Electrochemical Monitoring of the Fluorescence Emission of Tetrazine and Bodipy Dyes Using Total Internal Reflection Fluorescence Microscopy Coupled to Electrochemistry

Abstract

A very sensitive technique where an electrochemical cell is coupled to a total internal reflection fluorescence microscopy setup is described and applied for the first time to the electrochemical monitoring of the fluorescence of organic dyes in solution. It is shown that this setup basically allows both spatial and time resolution for the recorded fluorescence signal as a function of the electrode potential: indeed the variations of the emission intensity are recorded within the diffusion layer for a classical cyclic voltammetry or chronoamperometry experiment inducing the redox conversion of an emissive form into a non emissive one (and conversely). Simultaneously, the variations of the emissive state lifetime are measured to discriminate between a mechanism involving only the conversion into a non emissive form from one involving a quenching between the emitter and the electrogenerated species. The results concerning the investigation of the electrochemical monitoring of the fluorescence properties for two types of original dyes are presented, demonstrating the possibility to switch on and off the emission in a fully reversible way and to investigate in depth the mechanisms associated to this switch.

Novel s-tetrazine-based dyes with enhanced two-photon absorption cross-section

“…[14][15][16][17][18][19] Tetrazine derivatives are also used in coordination chemistry [20][21][22][23][24] because they can form complexes with electron-rich metals. In addition, some tetrazine derivatives show strong electrofluorochromism [25][26][27][28][29][30][31][32] and have been utilized in pollutant detection. 33 Recently, it has also been shown that they can be used efficiently as electron carrier in n-type field effect transistors.…”

On-demand in situ generation of oxygen in a nanofluidic embedded planar microband electrochemical reactor

“…However, the capacity to use in situ generated O 2 effectively supposes knowledge of its spatial and temporal distribution, especially when the reagent is generated in flowing conditions for delivery to a downstream reaction site. In order to quantitatively determine the amount and spatiotemporal distribution of O 2 generated in the nanochannel, fluorescence microscopy (Miomandre et al 2011a, b) is used to optically monitor the reaction using pH-sensitive fluorescein emission (Loete et al 2006). Finite element modeling is used to calculate the concentrations and distributions of H + and O 2 in the nanochannel by simultaneously accounting for water oxidation, transport phenomena, and acid–base reactions.…”

Observing the Reversible Single Molecule Electrochemistry of Alexa Fluor 647 Dyes by Total Internal Reflection Fluorescence Microscopy

“…Controllable stochastic single molecule switching enables imaging and localization of individual fluorophores with nanoscale resolution below the AbbØ diffraction limit of light. [10][11][12][13][14] There are experimental restrictions encountered by electrochemical modulation of fluorescence that are not faced by optical methods.F irstly,t he surface fluorescent species must be maintained close to the electrode surface for oxidation and reduction to occur. Avoiding photobleaching while using an intense light source is an enduring challenge that imposes al imiting factor while extracting quantitative data from SMLM.…”