Ion-Switchable Quantum Dot Förster Resonance Energy Transfer Rates in Ratiometric Potassium Sensors
Abstract
The tools for optically imaging cellular potassium concentrations in real-time are currently limited to a small set of molecular indicator dyes. Quantum dot-based nanosensors are more photostable and tunable than organic indicators, but previous designs have fallen short in size, sensitivity, and selectivity. In this paper, we introduce a small, sensitive, and selective nanosensor for potassium measurements. A dynamic quencher modulates the fluorescence emitted by two different quantum dot species to produce a ratiometric signal. We characterized the potassium-modulated sensor properties and investigated the photonic interactions within the sensors. The quencher’s protonation changes in response to potassium, which modulates its Förster radiative energy transfer rate and the corresponding interaction radii with each quantum dot species. Finally, the nanosensors respond to changes in potassium concentrations typical of the cellular environment and thus provide a promising tool for imaging potassium fluxes during biological events.
- Authors:
-
- Northeastern Univ., Boston, MA (United States). Dept. of Pharmaceutical Sciences
- Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Electrical Engineering
- Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Materials Science and Engineering
- Publication Date:
- Research Org.:
- Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Northeastern Univ., Boston, MA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); National Inst. of Health (NIH) (United States); National Academy of Sciences Ford Foundation (United States)
- OSTI Identifier:
- 1467074
- Grant/Contract Number:
- FG02-07ER46474; R01NS081641; F32EB015847; 2014-PGA084488
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ACS Nano
- Additional Journal Information:
- Journal Volume: 10; Journal Issue: 4; Journal ID: ISSN 1936-0851
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 77 NANOSCIENCE AND NANOTECHNOLOGY; FRET; ion sensing; nanosensor; optode; quantum dot
Citation Formats
Ruckh, Timothy T., Skipwith, Christopher G., Chang, Wendi, Senko, Alexander W., Bulovic, Vladimir, Anikeeva, Polina O., and Clark, Heather A. Ion-Switchable Quantum Dot Förster Resonance Energy Transfer Rates in Ratiometric Potassium Sensors. United States: N. p., 2016.
Web. doi:10.1021/acsnano.5b05396.
Ruckh, Timothy T., Skipwith, Christopher G., Chang, Wendi, Senko, Alexander W., Bulovic, Vladimir, Anikeeva, Polina O., & Clark, Heather A. Ion-Switchable Quantum Dot Förster Resonance Energy Transfer Rates in Ratiometric Potassium Sensors. United States. https://doi.org/10.1021/acsnano.5b05396
Ruckh, Timothy T., Skipwith, Christopher G., Chang, Wendi, Senko, Alexander W., Bulovic, Vladimir, Anikeeva, Polina O., and Clark, Heather A. Mon .
"Ion-Switchable Quantum Dot Förster Resonance Energy Transfer Rates in Ratiometric Potassium Sensors". United States. https://doi.org/10.1021/acsnano.5b05396. https://www.osti.gov/servlets/purl/1467074.
@article{osti_1467074,
title = {Ion-Switchable Quantum Dot Förster Resonance Energy Transfer Rates in Ratiometric Potassium Sensors},
author = {Ruckh, Timothy T. and Skipwith, Christopher G. and Chang, Wendi and Senko, Alexander W. and Bulovic, Vladimir and Anikeeva, Polina O. and Clark, Heather A.},
abstractNote = {The tools for optically imaging cellular potassium concentrations in real-time are currently limited to a small set of molecular indicator dyes. Quantum dot-based nanosensors are more photostable and tunable than organic indicators, but previous designs have fallen short in size, sensitivity, and selectivity. In this paper, we introduce a small, sensitive, and selective nanosensor for potassium measurements. A dynamic quencher modulates the fluorescence emitted by two different quantum dot species to produce a ratiometric signal. We characterized the potassium-modulated sensor properties and investigated the photonic interactions within the sensors. The quencher’s protonation changes in response to potassium, which modulates its Förster radiative energy transfer rate and the corresponding interaction radii with each quantum dot species. Finally, the nanosensors respond to changes in potassium concentrations typical of the cellular environment and thus provide a promising tool for imaging potassium fluxes during biological events.},
doi = {10.1021/acsnano.5b05396},
journal = {ACS Nano},
number = 4,
volume = 10,
place = {United States},
year = {Mon Apr 18 00:00:00 EDT 2016},
month = {Mon Apr 18 00:00:00 EDT 2016}
}
Web of Science
Works referenced in this record:
Picosecond Energy Transfer in Quantum Dot Langmuir−Blodgett Nanoassemblies
journal, December 2003
- Achermann, Marc; Petruska, Melissa A.; Crooker, Scott A.
- The Journal of Physical Chemistry B, Vol. 107, Issue 50
Spatial Distribution of Synaptically Activated Sodium Concentration Changes in Cerebellar Purkinje Neurons
journal, January 1997
- Callaway, Joseph C.; Ross, William N.
- Journal of Neurophysiology, Vol. 77, Issue 1
Potassium ion recognition by 15-crown-5 functionalized CdSe/ZnS quantum dots in H 2 O
journal, January 2006
- Chen, Chun-Yen; Cheng, Chiu-Ting; Lai, Chih-Wei
- Chem. Commun., Issue 3
Multiplexed Flow Cytometric Sensing of Blood Electrolytes in Physiological Samples Using Fluorescent Bulk Optode Microspheres
journal, November 2007
- Xu, Chao; Wygladacz, Katarzyna; Retter, Robert
- Analytical Chemistry, Vol. 79, Issue 24
Ion-Selective Optodes Measure Extracellular Potassium Flux in Excitable Cells: Ion-Selective Optodes Measure Extracellular Potassium Flux in Excitable Cells …
journal, August 2009
- Harjes, Daniel I.; Dubach, J. Matthew; Rosenzweig, Anthony
- Macromolecular Rapid Communications, Vol. 31, Issue 2
K+-selective nanospheres: maximising response range and minimising response time
journal, January 2006
- Ruedas-Rama, Maria Jose; Hall, Elizabeth A. H.
- The Analyst, Vol. 131, Issue 12
Carrier-Based Ion-Selective Electrodes and Bulk Optodes. 1. General Characteristics
journal, December 1997
- Bakker, Eric; Bühlmann, Philippe; Pretsch, Ernö
- Chemical Reviews, Vol. 97, Issue 8, p. 3083-3132
Enhancing humoral responses to a malaria antigen with nanoparticle vaccines that expand Tfh cells and promote germinal center induction
journal, January 2012
- Moon, J. J.; Suh, H.; Li, A. V.
- Proceedings of the National Academy of Sciences, Vol. 109, Issue 4
Long-range resonance transfer of electronic excitations in close-packed CdSe quantum-dot solids
journal, September 1996
- Kagan, C. R.; Murray, C. B.; Bawendi, M. G.
- Physical Review B, Vol. 54, Issue 12
Understanding the Role of Surface Charges in Cellular Adsorption versus Internalization by Selectively Removing Gold Nanoparticles on the Cell Surface with a I 2 /KI Etchant
journal, March 2009
- Cho, Eun Chul; Xie, Jingwei; Wurm, Patricia A.
- Nano Letters, Vol. 9, Issue 3
Unconventional Role of the Inwardly Rectifying Potassium Channel Kir2.2 as a Constitutive Activator of RelA in Cancer
journal, December 2012
- Lee, Inkyoung; Lee, Sook-Ja; Kang, Tong Mook
- Cancer Research, Vol. 73, Issue 3
Elevation of intradendritic sodium concentration mediated by synaptic activation of metabotropic glutamate receptors in cerebellar Purkinje cells: Sodium signalling mediated by mGluR1 EPSC
journal, June 2000
- Knöpfel, T.; Anchisi, D.; Alojado, M. E.
- European Journal of Neuroscience, Vol. 12, Issue 6
Biodegradable Optode-Based Nanosensors for in Vivo Monitoring
journal, June 2012
- Balaconis, Mary K.; Clark, Heather A.
- Analytical Chemistry, Vol. 84, Issue 13
Selectivity of ion-sensitive bulk optodes
journal, September 1992
- Bakker, Eric.; Simon, Wilhelm.
- Analytical Chemistry, Vol. 64, Issue 17
Synthesis of a Sensitive and Selective Potassium-Sensing Fluoroionophore
journal, February 2010
- Carpenter, Richard D.; Verkman, A. S.
- Organic Letters, Vol. 12, Issue 6
Subsets of ATP-sensitive potassium channel (K ATP ) inhibitors increase gap junctional intercellular communication in metastatic cancer cell lines independent of SUR expression
journal, November 2011
- Bodenstine, Thomas M.; Vaidya, Kedar S.; Ismail, Aimen
- FEBS Letters, Vol. 586, Issue 1
Optimization of a GCaMP Calcium Indicator for Neural Activity Imaging
journal, October 2012
- Akerboom, J.; Chen, T. -W.; Wardill, T. J.
- Journal of Neuroscience, Vol. 32, Issue 40
Calcium Green FlAsH as a genetically targeted small-molecule calcium indicator
journal, June 2007
- Tour, Oded; Adams, Stephen R.; Kerr, Rex A.
- Nature Chemical Biology, Vol. 3, Issue 7
Ion-Selective Nano-optodes Incorporating Quantum Dots
journal, July 2007
- Dubach, J. Matthew; Harjes, Daniel I.; Clark, Heather A.
- Journal of the American Chemical Society, Vol. 129, Issue 27
Multiplexed Sensing of Ions with Barcoded Polyelectrolyte Capsules
journal, November 2011
- del Mercato, Loretta L.; Abbasi, Azhar Z.; Ochs, Markus
- ACS Nano, Vol. 5, Issue 12
Therapeutic cell engineering with surface-conjugated synthetic nanoparticles
journal, August 2010
- Stephan, Matthias T.; Moon, James J.; Um, Soong Ho
- Nature Medicine, Vol. 16, Issue 9
Localizable and Highly Sensitive Calcium Indicator Based on a BODIPY Fluorophore
journal, June 2010
- Kamiya, Mako; Johnsson, Kai
- Analytical Chemistry, Vol. 82, Issue 15
K+ waves in brain cortex visualized using a long-wavelength K+-sensing fluorescent indicator
journal, October 2005
- Padmawar, Prashant; Yao, Xiaoming; Bloch, Orin
- Nature Methods, Vol. 2, Issue 11
Genetic visualization with an improved GCaMP calcium indicator reveals spatiotemporal activation of the spinal motor neurons in zebrafish
journal, March 2011
- Muto, A.; Ohkura, M.; Kotani, T.
- Proceedings of the National Academy of Sciences, Vol. 108, Issue 13
A Highly Potassium-Selective Ratiometric Fluorescent Indicator Based on BODIPY Azacrown Ether Excitable with Visible Light
journal, September 2005
- Baruah, Mukulesh; Qin, Wenwu; Vallée, Renaud A. L.
- Organic Letters, Vol. 7, Issue 20
Sodium Imaging of Climbing Fiber Innervation Fields in Developing Mouse Purkinje Cells
journal, May 2003
- Scelfo, Bibiana; Strata, Piergiorgio; Knöpfel, Thomas
- Journal of Neurophysiology, Vol. 89, Issue 5
Two-Photon Sodium Imaging in Dendritic Spines
journal, November 2012
- Rose, C. R.
- Cold Spring Harbor Protocols, Vol. 2012, Issue 11
Sodium‐Ion‐Selective Two‐Photon Fluorescent Probe for In Vivo Imaging
journal, January 2010
- Kim, Mi Kyung; Lim, Chang Su; Hong, Jong Tae
- Angewandte Chemie International Edition, Vol. 49, Issue 2
Sodium Sensing in Neurons with a Dendrimer-Based Nanoprobe
journal, January 2012
- Lamy, Christophe M.; Sallin, Olivier; Loussert, Céline
- ACS Nano, Vol. 6, Issue 2
Optimized ratiometric calcium sensors for functional in vivo imaging of neurons and T lymphocytes
journal, January 2014
- Thestrup, Thomas; Litzlbauer, Julia; Bartholomäus, Ingo
- Nature Methods, Vol. 11, Issue 2
Optical Nanosensors for Chemical Analysis inside Single Living Cells. 2. Sensors for pH and Calcium and the Intracellular Application of PEBBLE Sensors
journal, November 1999
- Clark, Heather A.; Kopelman, Raoul; Tjalkens, Ron
- Analytical Chemistry, Vol. 71, Issue 21
Fluorescent Recognition of Potassium and Calcium Ions Using Functionalised CdSe / ZnS Quantum Dots
journal, March 2009
- Singh, Narinder; Mulrooney, Ray C.; Kaur, Navneet
- Journal of Fluorescence, Vol. 19, Issue 5
A genetically encoded calcium indicator for chronic in vivo two-photon imaging
journal, August 2008
- Mank, Marco; Santos, Alexandre Ferrão; Direnberger, Stephan
- Nature Methods, Vol. 5, Issue 9, p. 805-811
Fiji: an open-source platform for biological-image analysis
journal, June 2012
- Schindelin, Johannes; Arganda-Carreras, Ignacio; Frise, Erwin
- Nature Methods, Vol. 9, Issue 7
Multicolor Quantum Dot Encoding for Polymeric Particle-Based Optical Ion Sensors
journal, May 2007
- Xu, Chao; Bakker, Eric
- Analytical Chemistry, Vol. 79, Issue 10
Visualizing sodium dynamics in isolated cardiomyocytes using fluorescent nanosensors
journal, September 2009
- Dubach, J. M.; Das, S.; Rosenzweig, A.
- Proceedings of the National Academy of Sciences, Vol. 106, Issue 38
Two-Dimensional Förster Resonant Energy Transfer in a Mixed Quantum Dot Monolayer: Experiment and Theory
journal, February 2009
- Lunz, Manuela; Bradley, A. Louise; Chen, Wei-Yu
- The Journal of Physical Chemistry C, Vol. 113, Issue 8
Size and Shape of Protein Molecules at the Nanometer Level Determined by Sedimentation, Gel Filtration, and Electron Microscopy
journal, May 2009
- Erickson, Harold P.
- Biological Procedures Online, Vol. 11, Issue 1
A Novel Optical Intracellular Imaging Approach for Potassium Dynamics in Astrocytes
journal, October 2014
- Rimmele, Theresa S.; Chatton, Jean-Yves
- PLoS ONE, Vol. 9, Issue 10
Dynamic reciprocity of sodium and potassium channel expression in a macromolecular complex controls cardiac excitability and arrhythmia
journal, April 2012
- Milstein, M. L.; Musa, H.; Balbuena, D. P.
- Proceedings of the National Academy of Sciences, Vol. 109, Issue 31
Theoretical aspects of bulk optode membranes
journal, August 1992
- Seiler, K.; Simon, W.
- Analytica Chimica Acta, Vol. 266, Issue 1
Optical Nanosensors for Chemical Analysis inside Single Living Cells. 1. Fabrication, Characterization, and Methods for Intracellular Delivery of PEBBLE Sensors
journal, November 1999
- Clark, Heather A.; Hoyer, Marion; Philbert, Martin A.
- Analytical Chemistry, Vol. 71, Issue 21
Polymer-Free Optode Nanosensors for Dynamic, Reversible and Ratiometric Sodium Imaging in the Physiological Range
journal, November 2013
- Ruckh, Timothy T.; Mehta, Ankeeta A.; Dubach, J. Matthew
- Scientific Reports, Vol. 3, Issue 1
Carrier-Based Ion-Selective Electrodes and Bulk Optodes. 2. Ionophores for Potentiometric and Optical Sensors
journal, June 1998
- Bühlmann, Philippe; Pretsch, Ernö; Bakker, Eric
- Chemical Reviews, Vol. 98, Issue 4
Potassium channel activation inhibits proliferation of breast cancer cells by activating a senescence program
journal, June 2013
- Lansu, K.; Gentile, S.
- Cell Death & Disease, Vol. 4, Issue 6
Fluorescent indicators for cytosolic sodium
journal, November 1989
- Minta, A.; Tsien, R. Y.
- Journal of Biological Chemistry, Vol. 264, Issue 32
Works referencing / citing this record:
Rhodamine based NIR and ratiometric fluorescent sensor for selective identification of potassium ion: application in biological sample
text, January 2018
- Kaur, Rajinder; Sahoo, Suban Kumar; Kuwar, Anil
- Taylor & Francis
An ionophore-based persistent luminescent ‘Glow Sensor’ for sodium detection
journal, January 2019
- Ferris, Mark S.; Behr, Madeline R.; Cash, Kevin J.
- RSC Advances, Vol. 9, Issue 56
Rhodamine based NIR and ratiometric fluorescent sensor for selective identification of potassium ion: application in biological sample
journal, October 2018
- Kaur, Rajinder; Sahoo, Suban Kumar; Kuwar, Anil
- Supramolecular Chemistry, Vol. 31, Issue 1
Multifunctional fluorescent naphthalimide self-assembly system for the detection of Cu 2+ and K + and continuous sensing of organic amines and gaseous acids
journal, January 2019
- Cao, Xinhua; Li, Yiran; Gao, Aiping
- Journal of Materials Chemistry C, Vol. 7, Issue 34
Silicon nanohybrid-based SERS chips armed with an internal standard for broad-range, sensitive and reproducible simultaneous quantification of lead( ii ) and mercury( ii ) in real systems
journal, January 2018
- Shi, Yu; Chen, Na; Su, Yuanyuan
- Nanoscale, Vol. 10, Issue 8
Label-free fluorescent immunoassay for Cu 2+ ion detection based on UV degradation of immunocomplex and metal ion chelates
journal, January 2017
- Shu, Qi; Liu, Mengli; Ouyang, Hui
- Nanoscale, Vol. 9, Issue 34
Ratiometric optical nanoprobes enable accurate molecular detection and imaging
journal, January 2018
- Huang, Xiaolin; Song, Jibin; Yung, Bryant C.
- Chemical Society Reviews, Vol. 47, Issue 8