Effect of stereochemistry on nanoscale assembly of ABA triblock copolymers with crystallizable blocks

Yin, Xuechen; Hewitt, David R.O.; Zheng, Bingqian; Quah, Suan P.; Stanley, Christopher B.; Grubbs, Robert B.; Bhatia, Surita R.

doi:10.1016/j.polymer.2021.123683

Effect of stereochemistry on nanoscale assembly of ABA triblock copolymers with crystallizable blocks

Journal Article · Sat May 01 00:00:00 EDT 2021 · Polymer

DOI:https://doi.org/10.1016/j.polymer.2021.123683· OSTI ID:1813236

^[1]; Hewitt, David R.O. ^[1]; Zheng, Bingqian ^[1]; Quah, Suan P. ^[1]; ^[2]; Grubbs, Robert B. ^[1]; ^[1]

Stony Brook Univ., NY (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

We report on the nanoscale assembly of poly(lactic acid)-b-poly(ethylene oxide)-b-poly(lactic acid) (PLA-PEO-PLA) triblock copolymers in water, focusing on the effect of stereochemistry, where the PLA blocks are statistical copolymers of l-lactide and d-lactide with l/d ratios of 100/0, 95/5, 90/10, 85/15, 75/25, and 50/50. Small-angle neutron scattering (SANS) shows a nearly constant d-spacing as concentration varies in triblock systems with l/d ratios of 90/10 and 95/5, which we attribute to inhomogeneity in the structure of these gels, supported by previous USANS and confocal microscopy studies. The SANS data fit well to a core-shell ellipsoid form factor model with a hard-sphere structure factor. Polymeric micelles with l/d ratios from 75/25 to 85/15 displayed very high aggregation numbers, consistent with a strong interaction between PLA chains and the enhanced storage modulus observed in rheological studies of these systems. While the 90/10 and 95/5 samples showed lower aggregation numbers, their SANS profiles shows close spacing between micelles, which may promote a high fraction of intermicellar bridging chains, also consistent with a higher storage modulus. Overall, these results provide insight into the micellar assembly behavior of block copolymers with a crystallizable block, and indicate that tuning stereochemistry of PLA-based block copolymers is an effective means of modifying micellar properties for specific applications.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1813236

Journal Information:: Polymer, Journal Name: Polymer Journal Issue: 1 Vol. 223; ISSN 0032-3861

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (52)

Double-Network Hydrogels with Extremely High Mechanical Strength Gong, J. P.; Katsuyama, Y.; Kurokawa, T. Advanced Materials, Vol. 15, Issue 14 https://doi.org/10.1002/adma.200304907	journal	July 2003
Design of Environment-Sensitive Supramolecular Assemblies for Intracellular Drug Delivery: Polymeric Micelles that are Responsive to Intracellular pH Change Bae, Younsoo; Fukushima, Shigeto; Harada, Atsushi Angewandte Chemie International Edition, Vol. 42, Issue 38 https://doi.org/10.1002/anie.200250653	journal	October 2003
Synthesis and Rheological Properties of Polylactide/Poly(ethylene glycol) Multiblock Copolymers Li, Feng; Li, Suming; Vert, Michel Macromolecular Bioscience, Vol. 5, Issue 11 https://doi.org/10.1002/mabi.200500143	journal	November 2005
Novel Structural Changes during Temperature-Induced Self-Assembling and Gelation of PLGA-PEG-PLGA Triblock Copolymer in Aqueous Solutions Khorshid, Neda Khameh; Zhu, Kaizheng; Knudsen, Kenneth D. Macromolecular Bioscience, Vol. 16, Issue 12 https://doi.org/10.1002/mabi.201600277	journal	October 2016
Tuning of Sol-Gel Transition in the Mixed Polymer Micelle Solutions of Copolymer Mixtures Consisting of Enantiomeric Diblock and Triblock Copolymers of Polylactide and Poly(ethylene glycol) Hsu, Yu-I.; Masutani, Kazunari; Yamaoka, Tetsuji Macromolecular Chemistry and Physics, Vol. 216, Issue 8 https://doi.org/10.1002/macp.201400581	journal	February 2015
Effect of homopolymer solubilization on triblock gel structure and mechanical response: Triblock Gel Structure and Mechanical Response Seitz, Michelle E.; Rottsolk, Rebecca L.; Shull, Kenneth R. Journal of Polymer Science Part B: Polymer Physics, Vol. 48, Issue 13 https://doi.org/10.1002/polb.21963	journal	March 2010
Rheological studies of PLLA–PEO–PLLA triblock copolymer hydrogels Aamer, K. Biomaterials, Vol. 25, Issue 6 https://doi.org/10.1016/S0142-9612(03)00632-X	journal	March 2004
Scattering from block copolymer micelles Pedersen, Jan Skov; Svaneborg, Carsten Current Opinion in Colloid & Interface Science, Vol. 7, Issue 3-4 https://doi.org/10.1016/S1359-0294(02)00044-4	journal	August 2002
Mathematical modeling of degradation for bulk-erosive polymers: Applications in tissue engineering scaffolds and drug delivery systems Chen, Yuhang; Zhou, Shiwei; Li, Qing Acta Biomaterialia, Vol. 7, Issue 3 https://doi.org/10.1016/j.actbio.2010.09.038	journal	March 2011
Physical and mechanical properties of PLA, and their functions in widespread applications — A comprehensive review Farah, Shady; Anderson, Daniel G.; Langer, Robert Advanced Drug Delivery Reviews, Vol. 107 https://doi.org/10.1016/j.addr.2016.06.012	journal	December 2016
Hierarchical assembly in PLA-PEO-PLA hydrogels with crystalline domains and effect of block stereochemistry Yin, Xuechen; Hewitt, David R. O.; Preston, Alyssa N. Colloids and Surfaces B: Biointerfaces, Vol. 180 https://doi.org/10.1016/j.colsurfb.2019.04.031	journal	August 2019
Biomedical applications of hydrogels: A review of patents and commercial products Caló, Enrica; Khutoryanskiy, Vitaliy V. European Polymer Journal, Vol. 65 https://doi.org/10.1016/j.eurpolymj.2014.11.024	journal	April 2015
Novel drug release profiles from micellar solutions of PLA–PEO–PLA triblock copolymers Agrawal, Sarvesh K.; Sanabria-DeLong, Naomi; Coburn, Jeannine M. Journal of Controlled Release, Vol. 112, Issue 1 https://doi.org/10.1016/j.jconrel.2005.12.024	journal	May 2006
Tumor pH-responsive flower-like micelles of poly(l-lactic acid)-b-poly(ethylene glycol)-b-poly(l-histidine) Lee, Eun Seong; Oh, Kyung Taek; Kim, Dongin Journal of Controlled Release, Vol. 123, Issue 1 https://doi.org/10.1016/j.jconrel.2007.08.006	journal	October 2007
Modelling the degradation and elastic properties of poly(lactic-co-glycolic acid) films and regular open-cell tissue engineering scaffolds Shirazi, Reyhaneh Neghabat; Ronan, William; Rochev, Yury Journal of the Mechanical Behavior of Biomedical Materials, Vol. 54 https://doi.org/10.1016/j.jmbbm.2015.08.030	journal	February 2016
Mantid—Data analysis and visualization package for neutron scattering and μ SR experiments Arnold, O.; Bilheux, J. C.; Borreguero, J. M. Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, Vol. 764 https://doi.org/10.1016/j.nima.2014.07.029	journal	November 2014
Biodegradable polymers as biomaterials Nair, Lakshmi S.; Laurencin, Cato T. Progress in Polymer Science, Vol. 32, Issue 8-9 https://doi.org/10.1016/j.progpolymsci.2007.05.017	journal	August 2007
Lifetime prediction of biodegradable polymers Laycock, Bronwyn; Nikolić, Melissa; Colwell, John M. Progress in Polymer Science, Vol. 71 https://doi.org/10.1016/j.progpolymsci.2017.02.004	journal	August 2017
Theoretical modeling and simulations of self-assembly of copolymers in solution Zhang, Qian; Lin, Jiaping; Wang, Liquan Progress in Polymer Science, Vol. 75 https://doi.org/10.1016/j.progpolymsci.2017.04.003	journal	December 2017
Mesoscopic Structures of Poly(carboxybetaine) Block Copolymer and Poly(ethylene glycol) Block Copolymer in Solutions Liao, Mingrui; Liu, Hongyan; Guo, Hongyu Langmuir, Vol. 33, Issue 30 https://doi.org/10.1021/acs.langmuir.7b01610	journal	July 2017
Chain Exchange Kinetics of Asymmetric B ₁ AB ₂ Linear Triblock and AB ₁ B ₂ Branched Triblock Copolymers Peters, Andrew J.; Lodge, Timothy P. Macromolecules, Vol. 50, Issue 16 https://doi.org/10.1021/acs.macromol.7b01046	journal	August 2017
Controlled Thermoresponsive Hydrogels by Stereocomplexed PLA-PEG-PLA Prepared via Hybrid Micelles of Pre-Mixed Copolymers with Different PEG Lengths Abebe, Daniel G.; Fujiwara, Tomoko Biomacromolecules, Vol. 13, Issue 6 https://doi.org/10.1021/bm300325v	journal	May 2012
Solvent isotope effects on alkytrimethylammonium bromide micelles as a function of alkyl chain length Berr, S. S. The Journal of Physical Chemistry, Vol. 91, Issue 18 https://doi.org/10.1021/j100302a024	journal	August 1987
Micro- to Nanoscale Structure of Biocompatible PLA−PEO−PLA Hydrogels Agrawal, Sarvesh K.; Sanabria-DeLong, Naomi; Jemian, Pete R. Langmuir, Vol. 23, Issue 9 https://doi.org/10.1021/la063390x	journal	April 2007
Energetics of Association in Poly(lactic acid)-based Hydrogels with Crystalline and Nanoparticle−Polymer Junctions Agrawal, Sarvesh K.; Sanabria-DeLong, Naomi; Bhatia, Sujata K. Langmuir, Vol. 26, Issue 22 https://doi.org/10.1021/la102760g	journal	October 2010
Looped Structure of Flowerlike Micelles Revealed by ¹ H NMR Relaxometry and Light Scattering de Graaf, Albert J.; Boere, Kristel W. M.; Kemmink, Johan Langmuir, Vol. 27, Issue 16 https://doi.org/10.1021/la2019605	journal	August 2011
Hard-sphere interactions between spherical domains in diblock copolymers Kinning, David J.; Thomas, Edwin L. Macromolecules, Vol. 17, Issue 9 https://doi.org/10.1021/ma00139a013	journal	September 1984
Thermodynamic and hydrodynamic properties of dilute solutions of cyclic and linear polystyrenes Hadziioannou, G.; Cotts, P. M.; ten Brinke, G. Macromolecules, Vol. 20, Issue 3 https://doi.org/10.1021/ma00169a006	journal	March 1987
Stereocomplex formation between enantiomeric poly(lactides) Ikada, Yoshito; Jamshidi, Khosrow; Tsuji, Hideto Macromolecules, Vol. 20, Issue 4 https://doi.org/10.1021/ma00170a034	journal	April 1987
Controlling Hydrogel Properties by Crystallization of Hydrophobic Domains Sanabria-DeLong, Naomi; Agrawal, Sarvesh K.; Bhatia, Surita R. Macromolecules, Vol. 39, Issue 4 https://doi.org/10.1021/ma052243n	journal	February 2006
Structural Characterization of PLA−PEO−PLA Solutions and Hydrogels: Crystalline vs Amorphous PLA Domains Agrawal, Sarvesh K.; Sanabria-DeLong, Naomi; Tew, Gregory N. Macromolecules, Vol. 41, Issue 5 https://doi.org/10.1021/ma070634r	journal	March 2008
Degradation of Poly(ethylene oxide) in Aqueous Solutions by Ultrasonic Waves Duval, Michel; Gross, Elisa Macromolecules, Vol. 46, Issue 12 https://doi.org/10.1021/ma400737g	journal	June 2013
Amidine-Mediated Zwitterionic Polymerization of Lactide Brown, Hayley A.; De Crisci, Antonio G.; Hedrick, James L. ACS Macro Letters, Vol. 1, Issue 9 https://doi.org/10.1021/mz300276u	journal	August 2012
Organic Catalysis for Ring-Opening Polymerization Dove, Andrew P. ACS Macro Letters, Vol. 1, Issue 12 https://doi.org/10.1021/mz3005956	journal	November 2012
Tuneable enhancement of the salt and thermal stability of polymeric micelles by cyclized amphiphiles Honda, Satoshi; Yamamoto, Takuya; Tezuka, Yasuyuki Nature Communications, Vol. 4, Issue 1 https://doi.org/10.1038/ncomms2585	journal	March 2013
Structural reorganization of cylindrical nanoparticles triggered by polylactide stereocomplexation Sun, Liang; Pitto-Barry, Anaïs; Kirby, Nigel Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms6746	journal	December 2014
Understanding the CDSA of poly(lactide) containing triblock copolymers Yu, Wei; Inam, Maria; Jones, Joseph R. Polymer Chemistry, Vol. 8, Issue 36 https://doi.org/10.1039/C7PY01056G	journal	January 2017
1D vs. 2D shape selectivity in the crystallization-driven self-assembly of polylactide block copolymers Inam, Maria; Cambridge, Graeme; Pitto-Barry, Anaïs Chemical Science, Vol. 8, Issue 6 https://doi.org/10.1039/C7SC00641A	journal	January 2017
Stereocomplexed physical hydrogels with high strength and tunable crystallizability Cao, Heqing; Chang, Xiaohua; Mao, Hailiang Soft Matter, Vol. 13, Issue 45 https://doi.org/10.1039/C7SM01491K	journal	January 2017
Impact of stereochemistry on rheology and nanostructure of PLA–PEO–PLA triblocks: stiff gels at intermediate l/d -lactide ratios Yin, Xuechen; Hewitt, David R. O.; Quah, Suan P. Soft Matter, Vol. 14, Issue 35 https://doi.org/10.1039/C8SM01559G	journal	January 2018
Morphology prediction of block copolymers for drug delivery by mesoscale simulations Posocco, Paola; Fermeglia, Maurizio; Pricl, Sabrina Journal of Materials Chemistry, Vol. 20, Issue 36 https://doi.org/10.1039/c0jm01301c	journal	January 2010
Computational and experimental investigation of morphology in thermoplastic elastomer gels composed of AB/ABA blends in B-selective solvent Sliozberg, Y. R.; Strawhecker, K. E.; Andzelm, J. W. Soft Matter, Vol. 7, Issue 16 https://doi.org/10.1039/c1sm05820g	journal	January 2011
Self-assembly of block copolymers Mai, Yiyong; Eisenberg, Adi Chemical Society Reviews, Vol. 41, Issue 18 https://doi.org/10.1039/c2cs35115c	journal	January 2012
Analysis of small angle neutron scattering spectra from polydisperse interacting colloids Kotlarchyk, Michael; Chen, Sow‐Hsin The Journal of Chemical Physics, Vol. 79, Issue 5 https://doi.org/10.1063/1.446055	journal	September 1983
Association of a multifunctional ionic block copolymer in a selective solvent Etampawala, Thusitha N.; Aryal, Dipak; Osti, Naresh C. The Journal of Chemical Physics, Vol. 145, Issue 18 https://doi.org/10.1063/1.4967291	journal	November 2016
Hard sphere-like glass transition in eye lens α-crystallin solutions Foffi, Giuseppe; Savin, Gabriela; Bucciarelli, Saskia Proceedings of the National Academy of Sciences, Vol. 111, Issue 47 https://doi.org/10.1073/pnas.1406990111	journal	November 2014
Decoupling of size and shape fluctuations in heteropolymeric sequences reconciles discrepancies in SAXS vs. FRET measurements Fuertes, Gustavo; Banterle, Niccolò; Ruff, Kiersten M. Proceedings of the National Academy of Sciences, Vol. 114, Issue 31 https://doi.org/10.1073/pnas.1704692114	journal	July 2017
Control of Scaffold Degradation in Tissue Engineering: A Review Zhang, Hongbo; Zhou, Li; Zhang, Wenjun Tissue Engineering Part B: Reviews, Vol. 20, Issue 5 https://doi.org/10.1089/ten.teb.2013.0452	journal	October 2014
Design of block-copolymer-based micelles for active and passive targeting Lebouille, Jérôme G. J. L.; Leermakers, Frans A. M.; Cohen Stuart, Martien A. Physical Review E, Vol. 94, Issue 4 https://doi.org/10.1103/PhysRevE.94.042503	journal	October 2016
Absolute calibration of small-angle neutron scattering data Wignall, G. D.; Bates, F. S. Journal of Applied Crystallography, Vol. 20, Issue 1 https://doi.org/10.1107/S0021889887087181	journal	February 1987
Preparation of Curcumin Loaded Poly(Vinyl Alcohol)-Poly(Ethylene Oxide)-Carboxymethyl Cellulose Membranes for Wound Care Application Agarwal, Roopali; Alam, M. Sarwar; Gupta, Bhuvanesh Journal of Biomaterials and Tissue Engineering, Vol. 3, Issue 3 https://doi.org/10.1166/jbt.2013.1092	journal	June 2013
Rheological characterization of biocompatible associative polymer hydrogels with crystalline and amorphous endblocks Agrawal, Sarvesh K.; Sanabria-DeLong, Naomi; Tew, Gregory N. Journal of Materials Research, Vol. 21, Issue 8 https://doi.org/10.1557/jmr.2006.0261	journal	August 2006

Similar Records

Combining Ring-Opening Metathesis Polymerization and Cyclic Ester Ring-Opening Polymerization To Form ABA Triblock Copolymers from 1,5-Cyclooctadiene and D,L-Lactide

Journal Article · Fri Jul 31 00:00:00 EDT 2009 · Macromolecules · OSTI ID:1005747

“Uncontrolled” Preparation of Disperse Poly(lactide)- block -poly(styrene)- block -poly(lactide) for Nanopatterning Applications

Journal Article · Mon Nov 07 23:00:00 EST 2016 · Macromolecules · OSTI ID:1351389

Equilibrium Structure of a Triblock Copolymer System Revealed by Mesoscale Simulation and Neutron Scattering

Journal Article · Mon Dec 31 23:00:00 EST 2012 · Physica B: Condensed Matter · OSTI ID:1110916

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Block copolymer
Hydrogel
Poly(lactic acid)

Effect of stereochemistry on nanoscale assembly of ABA triblock copolymers with crystallizable blocks

Citation Formats

References (52)

Similar Records

Related Subjects