Nonlinear Optical Chemosensor for Sodium Ion Based on Rhodol Chromophore

Poronik, Yevgen M.; Clermont, Guillame; Blanchard‐Desce, Mireille; Gryko, Daniel T.

doi:10.1021/jo401653t

Cited by 49 publications

(18 citation statements)

References 94 publications

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“…A plot of two-photon cross-section vs. excitation wavelength reveals a σ TPA maximum of 120 GM at 820 nm for RVF5 (Fig. 3B), which corresponds well to literature values for a related rhodol (115 GM at 820 nm, in ethanol) (34). For comparison, VF2.1.Cl displays a weaker σ TPA , ∼40 GM at its λ max of 780 nm.…”

Section: Resultssupporting

confidence: 85%

Voltage-sensitive rhodol with enhanced two-photon brightness

Kulkarni

Kramer

Pourmandi

et al. 2017

Proc. Natl. Acad. Sci. U.S.A.

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We have designed, synthesized, and applied a rhodol-based chromophore to a molecular wire-based platform for voltage sensing to achieve fast, sensitive, and bright voltage sensing using twophoton (2P) illumination. Rhodol VoltageFluor-5 (RVF5) is a voltage-sensitive dye with improved 2P cross-section for use in thick tissue or brain samples. RVF5 features a dichlororhodol core with pyrrolidyl substitution at the nitrogen center. In mammalian cells under one-photon (1P) illumination, RVF5 demonstrates high voltage sensitivity (28% ΔF/F per 100 mV) and improved photostability relative to first-generation voltage sensors. This photostability enables multisite optical recordings from neurons lacking tuberous sclerosis complex 1, Tsc1, in a mouse model of genetic epilepsy. Using RVF5, we show that Tsc1 KO neurons exhibit increased activity relative to wild-type neurons and additionally show that the proportion of active neurons in the network increases with the loss of Tsc1. The high photostability and voltage sensitivity of RVF5 is recapitulated under 2P illumination. Finally, the ability to chemically tune the 2P absorption profile through the use of rhodol scaffolds affords the unique opportunity to image neuronal voltage changes in acutely prepared mouse brain slices using 2P illumination. Stimulation of the mouse hippocampus evoked spiking activity that was readily discerned with bath-applied RVF5, demonstrating the utility of RVF5 and molecular wire-based voltage sensors with 2P-optimized fluorophores for imaging voltage in intact brain tissue. Neuronal membrane potential dynamics drive neurotransmitter release and are therefore responsible for the unique physiology associated with neurons at cellular, circuit, and organismal levels. Despite the central importance of proper neuronal firing to human health, an integrated understanding of neuronal activity in the context of larger brain circuits remains elusive, due in part to a lack of methods for interrogating membrane potential dynamics with sufficient spatial and temporal resolution.Traditional methods for monitoring membrane potential rely heavily on the use of invasive electrodes, through one of two methods. The first method, patch-clamp electrophysiology, uses a single electrode to make contact with or puncture a cell to record changes in membrane potential, sacrificing throughput and spatial resolution to achieve a comprehensive description of a single cellular electrophysiological profile. A second method uses multielectrode arrays (MEAs), in which patterned arrays of electrodes introduced to cells or tissues report on electrical changes. Spatial resolution of MEAs depends on the number and positioning of the electrodes within the array. Although throughput is improved relative to patch-clamp electrophysiology, the extracellularly recorded signals are typically less sensitive than whole-cell methods and can be an amalgamation of several cells, making deconvolution of recorded signals and precise correlation to specific cells difficult or impossible. Addi...

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Section: Resultssupporting

confidence: 85%

Voltage-sensitive rhodol with enhanced two-photon brightness

Kulkarni

Kramer

Pourmandi

et al. 2017

Proc. Natl. Acad. Sci. U.S.A.

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“…The observed substantial solvatochromism is unique to the P=O‐substituted rhodols. O‐bridged rhodols show only a moderate response to solvent polarity, whereas Si‐ and C‐bridged rhodols have only been studied in aqueous solution . Although a MeOH solution of 2 b still showed a broad absorption band, the strong hydrogen‐bond donor solvent 2,2,2‐trifluoroethanol (TFE) afforded spectra similar to those observed in water, despite its lower polarity in terms of orientation polarizability Δ f (TFE: 0.26, MeOH: 0.31, and H 2 O: 0.32).…”

Section: Figurementioning

confidence: 99%

“…[1][2][3][4] However,u nlike fluoresceins and rhodamines, the structures of rhodolsa re charge-neutral and unsymmetric. This characteristic featurei mparts rhodols with useful applications as fluorescent probes in the context of, for example, monitoring H + and metal ions, [5,6] biological thiols, [7] reactive oxygen or nitrogen species, [8] enzymatic activity, [9,10] and the cell membrane potential [11] in living cells.…”

mentioning

confidence: 99%

Selective Conversion of P=O‐Bridged Rhodamines into P=O‐Rhodols: Solvatochromic Near‐Infrared Fluorophores

Grzybowski

Taki

Yamaguchi

2017

Chemistry A European J

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The substitution of an oxygen atom in rhodols with a phosphine oxide (P=O) moiety affords P=O-bridged rhodols as a new type of near-infrared (NIR) fluorophore. This compound class can be readily accessed upon exposure of the corresponding rhodamines to aqueous basic conditions. The electron-withdrawing effect of the P=O group facilitates the hydrolytic deamination, and, moreover, prolonged exposure to aqueous basic conditions generates P=O-bridged fluoresceins, that is, a series of three P=O-bridged xanthene dyes is available in one simple operation. The P=O-bridged rhodols show significant bathochromic shifts of the longest-wavelength absorption maximum (Δλ=125 nm; >3600 cm ) upon changing the solvent from toluene to water, whereas the emission is shifted less drastically (Δλ=70 nm; 1600 cm ). The hydrogen bonding between the P=O and C=O groups with protic solvents results in substantial stabilization of the LUMO level, which is responsible for the solvatochromism.

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“…The popularity of two-photon imaging for imaging intact brains and brain slices made a VoltageFluor optimized for two-photon absorption an attractive chemical target. Rhodols, a group of xanthene chromophores that are intermediates between fluoresceins and rhodamines (Whitaker et al 1992), are well-suited for imaging applications (Dodani et al 2014), due in part to their several-fold higher two-photon excitation cross sections than their fluorescein counterparts (Poronik et al 2013). Rhodols are also relatively photostable compared to fluorescein-based dyes, potentially enabling long-term optical recordings of neurons in a variety of biological sample preparations.…”

Section: Accessing Two-photon Infrared Excitation For Imaging In Thicmentioning

confidence: 99%

Making Life Visible: Fluorescent Indicators to Probe Membrane Potential

et al. 2019

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Cell membranes are central to all life on earth. The lipid bilayer composing cell membranes enables discrimination between the cell and its external environment. Far from a passive bystander, the lipid membrane plays an active role in sequestering and accumulating genetic material, proteins, nutrients and ions essential for life. Indeed, cells allocate a significant portion of their energy budget to maintain an unequal distribution of ions across the cell membrane. The unequal distribution of ions across the cell membrane results in an electrochemical potential, or voltage. Rapid changes in this membrane voltage drive the unique physiology of excitable cells like neurons and cardiomyocytes. Despite the central importance of voltage in the brain and body, the full contributions of voltage changes to both physiology and disease remain incompletely characterized due to a lack of methods that can report on membrane potential with high fidelity, high throughput, and minimal invasiveness. Voltage imaging with fluorescent dyes offers a solution to this problem because it combines a direct readout of voltage changes, providing temporal resolution, with an imaging approach that offers spatial resolution. Attempts at voltage imaging with small molecules date back to the 1970s (Braubach et al. 2015; Loew 2015), and it is a measure of the difficulty of the task that voltage imaging has not yet become a widespread experimental approach. Rather, surrogates of voltage changes, notably Ca 2+ ion fluxes have become the primary means of assessing neuronal and cellular activity. This is due, in part, to the fact that the experimental constraints on Ca 2+ imaging are somewhat less stringent than voltage imaging in the context of neurobiology. First, transient fluctuations in intracellular Ca 2+ concentration follow timecourses that are 10-100,000 times slower than neuronal action potentials. Second, an individual cell can accumulate >1000-fold more Ca 2+ indicators relative to volt

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Nonlinear Optical Chemosensor for Sodium Ion Based on Rhodol Chromophore

Cited by 49 publications

References 94 publications

Voltage-sensitive rhodol with enhanced two-photon brightness

Voltage-sensitive rhodol with enhanced two-photon brightness

Selective Conversion of P=O‐Bridged Rhodamines into P=O‐Rhodols: Solvatochromic Near‐Infrared Fluorophores

Making Life Visible: Fluorescent Indicators to Probe Membrane Potential

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