Sensitive detection of enantiomeric excess in different acids though chiral induction in an oligo(p-phenylenevinylene) aggregate

F. Riobe, A.P.H.J. Schenning, D.B. Amabilino

Research output: Contribution to journalArticleAcademicpeer-review

12 Citations (Scopus)

Abstract

Induction of chirality in achiral aggregates of an oligo(p-phenylenevinylene) has been used to detect the enantiomeric excess in acids used in the resolution of chiral compounds. The chiral acids which induce helicity in the aggregates are present at only 10% of the concentration of the chromophore, whose chiroptical activity can be detected using circular dichroism spectroscopy. An ee of 10% in mixtures of (+) and (-) acids has been clearly evidenced in a series of samples using only 1.5 µg and concentration of approximately 10 µM of the chiral compound. The composition of both carboxylic and phosphoric acid derivatives can be detected, thanks to their binding to the dimerised core ureidotriazine unit attached at one end of the oligo(p-phenylenevinylene) which induces a preferred twist in the aggregated aromatic rod. This chiral arrangement is reflected in the Cotton effects that the assemblies show. The sign of the induced dichroic signal can be affected by the substituents around a stereogenic centre of otherwise identical configuration, and can lead to ambidextrous assemblies as seen in Cotton effects at different positions for different acids. While this technique can be used to detect enantiomeric excess, screening of the pure enantiomers is wise prior to the use of the method to detect scalemic mixtures. This supramolecular approach to evaluation of chiral content in samples could also be applied to other types of aggregates based on achiral molecules which show sensitivity to molecular chiral inducers.
Original languageEnglish
Pages (from-to)9152-9157
Number of pages7
JournalOrganic & Biomolecular Chemistry
Volume10
Issue number46
DOIs
Publication statusPublished - 2012

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induction
acids
Acids
cotton
assemblies
Cotton
Circular dichroism spectroscopy
Enantiomers
Chirality
phosphoric acid
enantiomers
Chromophores
Circular Dichroism
chirality
carboxylic acids
chromophores
dichroism
Spectrum Analysis
Screening
rods

Cite this

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title = "Sensitive detection of enantiomeric excess in different acids though chiral induction in an oligo(p-phenylenevinylene) aggregate",
abstract = "Induction of chirality in achiral aggregates of an oligo(p-phenylenevinylene) has been used to detect the enantiomeric excess in acids used in the resolution of chiral compounds. The chiral acids which induce helicity in the aggregates are present at only 10{\%} of the concentration of the chromophore, whose chiroptical activity can be detected using circular dichroism spectroscopy. An ee of 10{\%} in mixtures of (+) and (-) acids has been clearly evidenced in a series of samples using only 1.5 µg and concentration of approximately 10 µM of the chiral compound. The composition of both carboxylic and phosphoric acid derivatives can be detected, thanks to their binding to the dimerised core ureidotriazine unit attached at one end of the oligo(p-phenylenevinylene) which induces a preferred twist in the aggregated aromatic rod. This chiral arrangement is reflected in the Cotton effects that the assemblies show. The sign of the induced dichroic signal can be affected by the substituents around a stereogenic centre of otherwise identical configuration, and can lead to ambidextrous assemblies as seen in Cotton effects at different positions for different acids. While this technique can be used to detect enantiomeric excess, screening of the pure enantiomers is wise prior to the use of the method to detect scalemic mixtures. This supramolecular approach to evaluation of chiral content in samples could also be applied to other types of aggregates based on achiral molecules which show sensitivity to molecular chiral inducers.",
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Sensitive detection of enantiomeric excess in different acids though chiral induction in an oligo(p-phenylenevinylene) aggregate. / Riobe, F.; Schenning, A.P.H.J.; Amabilino, D.B.

In: Organic & Biomolecular Chemistry, Vol. 10, No. 46, 2012, p. 9152-9157.

Research output: Contribution to journalArticleAcademicpeer-review

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AB - Induction of chirality in achiral aggregates of an oligo(p-phenylenevinylene) has been used to detect the enantiomeric excess in acids used in the resolution of chiral compounds. The chiral acids which induce helicity in the aggregates are present at only 10% of the concentration of the chromophore, whose chiroptical activity can be detected using circular dichroism spectroscopy. An ee of 10% in mixtures of (+) and (-) acids has been clearly evidenced in a series of samples using only 1.5 µg and concentration of approximately 10 µM of the chiral compound. The composition of both carboxylic and phosphoric acid derivatives can be detected, thanks to their binding to the dimerised core ureidotriazine unit attached at one end of the oligo(p-phenylenevinylene) which induces a preferred twist in the aggregated aromatic rod. This chiral arrangement is reflected in the Cotton effects that the assemblies show. The sign of the induced dichroic signal can be affected by the substituents around a stereogenic centre of otherwise identical configuration, and can lead to ambidextrous assemblies as seen in Cotton effects at different positions for different acids. While this technique can be used to detect enantiomeric excess, screening of the pure enantiomers is wise prior to the use of the method to detect scalemic mixtures. This supramolecular approach to evaluation of chiral content in samples could also be applied to other types of aggregates based on achiral molecules which show sensitivity to molecular chiral inducers.

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