NBu4SH provides a convenient source of HS− soluble in organic solution for H2S and anion-binding research

Hartle, Matthew D.; Meininger, Daniel J.; Zakharov, Lev N.; Tonzetich, Zachary J.; Pluth, Michael D.

doi:10.1039/c5dt03355a

Cited by 34 publications

(32 citation statements)

References 29 publications

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“…Further addition of five equivalents of NBu 4 SH regenerated the HS − host-guest complex, confirming reversible binding. Importantly, the 13 C{ 1 H} resonances of the alkyne carbons did not shift significantly (Figures 3b, d), confirming that there was no covalent modification of the receptor scaffold. Figure S15).…”

Section: Graphical Abstractsupporting

confidence: 50%

“…Motivated by these challenges, we report here the first examples of synthetic receptors that reversibly bind HS − using solely supramolecular interactions (Figure 1c). To investigate whether HS − is a suitable guest for hosts 1-3, we titrated NBu 4 SH [13] into 0.5-1.0 mM solution of each host in 10% DMSO-d 6 /CD 3 CN and monitored the titrations by 1H NMR spectroscopy ( Figure S1). In each case, we observed that the urea NH resonances shifted significantly downfield upon HS − addition, consistent with anion binding (Figure 2).…”

Section: Author Manuscriptmentioning

confidence: 99%

“…To investigate whether HS À is asuitable guest for hosts 1-3,w et itrated a0 .5-1.0 mm solution of each host in 10 % [D 6 ]DMSO/CD 3 CN with NBu 4 SH [13] and monitored the titrations by 1 HNMR spectroscopy (Supporting Information, Figure S1). In each case,w eo bserved that the urea NH resonances shifted significantly downfield upon HS À addition, consistent with anion binding (Figure 2).…”

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A Synthetic Supramolecular Receptor for the Hydrosulfide Anion

et al. 2016

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Hydrogen sulfide (H 2 S) has emerged as a crucial biomolecule in physiology and cellular signaling. Key challenges associated with developing new chemical tools for understanding the biological roles of H 2 S include developing platforms that enable reversible binding of this important biomolecule. Here we report the first synthetic small molecule receptor for hydrosulfide anion, HS − , solely utilizing reversible, hydrogen-bonding interactions in a series of bis (ethynylaniline) Correspondence to: Michael M. Haley, haley@uoregon.edu; Michael D. Pluth, pluth@uoregon.edu; Darren W. Johnson, dwj@uoregon.edu. ‡ M. D. Hartle and R.J. Hansen contributed equally to this work Supporting information for this article is given via a link at the end of the document. HHS Public Access Author Manuscript Author ManuscriptAuthor ManuscriptAuthor Manuscript derivatives. Binding constants up to 90,300 ± 8700 M −1 were obtained. The fundamental science of reversible sulfide binding-in this case featuring a key CH···S hydrogen bond-will expand the possibility for discovery of sulfide protein targets and molecular recognition agents. Graphical AbstractLong known for its malodor and toxicity, hydrogen sulfide is the most recently discovered endogenously produced gasotransmitter. Here we report the first synthetic receptor for reversible binding of HS − as characterized spectroscopically in solution and crystallographically.Keywords anions; supramolecular chemistry; H 2 S; sulfide; anion binding Supramolecular hosts have been developed to selectively bind a variety of anionic species in solution, ranging from inorganic phosphates and phosphorylated biomolecules, to halides, to other anions of environmental and/or biological relevance. [1] These synthetic supramolecular receptors use reversible, mostly non-covalent interactions to select anions based on factors such as their basicity, shape/charge, softness/hardness, position on the Hofmeister series, hydrophobic/solvophobic effects, among others. Notably lacking in the anion binding literature are efforts to target hydrosulfide (HS − ), the smallest monoanionic sulfur species, which has recently gained interest as an important biomolecule. We report here the first examples of synthetic receptors that reversibly bind HS − using solely hydrogen bonding interactions. Importantly, a critical CH···S hydrogen bond is key to the strong binding of hydrosulfide, lending support to the hypothesis that appropriately polarized CH hydrogen bond donors [1f, 2] can target softer anions. [1e, 3] Hydrogen sulfide (H 2 S) plays diverse roles in the global sulfur cycle and has recently been implicated as an important biologically-relevant signaling molecule. [4] In the last decade, H 2 S (and its more prevalent HS − conjugate base form under biological conditions) has emerged as the third endogenously produced gasotransmitter, along with CO and NO. H 2 S is now implicated in diverse (patho)physiological functions in the cardiovascular, immune, gastrointestinal, as well as other systems...

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A Synthetic Supramolecular Receptor for the Hydrosulfide Anion

et al. 2016

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“…The sodium polysulfide salts defined were provided by Dojindo Laboratories (Munich, Germany and Kumamoto, Japan). Tetrabutyl ammonium sulfide (NBu 4 SH) was prepared as described in the literature (Hartle et al ., ). Sulfide stock solutions were prepared as previously described (Nagy et al ., ).…”

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confidence: 97%

Speciation of reactive sulfur species and their reactions with alkylating agents: do we have any clue about what is present inside the cell?

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et al. 2018

British J Pharmacology

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“…S32 †). 44 Such an experiment suggests that the interaction of S 2À ion with the carboxylic acid group of L2 potentially generates HS À species and anionic carboxylate group. Importantly, no change in the emission of L1 (having ester group) in presence of S 2À ion strongly support the role of free carboxylic acid in its sensing.…”

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confidence: 99%