Effect of Block Length and Side Chain Length Ratios on Determining a Multicompartment Micelle Structure

doi:https://doi.org/10.1021/acs.jpcb.9b02231

Title: Effect of Block Length and Side Chain Length Ratios on Determining a Multicompartment Micelle Structure

Full Record
Other Related Research

Abstract

Previous work has identified the importance of the lipophilic-fluorophilic block length ratio R _l in predicting the morphology of linear lipophilic-hydrophilic-fluorophilic (hereafter referred to as BAC) micelle systems. Here, a generalized form R of this structural parameter is developed that makes no assumption of BAC triblock copolymer linearity, while still providing accurate predictions of micelle morphology. Here, the morphologies of BAC micelles formed by triblock copolymers with R <<1 or R >>1 have similar features, with the only notable difference being an inversion of the lipophilic and fluorophilic regions. A destabilization of the single-core micelle structure occurs as R approaches unity from either direction. Finally, the extent to which micelle morphology depends on polymer architecture instead of composition alone is examined, with decreased patchiness observed in BAC systems with very long block lengths. Through modification of both the R-value and the polymer architecture, the micelle morphology can be effectively tuned for use in immobilized catalysis and nanoreactor applications.

Authors:

Callaway, Connor P. ^[1]; Lee, Seung Min ^[1]; Mallard, Mackenzie ^[1]; Clark, Benjamin ^[1];

^[1]

Georgia Institute of Technology, Atlanta, GA (United States)

Publication Date:: 2019-05-13

Research Org.:: Georgia Inst. of Technology, Atlanta, GA (United States)

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

OSTI Identifier:: 1657069

Grant/Contract Number:: FG02-03ER15459

Resource Type:: Journal Article: Accepted Manuscript

Journal Name:: Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry

Additional Journal Information:: Journal Volume: 123; Journal Issue: 22; Journal ID: ISSN 1520-6106

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 77 NANOSCIENCE AND NANOTECHNOLOGY; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; 97 MATHEMATICS AND COMPUTING; Multicompartment Micelle; Effect of block length; Side chain length; Dissipative particle dynamics simulation; Polymers; Polymer morphology; Micelles; Morphology; Copolymers

Citation Formats


                    Callaway, Connor P., Lee, Seung Min, Mallard, Mackenzie, Clark, Benjamin, and Jang, Seung Soon. Effect of Block Length and Side Chain Length Ratios on Determining a Multicompartment Micelle Structure.  United States: N. p., 2019. 
        Web.  doi:10.1021/acs.jpcb.9b02231.

Copy to clipboard


                    Callaway, Connor P., Lee, Seung Min, Mallard, Mackenzie, Clark, Benjamin, & Jang, Seung Soon. Effect of Block Length and Side Chain Length Ratios on Determining a Multicompartment Micelle Structure.  United States.  https://doi.org/10.1021/acs.jpcb.9b02231

Copy to clipboard


                    Callaway, Connor P., Lee, Seung Min, Mallard, Mackenzie, Clark, Benjamin, and Jang, Seung Soon. Mon .  
        "Effect of Block Length and Side Chain Length Ratios on Determining a Multicompartment Micelle Structure".  United States.  https://doi.org/10.1021/acs.jpcb.9b02231.  https://www.osti.gov/servlets/purl/1657069.

Copy to clipboard


                    
@article{osti_1657069,

  title        = {Effect of Block Length and Side Chain Length Ratios on Determining a Multicompartment Micelle Structure},

  author       = {Callaway, Connor P. and Lee, Seung Min and Mallard, Mackenzie and Clark, Benjamin and Jang, Seung Soon},

  abstractNote = {Previous work has identified the importance of the lipophilic-fluorophilic block length ratio Rl in predicting the morphology of linear lipophilic-hydrophilic-fluorophilic (hereafter referred to as BAC) micelle systems. Here, a generalized form R of this structural parameter is developed that makes no assumption of BAC triblock copolymer linearity, while still providing accurate predictions of micelle morphology. Here, the morphologies of BAC micelles formed by triblock copolymers with R <<1 or R >>1 have similar features, with the only notable difference being an inversion of the lipophilic and fluorophilic regions. A destabilization of the single-core micelle structure occurs as R approaches unity from either direction. Finally, the extent to which micelle morphology depends on polymer architecture instead of composition alone is examined, with decreased patchiness observed in BAC systems with very long block lengths. Through modification of both the R-value and the polymer architecture, the micelle morphology can be effectively tuned for use in immobilized catalysis and nanoreactor applications.},

  doi          = {10.1021/acs.jpcb.9b02231},

  url          = {https://www.osti.gov/biblio/1657069},
  journal      = {Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry},

  issn         = {1520-6106},

  number       = 22,

  volume       = 123,

  place        = {United States},

  year         = {2019},

  month        = {5}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Accepted Manuscript (DOE)

Publisher's Version of Record

https://doi.org/10.1021/acs.jpcb.9b02231

Other availability

Search WorldCat to find libraries that may hold this journal

Citation Metrics:

Cited by: 1 work

Citation information provided by
Web of Science

Save / Share:

Export Metadata

Save to My Library

Similar records in OSTI.GOV collections:

Structural Tunability of Multicompartment Micelles as a Function of Lipophilic–Fluorophilic Block Length Ratio

Journal Article Callaway, Connor P. ; Bond, Nicholas ; Hendrickson, Kayla ; ... - Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry

Structural variation in multicompartment micelles consisting of lipophilic–hydrophilic–fluorophilic (hereafter referred to as BAC) triblock copolymers is investigated using the dissipative particle dynamics simulation method. It is demonstrated from our results that the structure of BAC multicompartment micelles is effectively tuned as a function of the lipophilic–fluorophilic ratio parameter, here termed $$R_1$$, of the constituent linear triblock copolymers. In particular, a morphological deviation from onion-like ABC micelles arises in BAC micelle systems as $$R_1$$ increases. The morphologies of BAC micelles with $$R_1\ll$$1 or $$R_1\gg$$1 display striking similarities, with the only notable difference being an inversion of the lipophilic and fluorophilic regions.more »« less
Cited by 1
https://doi.org/10.1021/acs.jpcb.8b07769

Full Text Available
Dissipative particle dynamics simulation of multicompartment micelle nanoreactor with channel for reactants

Journal Article Lee, Seung Min ; Bond, Nicholas ; Callaway, Connor ; ... - RSC Advances

The structural variation of multicompartment micelles is investigated using a dissipative particle dynamics simulation method for nano-reactor application. It turns out that well-defined multicompartment micelles with channel structures can be generated through the self-assembly of triblock copolymers consisting of a hydrophilic (A), a lipophilic (B), and a fluorophobic (C) block arranged in a B–A–C sequence: The corona and core are formed by the hydrophilic A block and the fluorophilic C block, respectively while the channel between the aqueous phase and core is formed by the lipophilic B block and the core. By performing a set of simulations, it is confirmedmore »« less
https://doi.org/10.1039/C8RA07023G
Reversible Photoswitching in Poly(2-oxazoline) Nanoreactors

Journal Article Kuepfert, Michael ; Qu, Peiyuan ; Cohen, Aaron E. ; ... - Chemistry - A European Journal

This contribution reports light responsive catalytic nanoreactors based on poly(2-oxazoline) diblock copolymers. The hydrophobic block of the copolymer is a random copolymer consisting of a spiropyran functionalized 2-oxazoline (SPOx) and 2-(but-3-yn-1-yl)-4,5-dihydrooxazole (ButynOx), while the hydrophilic block is based on 2-methyl-2-oxazoline (MeOx). The block copolymer is terminated with tris(2-aminoethyl) amine (TREN) that serves as catalyst in a Knoevenagel condensation. Four block copolymers with different ButynOx/SPOx and hydrophilic/hydrophobic ratios are synthesized and self-assembled through solvent exchange. Micelles and vesicles of various sizes are observed by TEM, which undergo morphological and size changes in response to irradiation with UV light. We hypothesize thatmore »« less
https://doi.org/10.1002/chem.202000179

Full Text Available
Poly(methyl methacrylate)- block-poly( n-butyl methacrylate) Diblock Copolymer Micelles in an Ionic Liquid: Scaling of Core and Corona Size with Core Block Length

Journal Article Ma, Yuanchi ; Lodge, Timothy P. - Macromolecules

Here, the structure of poly(methyl methacrylate)-block-poly(n-butyl methacrylate) (PMMA-b-PnBMA) micelles in the room temperature ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][TFSI]), a selective solvent for the PMMA block, has been studied using dynamic light scattering (DLS) and small-angle X-ray scattering (SAXS). A series of seven PMMA-b-PnBMA diblock copolymers were prepared by reversible addition–fragmentation chain-transfer (RAFT) polymerization, in which the degree of polymerization of the PMMA block was kept constant while the PnBMA block length was varied. All the polymers formed spherical micelles at ambient temperature in dilute solution; their hydrodynamic radius (R _h) and core radius (R _c) were obtained by DLS andmore »« less
Cited by 10
https://doi.org/10.1021/acs.macromol.6b00315

Full Text Available
Polydispersity-Driven Block Copolymer Amphiphile Self-Assembly into Prolate-Spheroid Micelles

Journal Article Schmitt, Andrew L. ; Repollet-Pedrosa, Milton H. ; Mahanthappa, Mahesh K. - ACS Macro Lett.

The aqueous self-assembly behavior of polydisperse poly(ethylene oxide-b-1,4-butadiene-b-ethylene oxide) (OBO) macromolecular triblock amphiphiles is examined to discern the implications of continuous polydispersity in the hydrophobic block on the resulting aqueous micellar morphologies of otherwise monodisperse polymer surfactants. The chain length polydispersity and implicit composition polydispersity of these samples furnishes a distribution of preferred interfacial curvatures, resulting in dilute aqueous block copolymer dispersions exhibiting coexisting spherical and rod-like micelles with vesicles in a single sample with a O weight fraction, w{sub O}, of 0.18. At higher w{sub O} = 0.51-0.68, the peak in the interfacial curvature distribution shifts and we observemore »« less
https://doi.org/10.1021/mz200156s

Similar Records