TY - JOUR
T1 - PET-RAFT and SAXS
T2 - High Throughput Tools to Study Compactness and Flexibility of Single-Chain Polymer Nanoparticles
AU - Upadhya, Rahul
AU - Murthy, N. Sanjeeva
AU - Hoop, Cody L.
AU - Kosuri, Shashank
AU - Nanda, Vikas
AU - Kohn, Joachim
AU - Baum, Jean
AU - Gormley, Adam J.
N1 - Publisher Copyright: Copyright © 2019 American Chemical Society.
PY - 2019/11/12
Y1 - 2019/11/12
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=85074492235&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85074492235&partnerID=8YFLogxK
U2 - 10.1021/acs.macromol.9b01923
DO - 10.1021/acs.macromol.9b01923
M3 - Article
SN - 0024-9297
VL - 52
SP - 8295
EP - 8304
JO - Macromolecules
JF - Macromolecules
IS - 21
ER -