• Yuji Higaki
  • Atsushi Takahara
Part of the Biologically-Inspired Systems book series (BISY, volume 11)


This chapter reviews the anti-(bio)fouling systems based on polymer brushes. Charged polymer brushes are well-hydrated in aqueous solutions to produce liquid-infused smooth interface. Because of the extremely low interfacial tension in the water-infusion soft interfaces and water, the hydrated charged polymer brushes exhibit outstanding anti-fouling capability in aqueous solutions. We present here anti-(bio)fouling properties of the charged polymer brushes to oils, asphaltenes, and marine fouling organisms including barnacle cypris larvae, mussel larvae, and marine bacteria.


Charged polymers Polymer brushes Liquid-infused surfaces Wetting Hydration 



This research was financially supported by the Exploratory Research for Advanced Technology (ERATO), Japan Science and Technology Agency (JST). This work was performed under the Cooperative Research Program of “Network Joint Research Center for Materials and Devices”.


  1. Advincula RC, Brittain WJ, Caster KC, Rühe J (2004) Polymer brushes: synthesis, characterization and applications. Wiley, WeinheimCrossRefGoogle Scholar
  2. Ahmed N, Murosaki T, Kakugo A, Kurokawa T, Gong JP, Nogata Y (2011) Long-term in situ observation of barnacle growth on soft substrates with different elasticity and wettability. Soft Matter 7:7281–7290CrossRefGoogle Scholar
  3. Aldred N, Clare AS (2009) Chapter 2: Mechanisms and principles underlying temporary adhesion, surface exploration and settlement site selection by barnacle Cyprids: a short review. In: Functional surfaces in biology, vol 2. Springer, Berlin, pp 43–65CrossRefGoogle Scholar
  4. Aldred N, Li G, Gao Y, Clare AS, Jiang S (2010) Modulation of barnacle (Balanus amphitrite Darwin) cyprid settlement behavior by sulfobetaine and carboxybetaine methacrylate polymer coatings. Biofouling 26:673–683CrossRefGoogle Scholar
  5. Azzaroni O, Moya S, Farhan T, Brown AA, Huck WT (2005) Switching the properties of polyelectrolyte brushes via “hydrophobic collapse”. Macromolecules 38:10192–10199CrossRefGoogle Scholar
  6. Barthlott W, Neinhuis C (1997) Purity of the sacred lotus, or escape from contamination in biological surfaces. Planta 202:1–8CrossRefGoogle Scholar
  7. Bauer U, Federle W (2009) The insect-trapping rim of Nepenthes pitchers: surface structure and function. Plant Signal Behav 4:1019–1023CrossRefGoogle Scholar
  8. Bhushan B (2012) Bioinspired structured surfaces. Langmuir 28:1698–1714CrossRefGoogle Scholar
  9. Bittoun E, Marmur A (2012) The role of multiscale roughness in the lotus effect: is it essential for super-hydrophobicity? Langmuir 28:13933–13942CrossRefGoogle Scholar
  10. Bohn HF, Federle W (2004) Insect aquaplaning: Nepenthes pitcher plants capture prey with the peristome, a fully wettable water-lubricated anisotropic surface. Proc Natl Acad Sci U S A 101:14138–14143CrossRefGoogle Scholar
  11. Callow JA, Callow ME (2011) Trends in the development of environmentally friendly fouling-resistant marine coatings. Nat Commun 2:244–210CrossRefGoogle Scholar
  12. Chen S, Li L, Zhao C, Zheng J (2010) Surface hydration: principles and applications toward low-fouling/nonfouling biomaterials. Polymer 51:5283–5293CrossRefGoogle Scholar
  13. Chen W-L, Cordero R, Tran H, Ober CK (2017) 50th anniversary perspective: polymer brushes: novel surfaces for future materials. Macromolecules 50:4089–4113CrossRefGoogle Scholar
  14. Cheng G, Zhang Z, Chen S, Bryers JD, Jiang S (2007) Inhibition of bacterial adhesion and biofilm formation on zwitterionic surfaces. Biomaterials 28:4192–4199CrossRefGoogle Scholar
  15. Cheng G, Li G, Xue H, Chen S, Bryers JD, Jiang S (2009) Zwitterionic carboxybetaine polymer surfaces and their resistance to long-term biofilm formation. Biomaterials 30:5234–5240CrossRefGoogle Scholar
  16. Dunlop IE, Thomas RK, Titmus S, Osborne V, Edmondson S, Huck WTS, Klein J (2012) Structure and collapse of a surface-grown strong polyelectrolyte brush on sapphire. Langmuir 28:3187–3193CrossRefGoogle Scholar
  17. Flemming HC, Murthy PS, Venkatesan R, Cooksey K (2009) Marine and industrial biofouling, vol 4. Springer, Berlin/HeidelbergGoogle Scholar
  18. Fowkes FM (1963) Additivity of intermolecular forces at interfaces. i. determination of the contribution to surface and interfacial tensions of dispersion forces in various liquids. J Phys Chem 67:2538–2541CrossRefGoogle Scholar
  19. Galvin CJ, Dimitriou MD, Satija SK, Genzer J (2014) Swelling of polyelectrolyte and polyzwitterion brushes by humid vapors. J Am Chem Soc 136:12737–12745CrossRefGoogle Scholar
  20. Gaume L, Gorb S, Rowe N (2002) Function of epidermal surfaces in the trapping efficiency of Nepenthes alata pitchers. New Phytol 156:479–489CrossRefGoogle Scholar
  21. Hannisdal A, Ese M-H, Hemmingsen PV, Sjöblom J (2006) Particle-stabilized emulsions: effect of heavy crude oil components pre-adsorbed onto stabilizing solids. Colloids Surf A Physicochem Eng Asp 276:45–58CrossRefGoogle Scholar
  22. Higaki Y, Hatae K, Ishikawa T, Takanohashi T, Hayashi J-I, Takahara A (2014) Adsorption and desorption behavior of asphaltene on polymer-brush-immobilized surfaces. ACS Appl Mater Interfaces 6:20385–20389CrossRefGoogle Scholar
  23. Higaki Y, Nishida J, Takenaka A, Yoshimatsu R, Kobayashi M, Takahara A (2015) Versatile inhibition of marine organism settlement by zwitterionic polymer brushes. Polym J 47:811–818CrossRefGoogle Scholar
  24. Higaki Y et al (2017) Effect of charged group spacer length on hydration state in zwitterionic poly(sulfobetaine) brushes. Langmuir 33:8404–8412CrossRefGoogle Scholar
  25. Huang X, Wirth MJ (1997) Surface-initiated radical polymerization on porous silica. Anal Chem 69:4577–4580CrossRefGoogle Scholar
  26. Huang X, Chrisman JD, Zacharia NS (2013) Omniphobic slippery coatings based on lubricant-infused porous polyelectrolyte multilayers. ACS Macro Lett 2:826–829CrossRefGoogle Scholar
  27. Ishihara K, Ziats NP, Tierney BP, Nakabayashi N, Anderson JM (1991) Protein adsorption from human plasma is reduced on phospholipid polymers. J Biomed Mater Res 25:1397–1407CrossRefGoogle Scholar
  28. Ishihara K, Nomura H, Mihara T, Kurita K, Iwasaki Y, Nakabayashi N (1998) Why do phospholipid polymers reduce protein adsorption? J Biomed Mater Res 39:323–330CrossRefGoogle Scholar
  29. Jeon SI, Lee JH, Andrade JD, Degennes PG (1991) Protein surface interactions in the presence of polyethylene oxide .1. Simplified theory. J Colloid Interface Sci 142:149–158CrossRefGoogle Scholar
  30. Jiang S, Cao Z (2010) Ultralow-fouling, functionalizable, and hydrolyzable zwitterionic materials and their derivatives for biological applications. Adv Mater 22:920–932CrossRefGoogle Scholar
  31. Kitano H (2016) Characterization of polymer materials based on structure analyses of vicinal water. Polym J 48:15–24CrossRefGoogle Scholar
  32. Kitano H, Imai M, Mori T, Gemmei-Ide M, Yokoyama Y, Ishihara K (2003) Structure of water in the vicinity of phospholipid analogue copolymers as studied by vibrational spectroscopy. Langmuir 19:10260–10266CrossRefGoogle Scholar
  33. Klein J, Kumacheva E, Mahalu D, Perahia D, Fetters LJ (1994) Reduction of frictional forces between solid surfaces bearing polymer brushes. Nature 370:634–636CrossRefGoogle Scholar
  34. Kobayashi M, Terayama Y, Yamaguchi H, Terada M, Murakami D, Ishihara K, Takahara A (2012) Wettability and antifouling behavior on the surfaces of superhydrophilic polymer brushes. Langmuir 28:7212–7222CrossRefGoogle Scholar
  35. Kobayashi M, Terayama Y, Kikuchi M, Takahara A (2013) Chain dimensions and surface characterization of superhydrophilic polymer brushes with zwitterion side groups. Soft Matter 9:5138–5148CrossRefGoogle Scholar
  36. Kobayashi M, Tanaka H, Minn M, Sugimura J, Takahara A (2014a) Interferometry study of aqueous lubrication on the surface of polyelectrolyte brush. ACS Appl Mater Interfaces 6:20365–20371CrossRefGoogle Scholar
  37. Kobayashi M, Ishihara K, Takahara A (2014b) Neutron reflectivity study of the swollen structure of polyzwitterion and polyeletrolyte brushes in aqueous solution. J Biomater Sci Polym Ed 25:1673–1686CrossRefGoogle Scholar
  38. Lee S, Spencer ND (2008) Sweet, hairy, soft, and slippery. Science 319:575–576CrossRefGoogle Scholar
  39. Lee BP, Messersmith PB, Israelachvili JN, Waite JH (2011) Mussel-inspired adhesives and coatings. Annu Rev Mater Res 41:99–132CrossRefGoogle Scholar
  40. Lejars M, Margaillan A, Bressy C (2012) Fouling release coatings: a nontoxic alternative to biocidal antifouling coatings. Chem Rev 112:4347–4390CrossRefGoogle Scholar
  41. Leng C, Han X, Shao Q, Zhu Y, Li Y, Jiang S, Chen Z (2014) In situ probing of the surface hydration of zwitterionic polymer brushes: structural and environmental effects. J Phys Chem C 118:15840–15845CrossRefGoogle Scholar
  42. Leontaritis KJ, Mansoori GA (1988) Asphaltene deposition: a survey of field experiences and research approaches. J Pet Sci Eng 1:229–239CrossRefGoogle Scholar
  43. Liu L, Kou R, Liu G (2017) Ion specificities of artificial macromolecules. Soft Matter 13:68–80CrossRefGoogle Scholar
  44. Ma W, Higaki Y, Otsuka H, Takahara A (2013) Perfluoropolyether-infused nano-texture: a versatile approach to omniphobic coatings with low hysteresis and high transparency. Chem Commun 49:597–599CrossRefGoogle Scholar
  45. Magin CM, Finlay JA, Clay G, Callow ME, Callow JA, Brennan AB (2011) Antifouling performance of cross-linked hydrogels: refinement of an attachment model. Biomacromolecules 12:915–922CrossRefGoogle Scholar
  46. Marshall KC, Stout R, Mitchell R (1971) Mechanism of the initial events in the sorption of marine bacteria to surfaces. J Gen Microbiol 68:337–348CrossRefGoogle Scholar
  47. Milner ST (1991) Polymer brushes. Science 251:905–914CrossRefGoogle Scholar
  48. Miranda DF, Urata C, Masheder B, Dunderdale GJ, Yagihashi M, Hozumi A (2014) Physically and chemically stable ionic liquid-infused textured surfaces showing excellent dynamic omniphobicity. APL Mater 2:056108CrossRefGoogle Scholar
  49. Morisaki H, Nagai S, Ohshima H, Ikemoto E, Kogure K (1999) The effect of motility and cell-surface polymers on bacterial attachment. Microbiology 145:2797–2802CrossRefGoogle Scholar
  50. Murakami D, Kobayashi M, Moriwaki T, Ikemoto Y, Jinnai H, Takahara A (2013) Spreading and structuring of water on superhydrophilic polyelectrolyte brush surfaces. Langmuir 29:1148–1151CrossRefGoogle Scholar
  51. Murakami D, Kobayashi M, Higaki Y, Jinnai H, Takahara A (2016) Swollen structure and electrostatic interactions of polyelectrolyte brush in aqueous solution. Polymer 98:464–469CrossRefGoogle Scholar
  52. Murdoch TJ, Willott JD, de Vos WM, Nelson A, Prescott SW, Wanless EJ, Webber GB (2016) Influence of anion hydrophilicity on the conformation of a hydrophobic weak polyelectrolyte brush. Macromolecules 49:9605–9617CrossRefGoogle Scholar
  53. Nagasawa D, Azuma T, Noguchi H, Uosaki K, Takai M (2015) Role of interfacial water in protein adsorption onto polymer brushes as studied by SFG spectroscopy and QCM. J Phys Chem C 119:17193–17201CrossRefGoogle Scholar
  54. Raviv U, Giasson S, Kampf N, Gohy J-F, Jérôme R, Klein J (2003) Lubrication by charged polymers. Nature 425:163–165CrossRefGoogle Scholar
  55. Schumacher JF et al (2007a) Engineered antifouling microtopographies-effect of feature size, geometry, and roughness on settlement of zoospores of the green alga Ulva. Biofouling 23:55–62CrossRefGoogle Scholar
  56. Schumacher JF, Aldred N, Callow ME, Finlay JA, Callow JA, Clare AS, Brennan AB (2007b) Species-specific engineered antifouling topographies: correlations between the settlement of algal zoospores and barnacle cyprids. Biofouling 23:307–317CrossRefGoogle Scholar
  57. Shi C, Yan B, Xie L, Zhang L, Wang J, Takahara A, Zeng H (2016) Long-range hydrophilic attraction between water and polyelectrolyte surfaces in oil. Angew Chem Int Ed 55:15017–15021CrossRefGoogle Scholar
  58. Sin MC, Chen SH, Chang Y (2014) Hemocompatibility of zwitterionic interfaces and membranes. Polym J 46:436–443CrossRefGoogle Scholar
  59. Spencer ND (2014) Aqueous lubrication with poly(ethylene glycol) brushes. Tribol Online 9:143–153CrossRefGoogle Scholar
  60. Stuart MAC et al (2010) Emerging applications of stimuli-responsive polymer materials. Nat Mater 9:101–113CrossRefGoogle Scholar
  61. Turgman-Cohen S, Fischer DA, Kilpatrick PK, Genzer J (2009) Asphaltene adsorption onto self-assembled monolayers of alkyltrichlorosilanes of varying chain length. ACS Appl Mater Interfaces 1:1347–1357CrossRefGoogle Scholar
  62. Tuteja A et al (2007) Designing superoleophobic surfaces. Science 318:1618–1622CrossRefGoogle Scholar
  63. Wang J, van der Tuuk Opedal N, Lu Q, Xu Z, Zeng H, Sjöblom J (2012a) Probing molecular interactions of an asphaltene model compound in organic solvents using a surface forces apparatus (SFA). Energy Fuel 26:2591–2599CrossRefGoogle Scholar
  64. Wang J, Lu Q, Harbottle D, Sjöblom J, Xu Z, Zeng H (2012b) Molecular interactions of a polyaromatic surfactant C5Pe in aqueous solutions studied by a surface forces apparatus. J Am Chem Soc 116:11187–11196Google Scholar
  65. Wang T, Wang X, Long Y, Liu G, Zhang G (2013) Ion-specific conformational behavior of polyzwitterionic brushes: exploiting it for protein adsorption/desorption control. Langmuir 29:6588–6596CrossRefGoogle Scholar
  66. Wong T-S, Kang SH, Tang SKY, Smythe EJ, Hatton BD, Grinthal A, Aizenberg J (2011) Bioinspired self-repairing slippery surfaces with pressure-stable omniphobicity. Nature 477:443–447CrossRefGoogle Scholar
  67. Yamazoe K, Higaki Y, Inutsuka Y, Miyawaki J, Cui Y-T, Takahara A, Harada Y (2017) Enhancement of the hydrogen-bonding network of water confined in a polyelectrolyte brush. Langmuir 33:3954–3959CrossRefGoogle Scholar
  68. Yebra DM, Kiil S, Dam-Johansen K (2004) Antifouling technology-past, present and future steps towards efficient and environmentally friendly antifouling coatings. Prog Org Coat 50:75–104CrossRefGoogle Scholar
  69. Zhang Z, Chao T, Chen S, Jiang S (2006a) Superlow fouling sulfobetaine and carboxybetaine polymers on glass slides. Langmuir 22:10072–10077CrossRefGoogle Scholar
  70. Zhang Z, Chen S, Chang Y, Jiang S (2006b) Surface grafted sulfobetaine polymers via atom transfer radical polymerization as superlow fouling coatings. J Phys Chem B 110:10799–10804CrossRefGoogle Scholar
  71. Zhang Z, Finlay JA, Wang L, Gao Y, Callow JA, Callow ME, Jiang S (2009) Polysulfobetaine-grafted surfaces as environmentally benign ultralow fouling marine coatings. Langmuir 25:13516–13521CrossRefGoogle Scholar
  72. Zhang Z, Moxey M, Alswieleh A, Morse AJ, Lewis AL, Geoghegan M, Leggett GJ (2016) Effect of salt on phosphorylcholine-based zwitterionic polymer brushes. Langmuir 32:5048–5057CrossRefGoogle Scholar
  73. Zoppe JO, Ataman NC, Mocny P, Wang J, Moraes J, Klok H-A (2017) Surface-initiated controlled radical polymerization: state-of-the-art, opportunities, and challenges in surface and interface engineering with polymer brushes. Chem Rev 117:1105–1318CrossRefGoogle Scholar

Copyright information

© Springer International Publishing AG, part of Springer Nature 2018

Authors and Affiliations

  1. 1.Institute for Materials Chemistry and Engineering, International Institute for Carbon-Neutral Energy Research (WPI-I2CNER)Kyushu UniversityFukuokaJapan
  2. 2.Institute for Materials Chemistry and EngineeringKyushu UniversityFukuokaJapan

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