scholarly journals Advances in the Structural Design of Polyelectrolyte Complex Micelles

Author(s):  
Alexander E. Marras ◽  
Jeffrey M. Ting ◽  
Kaden C. Stevens ◽  
Matthew V. Tirrell
Molecules ◽  
2020 ◽  
Vol 25 (11) ◽  
pp. 2553
Author(s):  
Jeffrey M. Ting ◽  
Alexander E. Marras ◽  
Joseph D. Mitchell ◽  
Trinity R. Campagna ◽  
Matthew V. Tirrell

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.


Nano Letters ◽  
2018 ◽  
Vol 18 (11) ◽  
pp. 7111-7117 ◽  
Author(s):  
Michael Lueckheide ◽  
Jeffrey R. Vieregg ◽  
Alex J. Bologna ◽  
Lorraine Leon ◽  
Matthew V. Tirrell

2014 ◽  
Vol 2 (46) ◽  
pp. 8142-8153 ◽  
Author(s):  
Cheng-Hsiang Kuo ◽  
Lorraine Leon ◽  
Eun Ji Chung ◽  
Ru-Ting Huang ◽  
Timothy J. Sontag ◽  
...  

Polyelectrolyte complex micelles have great potential as gene delivery vehicles because of their ability to encapsulate charged nucleic acids forming a core by neutralizing their charge, while simultaneously protecting the nucleic acids from non-specific interactions and enzymatic degradation.


Langmuir ◽  
2010 ◽  
Vol 26 (12) ◽  
pp. 9802-9808 ◽  
Author(s):  
Saskia Lindhoud ◽  
Willem Norde ◽  
Martien A. Cohen Stuart

2016 ◽  
Vol 146 ◽  
pp. 152-160 ◽  
Author(s):  
Thiruganesh Ramasamy ◽  
Bijay Kumar Poudel ◽  
Himabindu Ruttala ◽  
Ju Yeon Choi ◽  
Truong Duy Hieu ◽  
...  

2019 ◽  
Author(s):  
Hao Wu ◽  
Jeffrey Ting ◽  
Matthew Tirrell

<div> <div> <p>Polyelectrolyte-based nanoscale self-assemblies, such as micelles, possess diverse desirable attributes such as capability for sequestering and protecting biomacromolecules against inhospitable environments, responsiveness to external stimuli, and tunability of physical behavior. However, little is known on the mechanisms of dissociation when micelles encounter and respond to environmental changes. Using salt-jump, time-dependent, light scattering, the pathway of dissociation is observed in polyelectrolyte complex micelles that have complex cores and neutral coronas. The micelle dissociation kinetics appear to be a three-staged process, in good agreement with the scattering data. Using kinetic models of amphiphilic block copolymer micelles in polyelectrolyte complexation-driven micelles, we derive an analytical expression for dissociation relaxation rates as a function of solvent temperature, salt concentration, and the length of the charged polymer blocks. The theoretical predictions are compatible with the experimental data from light scattering experiments. This study demonstrates experimentally the relaxation kinetics of polyelectrolyte complex micelle dissociation and illustrates the underlying mechanism governing the dissociation kinetics. It is anticipated that these findings can be generalized to other electrostatic interaction-driven self-assemblies to better understand the relationship among the kinetics of dissociation, constituent polymer properties, and environmental parameters.<br></p> </div> </div>


2019 ◽  
Author(s):  
Alexander Marras ◽  
Jeffrey Vieregg ◽  
Matthew Tirrell

We provide protocols and representative data for designing, assembling, and characterizing polyelectrolyte complex micelles (core-shell nanoparticles formed by polyelectrolytes and hydrophilic charged-uncharged block copolymers).


2020 ◽  
Author(s):  
Jeffrey Ting ◽  
Alexander Marras ◽  
Joseph Mitchell ◽  
Trinity Campagna ◽  
Matthew Tirrell

<p>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)-<i>block</i>-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)-<i>block</i>-poly((vinylbenzyl) trimethylammonium) (PEG-PVBTMA) and poly(ethylene glycol)-<i>block</i>-poly(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 core diameter of ~40 nm when PMPC-PVBTMA was used, and smaller particles between 20-30 nm for PEG-PLK and PEG-PVBTMA via SAXS analysis. Additionally, 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.</p>


2014 ◽  
Vol 2 (37) ◽  
pp. 6324 ◽  
Author(s):  
Thiruganesh Ramasamy ◽  
Jeong Hwan Kim ◽  
Ju Yeon Choi ◽  
Tuan Hiep Tran ◽  
Han-Gon Choi ◽  
...  

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