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Title: Impact of Nanoparticle Size and Surface Chemistry on Peptoid Self-Assembly

Journal Article · · ACS Nano
 [1];  [2]; ORCiD logo [3];  [4]; ORCiD logo [4]; ORCiD logo [3]; ORCiD logo [2]
  1. Univ. of Washington, Seattle, WA (United States); University of Washington
  2. Univ. of Washington, Seattle, WA (United States)
  3. Univ. of Washington, Seattle, WA (United States); Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  4. Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Univ. of Washington, Seattle, WA (United States)

Self-assembled organic nanomaterials can be generated by bottom-up assembly pathways where the structure is controlled by the organic sequence and altered using pH, temperature, and solvation. In contrast, self-assembled structures based on inorganic nanoparticles typically rely on physical packing and drying effects to achieve uniform superlattices. By combining these two chemistries to access inorganic–organic nanostructures, we aim to understand the key factors that govern the assembly pathway and structural outcomes in hybrid systems. In this work, we outline two assembly regimes between quantum dots (QDs) and reversibly binding peptoids. These regimes can be accessed by changing the solubility and size of the hybrid (peptoid-QD) monomer unit. The hybrid monomers are prepared via ligand exchange and assembled, and the resulting assemblies are studied using ex-situ transmission electron microscopy as a function of assembly time. In aqueous conditions, QDs were found to stabilize certain morphologies of peptoid intermediates and generate a final product consisting of multilayers of small peptoid sheets linked by QDs. The QDs were also seen to facilitate or inhibit assembly in organic solvents based on the relative hydrophobicity of the surface ligands, which ultimately dictated the solubility of the hybrid monomer unit. Increasing the size of the QDs led to large hybrid sheets with regions of highly ordered square-packed QDs. A second, smaller QD species can also be integrated to create binary hybrid lattices. Furthermore, these results create a set of design principles for controlling the structure and structural evolution of hybrid peptoid-QD assemblies and contribute to the predictive synthesis of complex hybrid matter.

Research Organization:
Univ. of Washington, Seattle, WA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation
Grant/Contract Number:
SC0019288; AC05-76RL01830
OSTI ID:
1873419
Journal Information:
ACS Nano, Journal Name: ACS Nano Journal Issue: 5 Vol. 16; ISSN 1936-0851
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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