Canopy Dynamics in Nanoscale Ionic Materials

Michael L. Jespersen; Peter A. Mirau; Ernst von Meerwall; Richard A. Vaia; Robert Rodriguez; Emmanuel P. Giannelis

doi:10.1021/nn100112h

Canopy Dynamics in Nanoscale Ionic Materials

Michael L. Jespersen, Peter A. Mirau, Ernst von Meerwall, Richard A. Vaia, Robert Rodriguez, Emmanuel P. Giannelis

Research output: Contribution to journal › Article › peer-review

72 Scopus citations

Abstract

Nanoscale ionic materials (NIMS) are organic - inorganic hybrids in which a core nanostructure is functionalized with a covalently attached corona and an ionically tethered organic canopy. NIMS are engineered to be liquids under ambient conditions in the absence of solvent and are of interest for a variety of applications. We have used nuclear magnetic resonance (NMR) relaxation and pulse-field gradient (PFG) diffusion experiments to measure the canopy dynamics of NIMS prepared from 18-nm silica cores modified by an alkylsilane monolayer possessing terminal sulfonic acid functionality, paired with an amine-terminated ethylene oxide/propylene oxide block copolymer canopy. Carbon NMR studies show that the block copolymer canopy is mobile both in the bulk and in the NIMS and that the fast (ns) dynamics are insensitive to the presence of the silica nanoparticles. Canopy diffusion in the NIMS is slowed relative to the neat canopy, but not to the degree predicted from the diffusion of hard-sphere particles. Canopy diffusion is not restricted to the surface of the nanoparticles and shows unexpected behavior upon addition of excess canopy. Taken together, these data indicate that the liquid-like behavior in NIMS is due to rapid exchange of the block copolymer canopy between the ionically modified nanoparticles. © 2010 American Chemical Society.

Original language	English (US)
Pages (from-to)	3735-3742
Number of pages	8
Journal	ACS Nano
Volume	4
Issue number	7
DOIs	https://doi.org/10.1021/nn100112h
State	Published - Jun 10 2010
Externally published	Yes

Bibliographical note

KAUST Repository Item: Exported on 2020-10-01
Acknowledged KAUST grant number(s): KUS-C1-018-02
Acknowledgements: Funding provided by the Air Force Office of Scientific Research is gratefully acknowledged. The diffusion portion of this work was supported by the National Science Foundation under Grant No. DMR 04 55117. This publication is based on work supported by Award No. KUS-C1-018-02, made by King Abdullah University of Science and Technology (KAUST). This research was carried out while M. Jespersen was an NRC Postdoctoral Fellow at the Air Force Research Laboratories. We thank H. Koerner and M. Tchoul for assistance with SAXS experiments and GPC experiments, respectively, as well as for productive discussions regarding this research.
This publication acknowledges KAUST support, but has no KAUST affiliated authors.

Access to Document

10.1021/nn100112h

Cite this

@article{811b9eb694d24ebc9828a2ce0b406f7e,

title = "Canopy Dynamics in Nanoscale Ionic Materials",

abstract = "Nanoscale ionic materials (NIMS) are organic - inorganic hybrids in which a core nanostructure is functionalized with a covalently attached corona and an ionically tethered organic canopy. NIMS are engineered to be liquids under ambient conditions in the absence of solvent and are of interest for a variety of applications. We have used nuclear magnetic resonance (NMR) relaxation and pulse-field gradient (PFG) diffusion experiments to measure the canopy dynamics of NIMS prepared from 18-nm silica cores modified by an alkylsilane monolayer possessing terminal sulfonic acid functionality, paired with an amine-terminated ethylene oxide/propylene oxide block copolymer canopy. Carbon NMR studies show that the block copolymer canopy is mobile both in the bulk and in the NIMS and that the fast (ns) dynamics are insensitive to the presence of the silica nanoparticles. Canopy diffusion in the NIMS is slowed relative to the neat canopy, but not to the degree predicted from the diffusion of hard-sphere particles. Canopy diffusion is not restricted to the surface of the nanoparticles and shows unexpected behavior upon addition of excess canopy. Taken together, these data indicate that the liquid-like behavior in NIMS is due to rapid exchange of the block copolymer canopy between the ionically modified nanoparticles. {\textcopyright} 2010 American Chemical Society.",

author = "Jespersen, {Michael L.} and Mirau, {Peter A.} and Meerwall, {Ernst von} and Vaia, {Richard A.} and Robert Rodriguez and Giannelis, {Emmanuel P.}",

note = "KAUST Repository Item: Exported on 2020-10-01 Acknowledged KAUST grant number(s): KUS-C1-018-02 Acknowledgements: Funding provided by the Air Force Office of Scientific Research is gratefully acknowledged. The diffusion portion of this work was supported by the National Science Foundation under Grant No. DMR 04 55117. This publication is based on work supported by Award No. KUS-C1-018-02, made by King Abdullah University of Science and Technology (KAUST). This research was carried out while M. Jespersen was an NRC Postdoctoral Fellow at the Air Force Research Laboratories. We thank H. Koerner and M. Tchoul for assistance with SAXS experiments and GPC experiments, respectively, as well as for productive discussions regarding this research. This publication acknowledges KAUST support, but has no KAUST affiliated authors.",

year = "2010",

month = jun,

day = "10",

doi = "10.1021/nn100112h",

language = "English (US)",

volume = "4",

pages = "3735--3742",

journal = "ACS Nano",

issn = "1936-0851",

publisher = "American Chemical Society",

number = "7",

}

TY - JOUR

T1 - Canopy Dynamics in Nanoscale Ionic Materials

AU - Jespersen, Michael L.

AU - Mirau, Peter A.

AU - Meerwall, Ernst von

AU - Vaia, Richard A.

AU - Rodriguez, Robert

AU - Giannelis, Emmanuel P.

N1 - KAUST Repository Item: Exported on 2020-10-01 Acknowledged KAUST grant number(s): KUS-C1-018-02 Acknowledgements: Funding provided by the Air Force Office of Scientific Research is gratefully acknowledged. The diffusion portion of this work was supported by the National Science Foundation under Grant No. DMR 04 55117. This publication is based on work supported by Award No. KUS-C1-018-02, made by King Abdullah University of Science and Technology (KAUST). This research was carried out while M. Jespersen was an NRC Postdoctoral Fellow at the Air Force Research Laboratories. We thank H. Koerner and M. Tchoul for assistance with SAXS experiments and GPC experiments, respectively, as well as for productive discussions regarding this research. This publication acknowledges KAUST support, but has no KAUST affiliated authors.

PY - 2010/6/10

Y1 - 2010/6/10

N2 - Nanoscale ionic materials (NIMS) are organic - inorganic hybrids in which a core nanostructure is functionalized with a covalently attached corona and an ionically tethered organic canopy. NIMS are engineered to be liquids under ambient conditions in the absence of solvent and are of interest for a variety of applications. We have used nuclear magnetic resonance (NMR) relaxation and pulse-field gradient (PFG) diffusion experiments to measure the canopy dynamics of NIMS prepared from 18-nm silica cores modified by an alkylsilane monolayer possessing terminal sulfonic acid functionality, paired with an amine-terminated ethylene oxide/propylene oxide block copolymer canopy. Carbon NMR studies show that the block copolymer canopy is mobile both in the bulk and in the NIMS and that the fast (ns) dynamics are insensitive to the presence of the silica nanoparticles. Canopy diffusion in the NIMS is slowed relative to the neat canopy, but not to the degree predicted from the diffusion of hard-sphere particles. Canopy diffusion is not restricted to the surface of the nanoparticles and shows unexpected behavior upon addition of excess canopy. Taken together, these data indicate that the liquid-like behavior in NIMS is due to rapid exchange of the block copolymer canopy between the ionically modified nanoparticles. © 2010 American Chemical Society.

AB - Nanoscale ionic materials (NIMS) are organic - inorganic hybrids in which a core nanostructure is functionalized with a covalently attached corona and an ionically tethered organic canopy. NIMS are engineered to be liquids under ambient conditions in the absence of solvent and are of interest for a variety of applications. We have used nuclear magnetic resonance (NMR) relaxation and pulse-field gradient (PFG) diffusion experiments to measure the canopy dynamics of NIMS prepared from 18-nm silica cores modified by an alkylsilane monolayer possessing terminal sulfonic acid functionality, paired with an amine-terminated ethylene oxide/propylene oxide block copolymer canopy. Carbon NMR studies show that the block copolymer canopy is mobile both in the bulk and in the NIMS and that the fast (ns) dynamics are insensitive to the presence of the silica nanoparticles. Canopy diffusion in the NIMS is slowed relative to the neat canopy, but not to the degree predicted from the diffusion of hard-sphere particles. Canopy diffusion is not restricted to the surface of the nanoparticles and shows unexpected behavior upon addition of excess canopy. Taken together, these data indicate that the liquid-like behavior in NIMS is due to rapid exchange of the block copolymer canopy between the ionically modified nanoparticles. © 2010 American Chemical Society.

UR - http://hdl.handle.net/10754/597720

UR - https://pubs.acs.org/doi/10.1021/nn100112h

UR - http://www.scopus.com/inward/record.url?scp=77955520126&partnerID=8YFLogxK

U2 - 10.1021/nn100112h

DO - 10.1021/nn100112h

M3 - Article

C2 - 20536222

SN - 1936-0851

VL - 4

SP - 3735

EP - 3742

JO - ACS Nano

JF - ACS Nano

IS - 7

ER -

Canopy Dynamics in Nanoscale Ionic Materials

Abstract

Bibliographical note

Access to Document

Other files and links

Fingerprint

Cite this