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Nucleation effects of high molecular weight polymer additives on low molecular weight gels

Polymer Journalvolume 50pages775786 (2018) | Download Citation


Polymeric species have been introduced to low molecular weight gelators to tailor their nucleation and rheological behavior. This work combines polymers and molecular gels (MGs) in a different manner by using polymers as the major component in a solution. Additionally, using polymers above their entanglement molecular weight is a step towards building polymer–MG composite materials. Specifically, a cholesterol-pyridine (CP) molecular gel was introduced to poly(ethylene oxide-co-epichlorohydrin) (EO-EPI) and poly(vinyl acetate) (PVAc), which have dissimilar chain conformations in anisole. Dynamic light scattering, scanning electron microscopy, and temperature-dependent small- and wide-angle X-ray studies were utilized to investigate the influence of the solution properties of high molecular weight EO-EPI and PVAc on the CP network structure. The collapsed chain conformation and aggregation of EO-EPI led to isolated, branched CP fiber networks, resulting in unexpectedly high dissociation temperatures. In contrast, PVAc gels displayed transient fiber networks, as evidenced by fiber wrapping and bundling. Cooperative interactions between PVAc and CP resulted in gels with dissociation temperatures higher than those of pure CP gels. These structural characteristics significantly influenced the gel mechanics. The collapsed chain conformation of EO-EPI led to weaker, more viscous gels, and the freely extended PVAc chain conformation led to interconnected, elastic gels independent of the molecular gel concentration.

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  1. 1.

    Dagnon KL, Shanmuganathan K, Weder C, Rowan SJ. Water-triggered modulus changes of cellulose nanofiber nanocomposites with hydrophobic polymer matrices. Macromolecules. 2012;45:4707–15.

  2. 2.

    Paul DR, Robeson LM. Polymer nanotechnology: nanocomposites. Polymer. 2008;49:3187–204.

  3. 3.

    Luo H, Hu J, Zhu Y. Path-dependent and selective multi-shape recovery of a polyurethane/cellulose-whisker nanocomposite. Mater Lett. 2012;89:172–5.

  4. 4.

    Wu T, Frydrych M, Kelly KO, Chen B. Poly(glycerol sebacate urethane)–cellulose nanocomposites with water-active shape-memory effects. Biomacromolecules. 2014;15:2663–71.

  5. 5.

    Huang ZM, Zhang YZ, Kotaki M, Ramakrishna S. A review on polymer nanofibers by electrospinning and their applications in nanocomposites. Compos Sci Technol. 2003;63:2223–53.

  6. 6.

    Jordan J, Jacob KI, Tannenbaum R, Sharaf MA, Jasiuk I. Experimental trends in polymer nanocomposites—a review. Mater Sci Eng A. 2005;393:1–11.

  7. 7.

    Cudjoe E, et al. Biomimetic reversible heat-stiffening polymer nanocomposites. ACS Cent Sci. 2017;3:886–94.

  8. 8.

    Sattar R, Kausar A, Siddiq M. Advances in thermoplastic polyurethane composites reinforced with carbon nanotubes and carbon nanofibers: a review. J Plast Film Sheet. 2014;31:186–224.

  9. 9.

    De Leon AC, et al. High performance polymer nanocomposites for additive manufacturing applications. React Funct Polym. 2016;103:141–55.

  10. 10.

    McNally, T, Potschke, P. Polymer-carbon nanotube composites. Woodhead Publishing Limited: Cambridge; 2011.

  11. 11.

    Stone DA, Wilusz E, Zukas W, Wnek G, Korley LTJ. Mechanical enhancement via self-assembled nanostructures in polymer nanocomposites. Soft Matter. 2011;7:2449–55.

  12. 12.

    Weiss, RG, Terech, P. Molecular gels: materials with self-assembled fibrillar networks. Springer: Netherlands; 2006.

  13. 13.

    Cui J, Shen Z, Wan X. Study on the gel to crystal transition of a novel sugar-appended gelator. Langmuir. 2010;26:97–103.

  14. 14.

    Reddy SMM, Shanmugam G, Duraipandy N, Kiran MS, Mandal AB. An additional fluorenylmethoxycarbonyl (Fmoc) moiety in di-Fmoc-functionalized L-lysine induces pH-controlled ambidextrous gelation with significant advantages. Soft Matter. 2015;11:8126–40.

  15. 15.

    Delbecq F, Kaneko N, Endo H, Kawai T. Solvation effects with a photoresponsive two-component 12-hydroxystearic acid-azobenzene additive organogel. J Colloid Interface Sci. 2012;384:94–98.

  16. 16.

    Pozzo J-L, Clavier GM, Desvergne J-P. Rational design of new acid-sensitive organogelators. J Mater Chem. 1998;8:2575–7.

  17. 17.

    Roy S, et al. Dramatic specific-ion effect in supramolecular hydrogels. Chem A Eur J. 2012;18:11723–31.

  18. 18.

    Yu, X, Chen, L, Zhang, M, Yi, T. Low-molecular-mass gels responding to ultrasound and mechanical stress: towards self-healing materials. Chem Soc Rev. 2014;43:5346–71.

  19. 19.

    Kiyonaka S, Zhou S-L, Hamachi I. pH-responsive phase transition of supramolecular hydrogel consisting of glycosylated amino acetate and carboxylic acid derivative. Supramol Chem. 2003;15:521–8.

  20. 20.

    Terech, P, Ostuni, E, Weiss, RG. Structural study of cholesteryl anthraquinone-2-carboxylate (CAQ) physical organogels by neutron and X-ray small angle scattering. J Phys Chem. 1966;100:3759–66.

  21. 21.

    Sakurai, K, Kimura, T, Gronwald, O, Inoue, K, Shinkai, S. A hexagonally organized elemental supramolecular structure of a sugar-appended organogelator observed by synchrotron X-ray source. Chem. Lett. 2001:746–7.

  22. 22.

    Lim GS, Jung BM, Lee SJ, Song HH, Kim C. Synthesis of polycatenar-type organogelators based on chalcone and study of their supramolecular architectures. Chem Mater. 2007;19:460–7.

  23. 23.

    Xing P, Chen H, Bai L, Hao A, Zhao Y. Superstructure formation and topological evolution achieved by self-organization of a highly adaptive dynamer. ACS Nano. 2016;10:2716–27.

  24. 24.

    Babu TM, Prasad E. Charge-transfer-assisted supramolecular 1 D nanofibers through a cholesteric structure-directing agent: self-assembly design for supramolecular optoelectronic materials. Chem A Eur J. 2015;1599:11972–5.

  25. 25.

    Links, DA, Dhinakaran, MK, Das, TM. Studies on a novel class of triaryl pyridine N-glycosylamine amphiphiles as super gelators. Org Biomol Chem. 2012:2077–83. https://doi.org/10.1039/c2ob06834f

  26. 26.

    Li JL, Liu XY. Architecture of supramolecular soft functional materials: from understanding to micro-/nanoscale engineering. Adv Funct Mater. 2010;20:3196–216.

  27. 27.

    Cornwell DJ, Smith DK. Expanding the scope of gels—combining polymers with low-molecular-weight gelators to yield modified self-assembling smart materials with high-tech applications. Mater Horiz. 2015;2:279–93.

  28. 28.

    Pont G, Chen L, Spiller DG, Adams DJ. The effect of polymer additives on the rheological properties of dipeptide hydrogelators. Soft Matter. 2012;8:7797.

  29. 29.

    Adhia YJ, Schloemer TH, Perez MT, McNeil AJ. Using polymeric additives to enhance molecular gelation: impact of poly(acrylic acid) on pyridine-based gelators. Soft Matter. 2012;8:430.

  30. 30.

    Zhang Z, et al. Enhancing gelation ability of a dendritic gelator through complexation with a polyelectrolyte. Chem A Eur J. 2009;15:2352–61.

  31. 31.

    Way AE, et al. Enhancing the mechanical properties of guanosine-based supramolecular hydrogels with guanosine-containing polymers. Macromolecules. 2014;47:1810–8.

  32. 32.

    Liu XY, et al. Creating new supramolecular materials by architecture of three-dimensional nanocrystal fiber networks. J Am Chem Soc. 2002;124:15055–63.

  33. 33.

    Landel, RF, Nielsen, LE. Mechanical properties of polymers and composites. CRC Press: New York, USA; 1993.

  34. 34.

    Malik S, Kawano Sichiro, Fujita N, Shinkai S. Pyridine-containing versatile gelators for post-modification of gel tissues toward construction of novel porphyrin nanotubes. Tetrahedron. 2007;63:7326–33.

  35. 35.

    Anisole. National Center for Biotechnology Information, PubChem Compound Database; CID=7519, https://pubchem.ncbi.nlm.nih.gov/compound/7519 (accessed May 2, 2018).

  36. 36.

    Geng S, Haque MMU, Oksman K. Crosslinked poly(vinyl acetate) (PVAc) reinforced with cellulose nanocrystals (CNC): structure and mechanical properties. Compos Sci Technol. 2016;126:35–42.

  37. 37.

    Wanasekara ND, Matolyak LE, Korley LTJ. Tunable mechanics in electrospun composites via hierarchical organization. ACS Appl Mater Interfaces. 2015;7:22970–9.

  38. 38.

    Qiu X, Hu S. ‘Smart’ materials based on cellulose: a review of the preparations, properties, and applications. Mater. 2013;6:738–81.

  39. 39.

    Miao C, Hamad WY. Cellulose reinforced polymer composites and nanocomposites: a critical review. Cellulose. 2013;20:2221–62.

  40. 40.

    Alexander SLM, Korley LTJ. Tunable hygromorphism: structural implications of low molecular weight gels and electrospun nanofibers in bilayer composites. Soft Matter. 2017;13:283–91.

  41. 41.

    Yan N, et al. Pyrenyl-linker-glucono gelators. Correlations of gel properties with gelator structures and characterization of solvent effects. Langmuir. 2013;29:793–805.

  42. 42.

    Huang Y, et al. Unusual C − I ··· O halogen bonding in triazole derivatives: gelation solvents at two extremes of polarity and formation of superorganogels. Langmuir. 2017;33:311–21.

  43. 43.

    Chakraborty P, Bairi P, Roy B, Nandi AK. Improved mechanical and electronic properties of co-assembled folic acid gel with aniline and polyaniline. ACS Appl Mater Interfaces. 2014;6:3615–22.

  44. 44.

    Zhang Y, et al. Electrospun biomimetic nanocomposite nanofibers of hydroxyapatite/chitosan for bone tissue engineering. Biomaterials. 2008;29:4314–22.

  45. 45.

    Xue P, et al. Functional organogel based on a salicylideneaniline derivative with enhanced fluorescence emission and photochromism. Chem A Eur J. 2007;13:8231–9.

  46. 46.

    Takeno H, Mochizuki T. A structural development of an organogel explored by synchrotron time-resolved small-angle X-ray scattering. Colloid Polym Sci. 2013;291:2783–9.

  47. 47.

    Wu Y, et al. Photoinduced reversible gel–sol transitions of dicholesterol-linked azobenzene derivatives through breaking and reforming of van der Waals interactions. Soft Matter. 2011;7:716–21.

  48. 48.

    Luo X, Li Z, Xiao W, Wang Q, Zhong J. Self-assembled organogels formed by monochain derivatives of ethylenediamine. J Colloid Interface Sci. 2009;336:803–7.

  49. 49.

    Chen W, Yang Y, Lee CH, Shen AQ. Confinement effects on the self-assembly of 1,3:2,4-di-p-methylbenzylidene sorbitol based organogel. Langmuir. 2008;24:10432–6.

  50. 50.

    Chakraborty P, Roy B, Bairi P, Nandi AK. Improved mechanical and photophysical properties of chitosan incorporated folic acid gel possessing the characteristics of dye and metal ion absorption. J Mater Chem. 2012;22:20291.

  51. 51.

    Li JL, Yuan B, Liu XY, Wang XG, Wang RY. Kinetically controlled homogenization and transformation of crystalline fiber networks in supramolecular materials. Cryst Growth Des. 2011;11:3227–34.

  52. 52.

    Sangeetha NM, Maitra U. Supramolecular gels: functions and uses. Chem Soc Rev. 2005;34:821–36.

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The authors acknowledge financial support from the DuPont Young Professor Grant. S. Alexander would like to thank the NSF Graduate Research Fellowship for financial support. This research used resources from the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract no. DE-AC02-06CH11357. This work made use of the MRSEC Shared Experimental Facilities at MIT, supported by the National Science Foundation under award number DMR-14-19807. Additionally, this work utilized the Advanced Materials Characterization Laboratory (AMCL) and the Keck Center for Advanced Microscopy and Microanalysis (Keck CAMM) at the University of Delaware for dynamic light scattering and scanning electron microscopy, respectively. This work also benefited from the use of the SasView application, originally developed under NSF award DMR-0520547. SasView contains code developed with funding from the European Union’s Horizon 2020 research and innovation programme under the SINE2020 project, Grant agreement no 654000.

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  1. Department of Macromolecular Science and Engineering, Case Western Reserve University, Cleveland, OH, 44106, USA

    • Symone L. M. Alexander
  2. Department of Materials Science and Engineering, University of Delaware, Newark, DE, 19716, USA

    • Symone L. M. Alexander
    •  & LaShanda T. J. Korley
  3. Department of Chemical and Biomolecular Engineering, University of Delaware, Newark, DE, 19716, USA

    • LaShanda T. J. Korley


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Correspondence to LaShanda T. J. Korley.

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