Supramolecular polymer transformation

A kinetic study

Jonathan Baram, Haim Weissman, Boris Rybtchinski

Research output: Contribution to journalArticle

24 Citations (Scopus)

Abstract

Investigation of supramolecular kinetics is essential for elucidating self-assembly mechanisms. Recently, we reported on a noncovalent system involving a bolaamphiphilic perylene diimide dimer that is kinetically trapped in water but can rearrange into a different, more ordered assembly in water/THF mixtures (Angew. Chem. Int. Ed. 2014, 53, 4123). Here we present a kinetic mechanistic study of this process by employing UV-vis spectroscopy. The transformation exhibits a rapid decrease in the red-shifted absorption band, which is monitored in order to track the kinetics at different temperatures (15-50 °C) and concentrations. Fitting the data with the 1D KJMA (Kolmogorov-Johnson-Mehl-Avrami) model affords the activation parameters. The latter as well as seeding experiments indicates that the transformation occurs without the detachment of covalent units, and that hydration dynamics plays a significant role in nucleation, with entropic factors being dominant. Switching off the transformation, and the formation of off-pathway intermediates were observed upon heating to temperatures above 55 °C. These insights into kinetically controlled supramolecular polymer transformations provide mechanistic information that is needed for a fundamental understanding of noncovalent processes, and the rational design of noncovalent materials.

Original languageEnglish
Pages (from-to)12068-12073
Number of pages6
JournalJournal of Physical Chemistry B
Volume118
Issue number41
DOIs
Publication statusPublished - Oct 16 2014

Fingerprint

Polymers
Kinetics
kinetics
polymers
Perylene
Water
Ultraviolet spectroscopy
Hydration
Dimers
Self assembly
Absorption spectra
Nucleation
inoculation
Chemical activation
detachment
water
hydration
self assembly
Heating
Temperature

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Materials Chemistry
  • Surfaces, Coatings and Films

Cite this

Supramolecular polymer transformation : A kinetic study. / Baram, Jonathan; Weissman, Haim; Rybtchinski, Boris.

In: Journal of Physical Chemistry B, Vol. 118, No. 41, 16.10.2014, p. 12068-12073.

Research output: Contribution to journalArticle

Baram, Jonathan ; Weissman, Haim ; Rybtchinski, Boris. / Supramolecular polymer transformation : A kinetic study. In: Journal of Physical Chemistry B. 2014 ; Vol. 118, No. 41. pp. 12068-12073.
@article{a98741bcf8034a4dbf607fbd48e1e669,
title = "Supramolecular polymer transformation: A kinetic study",
abstract = "Investigation of supramolecular kinetics is essential for elucidating self-assembly mechanisms. Recently, we reported on a noncovalent system involving a bolaamphiphilic perylene diimide dimer that is kinetically trapped in water but can rearrange into a different, more ordered assembly in water/THF mixtures (Angew. Chem. Int. Ed. 2014, 53, 4123). Here we present a kinetic mechanistic study of this process by employing UV-vis spectroscopy. The transformation exhibits a rapid decrease in the red-shifted absorption band, which is monitored in order to track the kinetics at different temperatures (15-50 °C) and concentrations. Fitting the data with the 1D KJMA (Kolmogorov-Johnson-Mehl-Avrami) model affords the activation parameters. The latter as well as seeding experiments indicates that the transformation occurs without the detachment of covalent units, and that hydration dynamics plays a significant role in nucleation, with entropic factors being dominant. Switching off the transformation, and the formation of off-pathway intermediates were observed upon heating to temperatures above 55 °C. These insights into kinetically controlled supramolecular polymer transformations provide mechanistic information that is needed for a fundamental understanding of noncovalent processes, and the rational design of noncovalent materials.",
author = "Jonathan Baram and Haim Weissman and Boris Rybtchinski",
year = "2014",
month = "10",
day = "16",
doi = "10.1021/jp507945t",
language = "English",
volume = "118",
pages = "12068--12073",
journal = "Journal of Physical Chemistry B Materials",
issn = "1520-6106",
publisher = "American Chemical Society",
number = "41",

}

TY - JOUR

T1 - Supramolecular polymer transformation

T2 - A kinetic study

AU - Baram, Jonathan

AU - Weissman, Haim

AU - Rybtchinski, Boris

PY - 2014/10/16

Y1 - 2014/10/16

N2 - Investigation of supramolecular kinetics is essential for elucidating self-assembly mechanisms. Recently, we reported on a noncovalent system involving a bolaamphiphilic perylene diimide dimer that is kinetically trapped in water but can rearrange into a different, more ordered assembly in water/THF mixtures (Angew. Chem. Int. Ed. 2014, 53, 4123). Here we present a kinetic mechanistic study of this process by employing UV-vis spectroscopy. The transformation exhibits a rapid decrease in the red-shifted absorption band, which is monitored in order to track the kinetics at different temperatures (15-50 °C) and concentrations. Fitting the data with the 1D KJMA (Kolmogorov-Johnson-Mehl-Avrami) model affords the activation parameters. The latter as well as seeding experiments indicates that the transformation occurs without the detachment of covalent units, and that hydration dynamics plays a significant role in nucleation, with entropic factors being dominant. Switching off the transformation, and the formation of off-pathway intermediates were observed upon heating to temperatures above 55 °C. These insights into kinetically controlled supramolecular polymer transformations provide mechanistic information that is needed for a fundamental understanding of noncovalent processes, and the rational design of noncovalent materials.

AB - Investigation of supramolecular kinetics is essential for elucidating self-assembly mechanisms. Recently, we reported on a noncovalent system involving a bolaamphiphilic perylene diimide dimer that is kinetically trapped in water but can rearrange into a different, more ordered assembly in water/THF mixtures (Angew. Chem. Int. Ed. 2014, 53, 4123). Here we present a kinetic mechanistic study of this process by employing UV-vis spectroscopy. The transformation exhibits a rapid decrease in the red-shifted absorption band, which is monitored in order to track the kinetics at different temperatures (15-50 °C) and concentrations. Fitting the data with the 1D KJMA (Kolmogorov-Johnson-Mehl-Avrami) model affords the activation parameters. The latter as well as seeding experiments indicates that the transformation occurs without the detachment of covalent units, and that hydration dynamics plays a significant role in nucleation, with entropic factors being dominant. Switching off the transformation, and the formation of off-pathway intermediates were observed upon heating to temperatures above 55 °C. These insights into kinetically controlled supramolecular polymer transformations provide mechanistic information that is needed for a fundamental understanding of noncovalent processes, and the rational design of noncovalent materials.

UR - http://www.scopus.com/inward/record.url?scp=84908006522&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84908006522&partnerID=8YFLogxK

U2 - 10.1021/jp507945t

DO - 10.1021/jp507945t

M3 - Article

VL - 118

SP - 12068

EP - 12073

JO - Journal of Physical Chemistry B Materials

JF - Journal of Physical Chemistry B Materials

SN - 1520-6106

IS - 41

ER -