Mechanism of the stereocomplex formation between enantiomeric poly(lactide)s

Loading...
Thumbnail Image
Date
1996
Authors
Brizzolara, Davide
Cantow, Hans-Joachim
Keller, Egbert
Domb, Abraham J.
Editors
Contact
Journal ISSN
Electronic ISSN
ISBN
Bibliographical data
Publisher
Series
DOI (citable link)
ArXiv-ID
International patent number
EU project number
Project
Open Access publication
Collections
Restricted until
Title in another language
Research Projects
Organizational Units
Journal Issue
Publication type
Journal article
Publication status
Published in
Macromolecules ; 29 (1996), 1. - pp. 191-197. - ISSN 0024-9297. - eISSN 1520-5835
Abstract
Poly(L-lactide) (PLLA) and poly(D-lactide) (PDLA) crystallize into a stereocomplex with a melting point 50 °C higher than the crystals of the enantiomers. The racemic crystal is formed by packing β-form 31-helices of opposite absolute configuration alternatingly side by side. Single crystals of the stereocomplex exhibit triangular shape. The drastic difference of the powder patterns evidences the different packing of the β-form in the stereocomplex and in crystals of the pure lactides. By force field simulation of the stereocomplex and the PLLA unit cells and of their powder patterns, the reasons for the different packing could be clarified. Between the β-helices in the stereocomplex, van der Waals forces cause a specific energetic interaction-driven packing and, consequently, higher melting point. Helices of identical absolute configuration pack different from pairs of enantiomer β-helices. Packing favors R-type helication. A well-defined 103-helix has not been found. Good agreement with the experimental powder patterns proves the correctness of the simulations. On the basis of morphology, packing calculations, and atomic force microscopy, we propose a model of stereocomplex crystal growth, which explains the triangular shape of single crystals. Thus, for polymer components beyond chain folding length, the stereocomplex formation by simultaneous folding of the two types of chains is plausible. The triangular type of crystallizing offers favorable position for the polymer loops during the crystal growth. Our study of the PLA complexation mechanism may offer a chance to predict other polymeric stereocomplexes and their properties.
Summary in another language
Subject (DDC)
570 Biosciences, Biology
Keywords
Conference
Review
undefined / . - undefined, undefined. - (undefined; undefined)
Cite This
ISO 690BRIZZOLARA, Davide, Hans-Joachim CANTOW, Kay DIEDERICHS, Egbert KELLER, Abraham J. DOMB, 1996. Mechanism of the stereocomplex formation between enantiomeric poly(lactide)s. In: Macromolecules. 29(1), pp. 191-197. ISSN 0024-9297. eISSN 1520-5835. Available under: doi: 10.1021/ma951144e
BibTex
@article{Brizzolara1996Mecha-6600,
  year={1996},
  doi={10.1021/ma951144e},
  title={Mechanism of the stereocomplex formation between enantiomeric poly(lactide)s},
  number={1},
  volume={29},
  issn={0024-9297},
  journal={Macromolecules},
  pages={191--197},
  author={Brizzolara, Davide and Cantow, Hans-Joachim and Diederichs, Kay and Keller, Egbert and Domb, Abraham J.}
}
RDF
<rdf:RDF
    xmlns:dcterms="http://purl.org/dc/terms/"
    xmlns:dc="http://purl.org/dc/elements/1.1/"
    xmlns:rdf="http://www.w3.org/1999/02/22-rdf-syntax-ns#"
    xmlns:bibo="http://purl.org/ontology/bibo/"
    xmlns:dspace="http://digital-repositories.org/ontologies/dspace/0.1.0#"
    xmlns:foaf="http://xmlns.com/foaf/0.1/"
    xmlns:void="http://rdfs.org/ns/void#"
    xmlns:xsd="http://www.w3.org/2001/XMLSchema#" > 
  <rdf:Description rdf:about="https://kops.uni-konstanz.de/server/rdf/resource/123456789/6600">
    <dc:creator>Keller, Egbert</dc:creator>
    <bibo:uri rdf:resource="http://kops.uni-konstanz.de/handle/123456789/6600"/>
    <dc:contributor>Diederichs, Kay</dc:contributor>
    <void:sparqlEndpoint rdf:resource="http://localhost/fuseki/dspace/sparql"/>
    <dc:creator>Cantow, Hans-Joachim</dc:creator>
    <dcterms:abstract xml:lang="deu">Poly(L-lactide) (PLLA) and poly(D-lactide) (PDLA) crystallize into a stereocomplex with a melting point 50 °C higher than the crystals of the enantiomers. The racemic crystal is formed by packing β-form 31-helices of opposite absolute configuration alternatingly side by side. Single crystals of the stereocomplex exhibit triangular shape. The drastic difference of the powder patterns evidences the different packing of the β-form in the stereocomplex and in crystals of the pure lactides. By force field simulation of the stereocomplex and the PLLA unit cells and of their powder patterns, the reasons for the different packing could be clarified. Between the β-helices in the stereocomplex, van der Waals forces cause a specific energetic interaction-driven packing and, consequently, higher melting point. Helices of identical absolute configuration pack different from pairs of enantiomer β-helices. Packing favors R-type helication. A well-defined 103-helix has not been found. Good agreement with the experimental powder patterns proves the correctness of the simulations. On the basis of morphology, packing calculations, and atomic force microscopy, we propose a model of stereocomplex crystal growth, which explains the triangular shape of single crystals. Thus, for polymer components beyond chain folding length, the stereocomplex formation by simultaneous folding of the two types of chains is plausible. The triangular type of crystallizing offers favorable position for the polymer loops during the crystal growth. Our study of the PLA complexation mechanism may offer a chance to predict other polymeric stereocomplexes and their properties.</dcterms:abstract>
    <dc:date rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2011-03-24T17:27:42Z</dc:date>
    <dspace:isPartOfCollection rdf:resource="https://kops.uni-konstanz.de/server/rdf/resource/123456789/28"/>
    <dc:language>eng</dc:language>
    <dc:creator>Brizzolara, Davide</dc:creator>
    <dc:format>application/pdf</dc:format>
    <dc:rights>Attribution-NonCommercial-NoDerivs 2.0 Generic</dc:rights>
    <dcterms:issued>1996</dcterms:issued>
    <dcterms:isPartOf rdf:resource="https://kops.uni-konstanz.de/server/rdf/resource/123456789/28"/>
    <dcterms:rights rdf:resource="http://creativecommons.org/licenses/by-nc-nd/2.0/"/>
    <dc:contributor>Domb, Abraham J.</dc:contributor>
    <dcterms:title>Mechanism of the stereocomplex formation between enantiomeric poly(lactide)s</dcterms:title>
    <dc:contributor>Cantow, Hans-Joachim</dc:contributor>
    <dcterms:hasPart rdf:resource="https://kops.uni-konstanz.de/bitstream/123456789/6600/1/Mechanism_of_the_stereocomplex_formation_between_enantiomeric_polylactides.pdf"/>
    <dc:contributor>Brizzolara, Davide</dc:contributor>
    <foaf:homepage rdf:resource="http://localhost:8080/"/>
    <dc:creator>Diederichs, Kay</dc:creator>
    <dc:creator>Domb, Abraham J.</dc:creator>
    <dcterms:bibliographicCitation>First publ. in: Macromolecules ; 29 (1996). - S. 191-197</dcterms:bibliographicCitation>
    <dc:contributor>Keller, Egbert</dc:contributor>
    <dspace:hasBitstream rdf:resource="https://kops.uni-konstanz.de/bitstream/123456789/6600/1/Mechanism_of_the_stereocomplex_formation_between_enantiomeric_polylactides.pdf"/>
  </rdf:Description>
</rdf:RDF>
Internal note
xmlui.Submission.submit.DescribeStep.inputForms.label.kops_note_fromSubmitter
Contact
URL of original publication
Test date of URL
Examination date of dissertation
Method of financing
Comment on publication
Alliance license
Corresponding Authors der Uni Konstanz vorhanden
International Co-Authors
Bibliography of Konstanz
No
Refereed