Multiscale Crystalline Structure of Confined Polypeptoid Films: The Effect of Alkyl Side Chain Branching

Wang, Qi; Kang, Liying; Xu, Xiangyu; Zhang, Meng; Chao, Albert; Chen, Jianxia; Han, Zhijing; Yu, Huihui; Li, Ruipeng; Zhao, Yixin; Zhang, Donghui; Jiang, Naisheng

doi:10.1021/acsmacrolett.2c00271

Title: Multiscale Crystalline Structure of Confined Polypeptoid Films: The Effect of Alkyl Side Chain Branching

Journal Article · Wed Aug 17 00:00:00 EDT 2022 · ACS Macro Letters

DOI:https://doi.org/10.1021/acsmacrolett.2c00271· OSTI ID:1890208

Wang, Qi ^[1]; Kang, Liying ^[1]; Xu, Xiangyu ^[1];

^[2]; Chao, Albert ^[2]; Chen, Jianxia ^[1]; Han, Zhijing ^[1]; Yu, Huihui ^[1]; Li, Ruipeng ^[3]; Zhao, Yixin ^[4];

^[2];

^[1]

Univ. of Science and Technology, Beijing (China)
Louisiana State Univ., Baton Rouge, LA (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States)
China Univ. of Mining and Technology, Beijing (China)

Here we report the effect of alkyl side chain branching on melt-recrystallization of nanoconfined polypeptoid films using poly(N-octyl glycine) (PNOG) and poly(N-2-ethyl-1-hexyl glycine) (PNEHG) as model systems. Upon cooling from the isotropic melt, confined PNOG molecules recrystallize into a near-perfect orthorhombic crystal structure with the board-like molecules stacked face-to-face in the substrate-parallel direction, resulting in long-range ordered wormlike lamellae that occupy the entire film. By contrast, rod-like PNEHG molecules bearing branched N-2-ethyl-1-hexyl side chains stack into a columnar hexagonal mesophase with their backbones oriented parallel to the substrates, forming micron-sized sheaf-like superstructures under confinement, exposing large areas of empty spaces in the film. These findings highlight the effect of alkyl side chain branching on the packing motif and multiscale crystalline structure of polypeptoids under a nanoconfined geometry.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Natural Science Foundation of China (NSFC); National Science Foundation (NSF); Fundamental Research Funds for the Central Universities

Grant/Contract Number:: SC0012704; 52073025; CHE 1609447; 2003458; FRF-IDRY-20-003

OSTI ID:: 1890208

Report Number(s):: BNL-223514-2022-JAAM

Journal Information:: ACS Macro Letters, Vol. 11, Issue 9; ISSN 2161-1653

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (41)

Polymer crystallization in quasi-two dimensions. I. Experimental results Reiter, Günter; Sommer, Jens-Uwe The Journal of Chemical Physics, Vol. 112, Issue 9 https://doi.org/10.1063/1.480984	journal	March 2000
Self-assembly of crystalline nanotubes from monodisperse amphiphilic diblock copolypeptoid tiles Sun, Jing; Jiang, Xi; Lund, Reidar Proceedings of the National Academy of Sciences, Vol. 113, Issue 15 https://doi.org/10.1073/pnas.1517169113	journal	March 2016
Crystallization and Melting Behaviors of Cyclic and Linear Polypeptoids with Alkyl Side Chains Lee, Chang-Uk; Li, Ang; Ghale, Kushal Macromolecules, Vol. 46, Issue 20 https://doi.org/10.1021/ma401067f	journal	October 2013
Modulating the Molecular Geometry and Solution Self-Assembly of Amphiphilic Polypeptoid Block Copolymers by Side Chain Branching Pattern Kang, Liying; Chao, Albert; Zhang, Meng Journal of the American Chemical Society, Vol. 143, Issue 15 https://doi.org/10.1021/jacs.1c01088	journal	April 2021
Synthesis and Characterization of Amphiphilic Cyclic Diblock Copolypeptoids from N -Heterocyclic Carbene-Mediated Zwitterionic Polymerization of N -Substituted N -Carboxyanhydride Lee, Chang-Uk; Smart, Thomas P.; Guo, Li Macromolecules, Vol. 44, Issue 24 https://doi.org/10.1021/ma2020936	journal	December 2011
X-ray Diffraction Studies of Multiple Orientation in Poly(9,9-bis(2-ethylhexyl)fluorene-2,7-diyl) Thin Films Knaapila, Matti; Lyons, Benjamin P.; Kisko, Kaisa The Journal of Physical Chemistry B, Vol. 107, Issue 45 https://doi.org/10.1021/jp035259t	journal	October 2003
Tuning Polythiophene Crystallization through Systematic Side Chain Functionalization Ho, Victor; Boudouris, Bryan W.; Segalman, Rachel A. Macromolecules, Vol. 43, Issue 19 https://doi.org/10.1021/ma101697m	journal	October 2010
Synthesis and Characterization of Cleavable Core-Cross-Linked Micelles Based on Amphiphilic Block Copolypeptoids as Smart Drug Carriers Li, Ang; Zhang, Donghui Biomacromolecules, Vol. 17, Issue 3 https://doi.org/10.1021/acs.biomac.5b01561	journal	February 2016
Diblock copolypeptoids: a review of phase separation, crystallization, self-assembly and biological applications Xuan, Sunting; Zuckermann, Ronald N. Journal of Materials Chemistry B, Vol. 8, Issue 25 https://doi.org/10.1039/D0TB00477D	journal	January 2020
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
New Peptidomimetic Polymers for Antifouling Surfaces Statz, Andrea R.; Meagher, Robert J.; Barron, Annelise E. Journal of the American Chemical Society, Vol. 127, Issue 22 https://doi.org/10.1021/ja0522534	journal	June 2005
Polypeptoid polymers: Synthesis, characterization, and properties Chan, Brandon A.; Xuan, Sunting; Li, Ang Biopolymers, Vol. 109, Issue 1 https://doi.org/10.1002/bip.23070	journal	October 2017
Crystallization-Driven Self-Assembly of Metallo-Polyelectrolyte Block Copolymers with a Polycaprolactone Core-Forming Segment Cha, Yujin; Jarrett-Wilkins, Charles; Rahman, Md Anisur ACS Macro Letters, Vol. 8, Issue 7 https://doi.org/10.1021/acsmacrolett.9b00335	journal	June 2019
Polymersomes with aggregation-induced emission based on amphiphilic block copolypeptoids Tao, Xinfeng; Chen, Hui; Trépout, Sylvain Chemical Communications, Vol. 55, Issue 90 https://doi.org/10.1039/C9CC07501A	journal	January 2019
Melting Behavior of Poly(3-(2′-ethyl)hexylthiophene) Beckingham, Bryan S.; Ho, Victor; Segalman, Rachel A. Macromolecules, Vol. 47, Issue 23 https://doi.org/10.1021/ma501915v	journal	November 2014
Imaging Unstained Synthetic Polymer Crystals and Defects on Atomic Length Scales Using Cryogenic Electron Microscopy Jiang, Xi; Greer, Douglas R.; Kundu, Joyjit Macromolecules, Vol. 51, Issue 19 https://doi.org/10.1021/acs.macromol.8b01508	journal	September 2018
Protein, cell and bacterial fouling resistance of polypeptoid-modified surfaces: effect of side-chain chemistry Statz, Andrea R.; Barron, Annelise E.; Messersmith, Phillip B. Soft Matter, Vol. 4, Issue 1 https://doi.org/10.1039/B711944E	journal	January 2008
50th Anniversary Perspective : Polymer Crystals and Crystallization: Personal Journeys in a Challenging Research Field Lotz, Bernard; Miyoshi, Toshikazu; Cheng, Stephen Z. D. Macromolecules, Vol. 50, Issue 16 https://doi.org/10.1021/acs.macromol.7b00907	journal	August 2017
Structural Analysis of Block Copolymer Thin Films with Grazing Incidence Small-Angle X-ray Scattering Lee, Byeongdu; Park, Insun; Yoon, Jinhwan Macromolecules, Vol. 38, Issue 10 https://doi.org/10.1021/ma047562d	journal	May 2005
Structure and Morphology in Highly Oriented Films of Poly(9,9-bis(n-octyl)fluorene-2,7-diyl) and Poly(9,9-bis(2-ethylhexyl)fluorene-2,7-diyl) Grown on Friction Transferred Poly(tetrafluoroethylene) Brinkmann, Martin; Charoenthai, Nipaphat; Traiphol, Rakchart Macromolecules, Vol. 42, Issue 21 https://doi.org/10.1021/ma901623s	journal	November 2009
Surface-Grafted Polysarcosine as a Peptoid Antifouling Polymer Brush Lau, King Hang Aaron; Ren, Chunlai; Sileika, Tadas S. Langmuir, Vol. 28, Issue 46 https://doi.org/10.1021/la302131n	journal	November 2012
Uniform, Large-Area, Highly Ordered Peptoid Monolayer and Bilayer Films for Sensing Applications Murray, Daniel J.; Kim, Jae Hong; Grzincic, Elissa M. Langmuir, Vol. 35, Issue 42 https://doi.org/10.1021/acs.langmuir.9b02557	journal	September 2019
Crystallization-Driven Two-Dimensional Nanosheet from Hierarchical Self-Assembly of Polypeptoid-Based Diblock Copolymers Shi, Zhekun; Wei, Yuhan; Zhu, Chenhui Macromolecules, Vol. 51, Issue 16 https://doi.org/10.1021/acs.macromol.8b00986	journal	August 2018
Direct Observation of Growth of Lamellae and Spherulites of a Semicrystalline Polymer by AFM Li, Lin; Chan, Chi-Ming; Yeung, King Lun Macromolecules, Vol. 34, Issue 2 https://doi.org/10.1021/ma000273e	journal	December 2000
Liquid-Crystalline Phase Behavior in Polypeptoid Diblock Copolymers Greer, Douglas R.; Stolberg, Michael A.; Xuan, Sunting Macromolecules, Vol. 51, Issue 23 https://doi.org/10.1021/acs.macromol.8b01952	journal	November 2018
Confined Crystallization within Cylindrical P3EHT Block Copolymer Microdomains Davidson, Emily C.; Segalman, Rachel A. Macromolecules, Vol. 50, Issue 16 https://doi.org/10.1021/acs.macromol.7b01323	journal	August 2017
Crystallization and morphology of ultrathin films of homopolymers and polymer blends Prud’homme, Robert E. Progress in Polymer Science, Vol. 54-55 https://doi.org/10.1016/j.progpolymsci.2015.11.001	journal	March 2016
Bioinspired Peptoid Nanotubes for Targeted Tumor Cell Imaging and Chemo‐Photodynamic Therapy Luo, Yanan; Song, Yang; Wang, Mingming Small, Vol. 15, Issue 43 https://doi.org/10.1002/smll.201902485	journal	August 2019
Cationic Polypeptoids with Optimized Molecular Characteristics toward Efficient Nonviral Gene Delivery Zhu, Lipeng; Simpson, Jessica M.; Xu, Xin ACS Applied Materials & Interfaces, Vol. 9, Issue 28 https://doi.org/10.1021/acsami.7b06031	journal	July 2017
Polymer spherulites: A critical review Crist, Buckley; Schultz, Jerold M. Progress in Polymer Science, Vol. 56 https://doi.org/10.1016/j.progpolymsci.2015.11.006	journal	May 2016
Substrate Effect on the Melting Temperature of Thin Polyethylene Films Wang, Y.; Rafailovich, M.; Sokolov, J. Physical Review Letters, Vol. 96, Issue 2 https://doi.org/10.1103/PhysRevLett.96.028303	journal	January 2006
Bestimmung der inneren Struktur und der Größe von Kolloidteilchen mittels Röntgenstrahlen Scherrer, P. Kolloidchemie Ein Lehrbuch https://doi.org/10.1007/978-3-662-33915-2_7	book	January 1912
Polymer crystallization of ultrathin films on solid substrates Liu, Yi-Xin; Chen, Er-Qiang Coordination Chemistry Reviews, Vol. 254, Issue 9-10 https://doi.org/10.1016/j.ccr.2010.02.017	journal	May 2010
What Controls the Lamellar Orientation at the Surface of Polymer Films during Crystallization? Wang, Yong; Chan, Chi-Ming; Ng, Kai-Mo Macromolecules, Vol. 41, Issue 7 https://doi.org/10.1021/ma7021309	journal	April 2008
Crystallization in the Thin and Ultrathin Films of Poly(ethylene−vinyl acetate) and Linear Low-Density Polyethylene Wang, Y.; Ge, S.; Rafailovich, M. Macromolecules, Vol. 37, Issue 9 https://doi.org/10.1021/ma030456b	journal	May 2004
Hierarchical supramolecular assembly of a single peptoid polymer into a planar nanobrush with two distinct molecular packing motifs Sun, Jing; Wang, Zhiwei; Zhu, Chenhui Proceedings of the National Academy of Sciences, Vol. 117, Issue 50 https://doi.org/10.1073/pnas.2011816117	journal	December 2020
Crystal Growth of Isotactic Polystyrene in Ultrathin Films: film Thickness Dependence Taguchi, Ken; Miyaji, Hideki; Izumi, Kunihide Journal of Macromolecular Science, Part B, Vol. 41, Issue 4-6 https://doi.org/10.1081/MB-120013081	journal	January 2002
Cyclic Topology Enhancing Structural Ordering and Stability of Comb-Shaped Polypeptoid Thin Films against Melt-Induced Dewetting Jiang, Naisheng; Chen, Jianxia; Yu, Tianyi Macromolecules, Vol. 53, Issue 17 https://doi.org/10.1021/acs.macromol.0c01205	journal	August 2020
Crystallization-Driven Self-Assembly of Coil–Comb-Shaped Polypeptoid Block Copolymers: Solution Morphology and Self-Assembly Pathways Jiang, Naisheng; Yu, Tianyi; Darvish, Omead A. Macromolecules, Vol. 52, Issue 22 https://doi.org/10.1021/acs.macromol.9b01546	journal	November 2019
In-Situ Hot Stage Atomic Force Microscopy Study of Poly(ε-caprolactone) Crystal Growth in Ultrathin Films Mareau, Vincent H.; Prud'homme, Robert E. Macromolecules, Vol. 38, Issue 2 https://doi.org/10.1021/ma0482359	journal	December 2004
Tunable Affinity and Molecular Architecture Lead to Diverse Self-Assembled Supramolecular Structures in Thin Films Hsu, Chih-Hao; Dong, Xue-Hui; Lin, Zhiwei ACS Nano, Vol. 10, Issue 1 https://doi.org/10.1021/acsnano.5b06038	journal	December 2015

Similar Records

Modulating the Molecular Geometry and Solution Self-Assembly of Amphiphilic Polypeptoid Block Copolymers by Side Chain Branching Pattern

Journal Article · Tue Apr 06 00:00:00 EDT 2021 · Journal of the American Chemical Society · OSTI ID:1890208

Kang, Liying; Chao, Albert; Zhang, Meng; +6 more

Cyclic Topology Enhancing Structural Ordering and Stability of Comb-Shaped Polypeptoid Thin Films against Melt-Induced Dewetting

Journal Article · Tue Aug 25 00:00:00 EDT 2020 · Macromolecules · OSTI ID:1890208

Jiang, Naisheng; Chen, Jianxia; Yu, Tianyi; +7 more

Liquid-Crystalline Phase Behavior in Polypeptoid Diblock Copolymers

Journal Article · Mon Nov 19 00:00:00 EST 2018 · Macromolecules · OSTI ID:1890208

Greer, Douglas R.; Stolberg, Michael A.; Xuan, Sunting; +3 more

Related Subjects

36 MATERIALS SCIENCE
crystal structure
crystallization
liquid chromatography
molecules
thin films

Title: Multiscale Crystalline Structure of Confined Polypeptoid Films: The Effect of Alkyl Side Chain Branching

Citation Formats

References (41)

Similar Records

Related Subjects