skip to main content


Title: A Cell Trappable Methyl Rhodol‐Based Fluorescent Probe for Hydrogen Sulfide Detection
Abstract

Hydrogen sulfide is a biologically important molecule and developing chemical tools that enable further investigations into the functions of H2S is essential. Fluorescent turn‐on H2S probes have been developed for usein celluloandin vivo, but the membrane permeability of these probes can lead to probe leakage and signal attenuation over time. Here we report a cell trappable fluorescent probe for H2S,CT‐MeRhoAz, which is based on a methylrhodolazide scaffold derivatized with an acetoxymethyl ester group. Prior to ester cleavage, theCT‐MeRhoAzprobe generates a 2500‐fold turn‐on response to H2S, which is enhanced to a 3000‐fold response for the carboxylic acid form of the probe. Additionally, the probe is highly selective for H2S over other biologically relevant sulfur, oxygen, and nitrogen‐based analytes. Live cell imaging experiments confirmed the biocompatibility ofCT‐MeRhoAzand also that it is cell trappable, unlike the parentMeRhoAzscaffold.

 
more » « less
NSF-PAR ID:
10370919
Author(s) / Creator(s):
 ;  ;  ;  ;  
Publisher / Repository:
Wiley Blackwell (John Wiley & Sons)
Date Published:
Journal Name:
Chemistry – An Asian Journal
Volume:
17
Issue:
16
ISSN:
1861-4728
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract

    Near‐infrared (NIR) fluorescent dyes with favorable photophysical properties are highly useful for bioimaging, but such dyes are still rare. The development of a unique class of NIR dyes via modifying the rhodol scaffold with fused tetrahydroquinoxaline rings is described. These new dyes showed large Stokes shifts (>110 nm). Among them, WR3, WR4, WR5, and WR6 displayed high fluorescence quantum yields and excellent photostability in aqueous solutions. Moreover, their fluorescence properties were tunable by easy modifications on the phenolic hydroxy group. Based on WR6, two NIR fluorescent turn‐on probes, WSP‐NIR and SeSP‐NIR, were devised for the detection of H2S. The probe SeSP‐NIR was applied in visualizing intracellular H2S. These dyes are expected to be useful fluorophore scaffolds in the development of new NIR probes for bioimaging.

     
    more » « less
  2. Abstract

    Near‐infrared (NIR) fluorescent dyes with favorable photophysical properties are highly useful for bioimaging, but such dyes are still rare. The development of a unique class of NIR dyes via modifying the rhodol scaffold with fused tetrahydroquinoxaline rings is described. These new dyes showed large Stokes shifts (>110 nm). Among them, WR3, WR4, WR5, and WR6 displayed high fluorescence quantum yields and excellent photostability in aqueous solutions. Moreover, their fluorescence properties were tunable by easy modifications on the phenolic hydroxy group. Based on WR6, two NIR fluorescent turn‐on probes, WSP‐NIR and SeSP‐NIR, were devised for the detection of H2S. The probe SeSP‐NIR was applied in visualizing intracellular H2S. These dyes are expected to be useful fluorophore scaffolds in the development of new NIR probes for bioimaging.

     
    more » « less
  3. Abstract

    The influence of strongly electron donating amino groups on a hydroxyaromatic 1,2,3‐triazolyl anion chemosensor was investigated with spectroscopic studies (ultraviolet‐visible [UV‐vis], fluorescence, and nuclear magnetic resonance [NMR]) and computational analyses. This work focused on2‐,3‐and4‐aminoderivatives of the parent molecule, 2‐(4‐phenyl‐1H‐1,2,3‐triazol‐1‐yl)phenol (PTP). The effect on signal‐output, selectivity, sensitivity, and the mechanism of response was explored. In all cases, the incorporation of the amino group enhances fluorescence during anion detection while retaining key properties (the receptor site, a blue‐fluorescent response, and the ability to detect F, H2PO4, and AcO—strongest response to F). Specifically, sensitivity to Fis impacted by the amino group's location. The2‐aminois most responsive to F, more thanPTPand the other amino regioisomers. Results from this work are important for developing predictive, structure‐signal tuning models, which will be used in the targeted design of sensors based on thePTPscaffold.

     
    more » « less
  4. Abstract

    Fluorescence imaging is a powerful tool for studying biologically relevant macromolecules, but its applicability is often limited by the fluorescent probe, which must demonstrate both high site‐specificity and emission efficiency. In this regard, M13 virus, a versatile biological scaffold, has previously been used to both assemble fluorophores on its viral capsid with molecular precision and to also target a variety of cells. Although M13‐fluorophore systems are highly selective, these complexes typically suffer from poor molecular detection limits due to low absorption cross‐sections and moderate quantum yields. To overcome these challenges, a coassembly of the M13 virus, cyanine 3 dye, and silver nanoparticles is developed to create a fluorescent tag capable of binding with molecular precision with high emissivity. Enhanced emission of cyanine 3 of up to 24‐fold is achieved by varying nanoparticle size and particle‐fluorophore separation. In addition, it is found that the fluorescence enhancement increases with increasing dye surface density on the viral capsid. Finally, this highly fluorescent probe is applied for in vitro staining ofE. coli. These results demonstrate an inexpensive framework for achieving tuned fluorescence enhancements. The methodology developed in this work is potentially amendable to fluorescent detection of a wide range of M13/cell combinations.

     
    more » « less
  5. Abstract

    Fluorine magnetic resonance imaging (19F MRI) has emerged as an attractive alternative to conventional1H MRI due to enhanced specificity deriving from negligible background signal in this modality. We report a dual nanoparticle conjugate (DNC) platform as an aptamer‐based sensor for use in19F MRI.DNCconsists of core–shell nanoparticles with a liquid perfluorocarbon core and a mesoporous silica shell (19F‐MSNs), which give a robust19F MR signal, and superparamagnetic iron oxide nanoparticles (SPIONs) as magnetic quenchers. Due to the strong magnetic quenching effects of SPIONs, this platform is uniquely sensitive and functions with a low concentration of SPIONs (4 equivalents) relative to19F‐MSNs. The probe functions as a “turn‐on” sensor using target‐induced dissociation of DNA aptamers. The thrombin binding aptamer was incorporated as a proof‐of‐concept (DNCThr), and we demonstrate a significant increase in19F MR signal intensity whenDNCThris incubated with human α‐thrombin. This proof‐of‐concept probe is highly versatile and can be adapted to sense ATP and kanamycin as well. Importantly,DNCThrgenerates a robust19F MRI “hot‐spot” signal in response to thrombin in live mice, establishing this platform as a practical, versatile, and biologically relevant molecular imaging probe.

     
    more » « less