Abstract
The segmental mobility of polymers at an interface in contact with air, a liquid or a solid is considerably different from that in the internal bulk phase. This review summarizes recent studies offering a concept that the polymer interface is a useful medium for the functionalization of solid polymer materials. Time- and space-resolved fluorescence spectroscopy using evanescent wave excitation revealed that the segmental mobility at the surface and the solid interface had a strong impact on the fluorescence properties of a dye well dispersed in a polymer film when the film thickness decreased. Furthermore, using a chiral polymer designed from the concept of a dynamic interface, enantioselective wetting was successfully demonstrated. The contact angle of chiral liquids on the film varied depending on the chirality of the liquid. This wetting resulted from the enantioselective surface reorganization involving local conformational changes of the polymer chains at the liquid interface, as confirmed using sum frequency generation vibrational spectroscopy.
Similar content being viewed by others
Log in or create a free account to read this content
Gain free access to this article, as well as selected content from this journal and more on nature.com
or
References
García, S. J., Fischer, H. R. & van der Zwaag, S. A critical appraisal of the potential of self healing polymeric coatings. Prog. Org. Coating 72, 211–221 (2011).
Coleman, J. N., Khan, U., Blau, W. J. & Gun’ko, Y. K. Small but strong: A review of the mechanical properties of carbon nanotube–polymer composites. Carbon 44, 1624–1652 (2006).
Balazs, A. C., Emrick, T. & Russell, T. P. Nanoparticle polymer composites: Where two small worlds meet. Science 314, 1107–1110 (2006).
Ishigure, T., Nihei, E. & Koike, Y. Graded-index polymer optical fiber for high-speed data communication. Applied Optics 33, 4261–4266 (1994).
Castner, D. G. & Ratner, B. D. Biomedical surface science: Foundations to frontiers. Surf. Sci. 500, 28–60 (2002).
Langer, R. & Tirrell, D. A. Designing materials for biology and medicine. Nature 428, 487–492 (2004).
Sun, Y. & Kwok, Y. C. Polymeric microfluidic system for DNA analysis. Anal. Chim. Acta 556, 80–96 (2006).
Baldan, A. Adhesively-bonded joints and repairs in metallic alloys, polymers and composite materials: Adhesives, adhesion theories and surface pretreatment. J. Mater. Sci. 39, 1–49 (2004).
Ihara, H., Shundo, A., Takafuji, M., Nagaoka, S. Polymer grafting to silica surface for high selective RP-HPLC. Encyclopedia of Chromatography 3rd edn (ed. Cazes J.) 1–11 (Taylor & Francis, London, UK, 2007).
Netza, R. R. & Andelman, D. Neutral and charged polymers at interfaces. Phys. Rep. 380, 1–95 (2003).
Luzinov, I., Minko, S. & Tsukruk, V. V. Adaptive and responsive surfaces through controlled reorganization of interfacial polymer layers. Prog. Polym. Sci. 29, 635–698 (2004).
Bucknall, D. G. Influence of interfaces on thin polymer film behaviour. Prog. Mater. Sci. 49, 713–786 (2004).
Fujii, Y., Morita, H., Takahara, A. & Tanaka, K. Mobility gradient of polystyrene in films supported on solid substrates. Adv. Polym. Sci. 252, 1–28 (2013).
Forrest, J. A., Dalnoki-Veress, K., Stevens, J. R. & Dutcher, J. R. Effect of free surfaces on the glass transition temperature of thin polymer films. Phys. Rev. Lett. 77, 2002–2005 (1996).
Tanaka, K., Taura, A., Ge, S. R., Takahara, A. & Kajiyama, T. Molecular weight dependence of surface dynamic viscoelastic properties for the monodisperse polystyrene film. Macromolecules 29, 3040–3042 (1996).
Tanaka, K., Takahara, A. & Kajiyama, T. Rheological analysis of surface relaxation process of monodisperse polystyrene films. Macromolecules 33, 7588–7593 (2000).
Tanaka, K., Takahara, A. & Kajiyama, T. Effect of polydispersity on surface molecular motion of polystyrene films. Macromolecules 30, 6626–6632 (1997).
Satomi, N., Tanaka, K., Takahara, A., Kajiyama, T., Ishizone, T. & Nakahama, S. Surface molecular motion of monodisperse α,ω-diamino-terminated and α,ω-dicarboxy-terminated polystyrenes. Macromolecules 34, 8761–8767 (2001).
Kajiyama, T., Kawaguchi, D., Sakai, A., Satomi, N., Tanaka, K. & Takahara, A. Determination factors on surface glass transition temperatures of polymeric solids. High Perform. Polym. 12, 587–597 (2000).
Bliznyuk, V. N., Assender, H. E. & Briggs, G. A. D. Surface glass transition temperature of amorphous polymers. A New insight with SFM. Macromolecules 35, 6613–6622 (2002).
Ngai, K. L., Rizos, A. K. & Plazek, D. J. Reduction of the glass temperature of thin freely standing polymer films caused by the decrease of the coupling parameter in the coupling model. J. Non-Cryst. Solids 235, 435–443 (1998).
Ellison, C. J. & Torkelson, J. M. The distribution of glass-transition temperatures in nanoscopically confined glass formers. Nat. Mater. 2, 695–700 (2003).
Miyazaki, T., Nishida, K. & Kanaya, T. Thermal expansion behavior of ultrathin polymer films supported on silicon substrate. Phys. Rev. E 69, 061803 1–6 (2004).
Tanaka, K., Tsuchimura, Y., Akabori, K., Ito, F. & Nagamura, T. Time- and space-resolved fluorescence study on interfacial mobility of polymers. Appl. Phys. Lett. 89, 061916 1–2 (2006).
Tanaka, K., Tateishi, Y., Okada, Y., Nagamura, T., Doi, M. & Morita, H. Interfacial mobility of polymers on inorganic solids. J. Phys. Chem. B 113, 4571–4577 (2009).
Tanaka, K., Fujii, Y., Atarashi, H., Akabori, K., Hino, M. & Nagamura, T. Nonsolvents cause swelling at the interface with poly(methyl methacrylate) films. Langmuir 24, 296–301 (2008).
Shundo, A., Hori, K., Penaloza, D. P., Yoshihiro, Y., Annaka, M. & Tanaka, K. Nonsolvents-induced swelling of poly(methyl methacrylate) nanoparticles. Phys. Chem. Chem. Phys. 15, 16574–16578 (2013).
Fujii, Y., Nagamura, T. & Tanaka, K. Nonsolvents-induced swelling of poly(methyl methacrylate) nanoparticles. J. Phys. Chem. B 114, 3457–3460 (2010).
Tateishi, Y., Kai, N., Noguchi, H., Uosaki, K., Nagamura, T. & Tanaka, K. Local conformation of poly(methyl methacrylate) at nitrogen and water interfaces. Polym. Chem. 1, 303–311 (2010).
Horinouchi, A., Atarashi, H., Fujii, Y. & Tanaka, K. Dynamics of water-induced surface reorganization in poly(methyl methacrylate) films. Macromolecules 45, 4638–4642 (2012).
Crenshaw, B. R. & Weder, C. Phase separation of excimer-forming fluorescent dyes and amorphous polymers: A Versatile mechanism for sensor applications. Adv. Mater. 17, 1471–1476 (2005).
Greene, N. T. & Shimizu, K. D. Colorimetric molecularly imprinted polymer sensor array using dye displacement. J. Am. Chem. Soc. 127, 5695–5700 (2005).
Onoda, M. & Tada, K. The maskless dye diffusion technique—A proposal of patterning techniques for polymer light-emitting device. Curr. Appl. Phys. 6, 887–890 (2006).
Kim, J. -M. The “precursor approach” to patterned fluorescence images in polymer films. Macromol. Rapid Commun. 28, 1191–1212 (2007).
Na, H. -S., Kim, J. -H., Hong, K. -M., Ko, B. -S., Kim, B. -C. & Han, Y. -K. Synthesis of azo dye containing polymers and application for optical data storage. Mol. Cryst. Liq. Cryst. 349, 35–38 (2000).
Maeda, M., Ishitobi, H., Sekkat, Z. & Kawata, S. Polarization storage by nonlinear orientational hole burning in azo dye-containing polymer films. Appl. Phys. Lett. 85, 351–353 (2004).
Nogueira, A. F., Longo, C. & Paoli, M. A. D. Polymers in dye sensitized solar cells: overview and perspectives. Coord. Chem. Rev. 248, 1455–1468 (2004).
Zhang, W., Cheng, Y. M., Yin, X. O. & Liu, B. Solid-state dye-sensitized solar cells with conjugated polymers as hole-transporting materials. Macromol. Chem. Phys. 212, 15–23 (2011).
Shundo, A., Okada, Y., Ito, F. & Tanaka, K. Fluorescence behavior of dyes in thin films of various polymers. Macromolecules 45, 329–335 (2012).
Kost, A., Tutt, L., Klein, M. B., Dougherty, T. K. & Elias, W. E. Optical limiting with C60 in polymethyl methacrylate. Opt. Lett. 18, 334–336 (1993).
Anthony, J., Leonhardt, R., Argyros, A. & Large, M. C. J. Characterization of a microstructured Zeonex terahertz fiber. J. Opt. Soc. Am. B 28, 1013–1018 (2011).
Matsuoka, H. Evanescent wave light scattering a fusion of the evanescent wave and light scattering techniques to the study of colloids and polymers near the interface. Macromol. Rapid Commun. 22, 51–67 (2001).
Wallace, W. E., van Zanten, J. H. & Wu, W. L. Influence of an impenetrable interface on a polymer glass-transition temperature. Phys. Rev. E 52, R3329–R3332 (1995).
Ito, F., Kakiuchi, T., Sakano, T. & Nagamura, T. Fluorescence properties of pyrene derivative aggregates formed in polymer matrix depending on concentration. Phys. Chem. Chem. Phys. 12, 10923–10927 (2010).
Phillips, D. & Rumbles, G. Excimer formation and energy transfer in vinyl(aromatic polymers). Polym. Photochem. 5, 153–170 (1984).
Senshu, K., Yamashita, S., Ito, M., Hirao, A. & Nakahama, S. Surface characterization of 2-hydroxyethyl methacrylate/styrene block copolymers by transmission electron microscopy observation and contact angle measurement. Langmuir 11, 2293–2300 (1995).
Pike, J. K., Ho, T. & Wynne, K. Water-induced surface rearrangements of poly(dimethylsiloxane−urea−urethane) segmented block copolymers. J. Chem. Mater. 8, 856–860 (1996).
Rangwalla, H., Schwab, A. D., Yurdumakan, B., Yablon, D. G., Yaganeh, M. S. & Dhinojwala, A. Molecular structure of an alkyl-side-chain polymer−water interface: origins of contact angle hysteresis. Langmuir 20, 8625–8633 (2004).
Li, G., Ye, S., Morita, S., Nishida, T. & Osawa, M. Hydrogen bonding on the surface of poly(2-methoxyethyl acrylate). J. Am. Chem. Soc. 126, 12198–12199 (2004).
Chen, Z. Understanding surfaces and buried interfaces of polymer materials at the molecular level using sum frequency generation vibrational spectroscopy. Polym. Int. 56, 577–587 (2007).
Shimomura, K., Ikai, T., Kanoh, S., Yashima, E. & Maeda, K. Switchable enantioseparation based on macromolecular memory of a helical polyacetylene in the solid state. Nat. Chem. 6, 429–434 (2014).
Chang, B., Zhang, M., Qing, G. & Sun, T. Dynamic biointerfaces: from recognition to function. Small 11, 1097–1112 (2015).
Shundo, A., Hori, K., Ikeda, T., Kimizuka, N. & Tanaka, K. Design of a dynamic polymer interface for chiral discrimination. J. Am. Chem. Soc. 135, 10282–10285 (2013).
des Barrio, J., Tejedor, R. M., Chinelatto, L. S., Sánchez, C., Piñol, M. & Oriol, L. Bistable mesomorphism and supramolecular stereomutation in chiral liquid crystal azopolymers. J. Mater. Chem. 19, 4922–4930 (2009).
Okamoto, Y. & Yashima, E. Polysaccharide derivatives for chromatographic separation of enantiomers. Angew. Chem., Int. Ed. 37, 1020–1043 (1998).
Shundo, A., Sakurai, T., Takafuji, M., Nagaoka, S. & Ihara, H. Molecular-length and chiral discriminations by β-structural poly(L-alanine) on silica. J. Chromatogr. A 1073, 169–174 (2005).
Jintoku, H., Takafuji, M., Oda, R. & Ihara, H. Enantioselective recognition by a highly ordered porphyrin-assembly on a chiral molecular gel. Chem. Commun. 48, 4881–4883 (2012).
Zhu, X. D., Suhr, H. & Shen, Y. R. Surface vibrational spectroscopy by infrared-visible sum frequency generation. Phys. Rev. B: Condens. Matter 35, 3047–3305 (1987).
Shen, Y. R. Surface properties probed by second-harmonic and sum-frequency generation. Nature 337, 519–525 (1989).
Chen, C., Clarke, M. L., Wang, J. & Chen, Z. Comparison of surface structures of poly(ethyl methacrylate) and poly(ethyl acrylate) in different chemical environments. Phys. Chem. Chem. Phys. 7, 2357–2363 (2005).
Rapp, M. & Ducker, W. A. Enantiospecific wetting. J. Am. Chem. Soc. 132, 18051–18053 (2010).
Acknowledgements
I deeply thank Professors Keiji Tanaka, Fuyuki Ito and Nobuo Kimizuka and Dr Koichiro Hori, Mrs Yohei Okada and Takuya Ikeda for their assistance and helpful discussions. This research was partly supported by Grant-in-Aid for Young Scientists (B) (No. 23750086) and for Challenging Exploratory Research (No. 25620176) from the Ministry of Education, Culture, Sports, Science and Technology, Japan.
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Competing interests
The authors declare no conflict of interest
Rights and permissions
About this article
Cite this article
Shundo, A. Dynamic structure and functionalization of polymer interfaces. Polym J 47, 719–726 (2015). https://doi.org/10.1038/pj.2015.60
Received:
Revised:
Accepted:
Published:
Issue date:
DOI: https://doi.org/10.1038/pj.2015.60


