Detection of Isomeric Microscopic Host–Guest Complexes. A Time-Evolving Cucurbit[7]uril Complex

Tootoonchi, Mohammad Hossein; Yi, Song; Kaifer, Ángel E.

doi:10.1021/ja404797y

Cited by 48 publications

(47 citation statements)

References 28 publications

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“…As to generating a kinetically trapped state as the first step (Fig. 1b(i)), there have been several host molecules that temporarily bind a kinetically favoured guest prior to the binding with a thermodynamically favoured guest31323334353637383940414243. Therefore, we envisioned a kinetically trapped host–guest system having the second step in which removal of the kinetic barrier can initiate the guest uptake or exchange (Fig.…”

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confidence: 99%

Anion-capped metallohost allows extremely slow guest uptake and on-demand acceleration of guest exchange

2017

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The switching of molecular recognition selectivity is important for tuning molecular functions based on host–guest binding. While the switching processes in artificial functional molecules are usually driven by changes of the thermodynamic stabilities, non-equilibrium phenomena also play an important role in biological systems. Thus, here we designed a host–guest system utilizing a non-equilibrium kinetically trapped state for on-demand and time-programmable control of molecular functions. We synthesized a bis(saloph) macrocyclic cobalt(III) metallohost 1(OTf)2, which has anion caps at both sides of the cation-binding site. The anion caps effectively retard the guest uptake/release so that we can easily make a non-equilibrium kinetically trapped state. Indeed, we can obtain a long-lived kinetically trapped state {[1·K]3++La3+} prior to the formation of the thermodynamically more stable state {[1·La]5++K+}. The guest exchange to the more stable state from this kinetically trapped state is significantly accelerated by exchange of TfO− anion caps by AcO− in an on-demand manner.

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confidence: 99%

Anion-capped metallohost allows extremely slow guest uptake and on-demand acceleration of guest exchange

2017

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“…18 The encapsulation of both end groups in CB7 catalyzed the conversion from the ferrocenyl-embedded into the thermodynamically more stable adamantyl-included forms. The sliding of CB7 over an ammonium moiety was found to be energetically unfavorable.…”

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confidence: 99%

Kinetics and Thermodynamics of Berberine Inclusion in Cucurbit[7]uril

Miskolczy

Biczók

2014

J. Phys. Chem. B

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“…[57] Furthermore, as is in the case for viologen and tetrathiafulvalene, CBn complexation of reduced (or oxidized) species, such as radical cations, can lead to their chemically chemical stabilisation and suppression of certain aggregation pathways, which may facilitate analyte-detection by spectroelectrochemistry. For instance, addition of CB7 to a ditopic analyte containing a ferrocenyland adamantyl-binding motif gave indicative square wave voltammetry (SWV) peak currents from which the amount of free and complexed ferrocenyl-and adamantyl moieties could be deduced at different stages of the equilibration process.…”

Section: Redox Sensingmentioning

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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Detection of Isomeric Microscopic Host–Guest Complexes. A Time-Evolving Cucurbit[7]uril Complex

Cited by 48 publications

References 28 publications

Anion-capped metallohost allows extremely slow guest uptake and on-demand acceleration of guest exchange

Anion-capped metallohost allows extremely slow guest uptake and on-demand acceleration of guest exchange

Kinetics and Thermodynamics of Berberine Inclusion in Cucurbit[7]uril

Chemical Sensors Based on Cucurbit[n]uril Macrocycles

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