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Esterase-Activated Perthiocarbonate Persulfide Donors Provide Insights into Persulfide Persistence and Stability

https://doi.org/10.1021/acschembio.1c00805

Fosnacht, Kaylin G. ; Cerda, Matthew M. ; Mullen, Emma J. ; Pigg, Hannah C. ; Pluth, Michael D. ( January 2022 , ACS Chemical Biology)

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Effect of curvature and placement of donor and acceptor units in cycloparaphenylenes: a computational study

https://doi.org/10.1039/D0SC03923C

Lovell, Terri C. ; Fosnacht, Kaylin G. ; Colwell, Curtis E. ; Jasti, Ramesh ( November 2020 , Chemical Science)

Cycloparaphenylenes have promise as novel fluorescent materials. However, shifting their fluorescence beyond 510 nm is difficult. Herein, we computationally explore the effect of incorporating electron accepting and electron donating units on CPP photophysical properties at the CAM-B3LYP/6-311G** level. We demonstrate that incorporation of donor and acceptor units may shift the CPP fluorescence as far as 1193 nm. This computational work directs the synthesis of bright red-emitting CPPs. Furthermore, the nanohoop architecture allows for interrogation of strain effects on common conjugated polymer donor and acceptor units. Strain results in a bathochromic shift versus linear variants, demonstrating the value of using strain to push the limits of low band gap materials.
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A Cell Trappable Methyl Rhodol‐Based Fluorescent Probe for Hydrogen Sulfide Detection

https://doi.org/10.1002/asia.202200426

Fosnacht, Kaylin G. ; Hammers, Matthew D. ; Earp, Mary S. ; Gilbert, Annie K. ; Pluth, Michael D. ( July 2022 , Chemistry – An Asian Journal)

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.

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