Structure and Thermal Transitions in a Biomedically Relevant Liquid Crystalline Poly(ester amide)
- Creators
- Bedoui, F.
- Murthy, N. S.
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Kohn, J.
Abstract
There is still a need to develop bioresorbable polymers with high strength and high modulus for load-bearing biomedical applications. Here we investigate the liquid crystalline structural features of poly(desaminotyrosyl-tyrosine dodecyl dodecanedioate), poly(DTD DD), a new bioresorbable poly(ester amide) that is currently studied in vivo as a slow-degrading implantable biomaterial for load bearing applications. Thermally induced structural changes in poly(DTD DD) were studied using simultaneously differential scanning calorimetry (DSC) and X-ray scattering. The hexatic SmB organization of the polymer chains that exists at room temperature becomes progressively disordered upon heating, changing into a SmF phase and then into a smectic C phase at 60 °C before turning into a free-flowing melt at 130 °C. X-ray scattering data and thermal analysis indicate the presence of a 2D ordered structure in the polymer melt. A structural model with an interesting 3-fold symmetry in the packing of the side chains around the rigid aromatic main chain, and the packing of these chains into fibrils is proposed. The liquid crystalline behavior of poly(DTD DD) makes it possible to melt process it at low temperatures without thermal degradation. This is a noteworthy advantage for the use of poly(DTD DD) as a high strength, readily processable, yet biodegradable polymer.
Additional Information
© 2017 American Chemical Society. Received: November 14, 2016; Revised: January 19, 2017; Publication Date (Web): February 20, 2017. This work was supported by RESBIO (Integrated Technology Resource for Polymeric Biomaterials) funded by the National Institutes of Health (NIBIB and NCMHD) under Grant P41 EB001046 and MAPS (Means for Making Polymer Materials Smart) funded by IDEX-SUPER Sorbonne Universités under Grant SU-15-R-EMR-06-1. The content is solely the responsibility of the authors and does not necessarily represent the official views of the NIH, NIBIB, or NCMHD. The authors thank Dr. Steven Weigand at the DND-CAT (supported by NSF Grant DMR-9304725, and the State of Illinois IBHE HECA NWU 96) at the Advanced Photon Source (supported by DOE Contract No. W-31-109-ENG-38), Argonne, IL, for enabling the collection of X-ray scattering data. The authors are grateful to Prof. William A. Goddard III for enabling the molecular simulations in the Materials Process and Simulation Center, California Institute of Technology, Pasadena, CA. The work was also supported by the New Jersey Center for Biomaterials at Rutgers University.Attached Files
Supplemental Material - ma6b02473_si_001.pdf
Supplemental Material - ma6b02473_si_002.pdf
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Additional details
- Eprint ID
- 74436
- Resolver ID
- CaltechAUTHORS:20170221-142726965
- P41EB001046
- NIH
- SU-15-R-EMR-06-1
- Sorbonne Universités
- DMR-9304725
- NSF
- IBHE HECA NWU 96
- State of Illinois
- W-31-109-ENG-38
- Department of Energy (DOE)
- Rutgers University
- Created
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2017-02-22Created from EPrint's datestamp field
- Updated
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2021-11-11Created from EPrint's last_modified field