Metalated polymer brush coatings with excellent transparence and antibacterial properties

Abstract

Surface-grafted polymer brushes with controlled properties and nanoscale thickness are ideal candidates for transparent coatings to prevent biofouling. However, maintaining long-term antibacterial performance in natural environments remains a significant challenge. In this study, we present a metalated polymer brush (Mt-PB) coating that combines excellent transparency with antimicrobial properties. The coating is prepared by incorporating transition metal ions (e.g., Cu and Ag) into surface-grafted polymer brushes through cooperative in situ reduction. Due to the ultra-thinness of the metalated brush layer (Cu-PB, ~60.07 nm; Ag-PB, ~57.45 nm), the resulting coating exhibits high optical transmittance (~86%) and superior antibacterial efficiency (~99.99% inhibition rate against E. coli and S. aureus). Additionally, the Mt-PB-coated lens demonstrates excellent antibacterial and antifouling durability, as evidenced by underwater detection tests that provide high-resolution images and stable transparency (Δ < 2%) for over a month of underwater exposure. These findings offer a promising strategy for developing transparent and antifouling coatings suitable for underwater optical devices.

Graphical abstract

Keywords

transparent coating / antibacterial / polymer brushes / transition metal

References

[1] Qian P Y , Cheng A , Wang R , Zhang R . Marine biofilms: diversity, interactions, and biofouling. Nature Reviews: Microbiology, 2022, 20(11): 671–684

[2] Leslie D C , Waterhouse A , Berthet J B , Valentin T M , Watters A L , Jain A , Kim P , Hatton B D , Nedder A , Donovan K . . A bioinspired omniphobic surface coating on medical devices prevents thrombosis and biofouling. Nature Biotechnology, 2014, 32(11): 1134–1140

[3] Jin H , Tian L , Bing W , Zhao J , Ren L . Bioinspired marine antifouling coatings: status, prospects, and future. Progress in Materials Science, 2022, 124: 100889

[4] Huang A , Guo Y , Zhu Y , Chen T , Yang Z , Song Y , Wasnik P , Li H , Peng S , Guo Z . . Durable washable wearable antibacterial thermoplastic polyurethane/carbon nanotube@ silver nanoparticles electrospun membrane strain sensors by multi-conductive network. Advanced Composites and Hybrid Materials, 2023, 6(3): 101

[5] Gu Y , Zhou H , Liu F , Zhou S , Wu W . A fluffy all-siloxane bottlebrush architecture for liquid-like slippery surfaces. Journal of Materials Chemistry A: Materials for Energy and Sustainability, 2023, 11(41): 22167–22177

[6] Chen R , Zhang Y , Xie Q , Chen Z , Ma C , Zhang G . Transparent polymer-ceramic hybrid antifouling coating with superior mechanical properties. Advanced Functional Materials, 2021, 31(19): 2011145

[7] Cao S , Wang J , Chen H , Chen D R . Progress of marine biofouling and antifouling technologies. Chinese Science Bulletin, 2011, 56(7): 598–612

[8] Sabaté del Río J , Henry O Y F , Jolly P , Ingber D E . An antifouling coating that enables affinity-based electrochemical biosensing in complex biological fluids. Nature Nanotechnology, 2019, 14(12): 1143–1149

[9] Xiong Y , Fang Z , Tang P , Li Y , Jiang H , Li J , Li Z , Wang G . MXene and cellulose nanofibers reinforced hydrogel with high strength and photothermal self-healing performances for marine antifouling. Carbohydrate Polymers, 2025, 348: 122879

[10] Tan N N , Ng Q H , Enche Ab Rahim S K , Ahmad A L , Hoo P Y , Chew T L . Synthesis of novel magneto-hybrid polyoxometalate composite membrane with simultaneous photocatalytic self-cleaning and antifouling functionalities. Frontiers of Chemical Science and Engineering, 2023, 17(10): 1450–1459

[11] Zhang L , Sha J , Chen R , Liu Q , Liu J , Yu J , Zhang H , Lin C , Zhou W , Wang J . Surface plasma Ag-decorated Bi₅O₇I microspheres uniformly distributed on a zwitterionic fluorinated polymer with superfunctional antifouling property. Applied Catalysis B: Environmental, 2020, 271: 118920

[12] Ye M , Wang S , Ji X , Tian Z , Dai L , Si C . Nanofibrillated cellulose-based superhydrophobic coating with antimicrobial performance. Advanced Composites and Hybrid Materials, 2023, 6(1): 30

[13] Cloutier M , Mantovani D , Rosei F . Antibacterial coatings: challenges, perspectives, and opportunities. Trends in Biotechnology, 2015, 33(11): 637–652

[14] Yang W J , Neoh K G , Kang E T , Teo S L M , Rittschof D . Polymer brush coatings for combating marine biofouling. Progress in Polymer Science, 2014, 39(5): 1017–1042

[15] Li S , Zhao Y , Tan R , Zhang W , Jin D , Wu D , Zhang T . Iron-gold galvanic-assisted rapid grafting of polymer brushes on n-silicon for a triboelectric nanogenerator. ACS Applied Polymer Materials, 2024, 6(1): 927–934

[16] Murad Bhayo A , Yang Y , He X . Polymer brushes: synthesis, characterization, properties, and applications. Progress in Materials Science, 2022, 130: 101000

[17] Olivier A , Meyer F , Raquez J M , Damman P , Dubois P . Surface-initiated controlled polymerization as a convenient method for designing functional polymer brushes: from self-assembled monolayers to patterned surfaces. Progress in Polymer Science, 2012, 37(1): 157–181

[18] Zoppe J O , Ataman N C , Mocny P , Wang J , Moraes J , Klok H A . Surface-initiated controlled radical polymerization: state-of-the-art, opportunities, and challenges in surface and interface engineering with polymer brushes. Chemical Reviews, 2017, 117(3): 1105–1318

[19] Zhang T , Benetti E M , Jordan R . Surface-initiated Cu(0)-mediated CRP for the rapid and controlled synthesis of quasi-3D structured polymer brushes. ACS Macro Letters, 2019, 8(2): 145–153

[20] Truong T N P , Randriamahazaka H , Ghilane J . Redox monomer ionic liquid based on quaternary ammonium: from electrochemistry to polymer brushes. Electrochemistry Communications, 2017, 82: 25–29

[21] Wei W , Faubel J L , Selvakumar H , Kovari D T , Tsao J , Rivas F , Mohabir A T , Krecker M , Rahbar E , Hall A R . . Self-regenerating giant hyaluronan polymer brushes. Nature Communications, 2019, 10(1): 5527

[22] Alfei S , Schito A M . From nanobiotechnology, positively charged biomimetic dendrimers as novel antibacterial agents: a review. Nanomaterials, 2020, 10(10): 2022

[23] Zhu Y , Xu C , Zhang N , Ding X , Yu B , Xu F J . Polycationic synergistic antibacterial agents with multiple functional components for efficient anti-infective therapy. Advanced Functional Materials, 2018, 28(14): 1706709

[24] Tan R , Hao P , Wu D , Yang H , Xia Y , Li S , Wang J , Liang L , Zhou J , Zhang T . Ice-inspired polymeric slippery surface with excellent smoothness, stability, and antifouling properties. ACS Applied Materials & Interfaces, 2023, 15(34): 41193–41200

[25] Soto A P . Surface nanopatterning with polymer brushes. Science, 2019, 366(6469): 1078–1079

[26] Ma S , Zhang X , Yu B , Zhou F . Brushing up functional materials. NPG Asia Materials, 2019, 11(1): 24

[27] Shao X , Wang J , Liu Z , Hu N , Zhang R , Quan C , Yao X , Dong C . Nano-copper ions assembled cellulose-based composite with antibacterial activity for biodegradable personal protective mask. Frontiers of Chemical Science and Engineering, 2023, 17(10): 1544–1554

[28] Pervaiz M , Sadiq S , Sadiq A , Younas U , Ashraf A , Saeed Z , Zuber M , Adnan A . Azo-Schiff base derivatives of transition metal complexes as antimicrobial agents. Coordination Chemistry Reviews, 2021, 447: 214128

[29] Das B , Gupta P . Multimetallic transition metal complexes: Luminescent probes for biomolecule sensing, ion detection, imaging, and therapeutic application. Coordination Chemistry Reviews, 2024, 504: 215656

[30] Yan J , Li B , Yu B , Huck W T S , Liu W , Zhou F . Controlled polymer-brush growth from microliter volumes using sacrificial-anode atom-transfer radical polymerization. Angewandte Chemie International Edition, 2013, 52(35): 9125–9129

[31] Zhang T , Du Y , Müller F , Amin I , Jordan R . Surface-initiated Cu⁰ mediated controlled radical polymerization (SI-CuCRP) using a copper plate. Polymer Chemistry, 2015, 6(14): 2726–2733

[32] Zhang S , Deng Y , Libanori A , Zhou Y , Yang J , Tat T , Yang L , Sun W , Zheng P , Zhu Y L . . In situ grown silver-polymer framework with coordination complexes for functional artificial tissues. Advanced Materials, 2023, 35(24): 2207916

[33] Yang C , Ding X , Ono R J , Lee H , Hsu L Y , Tong Y W , Hedrick J , Yang Y Y . Brush-like polycarbonates containing dopamine, cations, and peg providing a broad-spectrum, antibacterial, and antifouling surface via one-step coating. Advanced Materials, 2014, 26(43): 7346–7351

[34] Cheng H , Wang J , Yang Y , Shi H , Shi J , Jiao X , Han P , Yao X , Chen W , Wei X . . Ti₃C₂T_x MXene modified with ZnTCPP with bacteria capturing capability and enhanced visible light photocatalytic antibacterial activity. Small, 2022, 18(26): 2200857

[35] Che Y , Zhang T , Du Y , Amin I , Marschelke C , Jordan R . “On water” surface-initiated polymerization of hydrophobic monomers. Angewandte Chemie International Edition, 2018, 57(50): 16380–16384

[36] Ali Z , Ma J , Jin D , Cui R , Sun R . Clean production of lactic acid by selective carbon-carbon bond cleavage of biomass feedstock over a novel carbon-bismuth oxychloride photocatalyst. Frontiers of Chemical Science and Engineering, 2024, 18(2): 17

[37] Ren J , Zheng L , Su Y , Meng P , Zhou Q , Zeng H , Zhang T , Yu H . Competitive adsorption of Cd(II), Pb(II), and Cu(II) ions from acid mine drainage with zero-valent iron/phosphoric titanium dioxide: XPS qualitative analyses and DFT quantitative calculations. Chemical Engineering Journal, 2022, 445: 136778

[38] Li Y , Liang Y Q , Mao X M , Li H . Efficient removal of Cu(II) from an aqueous solution using a novel chitosan assisted EDTA-intercalated hydrotalcite-like compound composite: preparation, characterization, and adsorption mechanism. Chemical Engineering Journal, 2022, 438: 135531

[39] Park Y S , Kang S W . Role of ionic liquids in enhancing the performance of the polymer/AgCF₃SO₃/Al(NO₃)₃ complex for separation of propylene/propane mixture. Chemical Engineering Journal, 2016, 306: 973–977

[40] Pinto V C , Sousa P J , Vieira E M F , Gonçalves L M , Minas G . Antibiofouling strategy for optical sensors by chlorine generation using low-cost, transparent, and highly efficient electrodes based on platinum nanoparticles coated oxide. Chemical Engineering Journal, 2021, 404: 126479

[41] Hirosawa S , Takahashi Y , Hashizume H , Miyake T , Akamatsu Y . Synthesis and antibacterial activity of tripropeptin C derivatives modified at the carboxyl groups. Journal of Antibiotics, 2014, 67(3): 265–268

[42] Wu D , Yin X , Zhao Y , Wang Y , Li D , Yang F , Wang L , Chen Y , Wang J , Yang H . . Tinware-inspired aerobic surface-initiated controlled radical polymerization (SI-Sn⁰CRP) for biocompatible surface engineering. ACS Macro Letters, 2023, 12(1): 71–76

RIGHTS & PERMISSIONS

Higher Education Press