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PET-RAFT and SAXS: High Throughput Tools To Study Compactness and Flexibility of Single-Chain Polymer Nanoparticles

  • Rahul Upadhya
    Rahul Upadhya
    Department of Biomedical Engineering, Rutgers, The State University of New Jersey, Piscataway, New Jersey 08854, United States
  • N. Sanjeeva Murthy
    N. Sanjeeva Murthy
    New Jersey Center for Biomaterials, Rutgers, The State University of New Jersey, Piscataway, New Jersey 08854, United States
  • Cody L. Hoop
    Cody L. Hoop
    Department of Chemistry and Chemical Biology, Rutgers, The State University of New Jersey, Piscataway, New Jersey 08854, United States
    More by Cody L. Hoop
  • Shashank Kosuri
    Shashank Kosuri
    Department of Biomedical Engineering, Rutgers, The State University of New Jersey, Piscataway, New Jersey 08854, United States
  • Vikas Nanda
    Vikas Nanda
    Center for Advanced Biotechnology and Medicine and the Department of Biochemistry and Molecular Biology, Robert Wood Johnson Medical School, Rutgers, The State University of New Jersey, Piscataway, New Jersey 08854, United States
    More by Vikas Nanda
  • Joachim Kohn
    Joachim Kohn
    New Jersey Center for Biomaterials, Rutgers, The State University of New Jersey, Piscataway, New Jersey 08854, United States
    More by Joachim Kohn
  • Jean Baum
    Jean Baum
    Department of Chemistry and Chemical Biology, Rutgers, The State University of New Jersey, Piscataway, New Jersey 08854, United States
    More by Jean Baum
  • , and 
  • Adam J. Gormley*
    Adam J. Gormley
    Department of Biomedical Engineering, Rutgers, The State University of New Jersey, Piscataway, New Jersey 08854, United States
    *(A.J.G.) E-mail [email protected]
Cite this: Macromolecules 2019, 52, 21, 8295–8304
Publication Date (Web):October 25, 2019
https://doi.org/10.1021/acs.macromol.9b01923
Copyright © 2019 American Chemical Society

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    Abstract

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    From protein science, it is well understood that ordered folding and 3D structure mainly arise from balanced and noncovalent polar and nonpolar interactions, such as hydrogen bonding. Similarly, it is understood that single-chain polymer nanoparticles (SCNPs) will also compact and become more rigid with greater hydrophobicity and intrachain hydrogen bonding. Here, we couple high throughput photoinduced electron/energy transfer reversible addition–fragmentation chain-transfer (PET-RAFT) polymerization with high throughput small-angle X-ray scattering (SAXS) to characterize a large combinatorial library (>450) of several homopolymers, random heteropolymers, block copolymers, PEG-conjugated polymers, and other polymer-functionalized polymers. Coupling these two high throughput tools enables us to study the major influence(s) for compactness and flexibility in higher breadth than ever before possible. Not surprisingly, we found that many were either highly disordered in solution, in the case of a highly hydrophilic polymer, or insoluble if too hydrophobic. Remarkably, we also found a small group (9/457) of PEG-functionalized random heteropolymers and block copolymers that exhibited compactness and flexibility similar to that of bovine serum albumin (BSA) by dynamic light scattering (DLS), NMR, and SAXS. In general, we found that describing a rough association between compactness and flexibility parameters (Rg/Rh and Porod exponent, respectively) with log P, a quantity that describes hydrophobicity, helps to demonstrate and predict material parameters that lead to SCNPs with greater compactness, rigidity, and stability. Future implementation of this combinatorial and high throughput approach for characterizing SCNPs will allow for the creation of detailed design parameters for well-defined macromolecular chemistry.

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