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Title: Hyperexpandable, self-healing macromolecular crystals with integrated polymer networks

Abstract

Formation of condensed matter typically involves a trade-off between structural order and flexibility. As the extent and directionality of interactions between atomic or molecular components increase, materials generally become more ordered but less compliant and vice versa. Yet, high levels of structural order and flexibility need not necessarily be mutually exclusive: there are many biological (e.g., microtubules, flagella, viruses) and synthetic assemblies (e.g., dynamic molecular crystals and frameworks) that can undergo considerable structural transformations without losing their crystalline order and possess remarkable mechanical properties with utility in diverse applications such as selective sorption, separation, sensing, and mechanoactuation. Ultimately, however, the extent of structural changes by such flexible crystals and their elasticity are constrained by the necessity to maintain a continuous network of bonding interactions between the constituents of the lattice. Consequently, even the most dynamic porous materials tend to be brittle and isolated as microcrystalline powders,14 and flexible organic/inorganic molecular crystals cannot expand without fracturing. Owing to their rigidity, crystalline materials rarely display self-healing behavior. Here we report that macromolecular ferritin crystals with integrated hydrogel polymers can isotropically expand to 180% of their original dimensions and >500% of their original volume while retaining periodic order and faceted Wulff morphologies. Evenmore » after the separation of neighboring ferritin molecules by 50 Å upon lattice expansion, specific molecular contacts between them can be reformed upon lattice contraction, resulting in the recovery of atomic-level periodicity and the highest resolution ferritin structure reported. Dynamic bonding interactions between the hydrogel network and the ferritin molecules endow the crystals with the ability to resist fragmentation and self-heal efficiently, while the chemical tailorability of the ferritin molecules enables the creation of chemically and mechanically differentiated domains within single crystals.« less

Authors:
 [1];  [1];  [1];  [2];  [3]
  1. Univ. of California, San Diego, CA (United States). Dept. of Chemistry and Biochemistry
  2. Univ. of California, San Diego, CA (United States). Dept. of Physics
  3. Univ. of California, San Diego, CA (United States). Dept. of Chemistry and Biochemistry, and Materials Science and Engineering
Publication Date:
Research Org.:
Univ. of California, San Diego, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division; National Science Foundation (NSF)
OSTI Identifier:
1504265
Grant/Contract Number:  
SC0003844; AC02-06CH11357; AC02-76SF00515
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Nature (London)
Additional Journal Information:
Journal Volume: 557; Journal Issue: 7703; Journal ID: ISSN 0028-0836
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Zhang, Ling, Bailey, Jake B., Subramanian, Rohit H., Groisman, Alexander, and Tezcan, F. Akif. Hyperexpandable, self-healing macromolecular crystals with integrated polymer networks. United States: N. p., 2018. Web. doi:10.1038/s41586-018-0057-7.
Zhang, Ling, Bailey, Jake B., Subramanian, Rohit H., Groisman, Alexander, & Tezcan, F. Akif. Hyperexpandable, self-healing macromolecular crystals with integrated polymer networks. United States. doi:10.1038/s41586-018-0057-7.
Zhang, Ling, Bailey, Jake B., Subramanian, Rohit H., Groisman, Alexander, and Tezcan, F. Akif. Tue . "Hyperexpandable, self-healing macromolecular crystals with integrated polymer networks". United States. doi:10.1038/s41586-018-0057-7.
@article{osti_1504265,
title = {Hyperexpandable, self-healing macromolecular crystals with integrated polymer networks},
author = {Zhang, Ling and Bailey, Jake B. and Subramanian, Rohit H. and Groisman, Alexander and Tezcan, F. Akif},
abstractNote = {Formation of condensed matter typically involves a trade-off between structural order and flexibility. As the extent and directionality of interactions between atomic or molecular components increase, materials generally become more ordered but less compliant and vice versa. Yet, high levels of structural order and flexibility need not necessarily be mutually exclusive: there are many biological (e.g., microtubules, flagella, viruses) and synthetic assemblies (e.g., dynamic molecular crystals and frameworks) that can undergo considerable structural transformations without losing their crystalline order and possess remarkable mechanical properties with utility in diverse applications such as selective sorption, separation, sensing, and mechanoactuation. Ultimately, however, the extent of structural changes by such flexible crystals and their elasticity are constrained by the necessity to maintain a continuous network of bonding interactions between the constituents of the lattice. Consequently, even the most dynamic porous materials tend to be brittle and isolated as microcrystalline powders,14 and flexible organic/inorganic molecular crystals cannot expand without fracturing. Owing to their rigidity, crystalline materials rarely display self-healing behavior. Here we report that macromolecular ferritin crystals with integrated hydrogel polymers can isotropically expand to 180% of their original dimensions and >500% of their original volume while retaining periodic order and faceted Wulff morphologies. Even after the separation of neighboring ferritin molecules by 50 Å upon lattice expansion, specific molecular contacts between them can be reformed upon lattice contraction, resulting in the recovery of atomic-level periodicity and the highest resolution ferritin structure reported. Dynamic bonding interactions between the hydrogel network and the ferritin molecules endow the crystals with the ability to resist fragmentation and self-heal efficiently, while the chemical tailorability of the ferritin molecules enables the creation of chemically and mechanically differentiated domains within single crystals.},
doi = {10.1038/s41586-018-0057-7},
journal = {Nature (London)},
issn = {0028-0836},
number = 7703,
volume = 557,
place = {United States},
year = {2018},
month = {5}
}

Journal Article:
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Works referenced in this record:

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