TY - JOUR
T1 - Thermoresponsive polymer assemblies via variable temperature liquid-phase transmission electron microscopy and small angle X-ray scattering
AU - Korpanty, Joanna
AU - Parent, Lucas R.
AU - Hampu, Nicholas
AU - Weigand, Steven
AU - Gianneschi, Nathan C.
N1 - Funding Information:
Research in the N.C.G. group was conducted with government support under and awarded by DoD through the ARO (W911NF-17-1-0326) and a MURI grant (W911NF-15-1-0568). In addition, the authors thank the NSF for support of both the L.R.P and N.C.G. groups through a joint research grant (CHE-MSN 1905270). This research used EPIC facility of Northwestern University’s NUANCE Center, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205), the MRSEC program (NSF DMR1720139) at the Materials Research Center; the International Institute for Nanotechnology (IIN), the Keck Foundation, and the State of Illinois, through the IIN. This work also made use of the IMSERC at Northwestern University, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205); the State of Illinois and International Institute for Nanotechnology (IIN). Research reported in this publication was supported in part by instrumentation provided by the Office of The Director, National Institutes of Health of the National Institutes of Health under Award Number S10OD026871. The content is solely the responsibility of the authors and does not necessarily represent the official views of the National Institutes of Health. Use of the Advanced Photon Source (APS) at Argonne National Laboratory was supported by the U.S. Department of Energy, Office of Science, under Contract DE-AC02-06CH11357. SAXS measurements were performed at the DuPont-Northwestern-Dow Collaborative Access Team (DND-CAT) located at Sector 5 of the APS, supported by E. I. DuPont de Nemours and Co., The Dow Chemical Company, and Northwestern University. J.K. gratefully acknowledges support from the Ryan Fellowship and the International Institute for Nanotechnology at Northwestern University.
Publisher Copyright:
© 2021, The Author(s).
PY - 2021/12
Y1 - 2021/12
N2 - Herein, phase transitions of a class of thermally-responsive polymers, namely a homopolymer, diblock, and triblock copolymer, were studied to gain mechanistic insight into nanoscale assembly dynamics via variable temperature liquid-cell transmission electron microscopy (VT-LCTEM) correlated with variable temperature small angle X-ray scattering (VT-SAXS). We study thermoresponsive poly(diethylene glycol methyl ether methacrylate) (PDEGMA)-based block copolymers and mitigate sample damage by screening electron flux and solvent conditions during LCTEM and by evaluating polymer survival via post-mortem matrix-assisted laser desorption/ionization imaging mass spectrometry (MALDI-IMS). Our multimodal approach, utilizing VT-LCTEM with MS validation and VT-SAXS, is generalizable across polymeric systems and can be used to directly image solvated nanoscale structures and thermally-induced transitions. Our strategy of correlating VT-SAXS with VT-LCTEM provided direct insight into transient nanoscale intermediates formed during the thermally-triggered morphological transformation of a PDEGMA-based triblock. Notably, we observed the temperature-triggered formation and slow relaxation of core-shell particles with complex microphase separation in the core by both VT-SAXS and VT-LCTEM.
AB - Herein, phase transitions of a class of thermally-responsive polymers, namely a homopolymer, diblock, and triblock copolymer, were studied to gain mechanistic insight into nanoscale assembly dynamics via variable temperature liquid-cell transmission electron microscopy (VT-LCTEM) correlated with variable temperature small angle X-ray scattering (VT-SAXS). We study thermoresponsive poly(diethylene glycol methyl ether methacrylate) (PDEGMA)-based block copolymers and mitigate sample damage by screening electron flux and solvent conditions during LCTEM and by evaluating polymer survival via post-mortem matrix-assisted laser desorption/ionization imaging mass spectrometry (MALDI-IMS). Our multimodal approach, utilizing VT-LCTEM with MS validation and VT-SAXS, is generalizable across polymeric systems and can be used to directly image solvated nanoscale structures and thermally-induced transitions. Our strategy of correlating VT-SAXS with VT-LCTEM provided direct insight into transient nanoscale intermediates formed during the thermally-triggered morphological transformation of a PDEGMA-based triblock. Notably, we observed the temperature-triggered formation and slow relaxation of core-shell particles with complex microphase separation in the core by both VT-SAXS and VT-LCTEM.
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U2 - 10.1038/s41467-021-26773-z
DO - 10.1038/s41467-021-26773-z
M3 - Article
C2 - 34772926
AN - SCOPUS:85118972878
SN - 2041-1723
VL - 12
JO - Nature Communications
JF - Nature Communications
IS - 1
M1 - 6568
ER -