Aryl C–H⋯Cl− hydrogen bonding in a fluorescent anion sensor

Tresca, Blakely W.; Zakharov, Lev N.; Carroll, Calden N.; Johnson, Darren W.; Haley, Michael M.

doi:10.1039/c3cc44574g

Cited by 52 publications

(62 citation statements)

References 31 publications

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“…25 The crystal structure (Fig. 4, top) shows the chloride anion stabilised by five H-bonds, similar to what was observed in the structures of parent phenylurea 1d 17 and a benzene-core analogue of 1b ; 26 however, the urea N−H•••Cl bond distances (Table 1) in 1c•HCl are all shorter (Δd = 0.023–0.196 Å) than the analogous distances found in 1d•HCl , clearly illustrating the tighter binding of chloride when encapsulated by the macrocycle. This result shows that the binding pocket can accommodate a molecule of either HCl or H 2 O in the solid state along with minor changes in conformation, analogous to what was observed with our initial class of sulphonamide receptors.…”

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confidence: 61%

Synthesis and solid-state structures of a macrocyclic receptor based on the 2,6-bis(2-anilinoethynyl)pyridine scaffold

et al. 2014

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A fluorescent macrocyclic anion receptor based on the 2,6-bis(2-anilinoethynyl)pyridine scaffold has been synthesized to investigate the mechanism of fluorescence quenching in this class of compounds. X-ray crystallography reveals that the binding pocket of the receptor is a natural host to both H2O and HCl, accommodating either molecule in nearly identical environments. Our studies show that protonation, not collisional quenching, is responsible for the observed fluorescence quenching response.

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confidence: 61%

Synthesis and solid-state structures of a macrocyclic receptor based on the 2,6-bis(2-anilinoethynyl)pyridine scaffold

et al. 2014

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confidence: 64%

“…[2b, 15] The host conformation in [1•HS − ] is remarkably similar to the previously published chloride-bound structure, with an RMS distance between the two structures of only 0.184 Å ( Figure S16). [14] These data demonstrate the similar recognition geometries required for Cl − and HS − binding, again highlighting the potential for HS − to be a substrate for classical Cl − binding domains in both native and synthetic systems.In conclusion, we report a series of bis(ethynylaniline) derivatives capable of binding hydrosulfide anion with association constants as high as 90,300 ± 8700 M −1 , representing the first reversible binding of the hydrosulfide anion in a synthetic receptor. 1 H NMR and UV-Vis spectroscopy both indicate stronger binding of hydrosulfide by the phenyl core receptor 1; however, a greater selectivity for HS − is observed in the pyridine cores (2 and 3).…”

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confidence: 64%

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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“…Most of our bisurea arylethynyl systems, particularly the pyridine- and phenyl-based receptors, typically bind in a U conformation, 20,27,28 leading us to hypothesize receptor 1 + would adopt a similar U conformation with a five-point binding site involving the electrostatic pyridinium moiety (Fig. 4).…”

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confidence: 99%

“Off-on” aggregation-based fluorescent sensor for the detection of chloride in water

et al. 2015

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Receptors selective for anions in aqueous media are a crucial component in the detection of anions for biological and environmental applications. Recent sensor designs have taken advantage of systems known to aggregate in solution, eliciting a fluorescent response. Herein, we demonstrate a chloride-selective fluorescent response of receptor 1+, based on our well-established class of 2,6-bis(2-anilinoethynyl)pyridine bisureas. The fluorescence intensity ratio of 1+·Cl− aggregates in water is four times larger than the next most fluorescent anion complex, 1+·ClO4−. In addition, 1H NMR spectroscopic titrations demonstrate 1+ binds chloride more strongly than other biologically relevant anions in solutions of both DMSO-d6 and 50/50 DMSO-d6/MeCN-d3.

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Aryl C–H⋯Cl− hydrogen bonding in a fluorescent anion sensor

Cited by 52 publications

References 31 publications

Synthesis and solid-state structures of a macrocyclic receptor based on the 2,6-bis(2-anilinoethynyl)pyridine scaffold

Synthesis and solid-state structures of a macrocyclic receptor based on the 2,6-bis(2-anilinoethynyl)pyridine scaffold

A Synthetic Supramolecular Receptor for the Hydrosulfide Anion

“Off-on” aggregation-based fluorescent sensor for the detection of chloride in water

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