4.8 Article

Allomelanin: A Biopolymer of Intrinsic Microporosity

Journal

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 143, Issue 10, Pages 4005-4016

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/jacs.1c00748

Keywords

-

Funding

  1. MURI through the Air Force Office of Scientific Research [AFOSR FA9550-18-1-0142]
  2. Defense Threat Reduction Agency [HDTRA1-19-1-0010]
  3. Center for Regenerative Nanomedicine in the Simpson Querrey Institute at Northwestern University
  4. Department of Defense (DoD) through the National Defense Science & Engineering Graduate (NDSEG) Fellowship Program
  5. American Australian Association Dow Chemical Company Fellowship
  6. Human Frontier Science Program [LT000869/2018-C]
  7. Applied Research for Advancement of S&T Priorities Synthetic Biology for Military Environments program
  8. SHyNE Resource (NSF) [ECCS2025633]
  9. IIN
  10. Northwestern's MRSEC program [NSF DMR-1720139]
  11. Northwestern University
  12. Dow Chemical Company
  13. DuPont de Nemours, Inc.
  14. DOE Office of Science [DE-AC02-06CH11357]

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Research on artificial allomelanin analogues reveals high intrinsic microporosity and high BET surface area achievable through a simplified method. These synthetic allomelanin particles exhibit functions such as adsorbing ammonia and nerve agent simulants, as well as preventing agent breakthrough on breathable fabrics. Compared to naturally derived fungal melanin, synthetic analogues have higher porosity.
Melanin is a ubiquitous natural pigment found in a diverse array of organisms. Allomelanin is a class of nitrogen-free melanin often found in fungi. Herein, we find artificial allomelanin analogues exhibit high intrinsic microporosity and describe an approach for further increasing and tuning that porosity. Notably, the synthetic method involves an oxidative polymerization of 1,8-DHN in water, negating the need for multiple complex templating steps and avoiding expensive or complex chemical precursors. The well-defined morphologies of these nanomaterials were elucidated by a combination of electron microscopy and scattering methods, yielding to high-resolution 3D reconstruction based on small-angle X-ray scattering (SAXS) results. Synthetic allomelanin nanoparticles exhibit high BET areas, up to 860 m(2)/g, and are capable of ammonia capture up to 17.0 mmol/g at 1 bar. In addition, these nanomaterials can adsorb nerve agent simulants in solution and as a coating on fabrics with high breathability where they prevent breakthrough. We also confirmed that naturally derived fungal melanin can adsorb nerve gas simulants in solution efficiently despite lower porosity than synthetic analogues. Our approach inspires further analysis of yet to be discovered biological materials of this class where melanins with intrinsic microporosity may be linked to evolutionary advantages in relevant organisms and may in turn inspire the design of new high surface area materials.

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