Linking two worlds in polymer chemistry: The influence of block uniformity and dispersity in amphiphilic block copolypeptoids on their self‐assembly

Gangloff, Niklas; Höferth, Marcel; Stepanenko, Vladimir; Sochor, Benedikt; Schummer, Bernhard; Nickel, Joachim; Walles, Heike; Hanke, Randolf; Würthner, Frank; Zuckermann, Ronald N.; Luxenhofer, Robert

doi:10.1002/bip.23259

Title: Linking two worlds in polymer chemistry: The influence of block uniformity and dispersity in amphiphilic block copolypeptoids on their self‐assembly

Journal Article · 07 February 2019 · Biopolymers

DOI: https://doi.org/10.1002/bip.23259 · OSTI ID:1493863

^[1]; Höferth, Marcel ^[1]; Stepanenko, Vladimir ^[2]; Sochor, Benedikt ^[3]; Schummer, Bernhard ^[3]; Nickel, Joachim ^[4]; Walles, Heike ^[4]; Hanke, Randolf ^[3]; Würthner, Frank ^[2];

^[5];

^[6]

Lehrstuhl für Chemische Technologie der Materialsynthese Universität Würzburg Würzburg Germany
Institut für Organische Chemie &, Center for Nanosystems Chemistry (CNC) Universität Würzburg Würzburg Germany, Bavarian Polymer Institute (BPI) Universität Würzburg Würzburg Germany
Lehrstuhl für Röntgenmikroskopie Universität Würzburg Würzburg Germany
Lehrstuhl für Tissue Engineering und Regenerative Medizin Universitätsklinikum Würzburg Würzburg Germany
Molecular Foundry, Biological Nanostructures, Lawrence Berkeley National Laboratory United States of America
Lehrstuhl für Chemische Technologie der Materialsynthese Universität Würzburg Würzburg Germany, Bavarian Polymer Institute (BPI) Universität Würzburg Würzburg Germany

Abstract The self‐assembly of block copolymers has captured the interest of scientists for many decades because it can induce ordered structures and help to imitate complex structures found in nature. In contrast to proteins, nature's most functional hierarchical structures, conventional polymers are disperse in their length distribution. Here, we synthesized hydrophilic and hydrophobic polypeptoids via solid‐phase synthesis (uniform) and ring‐opening polymerization (disperse). Differential scanning calorimetry measurements showed that the uniform hydrophobic peptoids converge to a maximum of the melting temperature at a much lower chain length than their disperse analogs, showing that not only the chain length but also the dispersity has a considerable impact on the thermal properties of those homopolymers. These homopolymers were then coupled to yield amphiphilic block copolypeptoids. SAXS and AFM measurements confirm that the dispersity plays a major role in microphase separation of these macromolecules, and it appears that uniform hydrophobic blocks form more ordered structures.

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Sponsoring Organization:: USDOE

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1493863

Journal Information:: Biopolymers, Journal Name: Biopolymers Journal Issue: 4 Vol. 110; ISSN 0006-3525

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: United States

Language:: English

References (47)

Sequence Programmable Peptoid Polymers for Diverse Materials Applications Knight, Abigail S.; Zhou, Effie Y.; Francis, Matthew B. Advanced Materials, Vol. 27, Issue 38 https://doi.org/10.1002/adma.201500275	journal	April 2015
Poly(ethylene glycol) in Drug Delivery: Pros and Cons as Well as Potential Alternatives Knop, Katrin; Hoogenboom, Richard; Fischer, Dagmar Angewandte Chemie International Edition, Vol. 49, Issue 36 https://doi.org/10.1002/anie.200902672	journal	July 2010
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
Distribution and Tissue Uptake of Poly(ethylene glycol) with Different Molecular Weights after Intravenous Administration to Mice Yamaoka, Tetsuji; Tabata, Yasuhiko; Ikada, Yoshito Journal of Pharmaceutical Sciences, Vol. 83, Issue 4 https://doi.org/10.1002/jps.2600830432	journal	April 1994
Patterned Polypeptoid Brushes: Patterned Polypeptoid Brushes Schneider, Maximilian; Tang, Zian; Richter, Marcus Macromolecular Bioscience, Vol. 16, Issue 1 https://doi.org/10.1002/mabi.201500314	journal	November 2015
Self-Assembly of Amphiphilic Block Copolypeptoids with C ₂ -C ₅ Side Chains in Aqueous Solution Fetsch, Corinna; Flecks, Silvana; Gieseler, Dan Macromolecular Chemistry and Physics, Vol. 216, Issue 5 https://doi.org/10.1002/macp.201400534	journal	December 2014
Highly Defined Multiblock Copolypeptoids: Pushing the Limits of Living Nucleophilic Ring-Opening Polymerization Fetsch, Corinna; Luxenhofer, Robert Macromolecular Rapid Communications, Vol. 33, Issue 19 https://doi.org/10.1002/marc.201200189	journal	June 2012
Polypeptoids by Living Ring-Opening Polymerization of N-Substituted N-Carboxyanhydrides from Solid Supports Gangloff, Niklas; Fetsch, Corinna; Luxenhofer, Robert Macromolecular Rapid Communications, Vol. 34, Issue 12 https://doi.org/10.1002/marc.201300269	journal	May 2013
Degradation of poly(ethylene oxide) McGary, C. W. Journal of Polymer Science, Vol. 46, Issue 147 https://doi.org/10.1002/pol.1960.1204614705	journal	September 1960
Polydispersity and block copolymer self-assembly Lynd, Nathaniel A.; Meuler, Adam J.; Hillmyer, Marc A. Progress in Polymer Science, Vol. 33, Issue 9 https://doi.org/10.1016/j.progpolymsci.2008.07.003	journal	September 2008
Peptoids and Polypeptoids at the Frontier of Supra- and Macromolecular Engineering Gangloff, Niklas; Ulbricht, Juliane; Lorson, Thomas Chemical Reviews, Vol. 116, Issue 4 https://doi.org/10.1021/acs.chemrev.5b00201	journal	December 2015
Implicit-Solvent Coarse-Grained Simulation with a Fluctuating Interface Reveals a Molecular Mechanism for Peptoid Monolayer Buckling Haxton, Thomas K.; Zuckermann, Ronald N.; Whitelam, Stephen Journal of Chemical Theory and Computation, Vol. 12, Issue 1 https://doi.org/10.1021/acs.jctc.5b00910	journal	December 2015
Living Polymer Chains with Predictable Molecular Weight and Dispersity via Carbanionic Polymerization in Continuous Flow: Mixing Rate as a Key Parameter Morsbach, Jan; Müller, Axel H. E.; Berger-Nicoletti, Elena Macromolecules, Vol. 49, Issue 14 https://doi.org/10.1021/acs.macromol.6b00975	journal	July 2016
A Tetragonal Phase Self-Organized from Unimolecular Spheres Assembled from a Substituted Poly(2-oxazoline) Holerca, Marian N.; Sahoo, Dipankar; Peterca, Mihai Macromolecules, Vol. 50, Issue 1 https://doi.org/10.1021/acs.macromol.6b02298	journal	December 2016
Impact of Helical Chain Shape in Sequence-Defined Polymers on Polypeptoid Block Copolymer Self-Assembly Davidson, Emily C.; Rosales, Adrianne M.; Patterson, Anastasia L. Macromolecules, Vol. 51, Issue 5 https://doi.org/10.1021/acs.macromol.8b00055	journal	February 2018
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
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
Directed Growth of Polymer Nanorods Using Surface-Initiated Ring-Opening Polymerization of N -Allyl N -Carboxyanhydride Lu, Lu; Lahasky, Samuel H.; Zhang, Donghui ACS Applied Materials & Interfaces, Vol. 8, Issue 6 https://doi.org/10.1021/acsami.5b11358	journal	September 2015
Dispersity under Scrutiny: Phase Behavior Differences between Disperse and Discrete Low Molecular Weight Block Co-Oligomers van Genabeek, Bas; de Waal, Bas F. M.; Ligt, Bianca ACS Macro Letters, Vol. 6, Issue 7 https://doi.org/10.1021/acsmacrolett.7b00266	journal	June 2017
Consequences of Dispersity on the Self-Assembly of ABA-Type Amphiphilic Block Co-Oligomers Das, Anindita; Petkau-Milroy, Katja; Klerks, Gilian ACS Macro Letters, Vol. 7, Issue 5 https://doi.org/10.1021/acsmacrolett.8b00168	journal	April 2018
Glycosylated Peptoid Nanosheets as a Multivalent Scaffold for Protein Recognition Battigelli, Alessia; Kim, Jae Hong; Dehigaspitiya, Dilani C. ACS Nano, Vol. 12, Issue 3 https://doi.org/10.1021/acsnano.7b08018	journal	February 2018
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
Solid Phase Peptide Synthesis. I. The Synthesis of a Tetrapeptide Merrifield, R. B. Journal of the American Chemical Society, Vol. 85, Issue 14, p. 2149-2154 https://doi.org/10.1021/ja00897a025	journal	July 1963
Synthesis of Monodisperse Polymers from Proteins Yang, Jerry; Gitlin, Irina; Krishnamurthy, Vijay M. Journal of the American Chemical Society, Vol. 125, Issue 41 https://doi.org/10.1021/ja035978l	journal	October 2003
Synthesis and Self-Assembly of Discrete Dimethylsiloxane–Lactic Acid Diblock Co-oligomers: The Dononacontamer and Its Shorter Homologues van Genabeek, Bas; de Waal, Bas F. M.; Gosens, Mark M. J. Journal of the American Chemical Society, Vol. 138, Issue 12 https://doi.org/10.1021/jacs.6b00629	journal	March 2016
Amplifying (Im)perfection: The Impact of Crystallinity in Discrete and Disperse Block Co-oligomers van Genabeek, Bas; Lamers, Brigitte A. G.; de Waal, Bas F. M. Journal of the American Chemical Society, Vol. 139, Issue 42 https://doi.org/10.1021/jacs.7b08627	journal	October 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
Solution Self-Assemblies of Sequence-Defined Ionic Peptoid Block Copolymers Sternhagen, Garrett L.; Gupta, Sudipta; Zhang, Yueheng Journal of the American Chemical Society, Vol. 140, Issue 11 https://doi.org/10.1021/jacs.8b00461	journal	February 2018
Effect of Poly(acrylic acid) Block Length Distribution on Polystyrene- b -Poly(acrylic acid) Aggregates in Solution. 1. Vesicles Terreau, Owen; Luo, Laibin; Eisenberg, Adi Langmuir, Vol. 19, Issue 14 https://doi.org/10.1021/la0269715	journal	July 2003
Effect of Poly(acrylic acid) Block Length Distribution on Polystyrene- b -poly(acrylic acid) Block Copolymer Aggregates in Solution. 2. A Partial Phase Diagram Terreau, Owen; Bartels, Carl; Eisenberg, Adi Langmuir, Vol. 20, Issue 3 https://doi.org/10.1021/la035557h	journal	February 2004
Polypeptoid Brushes by Surface-Initiated Polymerization of N-Substituted Glycine N -Carboxyanhydrides Schneider, Maximilian; Fetsch, Corinna; Amin, Ihsan Langmuir, Vol. 29, Issue 23 https://doi.org/10.1021/la4009174	journal	May 2013
Effect of Polydispersity on the Formation of Vesicles from Amphiphilic Diblock Copolymers Jiang, Ying; Chen, Tao; Ye, Fangwei Macromolecules, Vol. 38, Issue 15 https://doi.org/10.1021/ma050424j	journal	July 2005
Influence of Polydispersity on the Self-Assembly of Diblock Copolymers Lynd, Nathaniel A.; Hillmyer, Marc A. Macromolecules, Vol. 38, Issue 21 https://doi.org/10.1021/ma051025r	journal	October 2005
Effects of Polydispersity on the Order−Disorder Transition in Block Copolymer Melts Lynd, Nathaniel A.; Hillmyer, Marc A. Macromolecules, Vol. 40, Issue 22 https://doi.org/10.1021/ma070962r	journal	October 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
Polypeptoids from N -Substituted Glycine N -Carboxyanhydrides: Hydrophilic, Hydrophobic, and Amphiphilic Polymers with Poisson Distribution Fetsch, Corinna; Grossmann, Arlett; Holz, Lisa Macromolecules, Vol. 44, Issue 17 https://doi.org/10.1021/ma201015y	journal	September 2011
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
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
Revisiting Secondary Structures in NCA Polymerization: Influences on the Analysis of Protected Polylysines Huesmann, David; Birke, Alexander; Klinker, Kristina Macromolecules, Vol. 47, Issue 3 https://doi.org/10.1021/ma5000392	journal	January 2014
Smectic ordering in solutions and films of a rod-like polymer owing to monodispersity of chain length Yu, Seungju M.; Conticello, Vincent P.; Zhang, Guanghui Nature, Vol. 389, Issue 6647 https://doi.org/10.1038/38254	journal	September 1997
Self-Assembly of Amphiphilic Block Copolypeptoids – Micelles, Worms and Polymersomes Fetsch, Corinna; Gaitzsch, Jens; Messager, Lea Scientific Reports, Vol. 6, Issue 1 https://doi.org/10.1038/srep33491	journal	September 2016
Overcoming the PEG-addiction: well-defined alternatives to PEG, from structure–property relationships to better defined therapeutics Barz, Matthias; Luxenhofer, Robert; Zentel, Rudolf Polymer Chemistry, Vol. 2, Issue 9 https://doi.org/10.1039/c0py00406e	journal	January 2011
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
Conformations of peptoids in nanosheets result from the interplay of backbone energetics and intermolecular interactions Edison, John R.; Spencer, Ryan K.; Butterfoss, Glenn L. Proceedings of the National Academy of Sciences, Vol. 115, Issue 22 https://doi.org/10.1073/pnas.1800397115	journal	May 2018
Peptoids: a modular approach to drug discovery. Simon, R. J.; Kania, R. S.; Zuckermann, R. N. Proceedings of the National Academy of Sciences, Vol. 89, Issue 20 https://doi.org/10.1073/pnas.89.20.9367	journal	October 1992
Thermal Properties of Aliphatic Polypeptoids Fetsch, Corinna; Luxenhofer, Robert Polymers, Vol. 5, Issue 1 https://doi.org/10.3390/polym5010112	journal	January 2013

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