Oxygen Sensing with Perfluorocarbon-Loaded Ultraporous Mesostructured Silica Nanoparticles

Amani L. Lee; Clifford T. Gee; Bradley P. Weegman; Samuel A. Einstein; Adam R. Juelfs; Hattie L. Ring; Katie R. Hurley; Sam M. Egger; Garrett Swindlehurst; Michael Garwood; William C.K. Pomerantz; Christy L. Haynes

doi:10.1021/acsnano.7b01006

Oxygen Sensing with Perfluorocarbon-Loaded Ultraporous Mesostructured Silica Nanoparticles

Amani L. Lee, Clifford T. Gee, Bradley P. Weegman, Samuel A. Einstein, Adam R. Juelfs, Hattie L. Ring, Katie R. Hurley, Sam M. Egger, Garrett Swindlehurst, Michael Garwood, William C.K. Pomerantz, Christy L. Haynes

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

39 Scopus citations

Abstract

Oxygen homeostasis is important in the regulation of biological function. Disease progression can be monitored by measuring oxygen levels, thus producing information for the design of therapeutic treatments. Noninvasive measurements of tissue oxygenation require the development of tools with minimal adverse effects and facile detection of features of interest. Fluorine magnetic resonance imaging (¹⁹F MRI) exploits the intrinsic properties of perfluorocarbon (PFC) liquids for anatomical imaging, cell tracking, and oxygen sensing. However, the highly hydrophobic and lipophobic properties of perfluorocarbons require the formation of emulsions for biological studies, though stabilizing these emulsions has been challenging. To enhance the stability and biological loading of perfluorocarbons, one option is to incorporate perfluorocarbon liquids into the internal space of biocompatible mesoporous silica nanoparticles. Here, we developed perfluorocarbon-loaded ultraporous mesostructured silica nanoparticles (PERFUMNs) as ¹⁹F MRI detectable oxygen-sensing probes. Ultraporous mesostructured silica nanoparticles (UMNs) have large internal cavities (average = 1.8 cm³ g^-1), facilitating an average 17% loading efficiency of PFCs, meeting the threshold fluorine concentrations needed for imaging studies. Perfluoro-15-crown-5-ether PERFUMNs have the highest equivalent nuclei per PFC molecule and a spin-lattice (T₁) relaxation-based oxygen sensitivity of 0.0032 mmHg^-1 s^-1 at 16.4 T. The option of loading PFCs after synthesizing UMNs, rather than traditional in situ core-shell syntheses, allows for use of a broad range of PFC liquids from a single material. The biocompatible and tunable chemistry of UMNs combined with the intrinsic properties of PFCs makes PERFUMNs a MRI sensor with potential for anatomical imaging, cell tracking, and metabolic spectroscopy with improved stability.

Original language	English (US)
Pages (from-to)	5623-5632
Number of pages	10
Journal	ACS nano
Volume	11
Issue number	6
DOIs	https://doi.org/10.1021/acsnano.7b01006
State	Published - Jun 27 2017

Bibliographical note

Funding Information:
This work was supported in part by the Minnesota Lions Diabetes Foundation, the Schott Family Foundation, the Carol Olson Memorial Diabetes Research Fund, and NIH Grants P41 EB015894 and S10 RR025031. Parts of this work were carried out in the Characterization Facility University of Minnesota, a member of the NSF-funded Materials Research Facilities Network the MRSEC program. Rabbit blood was properly collected under IACUC Protocol 1610-34243A by Ellorie R. Liljequist. Special thanks to members of the Lu Lab, University of Minnesota for providing the gases and apparatus to conduct oximetry studies in blood. A.L.L. would like to acknowledge the NIH chemistry-biology interface training grant 5T32GM008700-18 and the University of Minnesota's Diversity of Views and Experiences Fellowship for funding. C.T.G. would like to acknowledge the NIH chemistry-biology interface training grant T32-GM08700 and the University of Minnesota Interdisciplinary Doctoral Dissertation Fellowship for funding. A.R.J. would like to acknowledge the University of Minnesota Undergraduate Research Opportunities Program for funding.

Publisher Copyright:
© 2017 American Chemical Society.

Keywords

magnetic resonance
mesoporous silica nanoparticles
oximetry
perfluorocarbons
relaxometry
thermometry

How much support was provided by MRSEC?

Shared

Reporting period for MRSEC

Period 4

PubMed: MeSH publication types

Journal Article
Research Support, N.I.H., Extramural
Research Support, Non-U.S. Gov't
Research Support, U.S. Gov't, Non-P.H.S.

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10.1021/acsnano.7b01006

https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5515277

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abstract = "Oxygen homeostasis is important in the regulation of biological function. Disease progression can be monitored by measuring oxygen levels, thus producing information for the design of therapeutic treatments. Noninvasive measurements of tissue oxygenation require the development of tools with minimal adverse effects and facile detection of features of interest. Fluorine magnetic resonance imaging (19F MRI) exploits the intrinsic properties of perfluorocarbon (PFC) liquids for anatomical imaging, cell tracking, and oxygen sensing. However, the highly hydrophobic and lipophobic properties of perfluorocarbons require the formation of emulsions for biological studies, though stabilizing these emulsions has been challenging. To enhance the stability and biological loading of perfluorocarbons, one option is to incorporate perfluorocarbon liquids into the internal space of biocompatible mesoporous silica nanoparticles. Here, we developed perfluorocarbon-loaded ultraporous mesostructured silica nanoparticles (PERFUMNs) as 19F MRI detectable oxygen-sensing probes. Ultraporous mesostructured silica nanoparticles (UMNs) have large internal cavities (average = 1.8 cm3 g-1), facilitating an average 17% loading efficiency of PFCs, meeting the threshold fluorine concentrations needed for imaging studies. Perfluoro-15-crown-5-ether PERFUMNs have the highest equivalent nuclei per PFC molecule and a spin-lattice (T1) relaxation-based oxygen sensitivity of 0.0032 mmHg-1 s-1 at 16.4 T. The option of loading PFCs after synthesizing UMNs, rather than traditional in situ core-shell syntheses, allows for use of a broad range of PFC liquids from a single material. The biocompatible and tunable chemistry of UMNs combined with the intrinsic properties of PFCs makes PERFUMNs a MRI sensor with potential for anatomical imaging, cell tracking, and metabolic spectroscopy with improved stability.",

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author = "Lee, {Amani L.} and Gee, {Clifford T.} and Weegman, {Bradley P.} and Einstein, {Samuel A.} and Juelfs, {Adam R.} and Ring, {Hattie L.} and Hurley, {Katie R.} and Egger, {Sam M.} and Garrett Swindlehurst and Michael Garwood and Pomerantz, {William C.K.} and Haynes, {Christy L.}",

note = "Funding Information: This work was supported in part by the Minnesota Lions Diabetes Foundation, the Schott Family Foundation, the Carol Olson Memorial Diabetes Research Fund, and NIH Grants P41 EB015894 and S10 RR025031. Parts of this work were carried out in the Characterization Facility University of Minnesota, a member of the NSF-funded Materials Research Facilities Network the MRSEC program. Rabbit blood was properly collected under IACUC Protocol 1610-34243A by Ellorie R. Liljequist. Special thanks to members of the Lu Lab, University of Minnesota for providing the gases and apparatus to conduct oximetry studies in blood. A.L.L. would like to acknowledge the NIH chemistry-biology interface training grant 5T32GM008700-18 and the University of Minnesota's Diversity of Views and Experiences Fellowship for funding. C.T.G. would like to acknowledge the NIH chemistry-biology interface training grant T32-GM08700 and the University of Minnesota Interdisciplinary Doctoral Dissertation Fellowship for funding. A.R.J. would like to acknowledge the University of Minnesota Undergraduate Research Opportunities Program for funding. Publisher Copyright: {\textcopyright} 2017 American Chemical Society.",

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AU - Einstein, Samuel A.

AU - Juelfs, Adam R.

AU - Ring, Hattie L.

AU - Hurley, Katie R.

AU - Egger, Sam M.

AU - Swindlehurst, Garrett

AU - Garwood, Michael

AU - Pomerantz, William C.K.

AU - Haynes, Christy L.

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N2 - Oxygen homeostasis is important in the regulation of biological function. Disease progression can be monitored by measuring oxygen levels, thus producing information for the design of therapeutic treatments. Noninvasive measurements of tissue oxygenation require the development of tools with minimal adverse effects and facile detection of features of interest. Fluorine magnetic resonance imaging (19F MRI) exploits the intrinsic properties of perfluorocarbon (PFC) liquids for anatomical imaging, cell tracking, and oxygen sensing. However, the highly hydrophobic and lipophobic properties of perfluorocarbons require the formation of emulsions for biological studies, though stabilizing these emulsions has been challenging. To enhance the stability and biological loading of perfluorocarbons, one option is to incorporate perfluorocarbon liquids into the internal space of biocompatible mesoporous silica nanoparticles. Here, we developed perfluorocarbon-loaded ultraporous mesostructured silica nanoparticles (PERFUMNs) as 19F MRI detectable oxygen-sensing probes. Ultraporous mesostructured silica nanoparticles (UMNs) have large internal cavities (average = 1.8 cm3 g-1), facilitating an average 17% loading efficiency of PFCs, meeting the threshold fluorine concentrations needed for imaging studies. Perfluoro-15-crown-5-ether PERFUMNs have the highest equivalent nuclei per PFC molecule and a spin-lattice (T1) relaxation-based oxygen sensitivity of 0.0032 mmHg-1 s-1 at 16.4 T. The option of loading PFCs after synthesizing UMNs, rather than traditional in situ core-shell syntheses, allows for use of a broad range of PFC liquids from a single material. The biocompatible and tunable chemistry of UMNs combined with the intrinsic properties of PFCs makes PERFUMNs a MRI sensor with potential for anatomical imaging, cell tracking, and metabolic spectroscopy with improved stability.

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Oxygen Sensing with Perfluorocarbon-Loaded Ultraporous Mesostructured Silica Nanoparticles

Abstract

Bibliographical note

Keywords

How much support was provided by MRSEC?

Reporting period for MRSEC

PubMed: MeSH publication types

Access

OpenUrl availability

Other files and links

Fingerprint

MRSEC IRG-2: Sustainable Nanocrystal Materials

University of Minnesota MRSEC (DMR-1420013)

Cite this

Oxygen Sensing with Perfluorocarbon-Loaded Ultraporous Mesostructured Silica Nanoparticles

Abstract

Bibliographical note

Keywords

How much support was provided by MRSEC?

Reporting period for MRSEC

PubMed: MeSH publication types

Access

OpenUrl availability

Other files and links

Fingerprint

Projects

MRSEC IRG-2: Sustainable Nanocrystal Materials

University of Minnesota MRSEC (DMR-1420013)

Cite this