Redox-controlled chalcogen and pnictogen bonding: the case of a sulfonium/stibonium dication as a preanionophore for chloride anion transport

Park, Gyeongjin; Gabbaı̈, François P.

doi:10.1039/d0sc04417b

Cited by 60 publications

(52 citation statements)

References 55 publications

(78 reference statements)

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“…However, in recent years, non‐covalent sigma‐hole interactions, including halogen bonding (XB) and chalcogen bonding (ChB), have emerged as versatile intermolecular interactions for a variety of applications in supramolecular chemistry. [ 9 , 10 , 11 , 12 , 13 ] In the area of transmembrane anion transport, halogen bonding,[ 14 , 15 , 16 , 17 , 18 , 19 ] and more recently chalcogen [20] and pnictogen[ 21 , 22 , 23 ] bonding transporters represent effective alternatives to hydrogen bonding systems.…”

Section: Introductionmentioning

confidence: 99%

Highly Active Halogen Bonding and Chalcogen Bonding Chloride Transporters with Non‐Protonophoric Activity

Bickerton

Docker

Sterling

et al. 2021

Chemistry A European J

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Synthetic anion transporters show much promise as potential anti‐cancer agents and therapeutics for diseases associated with mis‐regulation of protein anion channels. In such applications high activity and anion selectivity are crucial to overcome competing proton or hydroxide transport which dissipates cellular pH gradients. Here, highly active bidentate halogen bonding and chalcogen bonding anion carriers based on electron deficient iodo‐ and telluromethyl−triazole derivatives are reported. Anion transport experiments in lipid bilayer vesicles reveal record nanomolar chloride transport activity for the bidentate halogen bonding anion carrier, and remarkably high chloride over proton/hydroxide selectivity for the chalcogen bonding anionophore. Computational studies provide further insight into the role of sigma‐hole mediated anion recognition and desolvation at the membrane interface. Comparison with hydrogen bonding analogues demonstrates the importance of employing sigma‐hole donor motifs in synthetic anionophores for achieving both high transport activity and selectivity.

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Section: Introductionmentioning

confidence: 99%

Highly Active Halogen Bonding and Chalcogen Bonding Chloride Transporters with Non‐Protonophoric Activity

Bickerton

Docker

Sterling

et al. 2021

Chemistry A European J

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“… 7 Other approaches have included transporters activated by the presence of reducing agents such as GSH found in higher concentrations in tumors than in the surrounding tissue. 8 With respect to light as the stimulus, only a few examples that are either based on azobenzene photoswitches modified with (thio)urea, 9 squaramide, 10 or amide 11 groups or on a photocleavable procarrier 12 are known in the literature. In most cases, however, a more detailed investigation into the mechanism of transport is still to follow.…”

Section: Introductionmentioning

confidence: 99%

Photomodulation of Transmembrane Transport and Potential by Stiff-Stilbene Based Bis(thio)ureas

et al. 2021

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Membrane transport proteins fulfill important regulatory functions in biology with a common trait being their ability to respond to stimuli in the environment. Various small-molecule receptors, capable of mediating transmembrane transport, have been successfully developed. However, to confer stimuli-responsiveness on them poses a fundamental challenge. Here we demonstrate photocontrol of transmembrane transport and electric potential using bis(thio)ureas derived from stiff-stilbene. UV–vis and 1 H NMR spectroscopy are used to monitor E – Z photoisomerization of these bis(thio)ureas and 1 H NMR titrations reveal stronger binding of chloride to the ( Z )-form than to the ( E )-form. Additional insight into the binding properties is provided by single crystal X-ray crystallographic analysis and DFT geometry optimization. Importantly, the ( Z )-isomers are much more active in transmembrane transport than the respective ( E )-isomers as shown through various assays. As a result, both membrane transport and depolarization can be modulated upon irradiation, opening up new prospects toward light-based therapeutics as well as physiological and optopharmacological tools for studying anion transport-associated diseases and to stimulate neuronal activity, respectively.

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“…Anion transport 24 − 37 with pnictogen bonds 38 − 44 has been realized recently 31 − 33 as logical continuation of the earlier studies with chalcogen 34 , 35 and halogen 36 , 37 bonds. These unorthodox interactions all originate from σ holes and, related to σ* antibonding orbitals, extend linearly from all covalent bonds made by the element ( Figure 1 a, see refs ( 44 ) and ( 38 ) for electrostatic potential surfaces).…”

mentioning

confidence: 60%

Pnictogen-Bonding Catalysis and Transport Combined: Polyether Transporters Made In Situ

Humeniuk

Gini

Hao

et al. 2021

JACS Au

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The combination of catalysis and transport across lipid bilayer membranes promises directional access to a solvent-free and structured nanospace that could accelerate, modulate, and, at best, enable new chemical reactions. To elaborate on these expectations, anion transport and catalysis with pnictogen and tetrel bonds are combined with polyether cascade cyclizations into bioinspired cation transporters. Characterized separately, synergistic anion and cation transporters of very high activity are identified. Combined for catalysis in membranes, cascade cyclizations are found to occur with a formal rate enhancement beyond one million compared to bulk solution and product formation is detected in situ as an increase in transport activity. With this operational system in place, intriguing perspectives open up to exploit all aspects of this unique nanospace for important chemical transformations.

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Redox-controlled chalcogen and pnictogen bonding: the case of a sulfonium/stibonium dication as a preanionophore for chloride anion transport

Abstract: We describe a sulfonium/stibonium dication that behaves as a preanionophore activatable by glutathione (GSH). Indeed, this dication is reduced by GSH to yield a thioether/stibonium monocation that readily transports Cl− across phospholipid membranes.

Cited by 60 publications

References 55 publications

Highly Active Halogen Bonding and Chalcogen Bonding Chloride Transporters with Non‐Protonophoric Activity

Highly Active Halogen Bonding and Chalcogen Bonding Chloride Transporters with Non‐Protonophoric Activity

Photomodulation of Transmembrane Transport and Potential by Stiff-Stilbene Based Bis(thio)ureas

Pnictogen-Bonding Catalysis and Transport Combined: Polyether Transporters Made In Situ

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