Sequence Effects on Block Copolymer Self-Assembly through Tuning Chain Conformation and Segregation Strength Utilizing Sequence-Defined Polypeptoids

Patterson, Anastasia L.; Danielsen, Scott P.  O.; Yu, Beihang; Davidson, Emily C.; Fredrickson, Glenn H.; Segalman, Rachel A.

doi:10.1021/acs.macromol.8b02298

Sequence Effects on Block Copolymer Self-Assembly through Tuning Chain Conformation and Segregation Strength Utilizing Sequence-Defined Polypeptoids

Journal Article · Thu Jan 31 04:00:00 EST 2019 · Macromolecules

DOI:https://doi.org/10.1021/acs.macromol.8b02298· OSTI ID:1495447

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Univ. of California, Santa Barbara, CA (United States)

Polymers with sequence control offer the possibility of tuning segregation strength with comonomer sequence instead of chemical identity. In this work, we have synthesized polystyrene-$$b$$-polypeptoid diblock copolymers that differ only in the sequence of comonomers in the polypeptoid block, where nonpolar phenyl side chains are incorporated to tune compatibility with polystyrene. Using small-angle X-ray scattering, we see that these materials readily self-assemble into lamellae, with domain spacings and order–disorder transition temperatures varying with sequence, despite identical composition. The ordered state is likely governed by chain conformational effects that localize compatibilizing comonomers at the block–block interface. These altered chain conformations are supported by simulations with self-consistent field theory (SCFT) and lead to the observed changes in domain spacing. However, the trends seen in the order–disorder transition are not captured by SCFT simulations or effective $$χ$$ parameters, measured in the disordered phase by approximating the copolypeptoid as a uniform block. The disagreement between measured thermodynamic properties and coarse-grained approaches like SCFT and effective $$χ$$ points to the importance of molecular-scale effects in sequence-defined materials. Additionally, a reversal in relative disordering temperatures between forward and inverse taper sequences is observed compared to previous studies, likely due to a combination of sequence definition at the monomer length scale and the use of a “styrene-like” compatibilizing side chain rather than a true polystyrene repeat unit. These results demonstrate that comonomer sequence tunes chain conformation and segregation strength, suggesting that sequence design could be used to target desired properties and morphologies in block copolymer materials while retaining important chemical functionalities.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS); SLAC National Accelerator Laboratory, Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL); Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC02-05CH11231; AC02-76SF00515; SC0012704; AC02-06CH11357

OSTI ID:: 1495447

Alternate ID(s):: OSTI ID: 1688507

Journal Information:: Macromolecules, Journal Name: Macromolecules Journal Issue: 3 Vol. 52; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: ENGLISH

References (48)

Sequence Control in Polymer Chemistry through the Passerini Three-Component Reaction Solleder, Susanne C.; Meier, Michael A. R. Angewandte Chemie International Edition, Vol. 53, Issue 3 https://doi.org/10.1002/anie.201308960	journal	December 2013
Tailored Polymer Microstructures Prepared by Atom Transfer Radical Copolymerization of Styrene and N-substituted Maleimides Lutz, Jean-François; Schmidt, Bernhard V. K. . J.; Pfeifer, Sebastian Macromolecular Rapid Communications, Vol. 32, Issue 2 https://doi.org/10.1002/marc.201000664	journal	January 2011
Improved numerical algorithm for exploring block copolymer mesophases Rasmussen, K. �.; Kalosakas, G. Journal of Polymer Science Part B: Polymer Physics, Vol. 40, Issue 16 https://doi.org/10.1002/polb.10238	journal	July 2002
Breadth of glass transition temperature in styrene/acrylic acid block, random, and gradient copolymers: Unusual sequence distribution effects: Breadth of T _g in S/AA Copolymers Wong, Christopher L. H.; Kim, Jungki; Torkelson, John M. Journal of Polymer Science Part B: Polymer Physics, Vol. 45, Issue 20 https://doi.org/10.1002/polb.21296	journal	August 2007
Microphase separation in block-random copolymers of styrene, 4-acetoxystyrene, and 4-hydroxystyrene: Microphase Separation in Block-Random Copolymers Quinn, Jeffrey D.; Register, Richard A. Journal of Polymer Science Part B: Polymer Physics, Vol. 47, Issue 21 https://doi.org/10.1002/polb.21807	journal	September 2009
Chiral N-substituted glycines can form stable helical conformations Armand, Philippe; Kirshenbaum, Kent; Falicov, Alexis Folding and Design, Vol. 2, Issue 6 https://doi.org/10.1016/S1359-0278(97)00051-5	journal	December 1997
Morphology and Proton Transport in Humidified Phosphonated Peptoid Block Copolymers Sun, Jing; Jiang, Xi; Siegmund, Aaron Macromolecules, Vol. 49, Issue 8 https://doi.org/10.1021/acs.macromol.6b00353	journal	April 2016
Synthesis of Monodisperse Sequence-Coded Polymers with Chain Lengths above DP100 Al Ouahabi, Abdelaziz; Kotera, Mitsuharu; Charles, Laurence ACS Macro Letters, Vol. 4, Issue 10 https://doi.org/10.1021/acsmacrolett.5b00606	journal	September 2015
Efficient method for the preparation of peptoids [oligo(N-substituted glycines)] by submonomer solid-phase synthesis Zuckermann, Ronald N.; Kerr, Janice M.; Kent, Stephen B. H. Journal of the American Chemical Society, Vol. 114, Issue 26 https://doi.org/10.1021/ja00052a076	journal	December 1992
Hierarchical Self-Assembly of a Biomimetic Diblock Copolypeptoid into Homochiral Superhelices Murnen, Hannah K.; Rosales, Adrianne M.; Jaworski, Jonathan N. Journal of the American Chemical Society, Vol. 132, Issue 45 https://doi.org/10.1021/ja106340f	journal	November 2010
Nanoscale Phase Separation in Sequence-Defined Peptoid Diblock Copolymers Sun, Jing; Teran, Alexander A.; Liao, Xunxun Journal of the American Chemical Society, Vol. 135, Issue 38 https://doi.org/10.1021/ja404233d	journal	September 2013
Crystallization in Sequence-Defined Peptoid Diblock Copolymers Induced by Microphase Separation Sun, Jing; Teran, Alexander A.; Liao, Xunxun Journal of the American Chemical Society, Vol. 136, Issue 5 https://doi.org/10.1021/ja412123y	journal	January 2014
Morphology-Conductivity Relationship in Crystalline and Amorphous Sequence-Defined Peptoid Block Copolymer Electrolytes Sun, Jing; Liao, Xunxun; Minor, Andrew M. Journal of the American Chemical Society, Vol. 136, Issue 42 https://doi.org/10.1021/ja5080689	journal	October 2014
A General Approach to Sequence-Controlled Polymers Using Macrocyclic Ring Opening Metathesis Polymerization Gutekunst, Will R.; Hawker, Craig J. Journal of the American Chemical Society, Vol. 137, Issue 25 https://doi.org/10.1021/jacs.5b04940	journal	June 2015
Iterative Exponential Growth Synthesis and Assembly of Uniform Diblock Copolymers Jiang, Yivan; Golder, Matthew R.; Nguyen, Hung V. -T. Journal of the American Chemical Society, Vol. 138, Issue 30 https://doi.org/10.1021/jacs.6b04964	journal	July 2016
A Peptoid Square Helix via Synergistic Control of Backbone Dihedral Angles Gorske, Benjamin C.; Mumford, Emily M.; Gerrity, Charles G. Journal of the American Chemical Society, Vol. 139, Issue 24 https://doi.org/10.1021/jacs.7b02319	journal	June 2017
Universal Relationship between Molecular Structure and Crystal Structure in Peptoid Polymers and Prevalence of the cis Backbone Conformation Greer, Douglas R.; Stolberg, Michael A.; Kundu, Joyjit Journal of the American Chemical Society, Vol. 140, Issue 2 https://doi.org/10.1021/jacs.7b11891	journal	January 2018
Introducing Variable Cell Shape Methods in Field Theory Simulations of Polymers ^† Barrat, Jean-Louis; Fredrickson, Glenn H.; Sides, Scott W. The Journal of Physical Chemistry B, Vol. 109, Issue 14 https://doi.org/10.1021/jp0455529	journal	April 2005
Interfacial Manipulations: Controlling Nanoscale Assembly in Bulk, Thin Film, and Solution Block Copolymer Systems Mastroianni, Sarah E.; Epps, Thomas H. Langmuir, Vol. 29, Issue 12 https://doi.org/10.1021/la304800t	journal	February 2013
Polymer Blend Compatibilization by Gradient Copolymer Addition during Melt Processing: Stabilization of Dispersed Phase to Static Coarsening Kim, Jungki; Gray, Maisha K.; Zhou, Hongying Macromolecules, Vol. 38, Issue 4 https://doi.org/10.1021/ma047549t	journal	February 2005
Synthesis and Crystallization of Precision ADMET Polyolefins Containing Halogens Boz, Emine; Wagener, Kenneth B.; Ghosal, Anindya Macromolecules, Vol. 39, Issue 13 https://doi.org/10.1021/ma0605088	journal	June 2006
Styrene/Butadiene Gradient Block Copolymers: Molecular and Mesoscopic Structures Jouenne, Stéphane; González-León, Juan A.; Ruzette, Anne-Valérie Macromolecules, Vol. 40, Issue 7 https://doi.org/10.1021/ma062723u	journal	April 2007
Synthesis and Morphology of Well-Defined Poly(ethylene- co -acrylic acid) Copolymers Baughman, Travis W.; Chan, Christopher D.; Winey, Karen I. Macromolecules, Vol. 40, Issue 18 https://doi.org/10.1021/ma070841r	journal	September 2007
Control of Crystallization and Melting Behavior in Sequence Specific Polypeptoids Rosales, Adrianne M.; Murnen, Hannah K.; Zuckermann, Ronald N. Macromolecules, Vol. 43, Issue 13 https://doi.org/10.1021/ma1002563	journal	July 2010
Double-Gyroid Network Morphology in Tapered Diblock Copolymers Roy, Raghunath; Park, Jong Keun; Young, Wen-Shiue Macromolecules, Vol. 44, Issue 10 https://doi.org/10.1021/ma1025847	journal	May 2011
Synthesis and Phase Behavior of Block-Random Copolymers of Styrene and Hydrogenated Isoprene Beckingham, Bryan S.; Register, Richard A. Macromolecules, Vol. 44, Issue 11 https://doi.org/10.1021/ma200913k	journal	June 2011
Effect of Architecture on the Phase Behavior of AB-Type Block Copolymer Melts Matsen, M. W. Macromolecules, Vol. 45, Issue 4 https://doi.org/10.1021/ma202782s	journal	February 2012
Tunable Phase Behavior of Polystyrene–Polypeptoid Block Copolymers Rosales, Adrianne M.; McCulloch, Bryan L.; Zuckermann, Ronald N. Macromolecules, Vol. 45, Issue 15 https://doi.org/10.1021/ma300625b	journal	July 2012
Impact of Hydrophobic Sequence Patterning on the Coil-to-Globule Transition of Protein-like Polymers Murnen, Hannah K.; Khokhlov, Alexei R.; Khalatur, Pavel G. Macromolecules, Vol. 45, Issue 12 https://doi.org/10.1021/ma300707t	journal	June 2012
Blockiness and Sequence Polydispersity Effects on the Phase Behavior and Interfacial Properties of Gradient Copolymers Ganesan, Venkat; Kumar, N. Arun; Pryamitsyn, Victor Macromolecules, Vol. 45, Issue 15 https://doi.org/10.1021/ma301136y	journal	July 2012
Effect of Tapering on Morphology and Interfacial Behavior of Diblock Copolymers from Molecular Dynamics Simulations Seo, Youngmi; Brown, Jonathan R.; Hall, Lisa M. Macromolecules, Vol. 48, Issue 14 https://doi.org/10.1021/ma502309h	journal	July 2015
Theory of Microphase Separation in Block Copolymers Leibler, Ludwik Macromolecules, Vol. 13, Issue 6 https://doi.org/10.1021/ma60078a047	journal	November 1980
Effect of Comonomer Sequence Distribution on the Adsorption of Random Copolymers onto Impenetrable Flat Surfaces Jhon, Young K.; Semler, James J.; Genzer, Jan Macromolecules, Vol. 42, Issue 7 https://doi.org/10.1021/ma8027936	journal	April 2009
Facile Synthesis of Functional Periodic Copolymers: A Step toward Polymer-Based Molecular Arrays. Berthet, Marie-Alix; Zarafshani, Zoya; Pfeifer, Sebastian Macromolecules, Vol. 43, Issue 1 https://doi.org/10.1021/ma902075q	journal	December 2009
Unifying Weak- and Strong-Segregation Block Copolymer Theories Matsen, M. W.; Bates, F. S. Macromolecules, Vol. 29, Issue 4 https://doi.org/10.1021/ma951138i	journal	January 1996
Iterative exponential growth of stereo- and sequence-controlled polymers Barnes, Jonathan C.; Ehrlich, Deborah J. C.; Gao, Angela X. Nature Chemistry, Vol. 7, Issue 10 https://doi.org/10.1038/nchem.2346	journal	September 2015
Free-floating ultrathin two-dimensional crystals from sequence-specific peptoid polymers Nam, Ki Tae; Shelby, Sarah A.; Choi, Philip H. Nature Materials, Vol. 9, Issue 5 https://doi.org/10.1038/nmat2742	journal	April 2010
Sequence and entropy-based control of complex coacervates Chang, Li-Wei; Lytle, Tyler K.; Radhakrishna, Mithun Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/s41467-017-01249-1	journal	November 2017
RAFT-mediated, visible light-initiated single unit monomer insertion and its application in the synthesis of sequence-defined polymers Fu, Changkui; Huang, Zixuan; Hawker, Craig J. Polymer Chemistry, Vol. 8, Issue 32 https://doi.org/10.1039/C7PY00713B	journal	January 2017
Manipulating ordering transitions in interfacially modified block copolymers Singh, Nripen; Tureau, Maëva S.; Epps, III, Thomas H. Soft Matter, Vol. 5, Issue 23 https://doi.org/10.1039/b908739g	journal	January 2009
Determination of the persistence length of helical and non-helical polypeptoids in solution Rosales, Adrianne M.; Murnen, Hannah K.; Kline, Steven R. Soft Matter, Vol. 8, Issue 13 https://doi.org/10.1039/c2sm07092h	journal	January 2012
Polypeptoids: a model system to study the effect of monomer sequence on polymer properties and self-assembly Rosales, Adrianne M.; Segalman, Rachel A.; Zuckermann, Ronald N. Soft Matter, Vol. 9, Issue 35 https://doi.org/10.1039/c3sm51421h	journal	January 2013
A SAXS/WAXS/GISAXS Beamline with Multilayer Monochromator Hexemer, Alexander; Bras, Wim; Glossinger, James Journal of Physics: Conference Series, Vol. 247 https://doi.org/10.1088/1742-6596/247/1/012007	journal	October 2010
Efficient computation of the structural phase behavior of block copolymers Tzeremes, G.; Rasmussen, K. Ø.; Lookman, T. Physical Review E, Vol. 65, Issue 4 https://doi.org/10.1103/PhysRevE.65.041806	journal	April 2002
Nika : software for two-dimensional data reduction Ilavsky, Jan Journal of Applied Crystallography, Vol. 45, Issue 2 https://doi.org/10.1107/S0021889812004037	journal	March 2012
Numerical Solution of Polymer Self-Consistent Field Theory Ceniceros, Hector D.; Fredrickson, Glenn H. Multiscale Modeling & Simulation, Vol. 2, Issue 3 https://doi.org/10.1137/030601338	journal	January 2004
Stability of dense hydrophobic-polar copolymer globules: Regular, random and designed sequences Govorun, E. N.; Khokhlov, A. R.; Semenov, A. N. The European Physical Journal E, Vol. 12, Issue 2 https://doi.org/10.1140/epje/i2003-10057-y	journal	October 2003
Structure and Properties of Tapered Block Polymers of Styrene and Isoprene Tsukahara, Yasuhisa; Nakamura, Norikazu; Hashimoto, Takeji Polymer Journal, Vol. 12, Issue 7 https://doi.org/10.1295/polymj.12.455	journal	July 1980

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Recent advances in crystallization and self‐assembly of polypeptoid polymers Zeng, Guangjian; Qiu, Lu; Wen, Tao POLYMER CRYSTALLIZATION, Vol. 2, Issue 3 https://doi.org/10.1002/pcr2.10065	journal	June 2019
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Micro- to macro-phase separation transition in sequence-defined coacervates Sing, Charles E. The Journal of Chemical Physics, Vol. 152, Issue 2 https://doi.org/10.1063/1.5140756	journal	January 2020