Abstract:<p>By only
publishing the positive and successful results of our research, we as a field
are limiting scientific advances and exercising poor stewardship of financial
resources. By moving toward norms that include disseminating failed, unexpected,
and tangential results, we have the opportunity to not only increase the
efficiency of science, but also advance new discoveries. Of the broad scientific
disciplines, chemistry in particular is poised to take advantage of
already-existing, relatively low-barrie… Show more
“…On the basis of these rate differences, we propose that the cyclic-PSe compounds react directly with NBD-Cl to form an intermediate that facilitates the subsequent liberation of selenide and NBD-SeH formation. Although the NBD-Cl trapping system confirms that these donors are a source of labile reduced Se, we caution other researchers that NBD-Cl trapping experiments should be complemented with other measurements for RSeS-releasing compounds to not inadvertently interpret direct donor alkylation as alkylation of released H 2 Se in solution …”
Hydrogen selenide (H 2 Se) is a central metabolite in the biological processing of selenium for incorporation into selenoproteins, which play crucial antioxidant roles in biological systems. Despite being integral to proper physiological function, this reactive selenium species (RSeS) has received limited attention. We recently reported an early example of a H 2 Se donor (TDN1042) that exhibited slow, sustained release through hydrolysis. Here we expand that technology based on the PSe motif to develop cyclic-PSe compounds with increased rates of hydrolysis and function through well-defined mechanisms as monitored by 31 P and 77 Se NMR spectroscopy. In addition, we report a colorimetric method based on the reaction of H 2 Se with NBD-Cl to generate NBD-SeH (λ max = 551 nm), which can be used to detect free H 2 Se. Furthermore, we use TOF-SIMS (time of flight secondary ion mass spectroscopy) to demonstrate that these H 2 Se donors are cell permeable and use this technique for spatial mapping of the intracellular Se content after H 2 Se delivery. Moreover, these H 2 Se donors reduce endogenous intracellular reactive oxygen species (ROS) levels. Taken together, this work expands the toolbox of H 2 Se donor technology and sets the stage for future work focused on the biological activity and beneficial applications of H 2 Se and related bioinorganic RSeS.
“…On the basis of these rate differences, we propose that the cyclic-PSe compounds react directly with NBD-Cl to form an intermediate that facilitates the subsequent liberation of selenide and NBD-SeH formation. Although the NBD-Cl trapping system confirms that these donors are a source of labile reduced Se, we caution other researchers that NBD-Cl trapping experiments should be complemented with other measurements for RSeS-releasing compounds to not inadvertently interpret direct donor alkylation as alkylation of released H 2 Se in solution …”
Hydrogen selenide (H 2 Se) is a central metabolite in the biological processing of selenium for incorporation into selenoproteins, which play crucial antioxidant roles in biological systems. Despite being integral to proper physiological function, this reactive selenium species (RSeS) has received limited attention. We recently reported an early example of a H 2 Se donor (TDN1042) that exhibited slow, sustained release through hydrolysis. Here we expand that technology based on the PSe motif to develop cyclic-PSe compounds with increased rates of hydrolysis and function through well-defined mechanisms as monitored by 31 P and 77 Se NMR spectroscopy. In addition, we report a colorimetric method based on the reaction of H 2 Se with NBD-Cl to generate NBD-SeH (λ max = 551 nm), which can be used to detect free H 2 Se. Furthermore, we use TOF-SIMS (time of flight secondary ion mass spectroscopy) to demonstrate that these H 2 Se donors are cell permeable and use this technique for spatial mapping of the intracellular Se content after H 2 Se delivery. Moreover, these H 2 Se donors reduce endogenous intracellular reactive oxygen species (ROS) levels. Taken together, this work expands the toolbox of H 2 Se donor technology and sets the stage for future work focused on the biological activity and beneficial applications of H 2 Se and related bioinorganic RSeS.
A novel fluorescent probe design based on the interlocking of a reactive thread in a rigid nanohoop fluorophore is reported. This rotaxane design leads to size-selective sensing of thiolates in organic solution.More broadly, the work suggests the promise of mechanical interlocking to enhance the selectivity of reaction-based probes.
File list (2)download file view on ChemRxiv H2S_rotaxane_preprint.pdf (0.93 MiB) download file view on ChemRxiv H2S_rotaxane_SI.pdf (1.47 MiB)
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