Structure and Thermal Transitions in a Biomedically Relevant Liquid Crystalline Poly(ester amide)

Bedoui, F.; Murthy, N. S.; Kohn, J.

doi:10.1021/acs.macromol.6b02473

Title: Structure and Thermal Transitions in a Biomedically Relevant Liquid Crystalline Poly(ester amide)

Journal Article · Mon Feb 20 00:00:00 EST 2017 · Macromolecules

DOI:https://doi.org/10.1021/acs.macromol.6b02473· OSTI ID:1352237

Bedoui, F. ^[1]; Murthy, N. S. ^[2];

^[3]

Sorbonne Univ., Compiègne (France). Univ. de Technologie de Compiègne; California Inst. of Technology, Pasadena, CA (United States)
Sorbonne Univ., Compiègne (France). Univ. de Technologie de Compiègne; Rutgers Univ., Piscataway, NJ (United States)
Rutgers Univ., Piscataway, NJ (United States)

There is still a need to develop bioresorbable polymers with high strength and high modulus for load-bearing biomedical applications. In this work 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.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Sponsoring Organization:: National Institutes of Health (NIH); IDEX-SUPER Sorbonne Universités; State of Illinois; USDOE

Grant/Contract Number:: P41 EB001046; SU-15-R-EMR-06-1; DMR-9304725; W-31-109-ENG-38

OSTI ID:: 1352237

Journal Information:: Macromolecules, Vol. 50, Issue 6; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: ENGLISH

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Cited by: 12 works

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References (36)

Physico-mechanical properties of degradable polymers used in medical applications: A comparative study Engelberg, Israel; Kohn, Joachim Biomaterials, Vol. 12, Issue 3 https://doi.org/10.1016/0142-9612(91)90037-b	journal	April 1991
Biorelevant characterization of biopolymers Jaffe, Michael; Ophir, Zohar; Pai, Vaishali Thermochimica Acta, Vol. 396, Issue 1-2 https://doi.org/10.1016/s0040-6031(02)00524-5	journal	February 2003
Thermotropic hexagonal phases in polymers: common features and classification Ungar, G. Polymer, Vol. 34, Issue 10 https://doi.org/10.1016/0032-3861(93)90730-x	journal	January 1993
Design, synthesis, and pr eliminary characterization of tyrosine-containing polyarylates: New biomaterials for medical applications Fiordeliso, James; Bron, Samuel; Kohn, Joachim Journal of Biomaterials Science, Polymer Edition, Vol. 5, Issue 6 https://doi.org/10.1163/156856294x00176	journal	January 1994
Synthesis and characterization of hydrogen-bonded thermotropic liquid crystalline aromatic-aliphatic poly(ester-amide)s from amido diol Sudha, J. D. Journal of Polymer Science Part A: Polymer Chemistry, Vol. 38, Issue 13 https://doi.org/10.1002/1099-0518(20000701)38:13<2469::aid-pola190>3.0.co;2-j	journal	January 2000
Thermal analysis of complex relaxation processes in poly(desaminotyrosyl-tyrosine arylates) Collins, George; Yoo, Seung-uk; Recber, Ali Polymer, Vol. 48, Issue 4 https://doi.org/10.1016/j.polymer.2006.11.049	journal	February 2007
Structural studies of liquid-crystalline poly(ester amides) Murthy, N. S.; Aharoni, S. M. Macromolecules, Vol. 25, Issue 3 https://doi.org/10.1021/ma00029a026	journal	February 1992
Conformation of alkylene segments of poly(esteramides) in their crystalline and mesomorphic states Aharoni, S. M.; Correale, S. T.; Hammond, W. B. Macromolecules, Vol. 22, Issue 3 https://doi.org/10.1021/ma00193a023	journal	March 1989
Polymers derived from the amino acid l-tyrosine: polycarbonates, polyarylates and copolymers with poly(ethylene glycol) Bourke, Sharon L.; Kohn, Joachim Advanced Drug Delivery Reviews, Vol. 55, Issue 4 https://doi.org/10.1016/S0169-409X(03)00038-3	journal	April 2003
Degradable Poly(ester amide)s for Biomedical Applications Rodriguez-Galan, Alfonso; Franco, Lourdes; Puiggali, Jordi Polymers, Vol. 3, Issue 1 https://doi.org/10.3390/polym3010065	journal	December 2010
A Combinatorial Approach for Polymer Design Brocchini, Stephen; James, Kenneth; Tangpasuthadol, Varawut Journal of the American Chemical Society, Vol. 119, Issue 19 https://doi.org/10.1021/ja970389z	journal	May 1997
Physical Properties of Polymers Handbook Mark, James E. https://doi.org/10.1007/978-0-387-69002-5	book	January 2007
Polymer Morphology Guo, Qipeng https://doi.org/10.1002/9781118892756	book	April 2016
Transitions in linear thermotropic polyesteramides Khan, A. H.; McIntyre, J. E.; Milburn, A. H. Polymer, Vol. 24, Issue 12 https://doi.org/10.1016/0032-3861(83)90180-5	journal	December 1983
Thermotropic liquid-crystalline polyesters and polyesteramides McIntyre, James E.; Milburn, Alexander H. British Polymer Journal, Vol. 13, Issue 1 https://doi.org/10.1002/pi.4980130103	journal	March 1981
Segmented copolymers with poly(ester amide) units of uniform length: synthesis Gaymans, R. J.; de Haan, J. L. Polymer, Vol. 34, Issue 20 https://doi.org/10.1016/0032-3861(93)90202-L	journal	October 1993
Sequential poly(ester amide)s based on glycine, diols, and dicarboxylic acids: Thermal polyesterification versus interfacial polyamidation. Characterization of polymers containing stiff units Asín, L.; Armelin, E.; Montané, J. Journal of Polymer Science Part A: Polymer Chemistry, Vol. 39, Issue 24 https://doi.org/10.1002/pola.10082	journal	November 2001
Liquid Crystal Polymers. IV. Liquid Crystalline Aromatic Polyesters Jackson, W. Jerome British Polymer Journal, Vol. 12, Issue 4 https://doi.org/10.1002/pi.4980120405	journal	December 1980
A comparison of degradable synthetic polymer fibers for anterior cruciate ligament reconstruction Tovar, Nick; Bourke, Sharon; Jaffe, Michael Journal of Biomedical Materials Research Part A, Vol. 9999A https://doi.org/10.1002/jbm.a.32567	journal	January 2009
ACL reconstruction using a novel hybrid scaffold composed of polyarylate fibers and collagen fibers Tovar, Nick; Murthy, N. Sanjeeva; Kohn, Joachim Journal of Biomedical Materials Research Part A, Vol. 100A, Issue 11 https://doi.org/10.1002/jbm.a.34229	journal	June 2012
Integration of Combinatorial Synthesis, Rapid Screening, and Computational Modeling in Biomaterials Development Smith, Jack R.; Seyda, Agnieszka; Weber, Norbert Macromolecular Rapid Communications, Vol. 25, Issue 1 https://doi.org/10.1002/marc.200300193	journal	January 2004
Process–structure–property relationships of erodable polymeric biomaterials: II—long range order in poly(desaminotyrosyl arylates) Jaffe, Michael; Ophir, Zohar; Collins, George Polymer, Vol. 44, Issue 19 https://doi.org/10.1016/S0032-3861(03)00559-7	journal	September 2003
Process-structure-property relationships of erodable polymeric biomaterials, I: Poly(desaminotyrosyl arylates) Jaffe, Michael; Pai, Vaishali; Ophir, Zohar Polymers for Advanced Technologies, Vol. 13, Issue 10-12 https://doi.org/10.1002/pat.278	journal	October 2002
General procedure for evaluating amorphous scattering and crystallinity from X-ray diffraction scans of semicrystalline polymers Murthy, N. S.; Minor, H. Polymer, Vol. 31, Issue 6 https://doi.org/10.1016/0032-3861(90)90243-R	journal	June 1990
The fibrillar structure of cellulosic man-made fibers spun from different solvent systems Lenz, J.; Schurz, J.; Wrentschur, E. Journal of Applied Polymer Science, Vol. 35, Issue 8 https://doi.org/10.1002/app.1988.070350801	journal	June 1988
Changes in void content and free volume in fibers during heat setting and their influence on dye diffusion and mechanical properties Murthy, N. S.; Reimschuessel, A. C.; Kramer, V. Journal of Applied Polymer Science, Vol. 40, Issue 12 https://doi.org/10.1002/app.1990.070400120	journal	July 1990
Analysis of small-angle X-Ray scattering from fibers: Structural changes in nylon 6 upon drawing and annealing Murthy, N. S.; Bednarczyk, C.; Moore, R. A. F. Journal of Polymer Science Part B: Polymer Physics, Vol. 34, Issue 5 https://doi.org/10.1002/(SICI)1099-0488(19960415)34:5<821::AID-POLB1>3.0.CO;2-P	journal	April 1996
Comparison of intensity profile analysis and correlation function methods for studying the lamellar structures of semi-crystalline polymers using small-angle X-ray scattering Wang, Z. -G.; Hsiao, B. S.; Murthy, N. S. Journal of Applied Crystallography, Vol. 33, Issue 3 https://doi.org/10.1107/S0021889899014193	journal	June 2000
Analysis of Lamellar Structure in Semicrystalline Polymers by Studying the Absorption of Water and Ethylene Glycol in Nylons Using Small-Angle Neutron Scattering Murthy, N. S.; Akkapeddi, M. K.; Orts, W. J. Macromolecules, Vol. 31, Issue 1 https://doi.org/10.1021/ma9707603	journal	January 1998
Liquid crystallinity in collagen solutions and magnetic orientation of collagen fibrils Murthy, N. S. Biopolymers, Vol. 23, Issue 7 https://doi.org/10.1002/bip.360230710	journal	July 1984
Liquid crystalline suspensions of poly(tetrafluoroethylene) 'whiskers' Folda, Thomas; Hoffmann, Heinz; Chanzy, Henri Nature, Vol. 333, Issue 6168 https://doi.org/10.1038/333055a0	journal	May 1988
Biforked mesogens : a new type of thermotropic liquid crystals Journal de Physique, Vol. 47, Issue 4 https://doi.org/10.1051/jphys:01986004704055300	journal	January 1986
OPLS3: A Force Field Providing Broad Coverage of Drug-like Small Molecules and Proteins Harder, Edward; Damm, Wolfgang; Maple, Jon Journal of Chemical Theory and Computation, Vol. 12, Issue 1 https://doi.org/10.1021/acs.jctc.5b00864	journal	December 2015
Positional order in the smectic-G, -F, and -C layers of HBHA Kumar, Satyendra Journal de Physique, Vol. 44, Issue 1 https://doi.org/10.1051/jphys:01983004401012300	journal	January 1983
Phase diagram exhibiting a smectic-A–smectic-C–smectic-Fmeeting point Raja, V. N.; Shankar Rao, D. S.; Krishna Prasad, S. Physical Review A, Vol. 46, Issue 2 https://doi.org/10.1103/PhysRevA.46.R726	journal	July 1992
Molecular Weight Dependence of Shear Viscosity of a Polymer Monolayer: Evidence for the Lack of Chain Entanglement in the Two-Dimensional Plane Sato, Nobuhiro; Ito, Shinzaburo; Yamamoto, Masahide Macromolecules, Vol. 31, Issue 8 https://doi.org/10.1021/ma971176x	journal	April 1998

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Amides
Fibers
X-ray scattering
Phase transitions
Polymers

Title: Structure and Thermal Transitions in a Biomedically Relevant Liquid Crystalline Poly(ester amide)

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