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Morphology and Crystallinity Control of Novel Spider Silk-like Block Copolymer

Published online by Cambridge University Press:  10 May 2012

Wenwen Huang
Affiliation:
Department of Physics and Astronomy, Center for Nanoscopic Physics, Tufts University, Medford, MA 02155, USA
Sreevidhya Krishnaji
Affiliation:
Department of Chemistry, Tufts University, Medford, MA 02155, USA
David Kaplan
Affiliation:
Department of Biomedical Engineering, Tufts University, Medford, MA 02155, USA
Peggy Cebe*
Affiliation:
Department of Physics and Astronomy, Center for Nanoscopic Physics, Tufts University, Medford, MA 02155, USA
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Abstract

A new family of A-B di-block copolymers based on the amino acid sequences of Nephila clavipes major ampulate dragline spider silk, which have a strong potential for applications in tissue regeneration and drug delivery, was synthesized and characterized. The morphology was assessed by SEM: HBA3 formed fibrillar structure and 2 μm diameter hollow micelles, while HBA4 and HBA6 formed hollow micelles in water solution. The secondary structures of water-cast spider silk-like block copolymer films were assessed by FTIR. The crystallinity was determined by Fourier self-deconvolution of the amide I spectra and confirmed by wide angle X-ray diffraction. Results indicate that the self-assembled morphology and the crystallinity can be varied by changing the length of A-block, and a minimum of 3 A-blocks are required to form β sheet crystalline regions in water-cast spider silk block copolymers. A theoretical model was used to predict the specific reversing heat capacity, Cp(T), which is crucial to the design of smart biomaterials. Excellent agreement was found between the theoretical value and the Cp(T) determined by temperature modulated differential scanning calorimetry. This method can serve as a standard by which to assess the thermal properties for other biologically inspired block copolymers, and then be further applied to control the biological interactions for use in drug delivery and smart biomaterials applications.

Type
Research Article
Copyright
Copyright © Materials Research Society 2012

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References

REFERENCES

1. Kluge, J.A., Rabotyagova, O.S., Leisk, G.G., Kaplan, D.L., Trends in Biotechnology 26 (2008) 244251.Google Scholar
2. McGrath, K., Kaplan, D., “ Protein-based materials” (Birkhäuser, Boston, 1997), p.103, 429 p.Google Scholar
3. Rabotyagova, O.S., Cebe, P., Kaplan, D.L., Biomacromolecules 10 (2009) 229236.Google Scholar
4. Krishnaji, S., Huang, W.W., Rabotyagova, O.S., Kharlampieva, E., Choi, I., Tsukruk, V. V., Naik, R., Cebe, P., Kaplan, D. L., Langmuir 27 (2011) 10001008.Google Scholar
5. Huang, W.W., Krishnaji, S., Hu, X., Kaplan, D., Cebe, P., Macromolecules 44 (2011) 52995309.Google Scholar
6. Huang, W.W., Krishnaji, S., Kaplan, D., Cebe, P., Journal of Thermal Analysis and Calorimetry in press (2012).Google Scholar
7. Warwicker, J.O., Journal of Molecular Biology 2 (1960) 350362.Google Scholar
8. Huang, W.W., Edenzon, K., Fernandez, L., Razmpour, S., Woodburn, J., Cebe, P., Journal of Applied Polymer Science 115 (2010) 32383248.Google Scholar
9. Barth, A., Zscherp, C., Quarterly Reviews of Biophysics 35 (2002) 369430.Google Scholar
10. Pyda, M., The Advanced THermal Analysis System (ATHAS) Data Bank, in: http://athas.prz.rzeszow.pl/Default.aspx?op=db.Google Scholar
11. Pyda, M., Hu, X., Cebe, P., Macromolecules 41 (2008) 47864793.Google Scholar