Rewritable Surface‐Grafted Polymer Brushes with Dynamic Covalent Linkages

Cui, Feichen; Zhang, Yipeng; Sui, Yang; Chen, Hongwen; Helms, Brett A.; Yan, Jiajun

doi:10.1002/anie.202410862

Title: Rewritable Surface‐Grafted Polymer Brushes with Dynamic Covalent Linkages

Journal Article · 24 November 2024 · Angewandte Chemie (International Edition)

DOI: https://doi.org/10.1002/anie.202410862 · OSTI ID:2479955

^[1];

^[2];

^[1]

School of Physical Science and Technology ShanghaiTech University Shanghai 201210 China
Materials Sciences Division Lawrence Berkeley National Laboratory Berkeley CA 94720 USA, The Molecular Foundry Lawrence Berkeley National Laboratory Berkeley CA 94720 USA

Abstract Surface grafting of polymer brushes drastically modifies surface properties, including wettability, compatibility, responsiveness, etc. A broad variety of functionalities can be introduced to the surface via different types of polymers. Bringing together properties of two or more types of polymer brushes to one surface opens up even more possibilities in brush‐modified materials. However, while it is generally feasible to introduce several chemical compositions along the brushes via copolymerization, it is challenging to vary the types of polymer brushes along a surface. Although previous studies have demonstrated binary brushes via orthogonal polymerization techniques or partial deactivation/regrafting, they commonly limit the number of polymer types to two. Here, we propose a strategy to introduce dynamic covalent diketoenamine linkages at the root of polymer brushes. The grafting density could be precisely tuned during surface functionalization. The surface‐anchored polymer brushes were cleaved by the addition of small molecule amines. New polymer brushes can be regrafted from the surface following refunctionalization of exposed sites. The maneuverability allows tuning of the types and densities of the polymer brushes, pointing the way to the preparation of a new generation of well‐defined brush‐modified materials with mixed grafts, with potential applications in the design of smart materials and surfaces.

View Accepted Manuscript (Publisher)

Cite

Export

Save

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 2479955

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 49 Vol. 63; ISSN 1433-7851

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

Country of Publication:: Germany

Language:: English

References (43)

Mechanically Robust and Self-Healable Superlattice Nanocomposites by Self-Assembly of Single-Component “Sticky” Polymer-Grafted Nanoparticles Williams, Gregory A.; Ishige, Ryohei; Cromwell, Olivia R. Advanced Materials, Vol. 27, Issue 26 https://doi.org/10.1002/adma.201500927	journal	May 2015
Engineering Surfaces through Sequential Stop-Flow Photopatterning Pester, Christian W.; Narupai, Benjaporn; Mattson, Kaila M. Advanced Materials, Vol. 28, Issue 42 https://doi.org/10.1002/adma.201602900	journal	September 2016
Polymer on Top: Current Limits and Future Perspectives of Quantitatively Evaluating Surface Grafting Michalek, Lukas; Barner, Leonie; Barner-Kowollik, Christopher Advanced Materials, Vol. 30, Issue 21 https://doi.org/10.1002/adma.201706321	journal	March 2018
Advanced Materials by Atom Transfer Radical Polymerization Matyjaszewski, Krzysztof Advanced Materials, Vol. 30, Issue 23 https://doi.org/10.1002/adma.201706441	journal	March 2018
Hybrid Dielectric Films of Inkjet‐Printable Core–Shell Nanoparticles Buchheit, Roman; Kuttich, Björn; González‐García, Lola Advanced Materials, Vol. 33, Issue 41 https://doi.org/10.1002/adma.202103087	journal	August 2021
Rising of Dynamic Polyimide Materials: A Versatile Dielectric for Electrical and Electronic Applications Wan, Baoquan; Dong, Xiaodi; Yang, Xing Advanced Materials, Vol. 35, Issue 39 https://doi.org/10.1002/adma.202301185	journal	August 2023
Brush-modified materials: Control of molecular architecture, assembly behavior, properties and applications Yan, Jiajun; Bockstaller, Michael R.; Matyjaszewski, Krzysztof Progress in Polymer Science, Vol. 100 https://doi.org/10.1016/j.progpolymsci.2019.101180	journal	January 2020
Polymer Brushes: Efficient Synthesis and Applications Feng, Chun; Huang, Xiaoyu Accounts of Chemical Research, Vol. 51, Issue 9 https://doi.org/10.1021/acs.accounts.8b00307	journal	August 2018
Silica Etching without HF in Particle Brushes Cui, Feichen; Sui, Yang; Zhang, Yipeng ACS Chemical Health & Safety, Vol. 30, Issue 6 https://doi.org/10.1021/acs.chas.3c00064	journal	September 2023
Probing and Manipulating Noncovalent Interactions in Functional Polymeric Systems Chen, Jingsi; Peng, Qiongyao; Peng, Xuwen Chemical Reviews, Vol. 122, Issue 18 https://doi.org/10.1021/acs.chemrev.2c00215	journal	September 2022
Synthesis, Assembly, and Applications of Hybrid Nanostructures for Biosensing Zhang, Shuaidi; Geryak, Ren; Geldmeier, Jeffrey Chemical Reviews, Vol. 117, Issue 20 https://doi.org/10.1021/acs.chemrev.7b00088	journal	September 2017
Magnetically Responsive Assemblies of Polymer-Brush-Decorated Nanoparticle Clusters That Exhibit Structural Color Ohno, Kohji; Sakaue, Motokazu; Mori, Chizuru Langmuir, Vol. 34, Issue 32 https://doi.org/10.1021/acs.langmuir.8b02073	journal	July 2018
Topologically Induced Heterogeneity in Gradient Copolymer Brush Particle Materials Zhao, Yuqi; Wang, Zongyu; Yu, Chenxi Macromolecules, Vol. 55, Issue 19 https://doi.org/10.1021/acs.macromol.2c01131	journal	July 2022
Opportunities, Challenges, and Pitfalls in Making, Characterizing, and Understanding Polymer Brushes Pester, Christian W.; Klok, Harm-Anton; Benetti, Edmondo M. Macromolecules, Vol. 56, Issue 24 https://doi.org/10.1021/acs.macromol.3c01292	journal	December 2023
Composition-Orientation Induced Mechanical Synergy in Nanoparticle Brushes with Grafted Gradient Copolymers Yin, Rongguan; Zhao, Yuqi; Jeong, Jaepil Macromolecules, Vol. 56, Issue 23 https://doi.org/10.1021/acs.macromol.3c01799	journal	November 2023
Amplified Responsiveness of Multilayered Polymer Grafts: Synergy between Brushes and Hydrogels Ramakrishna, Shivaprakash N.; Cirelli, Marco; Kooij, E. Stefan Macromolecules, Vol. 48, Issue 19 https://doi.org/10.1021/acs.macromol.5b01556	journal	September 2015
Matrix-free Particle Brush System with Bimodal Molecular Weight Distribution Prepared by SI-ATRP Yan, Jiajun; Kristufek, Tyler; Schmitt, Michael Macromolecules, Vol. 48, Issue 22 https://doi.org/10.1021/acs.macromol.5b01905	journal	October 2015
Synthesis of Hybrid Silica Nanoparticles Densely Grafted with Thermo and pH Dual-Responsive Brushes via Surface-Initiated ATRP Wu, Lei; Glebe, Ulrich; Böker, Alexander Macromolecules, Vol. 49, Issue 24 https://doi.org/10.1021/acs.macromol.6b01792	journal	December 2016
50th Anniversary Perspective : Are Polymer Nanocomposites Practical for Applications? Kumar, Sanat K.; Benicewicz, Brian C.; Vaia, Richard A. Macromolecules, Vol. 50, Issue 3 https://doi.org/10.1021/acs.macromol.6b02330	journal	January 2017
50th Anniversary Perspective : Polymer Brushes: Novel Surfaces for Future Materials Chen, Wei-Liang; Cordero, Roselynn; Tran, Hai Macromolecules, Vol. 50, Issue 11 https://doi.org/10.1021/acs.macromol.7b00450	journal	May 2017
Molecular Parameters Governing the Elastic Properties of Brush Particle Films Lee, Jaejun; Wang, Zongyu; Zhang, Jianan Macromolecules, Vol. 53, Issue 4 https://doi.org/10.1021/acs.macromol.9b01809	journal	February 2020
Fabrication and Deformation of Mechanochromic Nanocomposite Elastomers Based on Rubbery and Glassy Block Copolymer-Grafted Silica Nanoparticles Cheng, Chao-Hung; Masuda, Shiori; Nozaki, Shuhei Macromolecules, Vol. 53, Issue 11 https://doi.org/10.1021/acs.macromol.9b02031	journal	May 2020
Structural Color Materials Using Polymer-Brush-Decorated Hybrid Particles Ohno, Kohji; Mizuta, Yuuki ACS Applied Polymer Materials, Vol. 2, Issue 2 https://doi.org/10.1021/acsapm.9b00839	journal	November 2019
Functionalization of Inorganic Nanoparticles for Bioimaging Applications Erathodiyil, Nandanan; Ying, Jackie Y. Accounts of Chemical Research, Vol. 44, Issue 10 https://doi.org/10.1021/ar2000327	journal	October 2011
Gold Nanoparticles in Chemical and Biological Sensing Saha, Krishnendu; Agasti, Sarit S.; Kim, Chaekyu Chemical Reviews, Vol. 112, Issue 5 https://doi.org/10.1021/cr2001178	journal	February 2012
Polymer Brushes via Surface-Initiated Controlled Radical Polymerization: Synthesis, Characterization, Properties, and Applications Barbey, Raphael; Lavanant, Laurent; Paripovic, Dusko Chemical Reviews, Vol. 109, Issue 11 https://doi.org/10.1021/cr900045a	journal	November 2009
Environmentally Responsive “Hairy” Nanoparticles: Mixed Homopolymer Brushes on Silica Nanoparticles Synthesized by Living Radical Polymerization Techniques Li, Dejin; Sheng, Xia; Zhao, Bin Journal of the American Chemical Society, Vol. 127, Issue 17 https://doi.org/10.1021/ja0422561	journal	May 2005
Self-Assembly of Inorganic Nanoparticle Vesicles and Tubules Driven by Tethered Linear Block Copolymers He, Jie; Liu, Yijing; Babu, Taarika Journal of the American Chemical Society, Vol. 134, Issue 28 https://doi.org/10.1021/ja3032295	journal	July 2012
β-Ketoenamine-Linked Covalent Organic Frameworks Capable of Pseudocapacitive Energy Storage DeBlase, Catherine R.; Silberstein, Katharine E.; Truong, Thanh-Tam Journal of the American Chemical Society, Vol. 135, Issue 45 https://doi.org/10.1021/ja409421d	journal	October 2013
Adaptable Multivalent Hairy Inorganic Nanoparticles Bohannon, Caleb A.; Chancellor, Andrew J.; Kelly, Michael T. Journal of the American Chemical Society, Vol. 143, Issue 41 https://doi.org/10.1021/jacs.1c08261	journal	October 2021
β-Triketones as Reactive Handles for Polymer Diversification via Dynamic Catalyst-Free Diketoenamine Click Chemistry Trachsel, Lucca; Stewart, Kevin A.; Konar, Debabrata Journal of the American Chemical Society, Vol. 146, Issue 23 https://doi.org/10.1021/jacs.4c04664	journal	June 2024
Chemically Triggered Synthesis, Remodeling, and Degradation of Soft Materials Sun, Xiaolong; Chwatko, Malgorzata; Lee, Doo-Hee Journal of the American Chemical Society, Vol. 142, Issue 8 https://doi.org/10.1021/jacs.9b12122	journal	February 2020
Polymer-Grafted Nanoparticles with Variable Grafting Densities for High Energy Density Polymeric Nanocomposite Dielectric Capacitors Tawade, Bhausaheb V.; Singh, Maninderjeet; Apata, Ikeoluwa E. JACS Au, Vol. 3, Issue 5, p. 1365-1375 https://doi.org/10.1021/jacsau.3c00022	journal	April 2023
Surface-Initiated Polymerizations in Aqueous Media: Effect of Initiator Density Jones, Darren M.; Brown, Andrew A.; Huck, Wilhelm T. S. Langmuir, Vol. 18, Issue 4 https://doi.org/10.1021/la011365f	journal	January 2002
Suspensions of Silica Particles Grafted with Concentrated Polymer Brush: A New Family of Colloidal Crystals Ohno, Kohji; Morinaga, Takashi; Takeno, Satoshi Macromolecules, Vol. 39, Issue 3 https://doi.org/10.1021/ma0521708	journal	February 2006
Microphase Separation of High Grafting Density Asymmetric Mixed Homopolymer Brushes on Silica Particles Jiang, Xiaoming; Zhao, Bin; Zhong, Ganji Macromolecules, Vol. 43, Issue 19 https://doi.org/10.1021/ma101518a	journal	October 2010
Synthesis of Binary Polymer Brushes via Two-Step Reverse Atom Transfer Radical Polymerization Ye, Penglin; Dong, Hongchen; Zhong, Mingjiang Macromolecules, Vol. 44, Issue 7 https://doi.org/10.1021/ma1028533	journal	April 2011
Surface-Grafted Stimuli-Responsive Block Copolymer Brushes for the Thermo-, Photo- and pH-Sensitive Release of Dye Molecules Kumar, Surjith; Dory, Yves L.; Lepage, Martin Macromolecules, Vol. 44, Issue 18 https://doi.org/10.1021/ma2010102	journal	September 2011
Grafting Bimodal Polymer Brushes on Nanoparticles Using Controlled Radical Polymerization Rungta, Atri; Natarajan, Bharath; Neely, Tony Macromolecules, Vol. 45, Issue 23 https://doi.org/10.1021/ma3018876	journal	November 2012
Biofunctionalized Phospholipid-Capped Mesoporous Silica Nanoshuttles for Targeted Drug Delivery: Improved Water Suspensibility and Decreased Nonspecific Protein Binding Wang, Li-Sheng; Wu, Li-Chen; Lu, Shin-Yi ACS Nano, Vol. 4, Issue 8 https://doi.org/10.1021/nn901376h	journal	July 2010
Polymer brush hypersurface photolithography Carbonell, Carlos; Valles, Daniel; Wong, Alexa M. Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-020-14990-x	journal	March 2020
Closed-loop recycling of plastics enabled by dynamic covalent diketoenamine bonds Christensen, Peter R.; Scheuermann, Angelique M.; Loeffler, Kathryn E. Nature Chemistry, Vol. 11, Issue 5 https://doi.org/10.1038/s41557-019-0249-2	journal	April 2019
Recent advances in dynamic covalent chemistry Jin, Yinghua; Yu, Chao; Denman, Ryan J. Chemical Society Reviews, Vol. 42, Issue 16 https://doi.org/10.1039/c3cs60044k	journal	January 2013

Similar Records

Degradable cellulose‐based polymer brushes with controlled grafting densities

Journal Article · 2019 · Journal of Polymer Science. Part A, Polymer Chemistry · OSTI ID:1559346

Olszewski, Mateusz; Li, Lingchun; Xie, Guojun; +3 more

Binary mixed homopolymer brushes grafted on nanorod particles: A self-consistent field theory study

Journal Article · 2013 · Journal of Chemical Physics · OSTI ID:22251316

Ma, Xin; Yang, Yingzi; Tang, Ping; +3 more

Behavior of Surface-Anchored Poly(acrylic acid) Brushes with Grafting Density Gradients on Solid Substrates: 1. Experiment

Journal Article · 2006 · Macromolecules · OSTI ID:959886

Wu, T; Gong, P; Szleifer, I; +3 more

Title: Rewritable Surface‐Grafted Polymer Brushes with Dynamic Covalent Linkages

Citation Formats

References (43)

Similar Records

Related Subjects