Cooperativity in the folding of helical m-phenylene ethynylene oligomers based upon the 'Sergeants-and-Soldiers' principle

R.B. Prince, L. Brunsveld, J.S. Moore, E.W. Meijer

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Abstract

The 'Sergeants-and-Soldiers' principle has been examined in a series of m-phenylene ethynylene oligomers containing both chiral and achiral side chains. Circular dichroism (CD) spectroscopy was used to examine the twist sense bias of the helical conformation in the polar solvent acetonitrile. A nonlinear dependence of the CD signal on the amount of chiral side chains was observed revealing cooperative interactions among the side chains through the backbone. On the other hand, the experiments indicate that in acetonitrile a full bias of the helicity cannot be accomplished by chiral side chains alone. Nevertheless, the folded oligomers are highly ordered since the placement of a single chiral side chain at the beginning of an oligomer results in the induction of a strong twist sense bias into the ordered helical conformation
Original languageEnglish
Pages (from-to)4150-4154
JournalChemistry : A European Journal
Volume7
Issue number19
DOIs
Publication statusPublished - 2001

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Oligomers
Conformations
Circular dichroism spectroscopy
Dichroism
Experiments
acetonitrile

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title = "Cooperativity in the folding of helical m-phenylene ethynylene oligomers based upon the 'Sergeants-and-Soldiers' principle",
abstract = "The 'Sergeants-and-Soldiers' principle has been examined in a series of m-phenylene ethynylene oligomers containing both chiral and achiral side chains. Circular dichroism (CD) spectroscopy was used to examine the twist sense bias of the helical conformation in the polar solvent acetonitrile. A nonlinear dependence of the CD signal on the amount of chiral side chains was observed revealing cooperative interactions among the side chains through the backbone. On the other hand, the experiments indicate that in acetonitrile a full bias of the helicity cannot be accomplished by chiral side chains alone. Nevertheless, the folded oligomers are highly ordered since the placement of a single chiral side chain at the beginning of an oligomer results in the induction of a strong twist sense bias into the ordered helical conformation",
author = "R.B. Prince and L. Brunsveld and J.S. Moore and E.W. Meijer",
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Cooperativity in the folding of helical m-phenylene ethynylene oligomers based upon the 'Sergeants-and-Soldiers' principle. / Prince, R.B.; Brunsveld, L.; Moore, J.S.; Meijer, E.W.

In: Chemistry : A European Journal, Vol. 7, No. 19, 2001, p. 4150-4154.

Research output: Contribution to journalArticleAcademicpeer-review

TY - JOUR

T1 - Cooperativity in the folding of helical m-phenylene ethynylene oligomers based upon the 'Sergeants-and-Soldiers' principle

AU - Prince, R.B.

AU - Brunsveld, L.

AU - Moore, J.S.

AU - Meijer, E.W.

PY - 2001

Y1 - 2001

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AB - The 'Sergeants-and-Soldiers' principle has been examined in a series of m-phenylene ethynylene oligomers containing both chiral and achiral side chains. Circular dichroism (CD) spectroscopy was used to examine the twist sense bias of the helical conformation in the polar solvent acetonitrile. A nonlinear dependence of the CD signal on the amount of chiral side chains was observed revealing cooperative interactions among the side chains through the backbone. On the other hand, the experiments indicate that in acetonitrile a full bias of the helicity cannot be accomplished by chiral side chains alone. Nevertheless, the folded oligomers are highly ordered since the placement of a single chiral side chain at the beginning of an oligomer results in the induction of a strong twist sense bias into the ordered helical conformation

U2 - 10.1002/1521-3765(20011001)7:19<4150::AID-CHEM4150>3.0.CO;2-F

DO - 10.1002/1521-3765(20011001)7:19<4150::AID-CHEM4150>3.0.CO;2-F

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VL - 7

SP - 4150

EP - 4154

JO - Chemistry : A European Journal

JF - Chemistry : A European Journal

SN - 0947-6539

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