Recognition of primary amines in water by a zinc funnel complex based on calix[6]arene

Bistri, Olivia; Colasson, Benoît; Reinaud, Olivia

doi:10.1039/c1sc00738f

Cited by 39 publications

(54 citation statements)

References 62 publications

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“…This was attributed to charge neutralization. 62 As previously observed in organic solvents, 63 the tris-imidazolyl ligand coordinates Zn II in a tetrahedral environment, with the amino guest strongly embedded in the hydrophobic cavity of the macrocycle. However, no coordination was observed in water whatever the pH, although in organic solvents (MeCN, chloroform), stoechiometric coordination was observed at the same concentration.…”

Section: The Cavity Participates In the Ligand Design -The Ligand Is mentioning

confidence: 64%

“…This was attributed to the competitive protonation of the ligand (favored under acidic conditions) and to the formation of Zn(II)-hydroxo species of lower Lewis acidity (favored under basic conditions). 62 Hence, the molecular design of this ligand confers a micro-environment to the metal center that favors the formation of a mononuclear complex and prevents its precipitation. This ternary complex is formed in a highly synergistic and allosteric manner and stabilizes the neutral form of the amino guest.…”

Section: The Cavity Participates In the Ligand Design -The Ligand Is mentioning

confidence: 99%

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Supramolecular control of transition metal complexes in water by a hydrophobic cavity: a bio-inspired strategy

Bistri

Reinaud

2015

Org. Biomol. Chem.

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Supramolecular chemistry in water is a very challenging research area. In biology, water is the universal solvent where transition metal ions play major roles in molecular recognition and catalysis. In enzymes, it participates in substrate binding and/or activation in the heart of a pocket defined by the folded protein. The association of a hydrophobic cavity with a transition metal ion is thus a very appealing strategy for controlling the metal ion properties in the very competitive water solvent. Various systems based on intrinsically water-soluble macrocyclic structures such as cyclodextrins, cucurbituryls, and metallo-cages have been reported. Others use calixarenes and resorcinarenes functionalized with hydrophilic substituents. One approach for connecting a metal complex to these cavities is to graft a ligand for metal ion binding at their edge. Early work with cyclodextrins has shown Michaelis-Menten like catalysis displaying enhanced kinetics and substrate-selectivity. Remarkable examples of regio- and stereo-selective transformation of substrates have been reported as well. Dynamic two-phase systems for transition metal catalysis have also been developed. They rely on either water-transfer of the metal complex through ligand embedment or synergistic coordination of a metal ion and substrate hosting. Another strategy consists in using metallo-cages, which provide a well-defined hydrophobic space, to stabilize metal complexes in water. When the cages can host simultaneously a substrate and a reactive metal complex, size- and regio-selective catalysis was obtained. Finally, construction of a polydentate coordination site closely interlocked with a calixarene or resorcinarene macrocycle has been shown to be a very fruitful strategy for obtaining metal complexes with remarkable hosting properties. For each of these systems, the synergism resulting from the biomimetic association of a hydrophobic cavity and a metal ion is discussed within the objective of developing new tools for either selective molecular recognition (with analytical perspectives) or performant catalysis, in water.

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Section: The Cavity Participates In the Ligand Design -The Ligand Is mentioning

confidence: 64%

Section: The Cavity Participates In the Ligand Design -The Ligand Is mentioning

confidence: 99%

Supramolecular control of transition metal complexes in water by a hydrophobic cavity: a bio-inspired strategy

Bistri

Reinaud

2015

Org. Biomol. Chem.

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“…Quite remarkable is the selectivity in favor of the small rim, in which the binding constant is two orders of magnitude higher than at the large rim. As a reuslt, with a single bound Zn II center, a funnel complex displaying host–guest properties is generated: Zn II at the small rim readily undergoes substitution of its guest solvent by a primary alkylamine . The remarkable hosting properties of funnel complexes stem from the synergic association of a metal‐to‐ligand coordination to multiple non‐bonding interactions occurring inside the cavity of the calixarene: H‐bonding to the oxygen atoms at the small rim, CH‐π interactions between the aromatic walls of the calix core and the included alkyl chain and a solvo‐phobic effect.…”

Section: Resultsmentioning

confidence: 99%

“…Variation of the N‐donor at the small rim, that is, introduction of an aza‐cryptand, will enforce the Zn II coordination and thus make the probe more sensitive. Finally, the strategy can be extended to the fluorimetric detection of amines in water: the receptor can be made water‐soluble, and, as a result of the hydrophobic effect, give rise to a further degree of selectivity in favor of the more lipophilic amines. We also showed that such systems can be grafted on surfaces, which opens the way to fluorimetric analytical devices …”

Section: Resultsmentioning

confidence: 99%

Selective Fluorimetric Detection of Primary Alkylamines by a Calix[6]arene Funnel Complex

Rémy

Guyon

Rebilly

et al. 2017

Chemistry A European J

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The association of host-guest and coordination chemistry was used to develop a fluorescent molecular sensor. A calix[6]arene bearing three imidazole arms at the small rim and three quinoline fluorophores at the large rim was synthesized and characterized. A two-step coordination sequence was observed upon addition of Zn . The first Zn center binds the tris-imidazole small rim site, leading only to a small perturbation of the fluorescence. In contrast, a large bathochromic shift is observed upon binding of the second Zn center at the large rim as a result of the direct interaction of Zn with the quinoline fluorophores. The system acts as a selective receptor for primary amines. Host-guest adduct formation could be identified by a shift and enhancement of the fluorescence emission that is dependent on the length and shape of the primary amine. This system constitutes a fluorescent reporter with a selective response among primary amines.

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“…Such as trategy has previously been successfully applied to variousf unnel complexes, as illustrated by tris(imidazole)Zn II -based and trenCu II -based calix [6]arene systems, which serve as selective receptors forl ipophilic primary amines in water. [21,22] The second strategy relies on incorporation of an organo-soluble metal complex into micelles. This has been previously exemplified for am etallo-receptor with au ranyl-salophen complex for anion binding.…”

Section: Introductionmentioning

confidence: 99%

Submerging a Biomimetic Metallo‐Receptor in Water for Molecular Recognition: Micellar Incorporation or Water Solubilization? A Case Study

Collin

Parrot

Marcélis

et al. 2018

Chemistry A European J

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Molecular recognition in water is an important topic, but ac hallenging task due to the very competitive nature of the medium. The focusofthis study is the comparison of two different strategies for the water solubilization of ab iomimetic metallo-receptor based on ap oly(imidazole) resorcinarene core. Thef irst relies on an ew synthetic path for the introduction of hydrophilic substituents on the receptor,a taremote distance from the coordination site. The second involves the incorporation of the organosoluble metallo-receptor into dodecylphosphocholine (DPC) micelles, which mimic the proteic surrounding of the active site of metallo-enzymes.T he resorcinarene ligand can be transferred into water through both strategies,i nw hich it binds Zn II over aw ide pH window.Q uite surprisingly,v ery similar metal ion affinities, pH responses, and recognition properties were observed with both strategies. The systems behavea s remarkable receptors for small organic anionsi nw ater at near-physiologicalp H. These results show that, provided the biomimetic site is well structured and presents ar ecognition pocket, the micellar environmenth as very little impacto n either metal ion binding or guest hosting.H ence, micellar incorporation represents an easy alternative to difficult synthetic work, even for the binding of charged species( metal cations or anions), which opens new perspectivesf or molecular recognition in water,w hether for sensing, transport, or catalysis.[a] Dr.Supporting information and the ORCID identification number(s) for the author(s) of this articlecan be found under: https://doi.

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Recognition of primary amines in water by a zinc funnel complex based on calix[6]arene

Cited by 39 publications

References 62 publications

Supramolecular control of transition metal complexes in water by a hydrophobic cavity: a bio-inspired strategy

Supramolecular control of transition metal complexes in water by a hydrophobic cavity: a bio-inspired strategy

Selective Fluorimetric Detection of Primary Alkylamines by a Calix[6]arene Funnel Complex

Submerging a Biomimetic Metallo‐Receptor in Water for Molecular Recognition: Micellar Incorporation or Water Solubilization? A Case Study

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