Invited Review | Published:

Polymer Surface and Interfaces

Observation of polymer chain structures in two-dimensional films by atomic force microscopy

Polymer Journal volume 48, pages 314 (2016) | Download Citation

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Abstract

The visualization of polymer structures at the molecular level is one of the most important issues in polymer science; however, even using scanning probe microscopy techniques such as atomic force microscopy (AFM), it is still challenging to observe soft polymer materials at the molecular level. In this review, we show that using two-dimensional (2D) samples suitable for AFM observation, especially Langmuir–Blodgett films, and by optimizing the scan conditions, it is possible to obtain molecular images of various polymer structures by tapping-mode AFM. The molecular-level observations included isolated polymer chains and their movements on substrates, 2D folded-chain crystals and their melting behavior, crystallization behavior of single isolated chains, supramolecular multistranded stereocomplexes and chain packing in monolayers. The molecular-level information obtained by this type of direct observation is expected to greatly improve our understanding of physical properties of polymers.

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References

  1. 1.

    , , & Surface studies by scanning tunneling microscopy. Phys. Rev. Lett. 49, 57 (1982).

  2. 2.

    , & Atomic force microscope. Phys. Rev. Lett. 56, 930–933 (1986).

  3. 3.

    Insoluble Monolayers at Liquid–Gas Interface, (Interscience, New York, NY, USA, 1966).

  4. 4.

    An Introduction to Ultrathin Organic Films from Langmuir-Blodgett to Self-Assembly, (Academic Press, New York, NY, USA, 1991).

  5. 5.

    , & Visualization of single chain conformations of a synthetic polymer with atomic force microscopy. J. Am. Chem. Soc. 118, 3321–3322 (1996).

  6. 6.

    & Conformational change in isolated single synthetic polymer chain on mica surface observed by atomic force microscopy. J. Am. Chem. Soc. 125, 4907–4917 (2003).

  7. 7.

    , & 'Reptational' movements of single synthetic polymer chains on substrate observed by in-situ atomic force microscopy. Macromolecules 39, 1209–1215 (2006).

  8. 8.

    , & Peculiar ‘reptational’ movements of single synthetic polymer chains on substrate observed by AFM. Macomol. Rapid Commun. 29, 406–411 (2008).

  9. 9.

    , & Two-dimensional folded chain crystals of a synthetic polymer in a Langmuir-Blodgett film. J. Am. Chem. Soc. 127, 5788–5789 (2005).

  10. 10.

    & Significant melting point depression of two-dimensional folded-chain crystals of isotactic poly(methyl methacrylate)s observed by high-resolution in-situ atomic force microscopy. J. Phys. Chem. B 117, 5594–2605 (2013).

  11. 11.

    , , & Crystallization behavior of single isotactic poly(methyl methacrylate) chains visualizaaed by atomic force microscopy. J. Phys. Chem. B 119, 338–347 (2015).

  12. 12.

    , , , & Supramolecular helical structure of the stereocomplex composed of complementary isotactic and syndiotactic poly(methyl methacrylate)s as revealed by atomic force microscopy. Angew. Chem. Int. Ed. 46, 5348–5351 (2007).

  13. 13.

    , , , & Molecular weight recognition in the multiple-stranded helix of a synthetic polymer without specific monomer-monomer interaction. J. Am. Chem. Soc. 130, 6373–6380 (2008).

  14. 14.

    , , , & Visualization of polymer chain conformations in amorphous polyisocyanide Langmuir–Blodgett films by atomic force microscopy. J. Am. Chem. Soc. 132, 5604–5606 (2010).

  15. 15.

    & Visualization of two-dimensional single chain conformations solubilized in miscible polymer blend monolayer by atomic force microscopy. J. Phys. Chem. B 116, 6561–6568 (2012).

  16. 16.

    , , , & Functional polymers; scanning force microscopy insights. Phys. Chem. Chem. Phys. 8, 3927–3938 (2006).

  17. 17.

    Molecular Workbench for imaging and manipulation of single macromolecules and their complexes with the scanning force microscope. Top. Curr. Chem. 285, 77–102 (2008).

  18. 18.

    , & How atomic force microscopy has contributed to our understanding of polymer crystallization. Polymer 50, 4281–4292 (2009).

  19. 19.

    , & Visualization of synthetic helical polymers by high-resolution atomic force microscopy. Chem. Soc. Rev. 38, 737–746 (2009).

  20. 20.

    , & Probing soft matter with the atomic force microscopies: Imaging and force spectroscopy. Polym. Rev. 50, 235–286 (2010).

  21. 21.

    & Scanning Force Microscopy of Polymers, (Springer, Heidelberg, Germany, 2010).

  22. 22.

    Scanning force microscopy as applied to conformational studies in macromolecular research. Macromol. Rapid. Commun. 32, 1210–1246 (2011).

  23. 23.

    High-resolution visualization and compositional analysis of polymers with atomic force microscopy. Int. J. Polym. Anal. Charact. 16, 505–518 (2011).

  24. 24.

    & Fundamentals and Practices, (Wiley-VCH, Weinheim,Germany, 2012).

  25. 25.

    , , , , , , , & Reproducible imaging and dissection of plasmid DNA under liquid with the atomic force microscope. Science 256, 1180–1184 (1992).

  26. 26.

    & Biomolecular imaging with the atomic force microscope. Annu. Rev. Biophys. Biomol. Struct. 23, 115–139 (1994).

  27. 27.

    , , , , , , & Imaging and modification of polymers by scanning tunneling and atomic force microscopy. J. Appl. Phys. 64, 1178–1184 (1988).

  28. 28.

    Polystyrene monomolecular particles obtained by spreading dilute solutions on the water surface. Macromolecules 19, 2258–2263 (1986).

  29. 29.

    Monolayer of polystyrene monomolecular particles on a water surface studied by Langmuir-type film balance and transmission electron microscopy. Macromolecules 21, 749–755 (1988).

  30. 30.

    Accumulation of monomolecular polystyrene particles from a water surface onto a substrate. J. Polym. Sci. Part B 28, 105–111 (1990).

  31. 31.

    , , & Inadequacy of Lifshitz Theory for thin liquid films. Phys. Rev. Lett. 66, 2084–2087 (1991).

  32. 32.

    & Visualization of molecules—a first step to manipulation and controlled response. Chem. Rev. 101, 4099–4123 (2001).

  33. 33.

    , , , & Worm-like polystyrene brushes in thin films. Langmuir 13, 5368–5772 (1997).

  34. 34.

    , , , , & Spherical and cylindrical supermolecules from polymer backbones jacketed with quasi-equivalent dendritic coats. Nature 391, 161–164 (1998).

  35. 35.

    , , & Single flexible hydrophobic polyelectrolyte molecules adsorbed on solid substrate: transition between a stretched chain, necklace-like conformation and a globule. J. Am. Chem. Soc. 124, 3218–3219 (2002).

  36. 36.

    , , , & Single molecules and associates of heteroarm star copolymer visualized by atomic force microscopy. Macromolecules 36, 8704–8711 (2003).

  37. 37.

    , , , , , & Reversible collapse of brushlike macromolecules in ethanol and water vapours as revealed by real-time scanning force microscopy. Chem. Eur. J. 10, 4599–4605 (2004).

  38. 38.

    , , , , & Molecular motion in a spreading precursor film. Phys. Rev. Lett. 93, 206103 (2004).

  39. 39.

    & Surface Analysis with STM and AFM, Experimental and Theoretical Aspects of Image Analysis, (VCH, Weinheim, Germany, 1996).

  40. 40.

    , & Double strand helix of isotactic poly(methyl methacrylate). Macromolecules 9, 531–532 (1976).

  41. 41.

    , , & Two-dimensional hierarchical self-assembly of one-handed helical polymers on graphite. Angew. Chem. Int. Ed. 45, 1245–1248 (2006).

  42. 42.

    , , & Two-dimensional surface chirality control by solvent-induced helicity inversion of a helical polyacetylene on graphite. J. Am. Chem. Soc. 128, 5650–5651 (2006).

  43. 43.

    , , , , & Two-dimensional helix-bundle formation of a dynamic helical poly(phenylacetylene) with achiral pendant groups on graphite. Angew. Chem. Int. Ed. 46, 7605–7608 (2007).

  44. 44.

    , , , & Helix-Sense controlled polymerization of a single phenyl isocyanide enantiomer leading to diastereomeric helical polyisocyanides with opposite helix-sense and cholesteric liquid crystals with opposite twist-sense. J. Am. Chem. Soc. 128, 708–709 (2006).

  45. 45.

    , , , , , , & Two- and three-dimensional smectic ordering of single-handed helical polymers. J. Am. Chem. Soc. 130, 229–236 (2008).

  46. 46.

    , , , , & Double-stranded helical polymers consisting of complementary homopolymers. J. Am. Chem. Soc. 130, 7938–7945 (2008).

  47. 47.

    , , , , , & Hierarchical amplification of macromolecular helicity of dynamic helical poly(phenylacetylene)s composed of chiral and achiral phenylacetylenes in dilute solution, liquid crystal, and two-dimensional crystal. J. Am. Chem. Soc. 133, 108–114 (2011).

  48. 48.

    & Direct imaging of polyethylene films at single-chain resolution with torsional tapping atomic force microscopy. Phys. Rev. Lett. 107, 197801-1–197801-5 (2011).

  49. 49.

    , & Thickness dependence of the melting temperature of thin polymer films. Macromol. Rapid. Commun. 22, 386–389 (2001).

  50. 50.

    , , , , , , , , & Substrate effect on the melting temperature of thin polyethylene films. Phys. Rev. Lett. 96, 028303 (2006).

  51. 51.

    Molecular modelling of nucleation in polymers. Philos. Trans. R. Soc. Lond. Ser. A 361, 539–556 (2003).

  52. 52.

    & Aggregation of stereoregular poly(methyl methacrylates). Adv. Colloid Interface Sci. 27, 81–150 (1987).

  53. 53.

    & Complexation of stereoregular poly(methyl methacrylates). 14. The basic structure of the stereocomplex of isotactic and syndiotactic poly(methyl methacrylate). Macromolecules 22, 3337–3341 (1989).

  54. 54.

    & Thin-film behavior of poly(methyl methacrylates). 4. Stereocomplexation of isotactic and syndiotactic poly(methyl methacrylate) at the air-water interface. Macromolecules 25, 2725–2731 (1992).

  55. 55.

    , , & Crystalline complexes of syndiotactic poly(methyl methacrylate) with some organic solvents. Polymer 24, 119–122 (1983).

  56. 56.

    , , , , , & Molecular mapping of poly(methyl methacrylate) super-helix stereocomplexes. Chem. Sci. 6, 1370–1378 (2015).

  57. 57.

    , , & Uniform polymer in synthetic polymer chemistry. J. Polym. Sci. Part A 42, 416–431 (2004).

  58. 58.

    , & Self-recognition in helicate self-assembly: spontaneous formation of helical metal complexes from mixtures of ligands and metal ions. Proc. Natl Acad. Sci. USA 90, 5394–5398 (1993).

  59. 59.

    & Superamolecular self-recognition and self-assembly in gallium(III) catecholamide triple helices. Angew. Chem. Int. Ed. 36, 1440–1442 (1997).

  60. 60.

    , , , & DNA-like double helix formed by peptide nucleic acid. Nature 368, 561–563 (1994).

  61. 61.

    Scaling Concepts In Polymer Physics, (Cornell University Press, London, UK, 1979).

  62. 62.

    , , & Conformation of single poly(methyl methacrylate) chains in an ultra-thin film studied by scanning near-field optical microscopy. Polym J. 40, 274–280 (2008).

  63. 63.

    , , , , , & Perimeter length and form factor in two-dimensional polymer melts. Phys. Rev. E 79, 050802-1–050802-4 (2009).

  64. 64.

    Computer simulation study of two-dimensional polymer solution. Macromolecules 36, 5854–5862 (2003).

  65. 65.

    & Chain conformation in two-dimensional dense state. J. Chem. Phys. 121, 8158–8162 (2004).

  66. 66.

    & Two-dimensional microphase separation of a block copolymer in a Langmuir-Blodgett film. J. Am. Chem. Soc. 120, 423–424 (1998).

  67. 67.

    , , , , , & Individual bottle brush molecules in dense 2D layers restoring high degree of extension after collapse-decollapse cycle: directly measured scaling exponent. Eur. Phys. J. E 29, 73–85 (2009).

  68. 68.

    , , & Reversible hierarchical phase separation of a poly(methyl methacrylate) and poly(n-nonyl acrylate) blend in a Langmuir monolayer. Macromolecules 43, 9077–9086 (2010).

  69. 69.

    , & (eds). Noncontact Atomic Force Microscopy, Vol. 2 (Springer, Berlin, Germany, 2009).

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Acknowledgements

We thank our co-workers for their excellent contributions reported in this review. In particular, Emeritus Professors Naoya Ogata and Takeji Hashimoto and Professor Eiji Yashima are highly appreciated. Financial support from the Japan Science and Technology Agency and MEXT/JSPS KAKENHI Grand Numbers 20106009, 21350059, 23655208, 24655091, 24350113, 25107706 and 26620092 is greatly appreciated.

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  1. Department of Polymer Science and Engineering, Graduate School of Science and Engineering, Yamagata University, Yamagata, Japan

    • Jiro Kumaki

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The authors declare no conflict of interest.

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Correspondence to Jiro Kumaki.

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https://doi.org/10.1038/pj.2015.67

Supplementary Information accompanies the paper on Polymer Journal website (http://www.nature.com/pj)

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