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<record><TEI><teiHeader><fileDesc><titleStmt><title xml:lang="en">Calix[6]tren and copper(II): A third generation of funnel complexes on the way to redox calix-zymes</title>
<author><name sortKey="Izzet, Guillaume" sort="Izzet, Guillaume" uniqKey="Izzet G" first="Guillaume" last="Izzet">Guillaume Izzet</name>
<affiliation><nlm:aff id="N0x9b1b668.0x9d0bb70">Laboratoire de Chimie et Biochimie Pharmacologiques et Toxicologiques, Unité Mixte de Recherche Centre National de la Recherche Scientifique 8601, Université René Descartes, 45 Rue des Saints-Pères, 75270 Paris Cedex 06, France;</nlm:aff>
</affiliation>
</author>
<author><name sortKey="Douziech, Benedicte" sort="Douziech, Benedicte" uniqKey="Douziech B" first="Bénédicte" last="Douziech">Bénédicte Douziech</name>
<affiliation><nlm:aff id="N0x9b1b668.0x9d0bb70">Laboratoire de Chimie, Electrochimie Moléculaires, et Chimie Analytique, Unité Mixte de Recherche Centre National de la Recherche Scientifique 6521, Université de Bretagne Occidentale, 6 Avenue Le Gorgeu, 29238 Brest Cedex 3, France;</nlm:aff>
</affiliation>
</author>
<author><name sortKey="Prange, Thierry" sort="Prange, Thierry" uniqKey="Prange T" first="Thierry" last="Prangé">Thierry Prangé</name>
<affiliation><nlm:aff wicri:cut="; and" id="N0x9b1b668.0x9d0bb70">Laboratoire de Cristallographie et de RMN Biologiques, Unité Mixte de Recherche Centre National de la Recherche Scientifique 8015, Université René Descartes, 4 Avenue de l'Observatoire, 75006 Paris, France</nlm:aff>
</affiliation>
</author>
<author><name sortKey="Tomas, Alain" sort="Tomas, Alain" uniqKey="Tomas A" first="Alain" last="Tomas">Alain Tomas</name>
<affiliation><nlm:aff wicri:cut="; and" id="N0x9b1b668.0x9d0bb70">Laboratoire de Cristallographie et de RMN Biologiques, Unité Mixte de Recherche Centre National de la Recherche Scientifique 8015, Université René Descartes, 4 Avenue de l'Observatoire, 75006 Paris, France</nlm:aff>
</affiliation>
</author>
<author><name sortKey="Jabin, Ivan" sort="Jabin, Ivan" uniqKey="Jabin I" first="Ivan" last="Jabin">Ivan Jabin</name>
<affiliation><nlm:aff id="N0x9b1b668.0x9d0bb70">Unité de Recherche en Chimie Organique et Macromoléculaire, Université du Havre, 25 Rue Philippe Lebon, BP 540, 76058 Le Havre Cedex, France</nlm:aff>
</affiliation>
</author>
<author><name sortKey="Le Mest, Yves" sort="Le Mest, Yves" uniqKey="Le Mest Y" first="Yves" last="Le Mest">Yves Le Mest</name>
<affiliation><nlm:aff id="N0x9b1b668.0x9d0bb70">Laboratoire de Chimie, Electrochimie Moléculaires, et Chimie Analytique, Unité Mixte de Recherche Centre National de la Recherche Scientifique 6521, Université de Bretagne Occidentale, 6 Avenue Le Gorgeu, 29238 Brest Cedex 3, France;</nlm:aff>
</affiliation>
</author>
<author><name sortKey="Reinaud, Olivia" sort="Reinaud, Olivia" uniqKey="Reinaud O" first="Olivia" last="Reinaud">Olivia Reinaud</name>
<affiliation><nlm:aff id="N0x9b1b668.0x9d0bb70">Laboratoire de Chimie et Biochimie Pharmacologiques et Toxicologiques, Unité Mixte de Recherche Centre National de la Recherche Scientifique 8601, Université René Descartes, 45 Rue des Saints-Pères, 75270 Paris Cedex 06, France;</nlm:aff>
</affiliation>
</author>
</titleStmt>
<publicationStmt><idno type="wicri:source">PMC</idno>
<idno type="pmid">15867151</idno>
<idno type="pmc">1100775</idno>
<idno type="url">http://www.ncbi.nlm.nih.gov/pmc/articles/PMC1100775</idno>
<idno type="RBID">PMC:1100775</idno>
<idno type="doi">10.1073/pnas.0500240102</idno>
<date when="2005">2005</date>
<idno type="wicri:Area/Pmc/Corpus">000123</idno>
</publicationStmt>
<sourceDesc><biblStruct><analytic><title xml:lang="en" level="a" type="main">Calix[6]tren and copper(II): A third generation of funnel complexes on the way to redox calix-zymes</title>
<author><name sortKey="Izzet, Guillaume" sort="Izzet, Guillaume" uniqKey="Izzet G" first="Guillaume" last="Izzet">Guillaume Izzet</name>
<affiliation><nlm:aff id="N0x9b1b668.0x9d0bb70">Laboratoire de Chimie et Biochimie Pharmacologiques et Toxicologiques, Unité Mixte de Recherche Centre National de la Recherche Scientifique 8601, Université René Descartes, 45 Rue des Saints-Pères, 75270 Paris Cedex 06, France;</nlm:aff>
</affiliation>
</author>
<author><name sortKey="Douziech, Benedicte" sort="Douziech, Benedicte" uniqKey="Douziech B" first="Bénédicte" last="Douziech">Bénédicte Douziech</name>
<affiliation><nlm:aff id="N0x9b1b668.0x9d0bb70">Laboratoire de Chimie, Electrochimie Moléculaires, et Chimie Analytique, Unité Mixte de Recherche Centre National de la Recherche Scientifique 6521, Université de Bretagne Occidentale, 6 Avenue Le Gorgeu, 29238 Brest Cedex 3, France;</nlm:aff>
</affiliation>
</author>
<author><name sortKey="Prange, Thierry" sort="Prange, Thierry" uniqKey="Prange T" first="Thierry" last="Prangé">Thierry Prangé</name>
<affiliation><nlm:aff wicri:cut="; and" id="N0x9b1b668.0x9d0bb70">Laboratoire de Cristallographie et de RMN Biologiques, Unité Mixte de Recherche Centre National de la Recherche Scientifique 8015, Université René Descartes, 4 Avenue de l'Observatoire, 75006 Paris, France</nlm:aff>
</affiliation>
</author>
<author><name sortKey="Tomas, Alain" sort="Tomas, Alain" uniqKey="Tomas A" first="Alain" last="Tomas">Alain Tomas</name>
<affiliation><nlm:aff wicri:cut="; and" id="N0x9b1b668.0x9d0bb70">Laboratoire de Cristallographie et de RMN Biologiques, Unité Mixte de Recherche Centre National de la Recherche Scientifique 8015, Université René Descartes, 4 Avenue de l'Observatoire, 75006 Paris, France</nlm:aff>
</affiliation>
</author>
<author><name sortKey="Jabin, Ivan" sort="Jabin, Ivan" uniqKey="Jabin I" first="Ivan" last="Jabin">Ivan Jabin</name>
<affiliation><nlm:aff id="N0x9b1b668.0x9d0bb70">Unité de Recherche en Chimie Organique et Macromoléculaire, Université du Havre, 25 Rue Philippe Lebon, BP 540, 76058 Le Havre Cedex, France</nlm:aff>
</affiliation>
</author>
<author><name sortKey="Le Mest, Yves" sort="Le Mest, Yves" uniqKey="Le Mest Y" first="Yves" last="Le Mest">Yves Le Mest</name>
<affiliation><nlm:aff id="N0x9b1b668.0x9d0bb70">Laboratoire de Chimie, Electrochimie Moléculaires, et Chimie Analytique, Unité Mixte de Recherche Centre National de la Recherche Scientifique 6521, Université de Bretagne Occidentale, 6 Avenue Le Gorgeu, 29238 Brest Cedex 3, France;</nlm:aff>
</affiliation>
</author>
<author><name sortKey="Reinaud, Olivia" sort="Reinaud, Olivia" uniqKey="Reinaud O" first="Olivia" last="Reinaud">Olivia Reinaud</name>
<affiliation><nlm:aff id="N0x9b1b668.0x9d0bb70">Laboratoire de Chimie et Biochimie Pharmacologiques et Toxicologiques, Unité Mixte de Recherche Centre National de la Recherche Scientifique 8601, Université René Descartes, 45 Rue des Saints-Pères, 75270 Paris Cedex 06, France;</nlm:aff>
</affiliation>
</author>
</analytic>
<series><title level="j">Proceedings of the National Academy of Sciences of the United States of America</title>
<idno type="ISSN">0027-8424</idno>
<idno type="eISSN">1091-6490</idno>
<imprint><date when="2005">2005</date>
</imprint>
</series>
</biblStruct>
</sourceDesc>
</fileDesc>
<profileDesc><textClass></textClass>
</profileDesc>
</teiHeader>
<front><div type="abstract" xml:lang="en"><p>Mono-copper enzymes play an important role in biology and their functionality is based on Cu(II)/Cu(I) redox processes. Modeling a mono-nuclear site remains a challenge for a better understanding of its intrinsic reactivity. The first member of a third generation of calixarene-based mono-copper “funnel” complexes is described. The ligand is a calix[6]arene capped by a tren unit, hence presenting a <italic>N</italic>
<sub>4</sub>
coordination site confined in a cavity. Its Cu(II) complexes were characterized by electronic and EPR spectroscopies. The x-ray structure of one of them shows a five-coordinated metal ion in a slightly distorted trigonal bipyramidal geometry thanks to its coordination to a guest ligand L (ethanol). The latter sits in the heart of the hydrophobic calixarene cone that mimics the active site chamber and the hydrophobic access channel of enzymes. Competitive binding experiments showed a preference order dimethylformamide > ethanol > MeCN for L binding at the single exchangeable metal site. Cyclic voltammetry studies showed irreversible redox processes in CH<sub>2</sub>
Cl<sub>2</sub>
when L is an oxygen donor caused by the redox-driven ejection of the guest at the Cu(I) level. In the presence of MeCN, a pseudoreversible process was obtained, owing to a fast equilibrium between a fourand a five-coordinate Cu(I) species. Finally, a redox-driven ligand interchange of dimethylformamide for MeCN at the Cu(I) state allowed the trapping of the thermodynamically less stable Cu(II)-MeCN adduct. Hence, this work represents an important step toward the elaboration of a functional supramolecular model for redox mono-copper enzymes, named redox calix-zymes.</p>
</div>
</front>
</TEI>
<pmc article-type="research-article"><pmc-comment>The publisher of this article does not allow downloading of the full text in XML form.</pmc-comment>
<front><journal-meta><journal-id journal-id-type="nlm-ta">Proc Natl Acad Sci U S A</journal-id>
<journal-id journal-id-type="publisher-id">pnas</journal-id>
<journal-title>Proceedings of the National Academy of Sciences of the United States of America</journal-title>
<issn pub-type="ppub">0027-8424</issn>
<issn pub-type="epub">1091-6490</issn>
<publisher><publisher-name>National Academy of Sciences</publisher-name>
</publisher>
</journal-meta>
<article-meta><article-id pub-id-type="pmid">15867151</article-id>
<article-id pub-id-type="pmc">1100775</article-id>
<article-id pub-id-type="publisher-id">01026831</article-id>
<article-id pub-id-type="doi">10.1073/pnas.0500240102</article-id>
<article-categories><subj-group subj-group-type="heading"><subject>Physical Sciences</subject>
<subj-group><subject>Chemistry</subject>
</subj-group>
</subj-group>
</article-categories>
<title-group><article-title>Calix[6]tren and copper(II): A third generation of funnel complexes on the way to redox calix-zymes</article-title>
</title-group>
<contrib-group><contrib contrib-type="author"><name><surname>Izzet</surname>
<given-names>Guillaume</given-names>
</name>
<xref ref-type="aff" rid="N0x9b1b668.0x9d0bb70">*</xref>
</contrib>
<contrib contrib-type="author"><name><surname>Douziech</surname>
<given-names>Bénédicte</given-names>
</name>
<xref ref-type="aff" rid="N0x9b1b668.0x9d0bb70">†</xref>
</contrib>
<contrib contrib-type="author"><name><surname>Prangé</surname>
<given-names>Thierry</given-names>
</name>
<xref ref-type="aff" rid="N0x9b1b668.0x9d0bb70">‡</xref>
</contrib>
<contrib contrib-type="author"><name><surname>Tomas</surname>
<given-names>Alain</given-names>
</name>
<xref ref-type="aff" rid="N0x9b1b668.0x9d0bb70">‡</xref>
</contrib>
<contrib contrib-type="author"><name><surname>Jabin</surname>
<given-names>Ivan</given-names>
</name>
<xref ref-type="aff" rid="N0x9b1b668.0x9d0bb70">§</xref>
</contrib>
<contrib contrib-type="author"><name><surname>Le Mest</surname>
<given-names>Yves</given-names>
</name>
<xref ref-type="aff" rid="N0x9b1b668.0x9d0bb70">†</xref>
<xref ref-type="corresp" rid="cor1">¶</xref>
</contrib>
<contrib contrib-type="author"><name><surname>Reinaud</surname>
<given-names>Olivia</given-names>
</name>
<xref ref-type="aff" rid="N0x9b1b668.0x9d0bb70">*</xref>
<xref ref-type="corresp" rid="cor1">¶</xref>
</contrib>
</contrib-group>
<aff id="N0x9b1b668.0x9d0bb70"><label>*</label>
Laboratoire de Chimie et Biochimie Pharmacologiques et Toxicologiques, Unité Mixte de Recherche Centre National de la Recherche Scientifique 8601, Université René Descartes, 45 Rue des Saints-Pères, 75270 Paris Cedex 06, France;<label>†</label>
Laboratoire de Chimie, Electrochimie Moléculaires, et Chimie Analytique, Unité Mixte de Recherche Centre National de la Recherche Scientifique 6521, Université de Bretagne Occidentale, 6 Avenue Le Gorgeu, 29238 Brest Cedex 3, France;<label>‡</label>
Laboratoire de Cristallographie et de RMN Biologiques, Unité Mixte de Recherche Centre National de la Recherche Scientifique 8015, Université René Descartes, 4 Avenue de l'Observatoire, 75006 Paris, France; and<label>§</label>
Unité de Recherche en Chimie Organique et Macromoléculaire, Université du Havre, 25 Rue Philippe Lebon, BP 540, 76058 Le Havre Cedex, France</aff>
<author-notes><fn id="cor1"><label>¶</label>
<p> To whom correspondence may be addressed. E-mail: <email>olivia.reinaud@univ-paris5.fr</email>
or <email>yves.lemest@univ-brest.fr</email>
. </p>
</fn>
<fn><p>Edited by Jack Halpern, University of Chicago, Chicago, IL, and approved March 28, 2005</p>
</fn>
</author-notes>
<pub-date pub-type="ppub"><day>10</day>
<month>5</month>
<year>2005</year>
</pub-date>
<pub-date pub-type="epub"><day>2</day>
<month>5</month>
<year>2005</year>
</pub-date>
<volume>102</volume>
<issue>19</issue>
<fpage>6831</fpage>
<lpage>6836</lpage>
<history><date date-type="received"><day>12</day>
<month>1</month>
<year>2005</year>
</date>
</history>
<copyright-statement>Copyright © 2005, The National Academy of Sciences</copyright-statement>
<copyright-year>2005</copyright-year>
<abstract><p>Mono-copper enzymes play an important role in biology and their functionality is based on Cu(II)/Cu(I) redox processes. Modeling a mono-nuclear site remains a challenge for a better understanding of its intrinsic reactivity. The first member of a third generation of calixarene-based mono-copper “funnel” complexes is described. The ligand is a calix[6]arene capped by a tren unit, hence presenting a <italic>N</italic>
<sub>4</sub>
coordination site confined in a cavity. Its Cu(II) complexes were characterized by electronic and EPR spectroscopies. The x-ray structure of one of them shows a five-coordinated metal ion in a slightly distorted trigonal bipyramidal geometry thanks to its coordination to a guest ligand L (ethanol). The latter sits in the heart of the hydrophobic calixarene cone that mimics the active site chamber and the hydrophobic access channel of enzymes. Competitive binding experiments showed a preference order dimethylformamide > ethanol > MeCN for L binding at the single exchangeable metal site. Cyclic voltammetry studies showed irreversible redox processes in CH<sub>2</sub>
Cl<sub>2</sub>
when L is an oxygen donor caused by the redox-driven ejection of the guest at the Cu(I) level. In the presence of MeCN, a pseudoreversible process was obtained, owing to a fast equilibrium between a fourand a five-coordinate Cu(I) species. Finally, a redox-driven ligand interchange of dimethylformamide for MeCN at the Cu(I) state allowed the trapping of the thermodynamically less stable Cu(II)-MeCN adduct. Hence, this work represents an important step toward the elaboration of a functional supramolecular model for redox mono-copper enzymes, named redox calix-zymes.</p>
</abstract>
<kwd-group><kwd>bioinorganic</kwd>
<kwd>supramolecular</kwd>
<kwd>electrochemistry</kwd>
<kwd>host–guest</kwd>
<kwd>enzyme model</kwd>
</kwd-group>
</article-meta>
<notes><fn-group><fn><p>Author contributions: Y.L.M. and O.R. designed research; G.I., B.D., Y.L.M., and O.R. performed research; I.J. contributed new reagents/analytic tools; G.I., B.D., T.P., A.T., Y.L.M., and O.R. analyzed data; and G.I., Y.L.M., and O.R. wrote the paper.</p>
</fn>
<fn><p>This paper was submitted directly (Track II) to the PNAS office.</p>
</fn>
<fn><p>Abbreviations: DMF, dimethylformamide; EtOH, ethanol; TBP, trigonal bipyramidal; CV, cyclic voltammetry.</p>
</fn>
<fn><p>Data deposition: The atomic coordinates have been deposited in the Cambridge Structural Database, Cambridge Crystallographic Data Centre, Cambridge CB2 1EZ, United Kingdom (CSD reference no. 260203).</p>
</fn>
</fn-group>
</notes>
</front>
</pmc>
</record>
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