Allosteric Tuning of the Intra‐Cavity Binding Properties of a Calix[6]arene through External Binding to a ZnII Center Coordinated to Amino Side Chains
Identifieur interne : 000F71 ( Main/Exploration ); précédent : 000F70; suivant : 000F72Allosteric Tuning of the Intra‐Cavity Binding Properties of a Calix[6]arene through External Binding to a ZnII Center Coordinated to Amino Side Chains
Auteurs : Ulrich Darbost ; Olivier Sénèque ; Yun Li ; Gildas Bertho ; Jérôme Marrot [France] ; Marie-Noëlle Rager [France] ; Olivia Reinaud [France] ; Ivan Jabin [France]Source :
- Chemistry – A European Journal [ 0947-6539 ] ; 2007-02-23.
English descriptors
- KwdEn :
- Binding Sites, Calixarenes (chemistry), Calixarenes (metabolism), Ligands, Magnetic Resonance Spectroscopy, Models, Molecular, Phenols (chemistry), Phenols (metabolism), Solutions, Stereoisomerism, X-Ray Diffraction, Zinc (metabolism), allosterism, calixarenes, host–guest systems, supramolecular chemistry, zinc.
- MESH :
- chemical , chemistry : Calixarenes, Phenols.
- chemical , metabolism : Calixarenes, Phenols, Zinc.
- Binding Sites, Ligands, Magnetic Resonance Spectroscopy, Models, Molecular, Solutions, Stereoisomerism, X-Ray Diffraction.
Abstract
Molecular recognition by calix[6]arene‐based receptors bearing three primary alkylamino side chain arms (1) is described. Complexation of ZnII ion provides the dinuclear μ‐hydroxo complex ${{\bf 2}{{{\rm OH}\hfill \atop {\rm G}\hfill}}}$, XRD characterization of which, together with solution studies, provided evidence of its hosting of neutral polar organic guests G. Treatment of this complex with a carboxylic acid or a sulfonamide (XH) results in the formation of mononuclear species ${{\bf 3}{{{\rm X}\hfill \atop {\rm G}\hfill}}}$, one of which (X = Cl) has been characterized by XRD. A dicationic complex ${{\bf 3}{{{\rm RNH}{_{2}}\hfill \atop {\rm G}\hfill}}}$ is obtained upon treatment of ${{\bf 2}{{{\rm OH}\hfill \atop {\rm G}\hfill}}}$ with a mixture of an alkylamine and a strong acid. Each of these ZnII complexes features a tetrahedral metal ion bound to the three amino arms of ligand 1 and to an exogenous ligand (either HO−, X−, or RNH2) sitting outside of the cavity. As a result, the metal ion structures the calixarene core, constraining it in a cone conformation suitable for guest hosting. The receptor properties of these compounds have been explored in detail and are compared with those of the trisammonium receptor ${{\bf 1}{{3\,{\rm H}{^{+}}\hfill \atop {\rm G}\hfill}}}$, based on the same calixarene core, as well as those of the trisimidazole‐based dicationic Zn funnel complexes. This study reveals very different host properties, in spite of the common hydrophobic, π‐basic, and hydrogen‐bonding acceptor properties of the calixarene cores. A harder external ligand produces a less polarized receptor that is consequently particularly sensitive to the hydrogen‐bonding ability of its guest. The less electron‐rich the apical ligand, and a fortiori the trisammonium host, the more sensitive the receptor to the dipole moment of the guest. All this stands in contrast with the funnel Zn complexes, in which the coordination link plays a dominant role. It is also shown that the asymmetry of an exo‐coordinated enantiopure amino ligand is sensed by the guest. This supramolecular system nicely illustrates how the receptor properties of a hydrophobic cavity can be allosterically tuned by the environment.
Url:
DOI: 10.1002/chem.200601040
Affiliations:
Links toward previous steps (curation, corpus...)
- to stream Istex, to step Corpus: 000C83
- to stream Istex, to step Curation: 000C83
- to stream Istex, to step Checkpoint: 000462
- to stream PubMed, to step Corpus: 000279
- to stream PubMed, to step Curation: 000279
- to stream PubMed, to step Checkpoint: 000279
- to stream Ncbi, to step Merge: 000173
- to stream Ncbi, to step Curation: 000173
- to stream Ncbi, to step Checkpoint: 000173
- to stream Main, to step Merge: 000F86
- to stream Main, to step Curation: 000F71
Le document en format XML
<record><TEI wicri:istexFullTextTei="biblStruct"><teiHeader><fileDesc><titleStmt><title xml:lang="en">Allosteric Tuning of the Intra‐Cavity Binding Properties of a Calix[6]arene through External Binding to a ZnII Center Coordinated to Amino Side Chains</title>
<author><name sortKey="Darbost, Ulrich" sort="Darbost, Ulrich" uniqKey="Darbost U" first="Ulrich" last="Darbost">Ulrich Darbost</name>
</author>
<author><name sortKey="Seneque, Olivier" sort="Seneque, Olivier" uniqKey="Seneque O" first="Olivier" last="Sénèque">Olivier Sénèque</name>
</author>
<author><name sortKey="Li, Yun" sort="Li, Yun" uniqKey="Li Y" first="Yun" last="Li">Yun Li</name>
</author>
<author><name sortKey="Bertho, Gildas" sort="Bertho, Gildas" uniqKey="Bertho G" first="Gildas" last="Bertho">Gildas Bertho</name>
</author>
<author><name sortKey="Marrot, Jerome" sort="Marrot, Jerome" uniqKey="Marrot J" first="Jérôme" last="Marrot">Jérôme Marrot</name>
</author>
<author><name sortKey="Rager, Marie Oelle" sort="Rager, Marie Oelle" uniqKey="Rager M" first="Marie-Noëlle" last="Rager">Marie-Noëlle Rager</name>
</author>
<author><name sortKey="Reinaud, Olivia" sort="Reinaud, Olivia" uniqKey="Reinaud O" first="Olivia" last="Reinaud">Olivia Reinaud</name>
</author>
<author><name sortKey="Jabin, Ivan" sort="Jabin, Ivan" uniqKey="Jabin I" first="Ivan" last="Jabin">Ivan Jabin</name>
</author>
</titleStmt>
<publicationStmt><idno type="wicri:source">ISTEX</idno>
<idno type="RBID">ISTEX:F49D95EB94D7748EF4C0EA0BD4DF59A593E68704</idno>
<date when="2007" year="2007">2007</date>
<idno type="doi">10.1002/chem.200601040</idno>
<idno type="url">https://api.istex.fr/document/F49D95EB94D7748EF4C0EA0BD4DF59A593E68704/fulltext/pdf</idno>
<idno type="wicri:Area/Istex/Corpus">000C83</idno>
<idno type="wicri:Area/Istex/Curation">000C83</idno>
<idno type="wicri:Area/Istex/Checkpoint">000462</idno>
<idno type="wicri:doubleKey">0947-6539:2007:Darbost U:allosteric:tuning:of</idno>
<idno type="wicri:source">PubMed</idno>
<idno type="RBID">pubmed:17143923</idno>
<idno type="wicri:Area/PubMed/Corpus">000279</idno>
<idno type="wicri:Area/PubMed/Curation">000279</idno>
<idno type="wicri:Area/PubMed/Checkpoint">000279</idno>
<idno type="wicri:Area/Ncbi/Merge">000173</idno>
<idno type="wicri:Area/Ncbi/Curation">000173</idno>
<idno type="wicri:Area/Ncbi/Checkpoint">000173</idno>
<idno type="wicri:doubleKey">0947-6539:2007:Darbost U:allosteric:tuning:of</idno>
<idno type="wicri:Area/Main/Merge">000F86</idno>
<idno type="wicri:Area/Main/Curation">000F71</idno>
<idno type="wicri:Area/Main/Exploration">000F71</idno>
</publicationStmt>
<sourceDesc><biblStruct><analytic><title level="a" type="main" xml:lang="en">Allosteric Tuning of the Intra‐Cavity Binding Properties of a Calix[6]arene through External Binding to a ZnII Center Coordinated to Amino Side Chains</title>
<author><name sortKey="Darbost, Ulrich" sort="Darbost, Ulrich" uniqKey="Darbost U" first="Ulrich" last="Darbost">Ulrich Darbost</name>
<affiliation><wicri:noCountry code="subField">(+33) 232‐744‐391</wicri:noCountry>
</affiliation>
</author>
<author><name sortKey="Seneque, Olivier" sort="Seneque, Olivier" uniqKey="Seneque O" first="Olivier" last="Sénèque">Olivier Sénèque</name>
<affiliation><wicri:noCountry code="subField">(+33) 142‐868‐387</wicri:noCountry>
</affiliation>
</author>
<author><name sortKey="Li, Yun" sort="Li, Yun" uniqKey="Li Y" first="Yun" last="Li">Yun Li</name>
<affiliation><wicri:noCountry code="subField">(+33) 142‐868‐387</wicri:noCountry>
</affiliation>
</author>
<author><name sortKey="Bertho, Gildas" sort="Bertho, Gildas" uniqKey="Bertho G" first="Gildas" last="Bertho">Gildas Bertho</name>
<affiliation><wicri:noCountry code="subField">(+33) 142‐868‐387</wicri:noCountry>
</affiliation>
</author>
<author><name sortKey="Marrot, Jerome" sort="Marrot, Jerome" uniqKey="Marrot J" first="Jérôme" last="Marrot">Jérôme Marrot</name>
<affiliation wicri:level="3"><country xml:lang="fr">France</country>
<wicri:regionArea>Institut Lavoisier, UMR CNRS 8180, Université de Versailles St‐Quentin en Yvelines, 45 av. des Etats‐Unis, 78035 Versailles cedex</wicri:regionArea>
<placeName><region type="region" nuts="2">Île-de-France</region>
<settlement type="city">Versailles</settlement>
</placeName>
</affiliation>
</author>
<author><name sortKey="Rager, Marie Oelle" sort="Rager, Marie Oelle" uniqKey="Rager M" first="Marie-Noëlle" last="Rager">Marie-Noëlle Rager</name>
<affiliation wicri:level="3"><country xml:lang="fr">France</country>
<wicri:regionArea>Service de RMN, Ecole Nationale Supérieure de Chimie de Paris (ENSCP), 11 rue Pierre et Marie Curie, 75231 Paris Cedex 05</wicri:regionArea>
<placeName><region type="region" nuts="2">Île-de-France</region>
<settlement type="city">Paris</settlement>
</placeName>
</affiliation>
</author>
<author><name sortKey="Reinaud, Olivia" sort="Reinaud, Olivia" uniqKey="Reinaud O" first="Olivia" last="Reinaud">Olivia Reinaud</name>
<affiliation></affiliation>
<affiliation wicri:level="1"><country wicri:rule="url">France</country>
</affiliation>
</author>
<author><name sortKey="Jabin, Ivan" sort="Jabin, Ivan" uniqKey="Jabin I" first="Ivan" last="Jabin">Ivan Jabin</name>
<affiliation></affiliation>
<affiliation wicri:level="1"><country wicri:rule="url">France</country>
</affiliation>
</author>
</analytic>
<monogr></monogr>
<series><title level="j">Chemistry – A European Journal</title>
<title level="j" type="abbrev">Chemistry – A European Journal</title>
<idno type="ISSN">0947-6539</idno>
<idno type="eISSN">1521-3765</idno>
<imprint><publisher>WILEY‐VCH Verlag</publisher>
<pubPlace>Weinheim</pubPlace>
<date type="published" when="2007-02-23">2007-02-23</date>
<biblScope unit="volume">13</biblScope>
<biblScope unit="issue">7</biblScope>
<biblScope unit="page" from="2078">2078</biblScope>
<biblScope unit="page" to="2088">2088</biblScope>
</imprint>
<idno type="ISSN">0947-6539</idno>
</series>
<idno type="istex">F49D95EB94D7748EF4C0EA0BD4DF59A593E68704</idno>
<idno type="DOI">10.1002/chem.200601040</idno>
<idno type="ArticleID">CHEM200601040</idno>
</biblStruct>
</sourceDesc>
<seriesStmt><idno type="ISSN">0947-6539</idno>
</seriesStmt>
</fileDesc>
<profileDesc><textClass><keywords scheme="KwdEn" xml:lang="en"><term>Binding Sites</term>
<term>Calixarenes (chemistry)</term>
<term>Calixarenes (metabolism)</term>
<term>Ligands</term>
<term>Magnetic Resonance Spectroscopy</term>
<term>Models, Molecular</term>
<term>Phenols (chemistry)</term>
<term>Phenols (metabolism)</term>
<term>Solutions</term>
<term>Stereoisomerism</term>
<term>X-Ray Diffraction</term>
<term>Zinc (metabolism)</term>
<term>allosterism</term>
<term>calixarenes</term>
<term>host–guest systems</term>
<term>supramolecular chemistry</term>
<term>zinc</term>
</keywords>
<keywords scheme="MESH" type="chemical" qualifier="chemistry" xml:lang="en"><term>Calixarenes</term>
<term>Phenols</term>
</keywords>
<keywords scheme="MESH" type="chemical" qualifier="metabolism" xml:lang="en"><term>Calixarenes</term>
<term>Phenols</term>
<term>Zinc</term>
</keywords>
<keywords scheme="MESH" xml:lang="en"><term>Binding Sites</term>
<term>Ligands</term>
<term>Magnetic Resonance Spectroscopy</term>
<term>Models, Molecular</term>
<term>Solutions</term>
<term>Stereoisomerism</term>
<term>X-Ray Diffraction</term>
</keywords>
</textClass>
<langUsage><language ident="en">en</language>
</langUsage>
</profileDesc>
</teiHeader>
<front><div type="abstract">Molecular recognition by calix[6]arene‐based receptors bearing three primary alkylamino side chain arms (1) is described. Complexation of ZnII ion provides the dinuclear μ‐hydroxo complex ${{\bf 2}{{{\rm OH}\hfill \atop {\rm G}\hfill}}}$, XRD characterization of which, together with solution studies, provided evidence of its hosting of neutral polar organic guests G. Treatment of this complex with a carboxylic acid or a sulfonamide (XH) results in the formation of mononuclear species ${{\bf 3}{{{\rm X}\hfill \atop {\rm G}\hfill}}}$, one of which (X = Cl) has been characterized by XRD. A dicationic complex ${{\bf 3}{{{\rm RNH}{_{2}}\hfill \atop {\rm G}\hfill}}}$ is obtained upon treatment of ${{\bf 2}{{{\rm OH}\hfill \atop {\rm G}\hfill}}}$ with a mixture of an alkylamine and a strong acid. Each of these ZnII complexes features a tetrahedral metal ion bound to the three amino arms of ligand 1 and to an exogenous ligand (either HO−, X−, or RNH2) sitting outside of the cavity. As a result, the metal ion structures the calixarene core, constraining it in a cone conformation suitable for guest hosting. The receptor properties of these compounds have been explored in detail and are compared with those of the trisammonium receptor ${{\bf 1}{{3\,{\rm H}{^{+}}\hfill \atop {\rm G}\hfill}}}$, based on the same calixarene core, as well as those of the trisimidazole‐based dicationic Zn funnel complexes. This study reveals very different host properties, in spite of the common hydrophobic, π‐basic, and hydrogen‐bonding acceptor properties of the calixarene cores. A harder external ligand produces a less polarized receptor that is consequently particularly sensitive to the hydrogen‐bonding ability of its guest. The less electron‐rich the apical ligand, and a fortiori the trisammonium host, the more sensitive the receptor to the dipole moment of the guest. All this stands in contrast with the funnel Zn complexes, in which the coordination link plays a dominant role. It is also shown that the asymmetry of an exo‐coordinated enantiopure amino ligand is sensed by the guest. This supramolecular system nicely illustrates how the receptor properties of a hydrophobic cavity can be allosterically tuned by the environment.</div>
</front>
</TEI>
<affiliations><list><country><li>France</li>
</country>
<region><li>Île-de-France</li>
</region>
<settlement><li>Paris</li>
<li>Versailles</li>
</settlement>
</list>
<tree><noCountry><name sortKey="Bertho, Gildas" sort="Bertho, Gildas" uniqKey="Bertho G" first="Gildas" last="Bertho">Gildas Bertho</name>
<name sortKey="Darbost, Ulrich" sort="Darbost, Ulrich" uniqKey="Darbost U" first="Ulrich" last="Darbost">Ulrich Darbost</name>
<name sortKey="Li, Yun" sort="Li, Yun" uniqKey="Li Y" first="Yun" last="Li">Yun Li</name>
<name sortKey="Seneque, Olivier" sort="Seneque, Olivier" uniqKey="Seneque O" first="Olivier" last="Sénèque">Olivier Sénèque</name>
</noCountry>
<country name="France"><region name="Île-de-France"><name sortKey="Marrot, Jerome" sort="Marrot, Jerome" uniqKey="Marrot J" first="Jérôme" last="Marrot">Jérôme Marrot</name>
</region>
<name sortKey="Jabin, Ivan" sort="Jabin, Ivan" uniqKey="Jabin I" first="Ivan" last="Jabin">Ivan Jabin</name>
<name sortKey="Rager, Marie Oelle" sort="Rager, Marie Oelle" uniqKey="Rager M" first="Marie-Noëlle" last="Rager">Marie-Noëlle Rager</name>
<name sortKey="Reinaud, Olivia" sort="Reinaud, Olivia" uniqKey="Reinaud O" first="Olivia" last="Reinaud">Olivia Reinaud</name>
</country>
</tree>
</affiliations>
</record>
Pour manipuler ce document sous Unix (Dilib)
EXPLOR_STEP=$WICRI_ROOT/Wicri/France/explor/LeHavreV1/Data/Main/Exploration
HfdSelect -h $EXPLOR_STEP/biblio.hfd -nk 000F71 | SxmlIndent | more
Ou
HfdSelect -h $EXPLOR_AREA/Data/Main/Exploration/biblio.hfd -nk 000F71 | SxmlIndent | more
Pour mettre un lien sur cette page dans le réseau Wicri
{{Explor lien |wiki= Wicri/France |area= LeHavreV1 |flux= Main |étape= Exploration |type= RBID |clé= ISTEX:F49D95EB94D7748EF4C0EA0BD4DF59A593E68704 |texte= Allosteric Tuning of the Intra‐Cavity Binding Properties of a Calix[6]arene through External Binding to a ZnII Center Coordinated to Amino Side Chains }}
This area was generated with Dilib version V0.6.25. |