Optical sensing of anions by macrocyclic and interlocked hosts

Tay, Hui Min; Beer, Paul D.

doi:10.1039/d1ob00601k

Cited by 48 publications

(42 citation statements)

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“…[30][31][32] As a result, increasing attention is being directed at the application of this capability in transmembrane anion transport, [33][34][35][36][37] ion extraction and remediation 38,39 as well as anion sensing. [40][41][42] The latter is highly relevant in many real-world scenarios, in particular environmental and healthcare monitoring. The reversible nature of non-covalent binding interactions in supramolecular host-guest systems is ideally suited for repeat and long-term sensing applications.…”

Section: Introductionmentioning

confidence: 99%

“…To this end, the generation of anion sensors by integration of suitable optical or electrochemical reporter groups into hydrogen bond donor anion receptor structural frameworks has received enormous attention over the past few decades. 27,[40][41][42][43][44][45] In contrast, XB and ChB mediated anion sensing is a relatively new phenomenon, oen demonstrating enhanced selectivity, binding strength and enhanced signal transducing capabilities in comparison to HB based sensing analogues.…”

Section: Introductionmentioning

confidence: 99%

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Halogen bonding and chalcogen bonding mediated sensing

Hein

Beer

2022

Chem. Sci.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Halogen bonding and chalcogen bonding mediated sensing

Hein

Beer

2022

Chem. Sci.

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“…Macrocycles, bearing different functionalities, are often used in many areas, e.g., as drug carriers [ 1 ] or catalysts [ 2 , 3 ]. Macrocyclic compounds are also of interest as a synthetic targets, providing functional systems for sensors, e.g., [ 4 , 5 ], molecular devices and switches c.f. [ 6 , 7 ].…”

Section: Introductionmentioning

confidence: 99%

Products of Photo- and Thermochemical Rearrangement of 19-Membered di-tert-Butyl-Azoxybenzocrown

et al. 2022

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The preparation and characterization of products of the photochemical and thermochemical rearrangements of 19-membered azoxybenzocrowns with two, bulky, tert-butyl substituents in benzene rings in the para positions to oligooxyethylene fragments (meta positions to azoxy group, i.e., t-Bu-19-Azo-O have been presented. In photochemical rearrangement, two colored typical products were expected, i.e., 19-membered o-hydroxy-m,m′-di-tert-butyl-azobenzocrown (t-Bu-19-o-OH) and 19-membered p-hydroxy-m,m′-di-tert-butyl-azobenzocrown (t-Bu-19-p-OH). In experiments, two colored atypical macrocyclic derivatives, one 6-membered and one 5-membered ring, bearing an aldehyde group (t-Bu-19-al) or intramolecular ester group (t-Bu-20-ester), were obtained. Photochemical rearrangement led to one more macrocyclic product being isolated and identified: a 17-membered colorless compound, without an azo moiety, t-Bu-17-p-OH. The yield of the individual compounds was significantly influenced by the reaction conditions. Thermochemical rearrangement led to t-Bu-20-ester as the main product. The structures of the four crystalline products of the rearrangement—t-Bu-19-o-OH, t-Bu-19-p-OH, t-Bu-20-ester and t-Bu-17-p-OH—were determined by the X-ray method. Structures in solution of atypical derivatives (t-Bu-19-al and t-Bu-20-ester) and t-Bu-19-p-OH were defined using NMR spectroscopy. For the newly obtained hydroxyazobenzocrowns, the azo–phenol⇄quinone–hydrazone tautomeric equilibrium was investigated using spectroscopic methods. Complexation studies of alkali and alkaline earth metal cations were studied using UV-Vis absorption spectroscopy. 1H NMR spectroscopy was additionally used to study the cation recognition of metal cations. Cation binding studies in acetonitrile have shown high selectivity towards calcium over magnesium for t-Bu-19-o-OH.

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“…Anion sensing by synthetic receptors is a highly dynamic ongoing topic in supramolecular chemistry due to the major impact of anion binding and transport on physical and biological processes. To date, numerous anion receptors have been synthesized and characterized, namely molecules with hydrogen donating groups [1][2][3][4], aromatic substituents or permanent positive charge [5][6][7][8][9], functionalized macrocycles such as cyclopeptides [10][11][12][13][14], calixarenes, calixpyrroles, and cryptands [15,16], or cation complexes with organic ligands [7][8][9]13,17]. These receptors differ in the affinities and selectivities for anionic species, as well as in the analytical signal by which the anion binding is detected.…”

Section: Introductionmentioning

confidence: 99%

“…In that line, cyclopeptides are promising candidates for efficient anion sensors and anion transporters in vivo due to the abundance and orientation of anion-binding groups, including amide protons, and resistance to biodegradation when compared to their linear analogues. One of the most sensitive methods used for the detection of anion-receptor complex formation in solution is fluorimetry [15,[18][19][20][21][22]. The method is fast, reliable, and gives a multivariate response that is well suited for stability constants determination.…”

Section: Introductionmentioning

confidence: 99%

Anion-Sensing Properties of Cyclopentaphenylalanine

et al. 2022

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Cyclic pentaphenylalanine was studied as an efficient anion sensor for halides, thiocyanate and oxoanions in acetonitrile and methanol. Stability constants of the corresponding complexes were determined by means of fluorimetric, spectrophotometric, 1H NMR, and microcalorimetric titrations. A detailed structural overview of receptor–anion complexes was obtained by classical molecular dynamics (MD) simulations. The results of 1H NMR and MD studies indicated that the bound anions were coordinated by the amide groups of cyclopeptide, as expected. Circular dichroism (CD) titrations were also carried out in acetonitrile. To the best of our knowledge, this is the first example of the detection of anion binding by cyclopeptide using CD spectroscopy. The CD spectra were calculated from the structures obtained by MD simulations and were qualitatively in agreement with the experimental data. The stoichiometry of almost all complexes was 1:1 (receptor:anion), except for dihydrogen phosphate where the binding of dihydrogen phosphate dimer was observed in acetonitrile. The affinity of the cyclopeptide receptor was correlated with the structure of anion coordination sphere, as well as with the solvation properties of the examined solvents.

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Optical sensing of anions by macrocyclic and interlocked hosts

Abstract: The ubiquity of anions in biological and environmental systems has motivated the development of many novel anion receptors and sensors over the past two decades. Optical anion sensors, which undergo...

Cited by 48 publications

References 135 publications

Halogen bonding and chalcogen bonding mediated sensing

Halogen bonding and chalcogen bonding mediated sensing

Products of Photo- and Thermochemical Rearrangement of 19-Membered di-tert-Butyl-Azoxybenzocrown

Anion-Sensing Properties of Cyclopentaphenylalanine

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