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

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

Abstract

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 effectivemore »« less

Authors:

^[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)

Publication Date:: Sat May 01 00:00:00 EDT 2021

Research Org.:: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:: 1813236

Grant/Contract Number:: AC05-00OR22725

Resource Type:: Accepted Manuscript

Journal Name:: Polymer

Additional Journal Information:: Journal Volume: 223; Journal Issue: 1; Journal ID: ISSN 0032-3861

Publisher:: Elsevier

Country of Publication:: United States

Language:: English

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

Citation Formats


                    Yin, Xuechen, Hewitt, David R.O., Zheng, Bingqian, Quah, Suan P., Stanley, Christopher B., Grubbs, Robert B., and Bhatia, Surita R. Effect of stereochemistry on nanoscale assembly of ABA triblock copolymers with crystallizable blocks.  United States: N. p., 2021. 
Web.  doi:10.1016/j.polymer.2021.123683.

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                    Yin, Xuechen, Hewitt, David R.O., Zheng, Bingqian, Quah, Suan P., Stanley, Christopher B., Grubbs, Robert B., & Bhatia, Surita R. Effect of stereochemistry on nanoscale assembly of ABA triblock copolymers with crystallizable blocks.  United States.  https://doi.org/10.1016/j.polymer.2021.123683

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                    Yin, Xuechen, Hewitt, David R.O., Zheng, Bingqian, Quah, Suan P., Stanley, Christopher B., Grubbs, Robert B., and Bhatia, Surita R. Sat .  
"Effect of stereochemistry on nanoscale assembly of ABA triblock copolymers with crystallizable blocks".  United States.  https://doi.org/10.1016/j.polymer.2021.123683.  https://www.osti.gov/servlets/purl/1813236.

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@article{osti_1813236,

  title        = {Effect of stereochemistry on nanoscale assembly of ABA triblock copolymers with crystallizable blocks},

  author       = {Yin, Xuechen and Hewitt, David R.O. and Zheng, Bingqian and Quah, Suan P. and Stanley, Christopher B. and Grubbs, Robert B. and Bhatia, Surita R.},

  abstractNote = {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.},

  doi          = {10.1016/j.polymer.2021.123683},

  journal      = {Polymer},

  number       = 1,

  volume       = 223,

  place        = {United States},

  year         = {Sat May 01 00:00:00 EDT 2021},

  month        = {Sat May 01 00:00:00 EDT 2021}

}

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

Abstract

Citation Formats

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Computational and experimental investigation of morphology in thermoplastic elastomer gels composed of AB/ABA blends in B-selective solvent journal, January 2011

Effect of homopolymer solubilization on triblock gel structure and mechanical response: Triblock Gel Structure and Mechanical Response journal, March 2010

Modelling the degradation and elastic properties of poly(lactic-co-glycolic acid) films and regular open-cell tissue engineering scaffolds journal, February 2016

Morphology prediction of block copolymers for drug delivery by mesoscale simulations journal, January 2010

Controlling Hydrogel Properties by Crystallization of Hydrophobic Domains journal, February 2006

Amidine-Mediated Zwitterionic Polymerization of Lactide journal, August 2012

Hard-sphere interactions between spherical domains in diblock copolymers journal, September 1984

Physical and mechanical properties of PLA, and their functions in widespread applications — A comprehensive review journal, December 2016

Hard sphere-like glass transition in eye lens α-crystallin solutions journal, November 2014

Hierarchical assembly in PLA-PEO-PLA hydrogels with crystalline domains and effect of block stereochemistry journal, August 2019

Scattering from block copolymer micelles journal, August 2002

Stereocomplex formation between enantiomeric poly(lactides) journal, April 1987

Synthesis and Rheological Properties of Polylactide/Poly(ethylene glycol) Multiblock Copolymers journal, November 2005

Solvent isotope effects on alkytrimethylammonium bromide micelles as a function of alkyl chain length journal, August 1987

Novel drug release profiles from micellar solutions of PLA–PEO–PLA triblock copolymers
journal, May 2006

Mantid—Data analysis and visualization package for neutron scattering and $μ$ SR experiments
journal, November 2014

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)
journal, February 2015

Tumor pH-responsive flower-like micelles of poly(l-lactic acid)-b-poly(ethylene glycol)-b-poly(l-histidine)
journal, October 2007

Mathematical modeling of degradation for bulk-erosive polymers: Applications in tissue engineering scaffolds and drug delivery systems
journal, March 2011

Control of Scaffold Degradation in Tissue Engineering: A Review
journal, October 2014

Absolute calibration of small-angle neutron scattering data
journal, February 1987

Mesoscopic Structures of Poly(carboxybetaine) Block Copolymer and Poly(ethylene glycol) Block Copolymer in Solutions
journal, July 2017

Thermodynamic and hydrodynamic properties of dilute solutions of cyclic and linear polystyrenes
journal, March 1987

Structural reorganization of cylindrical nanoparticles triggered by polylactide stereocomplexation
journal, December 2014

Preparation of Curcumin Loaded Poly(Vinyl Alcohol)-Poly(Ethylene Oxide)-Carboxymethyl Cellulose Membranes for Wound Care Application
journal, June 2013

Tuneable enhancement of the salt and thermal stability of polymeric micelles by cyclized amphiphiles
journal, March 2013

Lifetime prediction of biodegradable polymers
journal, August 2017

Double-Network Hydrogels with Extremely High Mechanical Strength
journal, July 2003

Self-assembly of block copolymers
journal, January 2012

Chain Exchange Kinetics of Asymmetric B ₁ AB ₂ Linear Triblock and AB ₁ B ₂ Branched Triblock Copolymers
journal, August 2017

Energetics of Association in Poly(lactic acid)-based Hydrogels with Crystalline and Nanoparticle−Polymer Junctions
journal, October 2010

Biodegradable polymers as biomaterials
journal, August 2007

Organic Catalysis for Ring-Opening Polymerization
journal, November 2012

Looped Structure of Flowerlike Micelles Revealed by ¹ H NMR Relaxometry and Light Scattering
journal, August 2011

Controlled Thermoresponsive Hydrogels by Stereocomplexed PLA-PEG-PLA Prepared via Hybrid Micelles of Pre-Mixed Copolymers with Different PEG Lengths
journal, May 2012

Theoretical modeling and simulations of self-assembly of copolymers in solution
journal, December 2017

Rheological characterization of biocompatible associative polymer hydrogels with crystalline and amorphous endblocks
journal, August 2006

Impact of stereochemistry on rheology and nanostructure of PLA–PEO–PLA triblocks: stiff gels at intermediate l/d -lactide ratios
journal, January 2018

Decoupling of size and shape fluctuations in heteropolymeric sequences reconciles discrepancies in SAXS vs. FRET measurements
journal, July 2017

Novel Structural Changes during Temperature-Induced Self-Assembling and Gelation of PLGA-PEG-PLGA Triblock Copolymer in Aqueous Solutions
journal, October 2016

Stereocomplexed physical hydrogels with high strength and tunable crystallizability
journal, January 2017

1D vs. 2D shape selectivity in the crystallization-driven self-assembly of polylactide block copolymers
journal, January 2017

Analysis of small angle neutron scattering spectra from polydisperse interacting colloids
journal, September 1983

Association of a multifunctional ionic block copolymer in a selective solvent
journal, November 2016

Design of block-copolymer-based micelles for active and passive targeting
journal, October 2016

Biomedical applications of hydrogels: A review of patents and commercial products
journal, April 2015

Structural Characterization of PLA−PEO−PLA Solutions and Hydrogels: Crystalline vs Amorphous PLA Domains
journal, March 2008

Understanding the CDSA of poly(lactide) containing triblock copolymers
journal, January 2017

Degradation of Poly(ethylene oxide) in Aqueous Solutions by Ultrasonic Waves
journal, June 2013

Micro- to Nanoscale Structure of Biocompatible PLA−PEO−PLA Hydrogels
journal, April 2007

Design of Environment-Sensitive Supramolecular Assemblies for Intracellular Drug Delivery: Polymeric Micelles that are Responsive to Intracellular pH Change
journal, October 2003

Rheological studies of PLLA–PEO–PLLA triblock copolymer hydrogels
journal, March 2004

Computational and experimental investigation of morphology in thermoplastic elastomer gels composed of AB/ABA blends in B-selective solvent
journal, January 2011

Effect of homopolymer solubilization on triblock gel structure and mechanical response: Triblock Gel Structure and Mechanical Response
journal, March 2010

Modelling the degradation and elastic properties of poly(lactic-co-glycolic acid) films and regular open-cell tissue engineering scaffolds
journal, February 2016

Morphology prediction of block copolymers for drug delivery by mesoscale simulations
journal, January 2010

Controlling Hydrogel Properties by Crystallization of Hydrophobic Domains
journal, February 2006

Amidine-Mediated Zwitterionic Polymerization of Lactide
journal, August 2012

Hard-sphere interactions between spherical domains in diblock copolymers
journal, September 1984

Physical and mechanical properties of PLA, and their functions in widespread applications — A comprehensive review
journal, December 2016

Hard sphere-like glass transition in eye lens α-crystallin solutions
journal, November 2014

Hierarchical assembly in PLA-PEO-PLA hydrogels with crystalline domains and effect of block stereochemistry
journal, August 2019

Scattering from block copolymer micelles
journal, August 2002

Stereocomplex formation between enantiomeric poly(lactides)
journal, April 1987

Synthesis and Rheological Properties of Polylactide/Poly(ethylene glycol) Multiblock Copolymers
journal, November 2005

Solvent isotope effects on alkytrimethylammonium bromide micelles as a function of alkyl chain length
journal, August 1987