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Title: Hierarchical spidroin micellar nanoparticles as the fundamental precursors of spider silks

Abstract

Many natural silks produced by spiders and insects are unique materials in their exceptional toughness and tensile strength, while being lightweight and biodegradable–properties that are currently unparalleled in synthetic materials. Myriad approaches have been attempted to prepare artificial silks from recombinant spider silk spidroins but have each failed to achieve the advantageous properties of the natural material. This is because of an incomplete understanding of the in vivo spidroin-to-fiber spinning process and, particularly, because of a lack of knowledge of the true morphological nature of spidroin nanostructures in the precursor dope solution and the mechanisms by which these nanostructures transform into micrometer-scale silk fibers. Herein we determine the physical form of the natural spidroin precursor nanostructures stored within spider glands that seed the formation of their silks and reveal the fundamental structural transformations that occur during the initial stages of extrusion en route to fiber formation. Using a combination of solution phase diffusion NMR and cryogenic transmission electron microscopy (cryo-TEM), we reveal direct evidence that the concentrated spidroin proteins are stored in the silk glands of black widow spiders as complex, hierarchical nanoassemblies (~300 nm diameter) that are composed of micellar subdomains, substructures that themselves are engaged in the initialmore » nanoscale transformations that occur in response to shear. We find that the established micelle theory of silk fiber precursor storage is incomplete and that the first steps toward liquid crystalline organization during silk spinning involve the fibrillization of nanoscale hierarchical micelle subdomains.« less

Authors:
 [1];  [2];  [2];  [2];  [3];  [2];  [1];  [4];  [4];  [4];  [1];  [2]
  1. Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry, Dept. of Materials Science and Engineering, and Dept. of Biomedical Engineering
  2. San Diego State Univ., San Diego, CA (United States). Dept. of Chemistry and Biochemistry
  3. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States). Materials Science Division
  4. Arizona State Univ., Tempe, AZ (United States). School of Molecular Sciences and the Magnetic Resonance Research Center
Publication Date:
Research Org.:
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1488786
Alternate Identifier(s):
OSTI ID: 1478447
Report Number(s):
LLNL-JRNL-748285
Journal ID: ISSN 0027-8424; 933298
Grant/Contract Number:  
AC52-07NA27344
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Volume: 115; Journal Issue: 45; Journal ID: ISSN 0027-8424
Publisher:
National Academy of Sciences, Washington, DC (United States)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Parent, Lucas R., Onofrei, David, Xu, Dian, Stengel, Dillan, Roehling, John D., Addison, J. Bennett, Forman, Christopher, Amin, Samrat A., Cherry, Brian R., Yarger, Jeffery L., Gianneschi, Nathan C., and Holland, Gregory P. Hierarchical spidroin micellar nanoparticles as the fundamental precursors of spider silks. United States: N. p., 2018. Web. doi:10.1073/pnas.1810203115.
Parent, Lucas R., Onofrei, David, Xu, Dian, Stengel, Dillan, Roehling, John D., Addison, J. Bennett, Forman, Christopher, Amin, Samrat A., Cherry, Brian R., Yarger, Jeffery L., Gianneschi, Nathan C., & Holland, Gregory P. Hierarchical spidroin micellar nanoparticles as the fundamental precursors of spider silks. United States. doi:10.1073/pnas.1810203115.
Parent, Lucas R., Onofrei, David, Xu, Dian, Stengel, Dillan, Roehling, John D., Addison, J. Bennett, Forman, Christopher, Amin, Samrat A., Cherry, Brian R., Yarger, Jeffery L., Gianneschi, Nathan C., and Holland, Gregory P. Mon . "Hierarchical spidroin micellar nanoparticles as the fundamental precursors of spider silks". United States. doi:10.1073/pnas.1810203115.
@article{osti_1488786,
title = {Hierarchical spidroin micellar nanoparticles as the fundamental precursors of spider silks},
author = {Parent, Lucas R. and Onofrei, David and Xu, Dian and Stengel, Dillan and Roehling, John D. and Addison, J. Bennett and Forman, Christopher and Amin, Samrat A. and Cherry, Brian R. and Yarger, Jeffery L. and Gianneschi, Nathan C. and Holland, Gregory P.},
abstractNote = {Many natural silks produced by spiders and insects are unique materials in their exceptional toughness and tensile strength, while being lightweight and biodegradable–properties that are currently unparalleled in synthetic materials. Myriad approaches have been attempted to prepare artificial silks from recombinant spider silk spidroins but have each failed to achieve the advantageous properties of the natural material. This is because of an incomplete understanding of the in vivo spidroin-to-fiber spinning process and, particularly, because of a lack of knowledge of the true morphological nature of spidroin nanostructures in the precursor dope solution and the mechanisms by which these nanostructures transform into micrometer-scale silk fibers. Herein we determine the physical form of the natural spidroin precursor nanostructures stored within spider glands that seed the formation of their silks and reveal the fundamental structural transformations that occur during the initial stages of extrusion en route to fiber formation. Using a combination of solution phase diffusion NMR and cryogenic transmission electron microscopy (cryo-TEM), we reveal direct evidence that the concentrated spidroin proteins are stored in the silk glands of black widow spiders as complex, hierarchical nanoassemblies (~300 nm diameter) that are composed of micellar subdomains, substructures that themselves are engaged in the initial nanoscale transformations that occur in response to shear. We find that the established micelle theory of silk fiber precursor storage is incomplete and that the first steps toward liquid crystalline organization during silk spinning involve the fibrillization of nanoscale hierarchical micelle subdomains.},
doi = {10.1073/pnas.1810203115},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
issn = {0027-8424},
number = 45,
volume = 115,
place = {United States},
year = {2018},
month = {10}
}

Journal Article:
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This content will become publicly available on October 22, 2019
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