Structural evolution of polylactide molecular bottlebrushes: Kinetics study by size exclusion chromatography, small angle neutron scattering, and simulations

Suk Kyun Ahn; Jan Michael Y. Carrillo; Youngkyu Han; Tae Hwan Kim; David Uhrig; Deanna L. Pickel; Kunlun Hong; S. Michael Kilbey; Bobby G. Sumpter; Gregory S. Smith; Changwoo Do

doi:10.1021/mz5003454

Structural evolution of polylactide molecular bottlebrushes: Kinetics study by size exclusion chromatography, small angle neutron scattering, and simulations

Suk Kyun Ahn, Jan Michael Y. Carrillo, Youngkyu Han, Tae Hwan Kim, David Uhrig, Deanna L. Pickel, Kunlun Hong, S. Michael Kilbey, Bobby G. Sumpter, Gregory S. Smith, Changwoo Do

Research output: Contribution to journal › Article › peer-review

27 Scopus citations

Abstract

Structural evolution from poly(lactide) (PLA) macromonomer to resultant PLA molecular bottlebrush during ring opening metathesis polymerization (ROMP) was investigated for the first time by combining size exclusion chromatography (SEC), small-angle neutron scattering (SANS), and coarse-grained molecular dynamics (CG-MD) simulations. Multiple aliquots were collected at various reaction times during ROMP and subsequently analyzed by SEC and SANS. These complementary techniques enable the understanding of systematic changes in conversion, molecular weight and dispersity as well as structural details of PLA molecular bottlebrushes. CG-MD simulation not only predicts the experimental observations, but it also provides further insight into the analysis and interpretation of data obtained in SEC and SANS experiments. We find that PLA molecular bottlebrushes undergo three conformational transitions with increasing conversion (i.e., increasing the backbone length): (1) from an elongated to a globular shape due to longer side chain at low conversion, (2) from a globular to an elongated shape at intermediate conversion caused by excluded volume of PLA side chain, and (3) the saturation of contour length at high conversion due to chain transfer reactions.

Original language	English
Pages (from-to)	862-866
Number of pages	5
Journal	ACS Macro Letters
Volume	3
Issue number	9
DOIs	https://doi.org/10.1021/mz5003454
State	Published - Sep 16 2014

Bibliographical note

Publisher Copyright:
© 2014 American Chemical Society.

Funding

Funders	Funder number
Ministry of Science ICT and Future Planning
U.S. Department of Energy

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10.1021/mz5003454

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Ahn, S. K., Carrillo, J. M. Y., Han, Y., Kim, T. H., Uhrig, D., Pickel, D. L., Hong, K., Kilbey, S. M., Sumpter, B. G., Smith, G. S., & Do, C. (2014). Structural evolution of polylactide molecular bottlebrushes: Kinetics study by size exclusion chromatography, small angle neutron scattering, and simulations. ACS Macro Letters, 3(9), 862-866. https://doi.org/10.1021/mz5003454

@article{b3e00c6fc6304cf3bc7a0c9c33d1e4a4,

title = "Structural evolution of polylactide molecular bottlebrushes: Kinetics study by size exclusion chromatography, small angle neutron scattering, and simulations",

abstract = "Structural evolution from poly(lactide) (PLA) macromonomer to resultant PLA molecular bottlebrush during ring opening metathesis polymerization (ROMP) was investigated for the first time by combining size exclusion chromatography (SEC), small-angle neutron scattering (SANS), and coarse-grained molecular dynamics (CG-MD) simulations. Multiple aliquots were collected at various reaction times during ROMP and subsequently analyzed by SEC and SANS. These complementary techniques enable the understanding of systematic changes in conversion, molecular weight and dispersity as well as structural details of PLA molecular bottlebrushes. CG-MD simulation not only predicts the experimental observations, but it also provides further insight into the analysis and interpretation of data obtained in SEC and SANS experiments. We find that PLA molecular bottlebrushes undergo three conformational transitions with increasing conversion (i.e., increasing the backbone length): (1) from an elongated to a globular shape due to longer side chain at low conversion, (2) from a globular to an elongated shape at intermediate conversion caused by excluded volume of PLA side chain, and (3) the saturation of contour length at high conversion due to chain transfer reactions.",

author = "Ahn, {Suk Kyun} and Carrillo, {Jan Michael Y.} and Youngkyu Han and Kim, {Tae Hwan} and David Uhrig and Pickel, {Deanna L.} and Kunlun Hong and Kilbey, {S. Michael} and Sumpter, {Bobby G.} and Smith, {Gregory S.} and Changwoo Do",

note = "Publisher Copyright: {\textcopyright} 2014 American Chemical Society.",

year = "2014",

month = sep,

day = "16",

doi = "10.1021/mz5003454",

language = "English",

volume = "3",

pages = "862--866",

journal = "ACS Macro Letters",

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AU - Ahn, Suk Kyun

AU - Carrillo, Jan Michael Y.

AU - Han, Youngkyu

AU - Kim, Tae Hwan

AU - Uhrig, David

AU - Pickel, Deanna L.

AU - Hong, Kunlun

AU - Kilbey, S. Michael

AU - Sumpter, Bobby G.

AU - Smith, Gregory S.

AU - Do, Changwoo

PY - 2014/9/16

Y1 - 2014/9/16

N2 - Structural evolution from poly(lactide) (PLA) macromonomer to resultant PLA molecular bottlebrush during ring opening metathesis polymerization (ROMP) was investigated for the first time by combining size exclusion chromatography (SEC), small-angle neutron scattering (SANS), and coarse-grained molecular dynamics (CG-MD) simulations. Multiple aliquots were collected at various reaction times during ROMP and subsequently analyzed by SEC and SANS. These complementary techniques enable the understanding of systematic changes in conversion, molecular weight and dispersity as well as structural details of PLA molecular bottlebrushes. CG-MD simulation not only predicts the experimental observations, but it also provides further insight into the analysis and interpretation of data obtained in SEC and SANS experiments. We find that PLA molecular bottlebrushes undergo three conformational transitions with increasing conversion (i.e., increasing the backbone length): (1) from an elongated to a globular shape due to longer side chain at low conversion, (2) from a globular to an elongated shape at intermediate conversion caused by excluded volume of PLA side chain, and (3) the saturation of contour length at high conversion due to chain transfer reactions.

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Structural evolution of polylactide molecular bottlebrushes: Kinetics study by size exclusion chromatography, small angle neutron scattering, and simulations

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