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

Journal Article · · Journal of the American Chemical Society

Solution self-assembly of coil-crystalline diblock copolypeptoids has attracted increasing attention due to its capability to form hierarchical nanostructures with tailorable morphologies and functionalities. While the N-substituent (or side chain) structures are known to affect the crystallization of polypeptoids, their roles in dictating the hierarchical solution self-assembly of diblock copolypeptoids are not fully understood. Herein, we designed and synthesized two types of diblock copolypeptoids, i.e., poly(N-methylglycine)-b-poly(N-octylglycine) (PNMG-b-PNOG) and poly(N-methylglycine)-b-poly(N-2-ethyl-1-hexylglycine) (PNMG-b-PNEHG), to investigate the influence of N-substituent structure on the crystalline packing and hierarchical self-assembly of diblock copolypeptoids in methanol. With a linear aliphatic N-substituent, the PNOG blocks pack into a highly ordered crystalline structure with a board-like molecular geometry, resulting in the self-assembly of PNMG-b-PNOG molecules into a hierarchical microflower morphology composed of radially arranged nanoribbon subunits. By contrast, the PNEHG blocks bearing bulky branched aliphatic N-substituents are rod-like and prefer to stack into a columnar hexagonal liquid crystalline mesophase, which drives PNMG-b-PNEHG molecules to self-assemble into symmetrical hexagonal nanosheets in solution. A combination of time-dependent small/wide-angle X-ray scattering and microscopic imaging analysis further revealed the self-assembly mechanisms for the formation of these microflowers and hexagonal nanosheets. These results highlight the significant impact of the N-substituent architecture (i.e., linear versus branched) on the supramolecular self-assembly of diblock copolypeptoids in solution, which can serve as an effective strategy to tune the geometry and hierarchical structure of polypeptoid-based nanomaterials.

Research Organization:
Brookhaven National Laboratory (BNL), Upton, NY (United States); Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division; National Institutes of Health, National Institute of General Medical Sciences; USDOE Office of Science (SC), Biological and Environmental Research (BER)
Grant/Contract Number:
SC0012704; AC02-06CH11357; P41 GM111244; S10 OD012331
OSTI ID:
1783968
Alternate ID(s):
OSTI ID: 1786004
Report Number(s):
BNL-221499-2021-JACI
Journal Information:
Journal of the American Chemical Society, Vol. 143, Issue 15; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

References (68)

Cyclic Poly(α-peptoid)s and Their Block Copolymers from N-Heterocyclic Carbene-Mediated Ring-Opening Polymerizations of N-Substituted N -Carboxylanhydrides journal December 2009
Form factors of block copolymer micelles with spherical, ellipsoidal and cylindrical cores journal June 2000
Two-Dimensional Self-Assembled Structures of Highly Ordered Bioactive Crystalline-Based Block Copolymers journal October 2017
Morphology and Proton Transport in Humidified Phosphonated Peptoid Block Copolymers journal April 2016
Self-assembly of crystalline nanotubes from monodisperse amphiphilic diblock copolypeptoid tiles journal March 2016
Crystallization and Melting Behaviors of Cyclic and Linear Polypeptoids with Alkyl Side Chains journal October 2013
Crystallization in Sequence-Defined Peptoid Diblock Copolymers Induced by Microphase Separation journal January 2014
Multidimensional hierarchical self-assembly of amphiphilic cylindrical block comicelles journal March 2015
Supramolecular Nanosheets Assembled from Poly(ethylene glycol)- b -poly( N -(2-phenylethyl)glycine) Diblock Copolymer Containing Crystallizable Hydrophobic Polypeptoid: Crystallization Driven Assembly Transition from Filaments to Nanosheets journal February 2019
Universal Relationship between Molecular Structure and Crystal Structure in Peptoid Polymers and Prevalence of the cis Backbone Conformation journal January 2018
Polypeptoid polymers: Synthesis, characterization, and properties journal October 2017
Crystallization-Driven Self-Assembly of Metallo-Polyelectrolyte Block Copolymers with a Polycaprolactone Core-Forming Segment journal June 2019
Polysarcosine-containing copolymers: Synthesis, characterization, self-assembly, and applications journal June 2018
Method of Comparing Solid-State Kinetic Data and Its Application to the Decomposition of Kaolinite, Brucite, and BaCO3 journal February 1972
From Heterogeneous to Homogeneous Nucleation of Isotactic Poly(propylene) Confined to Nanoporous Alumina journal April 2011
Imaging Unstained Synthetic Polymer Crystals and Defects on Atomic Length Scales Using Cryogenic Electron Microscopy journal September 2018
Permission to Enter Cell by Shape: Nanodisk vs Nanosphere journal July 2012
Tuning the Size of Cylindrical Micelles from Poly( l -lactide)- b -poly(acrylic acid) Diblock Copolymers Based on Crystallization-Driven Self-Assembly journal November 2013
Crystallization-Driven Two-Dimensional Nanosheet from Hierarchical Self-Assembly of Polypeptoid-Based Diblock Copolymers journal August 2018
A Stepwise “Micellization–Crystallization” Route to Oblate Ellipsoidal, Cylindrical, and Bilayer Micelles with Polyethylene Cores in Water journal November 2012
Synthesis and gelation of copolypept(o)ides with random and block structure: XIAO et al. journal August 2017
Liquid-Crystalline Phase Behavior in Polypeptoid Diblock Copolymers journal November 2018
Biomineralization and osteogenic differentiation modulated by substrate stiffness journal January 2020
Crystallization-Driven Self-Assembly of Block Copolymers with a Short Crystallizable Core-Forming Segment: Controlling Micelle Morphology through the Influence of Molar Mass and Solvent Selectivity journal March 2014
In Situ Synchrotron X-ray Scattering Study on Isotactic Polypropylene Crystallization under the Coexistence of Shear Flow and Carbon Nanotubes journal October 2011
Cylindrical Micelles of Controlled Length with a π-Conjugated Polythiophene Core via Crystallization-Driven Self-Assembly journal June 2011
Diffraction by DNA, carbon nanotubes and other helical nanostructures journal April 2005
Monodisperse Cylindrical Micelles of Controlled Length with a Liquid-Crystalline Perfluorinated Core by 1D “Self-Seeding” journal August 2016
Rod-coil copolymers: their aggregation behavior journal May 1990
Influence of Solvent Quality on the Self-Organization of Archetypical Hairy Rods−Branched and Linear Side Chain Polyfluorenes: Rodlike Chains versus “Beta-Sheets” in Solution journal September 2006
Hierarchical supramolecular assembly of a single peptoid polymer into a planar nanobrush with two distinct molecular packing motifs journal December 2020
Self-Organization of Rod−Coil Molecules with Layered Crystalline States into Thermotropic Liquid Crystalline Assemblies journal August 1998
Growth and Termination of Cylindrical Micelles via Liquid-Crystallization-Driven Self-Assembly journal October 2020
Getting into Shape: Reflections on a New Generation of Cylindrical Nanostructures’ Self-Assembly Using Polymer Building Blocks journal January 2019
Cylindrical Block Copolymer Micelles and Co-Micelles of Controlled Length and Architecture journal August 2007
Self-Assembled Smectic Phases in Rod-Coil Block Copolymers journal July 1996
Uniform Biodegradable Fiber-Like Micelles and Block Comicelles via “Living” Crystallization-Driven Self-Assembly of Poly( l -lactide) Block Copolymers: The Importance of Reducing Unimer Self-Nucleation via Hydrogen Bond Disruption journal October 2019
Polypeptoids: A perfect match for molecular definition and macromolecular engineering? journal April 2013
Crystallization-Driven Self-Assembly of Coil–Comb-Shaped Polypeptoid Block Copolymers: Solution Morphology and Self-Assembly Pathways journal November 2019
Monodisperse cylindrical micelles by crystallization-driven living self-assembly journal May 2010
Thermoreversible and Injectable ABC Polypeptoid Hydrogels: Controlling the Hydrogel Properties through Molecular Design journal January 2016
Smectic Ordering in Block-Copolymer Melts journal December 1991
1D vs. 2D shape selectivity in the crystallization-driven self-assembly of polylactide block copolymers journal January 2017
Self-Assembly of Organometallic Block Copolymers:  The Role of Crystallinity of the Core-Forming Polyferrocene Block in the Micellar Morphologies Formed by Poly(ferrocenylsilane- b -dimethylsiloxane) in n -Alkane Solvents journal November 2000
Lipid Rafts As a Membrane-Organizing Principle journal December 2009
Uniform, High Aspect Ratio Fiber-like Micelles and Block Co-micelles with a Crystalline π-Conjugated Polythiophene Core by Self-Seeding journal March 2014
Synthesis and Characterization of Amphiphilic Cyclic Diblock Copolypeptoids from N -Heterocyclic Carbene-Mediated Zwitterionic Polymerization of N -Substituted N -Carboxyanhydride journal December 2011
Polypeptoid Materials: Current Status and Future Perspectives journal May 2012
One-pot universal initiation-growth methods from a liquid crystalline block copolymer journal June 2019
Understanding the CDSA of poly(lactide) containing triblock copolymers journal January 2017
Crystallization-Driven Thermoreversible Gelation of Coil-Crystalline Cyclic and Linear Diblock Copolypeptoids journal April 2013
Development of Structural Complexity by Liquid-Crystal Self-assembly journal August 2013
Scattering Form Factor of Block Copolymer Micelles journal January 1996
Toward Uniform Nanofibers with a π-Conjugated Core: Optimizing the “Living” Crystallization-Driven Self-Assembly of Diblock Copolymers with a Poly(3-octylthiophene) Core-Forming Block journal July 2018
Polymers for gene delivery across length scales journal June 2006
Synthesis and Characterization of Well-Defined PEGylated Polypeptoids as Protein-Resistant Polymers journal February 2017
Kinetics of Phase Change. II Transformation‐Time Relations for Random Distribution of Nuclei journal February 1940
Two-dimensional assemblies from crystallizable homopolymers with charged termini journal January 2017
Nanoscale Phase Separation in Sequence-Defined Peptoid Diblock Copolymers journal September 2013
Solution crystallization of polyethylene at high temperatures: Part 1 Lateral crystal habits journal May 1985
50th Anniversary Perspective : Functional Nanoparticles from the Solution Self-Assembly of Block Copolymers journal April 2017
Precision Epitaxy for Aqueous 1D and 2D Poly(ε-caprolactone) Assemblies journal November 2017
Shape effects of filaments versus spherical particles in flow and drug delivery journal March 2007
Tailored hierarchical micelle architectures using living crystallization-driven self-assembly in two dimensions journal September 2014
Cyclic Topology Enhancing Structural Ordering and Stability of Comb-Shaped Polypeptoid Thin Films against Melt-Induced Dewetting journal August 2020
Synthesis, Characterization, and Photovoltaic Properties of a Low Band Gap Polymer Based on Silole-Containing Polythiophenes and 2,1,3-Benzothiadiazole journal December 2008
General Pathway toward Crystalline-Core Micelles with Tunable Morphology and Corona Segregation journal November 2011
Peptoids and Polypeptoids at the Frontier of Supra- and Macromolecular Engineering journal December 2015