Anisotropic Synthetic Allomelanin Materials via Solid-State Polymerization of Self-Assembled 1,8-Dihydroxynaphthalene Dimers

Xuhao Zhou; Xinyi Gong; Wei Cao; Christopher J. Forman; Julia Oktawiec; Liliana D'Alba; Hao Sun; Matthew P. Thompson; Ziying Hu; Utkarsh Kapoor; Naneki C. McCallum; Christos D. Malliakas; Omar K. Farha; Arthi Jayaraman; Matthew D. Shawkey; Nathan C. Gianneschi

doi:10.1002/anie.202103447

Anisotropic Synthetic Allomelanin Materials via Solid-State Polymerization of Self-Assembled 1,8-Dihydroxynaphthalene Dimers

Xuhao Zhou, Xinyi Gong, Wei Cao, Christopher J. Forman, Julia Oktawiec, Liliana D'Alba, Hao Sun, Matthew P. Thompson, Ziying Hu, Utkarsh Kapoor, Naneki C. McCallum, Christos D. Malliakas, Omar K. Farha, Arthi Jayaraman, Matthew D. Shawkey, Nathan C. Gianneschi^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

21 Scopus citations

Abstract

Melanosomes in nature have diverse morphologies, including spheres, rods, and platelets. By contrast, shapes of synthetic melanins have been almost entirely limited to spherical nanoparticles with few exceptions produced by complex templated synthetic methods. Here, we report a non-templated method to access synthetic melanins with a variety of architectures including spheres, sheets, and platelets. Three 1,8-dihydroxynaphthalene dimers (4-4′, 2-4′ and 2-2′) were used as self-assembling synthons. These dimers pack to form well-defined structures of varying morphologies depending on the isomer. Specifically, distinctive ellipsoidal platelets can be obtained using 4-4′ dimers. Solid-state polymerization of the preorganized dimers generates polymeric synthetic melanins while maintaining the initial particle morphologies. This work provides a new route to anisotropic synthetic melanins, where the building blocks are preorganized into specific shapes, followed by solid-state polymerization.

Original language	English (US)
Pages (from-to)	17464-17471
Number of pages	8
Journal	Angewandte Chemie - International Edition
Volume	60
Issue number	32
DOIs	https://doi.org/10.1002/anie.202103447
State	Published - Aug 2 2021

Funding

This work was supported by a MURI through the Air Force Office of Scientific Research (FA 9550‐18‐1‐0142 and supporting grant FA 9550‐18‐1‐0477). This work made use of the IMSERC facility, Jerome B. Cohen X‐Ray Diffraction facility, BioCryo facility of NUANCE Center of Northwestern University, supported by the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS‐2025633); the MRSEC program of the National Science Foundation (NSF DMR‐1720139) at the Materials Research Center of Northwestern University; the International Institute for Nanotechnology (IIN); and the State of Illinois, through the IIN. O.K.F. acknowledges the support from the Army Research Office, under Award No. W911NF1910340. M.D.S. acknowledges the support from a FWO Grant (No. G007117N). The authors would like to thank W. Fu at Zhejiang University, for the assistance in Figure preparation. This work was supported by a MURI through the Air Force Office of Scientific Research (FA 9550-18-1-0142 and supporting grant FA 9550-18-1-0477). This work made use of the IMSERC facility, Jerome B. Cohen X-Ray Diffraction facility, BioCryo facility of NUANCE Center of Northwestern University, supported by the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-2025633); the MRSEC program of the National Science Foundation (NSF DMR-1720139) at the Materials Research Center of Northwestern University; the International Institute for Nanotechnology (IIN); and the State of Illinois, through the IIN. O.K.F. acknowledges the support from the Army Research Office, under Award No. W911NF1910340. M.D.S. acknowledges the support from a FWO Grant (No. G007117N). The authors would like to thank W. Fu at Zhejiang University, for the assistance in Figure preparation.

Keywords

DHN melanin
allomelanin
anisotropy
melanin
solid-state polymerization

ASJC Scopus subject areas

Catalysis
General Chemistry

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10.1002/anie.202103447

Cite this

Zhou, X., Gong, X., Cao, W., Forman, C. J., Oktawiec, J., D'Alba, L., Sun, H., Thompson, M. P., Hu, Z., Kapoor, U., McCallum, N. C., Malliakas, C. D., Farha, O. K., Jayaraman, A., Shawkey, M. D., & Gianneschi, N. C. (2021). Anisotropic Synthetic Allomelanin Materials via Solid-State Polymerization of Self-Assembled 1,8-Dihydroxynaphthalene Dimers. Angewandte Chemie - International Edition, 60(32), 17464-17471. https://doi.org/10.1002/anie.202103447

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title = "Anisotropic Synthetic Allomelanin Materials via Solid-State Polymerization of Self-Assembled 1,8-Dihydroxynaphthalene Dimers",

abstract = "Melanosomes in nature have diverse morphologies, including spheres, rods, and platelets. By contrast, shapes of synthetic melanins have been almost entirely limited to spherical nanoparticles with few exceptions produced by complex templated synthetic methods. Here, we report a non-templated method to access synthetic melanins with a variety of architectures including spheres, sheets, and platelets. Three 1,8-dihydroxynaphthalene dimers (4-4′, 2-4′ and 2-2′) were used as self-assembling synthons. These dimers pack to form well-defined structures of varying morphologies depending on the isomer. Specifically, distinctive ellipsoidal platelets can be obtained using 4-4′ dimers. Solid-state polymerization of the preorganized dimers generates polymeric synthetic melanins while maintaining the initial particle morphologies. This work provides a new route to anisotropic synthetic melanins, where the building blocks are preorganized into specific shapes, followed by solid-state polymerization.",

keywords = "DHN melanin, allomelanin, anisotropy, melanin, solid-state polymerization",

author = "Xuhao Zhou and Xinyi Gong and Wei Cao and Forman, {Christopher J.} and Julia Oktawiec and Liliana D'Alba and Hao Sun and Thompson, {Matthew P.} and Ziying Hu and Utkarsh Kapoor and McCallum, {Naneki C.} and Malliakas, {Christos D.} and Farha, {Omar K.} and Arthi Jayaraman and Shawkey, {Matthew D.} and Gianneschi, {Nathan C.}",

note = "Publisher Copyright: {\textcopyright} 2021 Wiley-VCH GmbH.",

year = "2021",

month = aug,

day = "2",

doi = "10.1002/anie.202103447",

language = "English (US)",

volume = "60",

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Zhou, X, Gong, X, Cao, W, Forman, CJ, Oktawiec, J, D'Alba, L, Sun, H, Thompson, MP, Hu, Z, Kapoor, U, McCallum, NC, Malliakas, CD , Farha, OK, Jayaraman, A, Shawkey, MD & Gianneschi, NC 2021, 'Anisotropic Synthetic Allomelanin Materials via Solid-State Polymerization of Self-Assembled 1,8-Dihydroxynaphthalene Dimers', Angewandte Chemie - International Edition, vol. 60, no. 32, pp. 17464-17471. https://doi.org/10.1002/anie.202103447

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T1 - Anisotropic Synthetic Allomelanin Materials via Solid-State Polymerization of Self-Assembled 1,8-Dihydroxynaphthalene Dimers

AU - Zhou, Xuhao

AU - Gong, Xinyi

AU - Cao, Wei

AU - Forman, Christopher J.

AU - Oktawiec, Julia

AU - D'Alba, Liliana

AU - Sun, Hao

AU - Thompson, Matthew P.

AU - Hu, Ziying

AU - Kapoor, Utkarsh

AU - McCallum, Naneki C.

AU - Malliakas, Christos D.

AU - Farha, Omar K.

AU - Jayaraman, Arthi

AU - Shawkey, Matthew D.

AU - Gianneschi, Nathan C.

PY - 2021/8/2

Y1 - 2021/8/2

N2 - Melanosomes in nature have diverse morphologies, including spheres, rods, and platelets. By contrast, shapes of synthetic melanins have been almost entirely limited to spherical nanoparticles with few exceptions produced by complex templated synthetic methods. Here, we report a non-templated method to access synthetic melanins with a variety of architectures including spheres, sheets, and platelets. Three 1,8-dihydroxynaphthalene dimers (4-4′, 2-4′ and 2-2′) were used as self-assembling synthons. These dimers pack to form well-defined structures of varying morphologies depending on the isomer. Specifically, distinctive ellipsoidal platelets can be obtained using 4-4′ dimers. Solid-state polymerization of the preorganized dimers generates polymeric synthetic melanins while maintaining the initial particle morphologies. This work provides a new route to anisotropic synthetic melanins, where the building blocks are preorganized into specific shapes, followed by solid-state polymerization.

AB - Melanosomes in nature have diverse morphologies, including spheres, rods, and platelets. By contrast, shapes of synthetic melanins have been almost entirely limited to spherical nanoparticles with few exceptions produced by complex templated synthetic methods. Here, we report a non-templated method to access synthetic melanins with a variety of architectures including spheres, sheets, and platelets. Three 1,8-dihydroxynaphthalene dimers (4-4′, 2-4′ and 2-2′) were used as self-assembling synthons. These dimers pack to form well-defined structures of varying morphologies depending on the isomer. Specifically, distinctive ellipsoidal platelets can be obtained using 4-4′ dimers. Solid-state polymerization of the preorganized dimers generates polymeric synthetic melanins while maintaining the initial particle morphologies. This work provides a new route to anisotropic synthetic melanins, where the building blocks are preorganized into specific shapes, followed by solid-state polymerization.

KW - DHN melanin

KW - allomelanin

KW - anisotropy

KW - melanin

KW - solid-state polymerization

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DO - 10.1002/anie.202103447

M3 - Article

C2 - 33913253

AN - SCOPUS:85108438307

SN - 1433-7851

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JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

IS - 32

ER -

Anisotropic Synthetic Allomelanin Materials via Solid-State Polymerization of Self-Assembled 1,8-Dihydroxynaphthalene Dimers

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CCDC 2004586: Experimental Crystal Structure Determination

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Anisotropic Synthetic Allomelanin Materials via Solid-State Polymerization of Self-Assembled 1,8-Dihydroxynaphthalene Dimers

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Funding

Keywords

ASJC Scopus subject areas

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CCDC 2004586: Experimental Crystal Structure Determination

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