Cooperative, bottom‐up generation of rigid‐rod nanostructures through dynamic polymer chemistry
Identifieur interne : 002733 ( Main/Exploration ); précédent : 002732; suivant : 002734Cooperative, bottom‐up generation of rigid‐rod nanostructures through dynamic polymer chemistry
Auteurs : J Frantz Folmer-Andersen [France, États-Unis] ; Eric Buhler [France] ; Sauveur-Jean Candau [France] ; Sebastien Joulie [France] ; Marc Schmutz [France] ; Jean-Marie Lehn [France]Source :
- Polymer International [ 0959-8103 ] ; 2010-11.
English descriptors
- Teeft :
- Acidic conditions, Acylhydrazone, Acylhydrazone linkage, Acylhydrazone linkages, Ambient temperature, Amphiphilic, Angew, Angew chem, Anhydrous, Anhydrous meoh, Appropriate monomers mmol, Aromatic, Aromatic signals, Behaviour, Biomol chem, Calcd, Carbazole nitrogen, Cdcl3, Chem, Chem commun, Chemical industry, Chemical industry polym, Cisoid conformation, Column chromatography, Commun, Conformation, Cooling bath, Covalent, Dark residue, Deionized water, Dynamic character, Dynamic polymers, Electronic absorption, Etoac, Excess monomer, Experimental data, Extreme behaviour, Form factor, Further evidence, Gaspard monge, Good agreement, Grid preparation, Guinier, Guinier expression, Gyration, Helical, Hrms, Hydrazine hydrate, Imbalance, Imbalanced stoichiometry, Initial monomer concentrations, Intermediate oligomers, Intermediate regime, Intermonomer association, Large polymers, Lehn, Lehn angew chem, Lehn chem, Lehn chem commun, Lehn helv chim acta, Lehn proc natl acad, Linear mass densities, Linear mass density, Linear relationship, Mass spectrometer, Mass spectrometry, Meoh, Mmol, Mmol phosphate buffer, Molar absorptivity, Molecular models, Molecular weight, Monomer, Monomers mmol, Nanostructures, Nanostructures figure, Online version, Optical properties, Organic phase, Physical dimensions, Polyacylhydrazones, Polym, Polymer, Polymer backbone, Polymer chain, Polymer chain ends, Polymer concentrations, Polymer rods, Polymer solutions, Polymerization, Product distributions, Prog polym, Resonance donation, Resultant nanostructures, Reversible interconnections, Reversible polycondensation, Reversible polymerizations, Room temperature, Sans, Sans data, Secondary structure, Similar results, Sio2 gradient elution etoac etoac meoh, Size exclusion laser light, Solid curve, Solvent composition, Statistical model, Statistical polymerization, Statistical polymerization model, Statistical systems, Stoichiometry, Stoichiometry imbalance, Structural models, Structural parameters, Such behaviour, Surface area, Synthetic polymer chemistry, Theoretical curves, Total number, Transmission electron microscopy, Unit volume, Unreacted monomers, Variable lengths.
Abstract
A set of carbazole‐ and benzene‐derived di(aldehyde) and di(acylhydrazine) monomers containing hexaglyme groups to impart water solubility has been synthesized. Mixing a given di(aldehyde) and di(acylhydrazine) pair in acidic aqueous solution causes polymerization through reversible acylhydrazone condensation. The structures of the resultant amphiphilic polyacylhydrazones have been studied using 1H NMR spectroscopy, matrix‐assisted laser desorption ionization mass spectrometry, small‐angle neutron scattering, transmission electron microscopy, size exclusion chromatography/multi‐angle laser light scattering (SEC‐MALLS) and UV‐visible and fluorescence spectrophotometries. All the available data support the existence of structurally related rod‐like nanostructures of variable lengths and constant diameters of approximately 5 nm in all cases, which are interpreted as corresponding to individually folded polymer chains. On the basis of these studies, molecular models are proposed in which the hydrophobic, aromatic polymer backbones assume helical conformations allowing for hydrophobically driven π‐stacking, while exposing the hydrophilic hexaglyme groups to the solvent. The molecular models are in agreement with the observed physical dimensions of the nanostructures, and are further supported by the observation of strong hypochromic effects on changing the solvent from dimethylformamide to water. Additionally, the reversible polymerization process is found to be cooperative. 1H NMR and SEC‐MALLS studies reveal severe deviations from statistically predicted product distributions under imbalanced stoichiometry, which are characteristic of nucleation–elongation behaviour. Copyright © 2010 Society of Chemical Industry
Reversible polycondensation of amphiphilic di(aldehyde) and di(acylhydrazine) monomers in water gives polyacylhydrazones, which fold into rod‐like nanostructures. Resistance to molecular weight degradation indicates that the process is highly cooperative.
Url:
DOI: 10.1002/pi.2864
Affiliations:
- France, États-Unis
- Alsace (région administrative), Grand Est, Île-de-France
- Paris, Strasbourg
- Université de Strasbourg
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xml:lang="fr">France</country><wicri:regionArea>Laboratoire de Chimie Supramoléculaire, Institut de Science et d' Ingénierie Supramoléculaires (ISIS), Université de Strasbourg, 8 allée Gaspard Monge, 67000 Strasbourg</wicri:regionArea><placeName><region type="region" nuts="2">Grand Est</region><region type="old region" nuts="2">Alsace (région administrative)</region><settlement type="city">Strasbourg</settlement></placeName><orgName type="university">Université de Strasbourg</orgName></affiliation></author><author><name sortKey="Joulie, Sebastien" sort="Joulie, Sebastien" uniqKey="Joulie S" first="Sebastien" last="Joulie">Sebastien Joulie</name><affiliation wicri:level="3"><country xml:lang="fr">France</country><wicri:regionArea>Electron Microscopy Team, Institut Charles Sadron, CNRS‐UPR 22 6 rue Boussingault, 67083 Strasbourg Cedex</wicri:regionArea><placeName><region type="region" nuts="2">Grand Est</region><region type="old region" nuts="2">Alsace (région 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Strasbourg</orgName></affiliation></author></analytic><monogr></monogr><series><title level="j" type="main">Polymer International</title><title level="j" type="sub">Dedicated to François Schué</title><title level="j" type="alt">POLYMER INTERNATIONAL</title><idno type="ISSN">0959-8103</idno><idno type="eISSN">1097-0126</idno><imprint><biblScope unit="vol">59</biblScope><biblScope unit="issue">11</biblScope><biblScope unit="page" from="1477">1477</biblScope><biblScope unit="page" to="1491">1491</biblScope><biblScope unit="page-count">15</biblScope><publisher>John Wiley & Sons, Ltd.</publisher><pubPlace>Chichester, UK</pubPlace><date type="published" when="2010-11">2010-11</date></imprint><idno type="ISSN">0959-8103</idno></series></biblStruct></sourceDesc><seriesStmt><idno type="ISSN">0959-8103</idno></seriesStmt></fileDesc><profileDesc><textClass><keywords scheme="Teeft" xml:lang="en"><term>Acidic conditions</term><term>Acylhydrazone</term><term>Acylhydrazone linkage</term><term>Acylhydrazone linkages</term><term>Ambient temperature</term><term>Amphiphilic</term><term>Angew</term><term>Angew chem</term><term>Anhydrous</term><term>Anhydrous meoh</term><term>Appropriate monomers mmol</term><term>Aromatic</term><term>Aromatic signals</term><term>Behaviour</term><term>Biomol chem</term><term>Calcd</term><term>Carbazole nitrogen</term><term>Cdcl3</term><term>Chem</term><term>Chem commun</term><term>Chemical industry</term><term>Chemical industry polym</term><term>Cisoid conformation</term><term>Column chromatography</term><term>Commun</term><term>Conformation</term><term>Cooling bath</term><term>Covalent</term><term>Dark residue</term><term>Deionized water</term><term>Dynamic character</term><term>Dynamic polymers</term><term>Electronic absorption</term><term>Etoac</term><term>Excess monomer</term><term>Experimental data</term><term>Extreme behaviour</term><term>Form factor</term><term>Further evidence</term><term>Gaspard monge</term><term>Good agreement</term><term>Grid preparation</term><term>Guinier</term><term>Guinier expression</term><term>Gyration</term><term>Helical</term><term>Hrms</term><term>Hydrazine hydrate</term><term>Imbalance</term><term>Imbalanced stoichiometry</term><term>Initial monomer concentrations</term><term>Intermediate oligomers</term><term>Intermediate regime</term><term>Intermonomer association</term><term>Large polymers</term><term>Lehn</term><term>Lehn angew chem</term><term>Lehn chem</term><term>Lehn chem commun</term><term>Lehn helv chim acta</term><term>Lehn proc natl acad</term><term>Linear mass densities</term><term>Linear mass density</term><term>Linear relationship</term><term>Mass spectrometer</term><term>Mass spectrometry</term><term>Meoh</term><term>Mmol</term><term>Mmol phosphate buffer</term><term>Molar absorptivity</term><term>Molecular models</term><term>Molecular weight</term><term>Monomer</term><term>Monomers mmol</term><term>Nanostructures</term><term>Nanostructures figure</term><term>Online version</term><term>Optical properties</term><term>Organic phase</term><term>Physical dimensions</term><term>Polyacylhydrazones</term><term>Polym</term><term>Polymer</term><term>Polymer backbone</term><term>Polymer chain</term><term>Polymer chain ends</term><term>Polymer concentrations</term><term>Polymer rods</term><term>Polymer solutions</term><term>Polymerization</term><term>Product distributions</term><term>Prog polym</term><term>Resonance donation</term><term>Resultant nanostructures</term><term>Reversible interconnections</term><term>Reversible polycondensation</term><term>Reversible polymerizations</term><term>Room temperature</term><term>Sans</term><term>Sans data</term><term>Secondary structure</term><term>Similar results</term><term>Sio2 gradient elution etoac etoac meoh</term><term>Size exclusion laser light</term><term>Solid curve</term><term>Solvent composition</term><term>Statistical model</term><term>Statistical polymerization</term><term>Statistical polymerization model</term><term>Statistical systems</term><term>Stoichiometry</term><term>Stoichiometry imbalance</term><term>Structural models</term><term>Structural parameters</term><term>Such behaviour</term><term>Surface area</term><term>Synthetic polymer chemistry</term><term>Theoretical curves</term><term>Total number</term><term>Transmission electron microscopy</term><term>Unit volume</term><term>Unreacted monomers</term><term>Variable lengths</term></keywords></textClass></profileDesc></teiHeader><front><div type="abstract" xml:lang="en">A set of carbazole‐ and benzene‐derived di(aldehyde) and di(acylhydrazine) monomers containing hexaglyme groups to impart water solubility has been synthesized. Mixing a given di(aldehyde) and di(acylhydrazine) pair in acidic aqueous solution causes polymerization through reversible acylhydrazone condensation. The structures of the resultant amphiphilic polyacylhydrazones have been studied using 1H NMR spectroscopy, matrix‐assisted laser desorption ionization mass spectrometry, small‐angle neutron scattering, transmission electron microscopy, size exclusion chromatography/multi‐angle laser light scattering (SEC‐MALLS) and UV‐visible and fluorescence spectrophotometries. All the available data support the existence of structurally related rod‐like nanostructures of variable lengths and constant diameters of approximately 5 nm in all cases, which are interpreted as corresponding to individually folded polymer chains. On the basis of these studies, molecular models are proposed in which the hydrophobic, aromatic polymer backbones assume helical conformations allowing for hydrophobically driven π‐stacking, while exposing the hydrophilic hexaglyme groups to the solvent. The molecular models are in agreement with the observed physical dimensions of the nanostructures, and are further supported by the observation of strong hypochromic effects on changing the solvent from dimethylformamide to water. Additionally, the reversible polymerization process is found to be cooperative. 1H NMR and SEC‐MALLS studies reveal severe deviations from statistically predicted product distributions under imbalanced stoichiometry, which are characteristic of nucleation–elongation behaviour. Copyright © 2010 Society of Chemical Industry</div><div type="abstract" xml:lang="en">Reversible polycondensation of amphiphilic di(aldehyde) and di(acylhydrazine) monomers in water gives polyacylhydrazones, which fold into rod‐like nanostructures. Resistance to molecular weight degradation indicates that the process is highly cooperative.</div></front></TEI><affiliations><list><country><li>France</li><li>États-Unis</li></country><region><li>Alsace (région administrative)</li><li>Grand Est</li><li>Île-de-France</li></region><settlement><li>Paris</li><li>Strasbourg</li></settlement><orgName><li>Université de Strasbourg</li></orgName></list><tree><country name="France"><region name="Grand Est"><name sortKey="Folmer Ndersen, J Frantz" sort="Folmer Ndersen, J Frantz" uniqKey="Folmer Ndersen J" first="J Frantz" last="Folmer-Andersen">J Frantz Folmer-Andersen</name></region><name sortKey="Buhler, Eric" sort="Buhler, Eric" uniqKey="Buhler E" first="Eric" last="Buhler">Eric Buhler</name><name sortKey="Candau, Sauveur Ean" sort="Candau, Sauveur Ean" uniqKey="Candau S" first="Sauveur-Jean" last="Candau">Sauveur-Jean Candau</name><name sortKey="Joulie, Sebastien" sort="Joulie, Sebastien" uniqKey="Joulie S" first="Sebastien" last="Joulie">Sebastien Joulie</name><name sortKey="Lehn, Jean Arie" sort="Lehn, Jean Arie" uniqKey="Lehn J" first="Jean-Marie" last="Lehn">Jean-Marie Lehn</name><name sortKey="Lehn, Jean Arie" sort="Lehn, Jean Arie" uniqKey="Lehn J" first="Jean-Marie" last="Lehn">Jean-Marie Lehn</name><name sortKey="Lehn, Jean Arie" sort="Lehn, Jean Arie" uniqKey="Lehn J" first="Jean-Marie" last="Lehn">Jean-Marie Lehn</name><name sortKey="Schmutz, Marc" sort="Schmutz, Marc" uniqKey="Schmutz M" first="Marc" last="Schmutz">Marc Schmutz</name></country><country name="États-Unis"><noRegion><name sortKey="Folmer Ndersen, J Frantz" sort="Folmer Ndersen, J Frantz" uniqKey="Folmer Ndersen J" first="J Frantz" last="Folmer-Andersen">J Frantz Folmer-Andersen</name></noRegion></country></tree></affiliations></record>Pour manipuler ce document sous Unix (Dilib)
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