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Comparing Zwitterionic and PEG Exteriors of Polyelectrolyte Complex Micelles

Journal Article · · Molecules
 [1];  [2];  [3];  [3];  [2]
  1. Univ. of Chicago, IL (United States). Pritzker School of Molecular Engineering; Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division. Center for Molecular Engineering; OSTI
  2. Univ. of Chicago, IL (United States). Pritzker School of Molecular Engineering; Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division. Center for Molecular Engineering
  3. Univ. of Chicago, IL (United States). Pritzker School of Molecular Engineering
A series of model polyelectrolyte complex micelles (PCMs) was prepared to investigate the consequences of neutral and zwitterionic chemistries and distinct charged cores on the size and stability of nanocarriers. Using aqueous reversible addition-fragmentation chain transfer (RAFT) polymerization, we synthesized a well-defined diblock polyelectrolyte system, poly(2-methacryloyloxyethyl phosphorylcholine methacrylate)-block-poly((vinylbenzyl) trimethylammonium) (PMPC-PVBTMA), at various neutral and charged block lengths to compare directly against PCM structure–property relationships centered on poly(ethylene glycol)-block-poly((vinylbenzyl) trimethylammonium) (PEG-PVBTMA) and poly(ethylene glycol)-block-poly(l-lysine) (PEG-PLK). After complexation with a common polyanion, poly(sodium acrylate), the resulting PCMs were characterized by dynamic light scattering (DLS) and small angle X-ray scattering (SAXS). We observed uniform assemblies of spherical micelles with a diameter ~1.5–2× larger when PMPC-PVBTMA was used compared to PEG-PLK and PEG-PVBTMA via SAXS and DLS. In addition, PEG-PLK PCMs proved most resistant to dissolution by both monovalent and divalent salt, followed by PEG-PVBTMA then PMPC-PVBTMA. All micelle systems were serum stable in 100% fetal bovine serum over the course of 8 h by time-resolved DLS, demonstrating minimal interactions with serum proteins and potential as in vivo drug delivery vehicles. This thorough study of the synthesis, assembly, and characterization of zwitterionic polymers in PCMs advances the design space for charge-driven micelle assemblies.
Research Organization:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC)
Grant/Contract Number:
AC02-06CH11357; AC02-76SF00515
OSTI ID:
1815837
Journal Information:
Molecules, Journal Name: Molecules Journal Issue: 11 Vol. 25; ISSN MOLEFW; ISSN 1420-3049
Publisher:
MDPICopyright Statement
Country of Publication:
United States
Language:
English

References (72)

Dataset for Comparing Zwitterionic and PEG Exteriors of Polyelectrolyte Complex Micelles dataset January 2020
Molecular Understanding and Design of Zwitterionic Materials journal November 2014
Poly(ethylene glycol) in Drug Delivery: Pros and Cons as Well as Potential Alternatives journal July 2010
Critical update on 2-methacryloyloxyethyl phosphorylcholine (MPC) polymer science journal January 2015
Revolutionary advances in 2‐methacryloyloxyethyl phosphorylcholine polymers as biomaterials journal February 2019
Preparation and characterization of poly(2-methacryloyloxyethyl phosphorylcholine)-block-poly(D,L-lactide) polymer nanoparticles journal January 2007
Accelerated Blood Clearance Phenomenon Upon Repeated Injection of PEG-modified PLA-nanoparticles journal July 2009
The Materials Data Facility: Data Services to Advance Materials Science Research journal July 2016
Effect of water-soluble phospholipid polymers conjugated with papain on the enzymatic stability journal January 2004
Complex coacervate core micelles journal March 2009
Bulk and nanoscale polypeptide based polyelectrolyte complexes journal January 2017
Polyelectrolyte–protein complexes journal August 2005
Nanocarriers with tunable surface properties to unblock bottlenecks in systemic drug and gene delivery journal September 2015
Nonviral Gene Delivery with Cationic Glycopolymers journal April 2019
Beyond Unpredictability: The Importance of Reproducibility in Understanding the Protein Corona of Nanoparticles journal August 2018
Antifouling Stripes Prepared from Clickable Zwitterionic Copolymers journal July 2017
Reductively Responsive Gel Capsules Prepared Using a Water-Soluble Zwitterionic Block Copolymer Emulsifier journal July 2018
Enrichment and Distribution of Pb 2+ Ions in Zwitterionic Poly(cysteine methacrylate) Brushes at the Solid–Liquid Interface journal December 2019
50th Anniversary Perspective : A Perspective on Polyelectrolyte Solutions journal December 2017
Kinetics of Morphological Transition between Cylindrical and Spherical Micelles in a Mixture of Anionic–Neutral and Cationic–Neutral Block Copolymers Studied by Time-Resolved SAXS and USAXS journal May 2018
Charge-Density-Dominated Phase Behavior and Viscoelasticity of Polyelectrolyte Complex Coacervates journal June 2019
Mechanism of Dissociation Kinetics in Polyelectrolyte Complex Micelles journal January 2020
How Corona Formation Impacts Nanomaterials as Drug Carriers journal January 2020
Structure–Property Relationships of Oligonucleotide Polyelectrolyte Complex Micelles journal October 2018
Influence of Dipole Orientation on Solution Properties of Polyzwitterions journal January 2016
Synthesis and Assembly of Designer Styrenic Diblock Polyelectrolytes journal May 2018
Interparticle Interactions in Dilute Solutions of Polyelectrolyte Complex Micelles journal June 2019
Zwitterionic Nanocarrier Surface Chemistry Improves siRNA Tumor Delivery and Silencing Activity Relative to Polyethylene Glycol journal May 2017
Poly(2-methacryloyloxyethyl phosphorylcholine) for Protein Conjugation journal October 2008
Self-Assembly, Antipolyelectrolyte Effect, and Nonbiofouling Properties of Polyzwitterions journal April 2006
Evasion of the Accelerated Blood Clearance Phenomenon by Coating of Nanoparticles with Various Hydrophilic Polymers journal August 2010
Zwitterionic Polymers Exhibiting High Resistance to Nonspecific Protein Adsorption from Human Serum and Plasma journal May 2008
Synthesis and Solution Properties of Zwitterionic Polymers journal November 2002
Facile Synthesis of Well-Defined, Biocompatible Phosphorylcholine-Based Methacrylate Copolymers via Atom Transfer Radical Polymerization at 20 °C journal August 2001
Therapeutic Protein–Polymer Conjugates: Advancing Beyond PEGylation journal September 2014
Raman Spectroscopic Study on the Structure of Water in Aqueous Polyelectrolyte Solutions journal October 2000
On the Stability and Morphology of Complex Coacervate Core Micelles: From Spherical to Wormlike Micelles journal September 2012
Zwitteration: Coating Surfaces with Zwitterionic Functionality to Reduce Nonspecific Adsorption journal April 2014
Effect of Charged Segment Length on Physicochemical Properties of Core−Shell Type Polyion Complex Micelles from Block Ionomers journal July 2003
Glucose-Functionalized, Serum-Stable Polymeric Micelles from the Combination of Anionic and RAFT Polymerizations journal May 2012
Structural Evolution of Polyelectrolyte Complex Core Micelles and Ordered-Phase Bulk Materials journal November 2014
Facile Synthesis of Well-Defined Hydrophilic Methacrylic Macromonomers Using ATRP and Click Chemistry journal November 2008
Advancing Polymeric Delivery Systems Amidst a Nucleic Acid Therapy Renaissance journal October 2013
Poly(zwitterionic)protein conjugates offer increased stability without sacrificing binding affinity or bioactivity journal December 2011
Gel phase formation in dilute triblock copolyelectrolyte complexes journal February 2017
Polymer physics of intracellular phase transitions journal November 2015
Detailed study of the reversible addition–fragmentation chain transfer polymerization and co-polymerization of 2-methacryloyloxyethyl phosphorylcholine journal January 2011
Dynamics of polyzwitterions in salt-free and salt solutions journal January 2015
The effects of poly(zwitterions)s versus poly(ethylene glycol) surface coatings on the biodistribution of protein nanoparticles journal January 2016
RAFT polymerization to form stimuli-responsive polymers journal January 2017
Molecular engineering solutions for therapeutic peptide delivery journal January 2017
An introduction to zwitterionic polymer behavior and applications in solution and at surfaces journal January 2019
Wormlike micelles: where do we stand? Recent developments, linear rheology and scattering techniques journal January 2007
Transient network topology of interconnected polyelectrolyte complex micelles journal January 2011
Design of polymeric nanoparticles for biomedical delivery applications journal January 2012
Chain dimensions and surface characterization of superhydrophilic polymer brushes with zwitterion side groups journal January 2013
Analysis of Macromolecular Polydispersity in Intensity Correlation Spectroscopy: The Method of Cumulants journal December 1972
Effect of temperature on the structure and dynamics of triblock polyelectrolyte gels journal October 2018
Non-equilibrium phenomena and kinetic pathways in self-assembled polyelectrolyte complexes journal October 2018
Micro- to macro-phase separation transition in sequence-defined coacervates journal January 2020
Irena : tool suite for modeling and analysis of small-angle scattering journal February 2009
Regularized Positive Exponential Sum (REPES) Program - A Way of Inverting Laplace Transform Data Obtained by Dynamic Light Scattering journal January 1995
Dimension of Poly(2-methacryloyloxyethyl phosphorylcholine) in Aqueous Solutions with Various Ionic Strength journal November 2006
A data ecosystem to support machine learning in materials science journal October 2019
Dataset for Comparing Zwitterionic and PEG Exteriors of Polyelectrolyte Complex Micelles dataset January 2020
Interparticle Interactions in Dilute Solutions of Polyelectrolyte Complex Micelles dataset January 2019
Engineering Peptide-Based Polyelectrolyte Complexes with Increased Hydrophobicity journal March 2019
Polyelectrolyte Complexation of Oligonucleotides by Charged Hydrophobic—Neutral Hydrophilic Block Copolymers journal January 2019
Effect of Ionic Group on the Complex Coacervate Core Micelle Structure journal March 2019
Macro- and Microphase Separated Protein-Polyelectrolyte Complexes: Design Parameters and Current Progress journal March 2019
The Importance of Poly(ethylene glycol) Alternatives for Overcoming PEG Immunogenicity in Drug Delivery and Bioconjugation journal February 2020
Assembly and Characterization of Polyelectrolyte Complex Micelles journal January 2020