Journal of Thermal Analysis and Calorimetry

, Volume 109, Issue 3, pp 1193–1201 | Cite as

Thermal analysis of spider silk inspired di-block copolymers in the glass transition region by TMDSC

  • Wenwen Huang
  • Sreevidhya Krishnaji
  • David Kaplan
  • Peggy Cebe


We used advanced thermal analysis methods to characterize a new family of A-B di-block copolymers based on the amino acid sequences of Nephila clavipes major ampulate dragline spider silk. Using temperature modulated differential scanning calorimetry with a thermal cycling method and thermogravimetry, we captured the effect of bound water acting as a plasticizer for spider silk-like biopolymer films which had been cast from water solution and then dried. A low glass transition because of bound water removal was observed in the first heating cycle, after which, a shift of glass transition was observed in A-block film due to crystallization and annealing, and in BA film due to annealing. No shift of glass transition after bound water removal was observed in B-block film. The reversing heat capacities, Cp, for temperatures below and above the glass transition were measured and compared to the calculated values. The solid state heat capacity was modeled below Tg, based on the vibrational motions of the constituent poly(amino acid)s, heat capacities of which are known from the ATHAS Data Bank. Excellent agreement was found between the measured and calculated values of the heat capacity, showing that this model can serve as a standard method to predict the solid state Cp for other biologically inspired block-copolymers. We also calculated the liquid state heat capacities of the 100% amorphous biopolymer at Tg, and this predicted value can be use to determined the crystallinity of protein-based materials.


Nephila Clavipes spider dragline silk Block copolymer Heat capacity Glass transition Temperature modulated differential scanning calorimetry X-ray diffraction 


  1. 1.
    Altman GH, Diaz F, Jakuba C, Calabro T, Horan RL, Chen JS, Lu H, Richmond J, Kaplan DL. Silk-based biomaterials. Biomaterials. 2003;24(3):401–16.CrossRefGoogle Scholar
  2. 2.
    Kluge JA, Rabotyagova U, Leisk GG, Kaplan DL. Spider silks and their applications. Trends Biotechnol. 2008;26(5):244–51.CrossRefGoogle Scholar
  3. 3.
    Krishnaji ST, Huang WW, Rabotyagova O, Kharlampieva E, Choi I, Tsukruk VV, Naik R, Cebe P, Kaplan DL. Thin film assembly of spider silk-like block copolymers. Langmuir. 2011;27(3):1000–8.CrossRefGoogle Scholar
  4. 4.
    McGrath K, Kaplan D. Protein-based materials. Boston: Birkhäuser; 1997.Google Scholar
  5. 5.
    Hayashi CY, Shipley NH, Lewis RV. Hypotheses that correlate the sequence, structure, and mechanical properties of spider silk proteins. Int J Biol Macromol. 1999;24(2–3):271–5.CrossRefGoogle Scholar
  6. 6.
    Hayashi CY, Lewis RV. Molecular architecture and evolution of a modular spider silk protein gene. Science. 2000;287(5457):1477–9.CrossRefGoogle Scholar
  7. 7.
    Lee KY, Ha WS. DSC studies on bound water in silk fibroin/S-carboxymethyl kerateine blend films. Polymer. 1999;40(14):4131–4.CrossRefGoogle Scholar
  8. 8.
    Hu X, Kaplan D, Cebe P. Dynamic protein-water relationships during beta-sheet formation. Macromolecules. 2008;41(11):3939–48.CrossRefGoogle Scholar
  9. 9.
    Hu X, Lu Q, Kaplan DL, Cebe P. Microphase separation controlled beta-sheet crystallization kinetics in fibrous proteins. Macromolecules. 2009;42(6):2079–87.CrossRefGoogle Scholar
  10. 10.
    Pyda M. Conformational contribution to the heat capacity of the starch and water system. J Polym Sci Part B. 2001;39(23):3038–54.CrossRefGoogle Scholar
  11. 11.
    Pyda M, Hu X, Cebe P. Heat capacity of silk fibroin based on the vibrational motion of poly(amino acid)s in the presence and absence of water. Macromolecules. 2008;41(13):4786–93.CrossRefGoogle Scholar
  12. 12.
    Pyda M. Conformational heat capacity of interacting systems of polymer and water. Macromolecules. 2002;35(10):4009–16.CrossRefGoogle Scholar
  13. 13.
    Hu X, Kaplan D, Cebe P. Effect of water on the thermal properties of silk fibroin. Thermochim Acta. 2007;461(1–2):137–44.CrossRefGoogle Scholar
  14. 14.
    Hu X, Kaplan D, Cebe P. Thermal analysis of protein-metallic ion systems. J Therm Anal Calorim. 2009;96(3):827–34.CrossRefGoogle Scholar
  15. 15.
    Huang WW, Krishnaji S, Hu X, Kaplan D, Cebe P. Heat capacity of spider silk-like block copolymers. Macromolecules. 2011;44(13):5299–309.CrossRefGoogle Scholar
  16. 16.
    Pyda M The advanced thermal analysis system (ATHAS) data bank. Accessed 02 2011.
  17. 17.
    Wunderlich B. Study of the change in specific heat of monomeric and polymeric glasses during the glass. J Phys Chem. 1960;64(8):1052–6.CrossRefGoogle Scholar
  18. 18.
    Wunderlich B. Thermal analysis of polymeric materials. Berlin: Springer; 2005.Google Scholar
  19. 19.
    Hu X, Kaplan D, Cebe P. Determining beta-sheet crystallinity in fibrous proteins by thermal analysis and infrared spectroscopy. Macromolecules. 2006;39(18):6161–70.CrossRefGoogle Scholar
  20. 20.
    Huang WW, Edenzon K, Fernandez L, Razmpour S, Woodburn J, Cebe P. Nanocomposites of poly(vinylidene fluoride) with multiwalled carbon nanotubes. J Appl Polym Sci. 2010;115(6):3238–48.CrossRefGoogle Scholar
  21. 21.
    Buckley J, Cebe P, Cherdack D, Crawford J, Ince BS, Jenkins M, Pan JJ, Reveley M, Washington N, Wolchover N. Nanocomposites of poly(vinylidene fluoride) with organically modified silicate. Polymer. 2006;47(7):2411–22.CrossRefGoogle Scholar
  22. 22.
    Hodge RM, Bastow TJ, Edward GH, Simon GP, Hill AJ. Free volume and the mechanism of plasticization in water-swollen poly(vinyl alcohol). Macromolecules. 1996;29(25):8137–43.CrossRefGoogle Scholar
  23. 23.
    Kim YS, Dong LM, Hickner MA, Glass TE, Webb V, McGrath JE. State of water in disulfonated poly(arylene ether sulfone) copolymers and a perfluorosulfonic acid copolymer (nafion) and its effect on physical and electrochemical properties. Macromolecules. 2003;36(17):6281–5.CrossRefGoogle Scholar
  24. 24.
    Motta A, Fambri L, Migliaresi C. Regenerated silk fibroin films: thermal and dynamic mechanical analysis. Macromol Chem Phys. 2002;203(10–11):1658–65.CrossRefGoogle Scholar
  25. 25.
    Randzio SL, Flis-Kabulska I, Grolier JPE. Reexamination of phase transformations in the starch-water system. Macromolecules. 2002;35(23):8852–9.CrossRefGoogle Scholar
  26. 26.
    Lu SX, Cebe P. Effects of annealing on the disappearance and creation of constrained amorphous phase. Polymer. 1996;37(21):4857–63.CrossRefGoogle Scholar
  27. 27.
    Pyda M, Wunderlich B. Reversing and nonreversing heat capacity of poly(lactic acid) in the glass transition region by TMDSC. Macromolecules. 2005;38(25):10472–9.CrossRefGoogle Scholar
  28. 28.
    Chen H, Hu X, Cebe P. Thermal properties and phase transitions in blends of nylon-6 with silk fibroin. J Therm Anal Calorim. 2008;93(1):201–6.CrossRefGoogle Scholar
  29. 29.
    Wunderlich B. The ATHAS database on heat-capacities of polymers. Pure Appl Chem. 1995;67(6):1019–26.CrossRefGoogle Scholar
  30. 30.
    Menczel J, Wunderlich B. Heat-capacity hysteresis of semi-crystalline macromolecular glasses. J Polym Sci Part C. 1981;19(5):261–4.Google Scholar
  31. 31.
    Warwicker JO. Comparative studies of fibroins. 2. Crystal structures of various fibroins. J Mol Biol. 1960;2(6):350–62.CrossRefGoogle Scholar

Copyright information

© Akadémiai Kiadó, Budapest, Hungary 2012

Authors and Affiliations

  • Wenwen Huang
    • 1
  • Sreevidhya Krishnaji
    • 2
  • David Kaplan
    • 3
  • Peggy Cebe
    • 1
  1. 1.Department of Physics and AstronomyCenter for Nanoscopic Physics, Tufts UniversityMedfordUSA
  2. 2.Department of ChemistryTufts UniversityMedfordUSA
  3. 3.Department of Biomedical EngineeringTufts UniversityMedfordUSA

Personalised recommendations