrangements between two crystal structures result in a reversible on-off optical transition. In addition, ultrafast lifetime decay is experimentally validated, corroborating a recently raised hypothesis regarding the governing role of nπ∗ states in the emission formation. Collectively, our study supports that electronic interactions between non-fluorescent, non-absorbing molecules at the monomeric state may result in reversible optically active states by the formation of supramolecular fluorophores.

Original language	English
Article number	102695
Journal	iScience
Volume	24
Issue number	7
DOIs	https://doi.org/10.1016/j.isci.2021.102695
State	Published - 23 Jul 2021
Externally published	Yes

Bibliographical note

Publisher Copyright:
© 2021

Funding

Z.A.A. and T.K. contributed equally to this work. We thank our lab members for the fruitful discussions. This work was supported by the Israeli National Nanotechnology Initiative and Helmsley Charitable Trust (E.G.), the European Research Council BISON project (E.G.), the Clore Scholarship program and the Marian Gertner Institute (Z.A.A.). The work was supported by the Ministry of Science and Higher Education of the Russian Federation within the framework of state support for the creation and development of World-Class Research Centers "Digital biodesign and personalized healthcare" N o 075-15-2020-926 (E.S.). We thank members of the Gazit group for the helpful discussions. Z.A.A. and T.K. contributed equally to this work. We thank our lab members for the fruitful discussions. This work was supported by the Israeli National Nanotechnology Initiative and Helmsley Charitable Trust (E.G.), the European Research Council BISON project (E.G.), the Clore Scholarship program and the Marian Gertner Institute (Z.A.A.). The work was supported by the Ministry of Science and Higher Education of the Russian Federation within the framework of state support for the creation and development of World-Class Research Centers ?Digital biodesign and personalized healthcare? No075-15-2020-926 (E.S.). We thank members of the Gazit group for the helpful discussions. Z.A.A. T.K. S.S.-N. and E.G. conceived and designed the experiments. Z.A.A. T.K. N.B. R.A. S.S.-N. P.M. M.N.Q. E.P. A.R. I.S. A.H. E.S. and D.L. planned and performed the experiments. Z.A.A. T.K. and E.G. wrote the manuscript. D.L. performed PXRD experiments and analysis. All authors discussed the results, provided intellectual input and critical feedback, and commented on the manuscript. The authors declare no competing interests.

Funders	Funder number
A.H. E.S.
Israeli National Nanotechnology Initiative
Marian Gertner Institute
Leona M. and Harry B. Helmsley Charitable Trust
European Commission
Ministry of Education and Science of the Russian Federation	075-15-2020-926

Keywords

Biochemistry
chemistry
supramolecular chemistry

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10.1016/j.isci.2021.102695

Cite this

Arnon, Z. A., Kreiser, T., Yakimov, B., Brown, N., Aizen, R., Shaham-Niv, S., Makam, P., Qaisrani, M. N., Poli, E., Ruggiero, A., Slutsky, I., Hassanali, A., Shirshin, E., Levy, D., & Gazit, E. (2021). On-off transition and ultrafast decay of amino acid luminescence driven by modulation of supramolecular packing. iScience, 24(7), Article 102695. https://doi.org/10.1016/j.isci.2021.102695

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title = "On-off transition and ultrafast decay of amino acid luminescence driven by modulation of supramolecular packing",

abstract = "Luminescence of biomolecules in the visible range of the spectrum has been experimentally observed upon aggregation, contrary to their monomeric state. However, the physical basis for this phenomenon is still elusive. Here, we systematically examine all coded amino acids to provide non-biased empirical insights. Several amino acids, including non-aromatic, show intense visible luminescence. Lysine crystals display the highest signal, whereas the very chemically similar non-coded ornithine does not, implying a role for molecular packing rather than the chemical characteristics. Furthermore, cysteine shows luminescence that is indeed crystal packing dependent as repeated rearrangements between two crystal structures result in a reversible on-off optical transition. In addition, ultrafast lifetime decay is experimentally validated, corroborating a recently raised hypothesis regarding the governing role of nπ∗ states in the emission formation. Collectively, our study supports that electronic interactions between non-fluorescent, non-absorbing molecules at the monomeric state may result in reversible optically active states by the formation of supramolecular fluorophores.",

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Arnon, ZA, Kreiser, T, Yakimov, B, Brown, N, Aizen, R, Shaham-Niv, S, Makam, P, Qaisrani, MN, Poli, E, Ruggiero, A, Slutsky, I, Hassanali, A, Shirshin, E, Levy, D & Gazit, E 2021, 'On-off transition and ultrafast decay of amino acid luminescence driven by modulation of supramolecular packing', iScience, vol. 24, no. 7, 102695. https://doi.org/10.1016/j.isci.2021.102695

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T1 - On-off transition and ultrafast decay of amino acid luminescence driven by modulation of supramolecular packing

AU - Arnon, Zohar A.

AU - Kreiser, Topaz

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AU - Brown, Noam

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AU - Shaham-Niv, Shira

AU - Makam, Pandeeswar

AU - Qaisrani, Muhammad Nawaz

AU - Poli, Emiliano

AU - Ruggiero, Antonella

AU - Slutsky, Inna

AU - Hassanali, Ali

AU - Shirshin, Evgeny

AU - Levy, Davide

AU - Gazit, Ehud

PY - 2021/7/23

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N2 - Luminescence of biomolecules in the visible range of the spectrum has been experimentally observed upon aggregation, contrary to their monomeric state. However, the physical basis for this phenomenon is still elusive. Here, we systematically examine all coded amino acids to provide non-biased empirical insights. Several amino acids, including non-aromatic, show intense visible luminescence. Lysine crystals display the highest signal, whereas the very chemically similar non-coded ornithine does not, implying a role for molecular packing rather than the chemical characteristics. Furthermore, cysteine shows luminescence that is indeed crystal packing dependent as repeated rearrangements between two crystal structures result in a reversible on-off optical transition. In addition, ultrafast lifetime decay is experimentally validated, corroborating a recently raised hypothesis regarding the governing role of nπ∗ states in the emission formation. Collectively, our study supports that electronic interactions between non-fluorescent, non-absorbing molecules at the monomeric state may result in reversible optically active states by the formation of supramolecular fluorophores.

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On-off transition and ultrafast decay of amino acid luminescence driven by modulation of supramolecular packing

Abstract

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Keywords

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