Correction to “Comprehensive Synthesis of Monohydroxy–Cucurbit[<i>n</i>]urils (<i>n</i> = 5, 6, 7, 8): High Purity and High Conversions”

Ayhan, Mehmet Menaf; Karoui, Hakim; Hardy, Micaël; Rockenbauer, Antal; Charles, Laurence; Rosas, Roselyne; Udachin, Konstantin A.; Tordo, Paul; Bardelang, David; Ouari, Olivier

doi:10.1021/jacs.6b00188

Cited by 33 publications

(24 citation statements)

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“…13 Moreover, the challenge of accessing pure, monofunctionalised derivatives was further confirmed by these results describing the quantitative conversion of CB[n] to CB[n]-(OH) 1 being recently revisited; the co-authors have now substantially corrected their claims. 16 Herein we report the reactivity of CB[n] under oxidative conditions and show that accessing monofunctionalised derivatives through a straightforward oxidative free radical approach is not possible. The oxidation of CB[n] as part of a complex mixture hinders the oxidation of the larger CB [7] and CB [8] homologues.…”

Section: Cucurbit[n]urils Cb[n]mentioning

confidence: 99%

Modulating the oxidation of cucurbit[n]urils

2017

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The functionalisation of cucurbit[n]uril macrocycles carried out through an oxidative approach in water using ammonium persulfate was studied. Through complexation with a doubly-charged bisimidazolium guest we were able to detect, distinguish and quantify the presence of each CB[n]-(OH) (where 1 ≤ x ≤ 2n) derivative for the first time. The impact of oxidation on each CB[n] (n = 6-8) was studied individually, as well as in the presence of other competing CB[n] species. We were able to understand the reactivity of the parent CB[n] alongside its hydroxylated derivatives, CB[n]-(OH), and show that the oxidation of CB[n] through a free-radical approach cannot result in stoichiometric hydroxylation despite previous literature reports by Bardelang, Ouari and co-workers, J. Am. Chem. Soc., 2015, 137, 10238. Furthermore, an in-depth study on hydroxylation of CB[7] was conducted. Through DFT calculations we were able to show that the second hydroxy substituent is preferentially located on the same glycoluril unit. Moreover, through optimisation of the reaction conditions we were able to access a protocol for controlled oxidation to yield a chemically monofunctional CB[7] derivative.

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Section: Cucurbit[n]urils Cb[n]mentioning

confidence: 99%

Modulating the oxidation of cucurbit[n]urils

2017

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“…In recent work, we successfully prepared mono-and dihydroxylated OMeQ [6] using the method published by Bardelang and Ouari, [18,19] and fortunately we obtained the major trans-di-hydroxylated OMeQ [6] isomer. [21][22][23][24] For the symmetrical hexamethylcucurbit [3,3]uril (Me 6 Q [3,3]), the most valuable hydroxylated product could be the trihydroxylated {(OH) 3 Me 6 Q[3,3]}, which may be further modified at its three meta-positions and thus in three directions.…”

Section: Resultsmentioning

confidence: 99%

“…Moreover, (HO) 2n Q[n]s are not suitable for precise or targeted modification due to their many reactive sites. [17] Since Bardelang and Ouari developed a mild photochemical method to directly introduce limited hydroxyl groups on cucurbit[n]urils (n = 5, 6, 7, 8) using hydrogen peroxide and then UV light, [18,19] this method [3,3]uril (Me 6 Q [3,3]). For example, Isaacs and co-workers reacted C-type oligomers with a functionalized glycoluril to afford monofunctional Q[n]s, [12][13][14][15] Scherman and co-workers prepared monohydroxylated Q [6] [16] using a modified method described by Kim, [2] and Kim and co-workers recently prepared monohydroxylated Q [7] by introducing excess K 2 SO 4 to balance the oxidation of Q [7].…”

Section: Introductionmentioning

confidence: 99%

Mono‐, Di‐, and Tri‐Hydroxylated Symmetrical Hexamethylcucurbit[3,3]uril and Allylated Derivatives

et al. 2017

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Mono‐, di, and tri‐hydroxylated hexamethylcucurbit[3,3]urils (Q[n]s), {(OH)Me6Q[3,3], (OH)2Me6Q[3,3], and (OH)3Me6Q[3,3]}, have been prepared through a photochemical method whereby limited hydroxyl group(s) can be directly introduced on the parent symmetrical hexamethylcucurbit[3,3]uril (Me6Q[3,3]). These three hydroxylated Me6Q[3,3]s have been characterized by means of NMR, MS, and X‐ray crystallographic techniques. Further chemical allylation of these hydroxylated Me6Q[3,3]s has also been performed.

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“…[72] (However, CBn and CBn complexes can bind to certain proteins and thereby affect some enzymatic functions, e. g., that of type II endonucleases or proteases, as was shown by the groups of Nau and Pischel.) [40,71,76,77,78,79,80,81,82,83,84,85,86] Similarly, functionalisable acyclic CBn derivatives are also available, enabling the instalment of signalling units into the formally dark/transparent cucurbiturils. [40,71,76,77,78,79,80,81,82,83,84,85,86] Similarly, functionalisable acyclic CBn derivatives are also available, enabling the instalment of signalling units into the formally dark/transparent cucurbiturils.…”

Section: Analytementioning

confidence: 99%

Chemical Sensors Based on Cucurbit[n]uril Macrocycles

Sinn

Biedermann

2018

Israel Journal of Chemistry

147

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Cucurbit[n]urils (CBn) are glycoluril‐based macrocyclic hosts that bind many biologically, medicinally and environmentally relevant analytes with record high affinities in aqueous media. They are therefore prime candidates for the design of chemosensors that are operational in biological fluids, waste and drinking water and have promising potential to be utilized for in vitro and in vivo sensing and imaging applications. Unlike protein‐based antibodies, CBn can be prepared in multi kilogram scales, they are chemically robust and they show a desired fast analyte‐binding kinetics. Unlike protein‐based antibodies, CBn can be prepared in multi kilogram scales, are chemically robust and show a desired fast analyte‐binding kinetics Selective analyte detection and differentiation is possible owing to the charge‐ and size‐selective binding characteristics of the CBn members and due to the wide range of cyclic and acyclic CBn derivatives that differ in their analyte binding preference. Because CBn hosts are spectroscopically silent in the visible electromagnetic spectrum, optical signal transduction with CBn based chemosensing ensembles is typically performed by indicator displacement assays (IDA), which are easy to implement and applicable to both aliphatic and aromatic analytes. The extension to array‐based sensing with CBn chemosensors is straightforward. Associative binding assays (ABA), which are uniquely available with CB8‐based self‐assembled receptors offer superior analyte differentiation possibility due to emerging spectral fingerprints in the absorbance, circular dichroism (CD) and emission spectra for the receptor•analyte complexes. Direct signal generation is promising for inherently spectroscopically active analytes, for instance through absorbance, CD, emission and surface enhanced Raman spectroscopy (SERS). Sensitive NMR (19F, 129Xe) techniques, electron spin resonance (ESR), redox, and mass spectrometry are also valuable signal transduction options for specific analytes. CBn based chemosensors were successfully utilized for the monitoring of biophysical processes and enzymatic reactions with label free analytes or substrates in real time. These applications capitalize on the fast equilibration kinetics of CBn‐analyte complexes and the bio‐compatibility of CBn hosts. The tabulated large body of data extracted from reported CBn‐based binding studies is hoped to provide the reader with a valuable starting point for designing practically applicable CBn‐based sensors.

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Correction to “Comprehensive Synthesis of Monohydroxy–Cucurbit[n]urils (n = 5, 6, 7, 8): High Purity and High Conversions”

Cited by 33 publications

References 0 publications

Modulating the oxidation of cucurbit[n]urils

Modulating the oxidation of cucurbit[n]urils

Mono‐, Di‐, and Tri‐Hydroxylated Symmetrical Hexamethylcucurbit[3,3]uril and Allylated Derivatives

Chemical Sensors Based on Cucurbit[n]uril Macrocycles

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