Probing the limits of the majority-rules principle in a dynamic supramolecular polymer

M.M.J. Smulders, P.J.M. Stals, T. Mes, T.F.E. Paffen, A.P.H.J. Schenning, A.R.A. Palmans, E.W. Meijer

Research output: Contribution to journalArticleAcademicpeer-review

82 Citations (Scopus)
4 Downloads (Pure)

Abstract

By systematic variation of the chemical structure of benzene-1,3,5-tricarboxamide (BTA) derivatives, the effect of chemical structure on the amplification of chirality was studied and quantified. In combination with temperature-dependent amplification experiments, the limits of the majority-rules principle were also investigated. For all BTA derivatives a high, constant helix reversal penalty was determined, which is related to the intermolecular hydrogen bonds that are present in all studied derivatives. For asymmetrically substituted BTA derivatives an odd-even effect was found in the degree of chiral amplification when changing the position of the stereogenic center with respect to the amide functionality. It was found that the mismatch penalty could be directly related to the number of stereocenters present in the molecules. Increasing this number from one to three resulted in an increase in this energy penalty while leaving the helix reversal penalty unaffected. For the majority-rules principle this implies that a single stereocenter present in the molecule contains sufficient chiral information at the molecular level to result in a chirally amplified state at the supramolecular level. Further evidence that the mismatch penalty is directly related to the number of stereocenters was obtained from mixed majority-rules experiments where two BTA derivatives with different numbers of stereocenters with opposite stereoconfiguration were studied in a majority-rules experiment. Finally, the ultimate limits of chiral amplification for the majority-rules principle were investigated, revealing that, given a certain helix reversal penalty, there is an optimum to which the mismatch penalty can be reduced while also enhancing the degree of chiral amplification. Temperature-dependent majority-rules experiments could indeed confirm these simulations. These findings show the relevance of both energy penalties when trying to enhance the degree of chiral amplification for the majority-rules principle in a one-dimensional helical supramolecular polymer.
Original languageEnglish
Pages (from-to)620-626
Number of pages7
JournalJournal of the American Chemical Society
Volume132
Issue number2
DOIs
Publication statusPublished - 2010

Fingerprint

Amplification
Polymers
Derivatives
Benzene
Temperature
Experiments
Amides
Hydrogen
Molecules
Chirality
benzene-1,3,5-tricarboxamide
Hydrogen bonds

Cite this

@article{c22c7737e5cc45f4bc89db11ecf8c4fc,
title = "Probing the limits of the majority-rules principle in a dynamic supramolecular polymer",
abstract = "By systematic variation of the chemical structure of benzene-1,3,5-tricarboxamide (BTA) derivatives, the effect of chemical structure on the amplification of chirality was studied and quantified. In combination with temperature-dependent amplification experiments, the limits of the majority-rules principle were also investigated. For all BTA derivatives a high, constant helix reversal penalty was determined, which is related to the intermolecular hydrogen bonds that are present in all studied derivatives. For asymmetrically substituted BTA derivatives an odd-even effect was found in the degree of chiral amplification when changing the position of the stereogenic center with respect to the amide functionality. It was found that the mismatch penalty could be directly related to the number of stereocenters present in the molecules. Increasing this number from one to three resulted in an increase in this energy penalty while leaving the helix reversal penalty unaffected. For the majority-rules principle this implies that a single stereocenter present in the molecule contains sufficient chiral information at the molecular level to result in a chirally amplified state at the supramolecular level. Further evidence that the mismatch penalty is directly related to the number of stereocenters was obtained from mixed majority-rules experiments where two BTA derivatives with different numbers of stereocenters with opposite stereoconfiguration were studied in a majority-rules experiment. Finally, the ultimate limits of chiral amplification for the majority-rules principle were investigated, revealing that, given a certain helix reversal penalty, there is an optimum to which the mismatch penalty can be reduced while also enhancing the degree of chiral amplification. Temperature-dependent majority-rules experiments could indeed confirm these simulations. These findings show the relevance of both energy penalties when trying to enhance the degree of chiral amplification for the majority-rules principle in a one-dimensional helical supramolecular polymer.",
author = "M.M.J. Smulders and P.J.M. Stals and T. Mes and T.F.E. Paffen and A.P.H.J. Schenning and A.R.A. Palmans and E.W. Meijer",
year = "2010",
doi = "10.1021/ja9080875",
language = "English",
volume = "132",
pages = "620--626",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "2",

}

Probing the limits of the majority-rules principle in a dynamic supramolecular polymer. / Smulders, M.M.J.; Stals, P.J.M.; Mes, T.; Paffen, T.F.E.; Schenning, A.P.H.J.; Palmans, A.R.A.; Meijer, E.W.

In: Journal of the American Chemical Society, Vol. 132, No. 2, 2010, p. 620-626.

Research output: Contribution to journalArticleAcademicpeer-review

TY - JOUR

T1 - Probing the limits of the majority-rules principle in a dynamic supramolecular polymer

AU - Smulders, M.M.J.

AU - Stals, P.J.M.

AU - Mes, T.

AU - Paffen, T.F.E.

AU - Schenning, A.P.H.J.

AU - Palmans, A.R.A.

AU - Meijer, E.W.

PY - 2010

Y1 - 2010

N2 - By systematic variation of the chemical structure of benzene-1,3,5-tricarboxamide (BTA) derivatives, the effect of chemical structure on the amplification of chirality was studied and quantified. In combination with temperature-dependent amplification experiments, the limits of the majority-rules principle were also investigated. For all BTA derivatives a high, constant helix reversal penalty was determined, which is related to the intermolecular hydrogen bonds that are present in all studied derivatives. For asymmetrically substituted BTA derivatives an odd-even effect was found in the degree of chiral amplification when changing the position of the stereogenic center with respect to the amide functionality. It was found that the mismatch penalty could be directly related to the number of stereocenters present in the molecules. Increasing this number from one to three resulted in an increase in this energy penalty while leaving the helix reversal penalty unaffected. For the majority-rules principle this implies that a single stereocenter present in the molecule contains sufficient chiral information at the molecular level to result in a chirally amplified state at the supramolecular level. Further evidence that the mismatch penalty is directly related to the number of stereocenters was obtained from mixed majority-rules experiments where two BTA derivatives with different numbers of stereocenters with opposite stereoconfiguration were studied in a majority-rules experiment. Finally, the ultimate limits of chiral amplification for the majority-rules principle were investigated, revealing that, given a certain helix reversal penalty, there is an optimum to which the mismatch penalty can be reduced while also enhancing the degree of chiral amplification. Temperature-dependent majority-rules experiments could indeed confirm these simulations. These findings show the relevance of both energy penalties when trying to enhance the degree of chiral amplification for the majority-rules principle in a one-dimensional helical supramolecular polymer.

AB - By systematic variation of the chemical structure of benzene-1,3,5-tricarboxamide (BTA) derivatives, the effect of chemical structure on the amplification of chirality was studied and quantified. In combination with temperature-dependent amplification experiments, the limits of the majority-rules principle were also investigated. For all BTA derivatives a high, constant helix reversal penalty was determined, which is related to the intermolecular hydrogen bonds that are present in all studied derivatives. For asymmetrically substituted BTA derivatives an odd-even effect was found in the degree of chiral amplification when changing the position of the stereogenic center with respect to the amide functionality. It was found that the mismatch penalty could be directly related to the number of stereocenters present in the molecules. Increasing this number from one to three resulted in an increase in this energy penalty while leaving the helix reversal penalty unaffected. For the majority-rules principle this implies that a single stereocenter present in the molecule contains sufficient chiral information at the molecular level to result in a chirally amplified state at the supramolecular level. Further evidence that the mismatch penalty is directly related to the number of stereocenters was obtained from mixed majority-rules experiments where two BTA derivatives with different numbers of stereocenters with opposite stereoconfiguration were studied in a majority-rules experiment. Finally, the ultimate limits of chiral amplification for the majority-rules principle were investigated, revealing that, given a certain helix reversal penalty, there is an optimum to which the mismatch penalty can be reduced while also enhancing the degree of chiral amplification. Temperature-dependent majority-rules experiments could indeed confirm these simulations. These findings show the relevance of both energy penalties when trying to enhance the degree of chiral amplification for the majority-rules principle in a one-dimensional helical supramolecular polymer.

U2 - 10.1021/ja9080875

DO - 10.1021/ja9080875

M3 - Article

C2 - 20014837

VL - 132

SP - 620

EP - 626

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 2

ER -