The effect of meta versus para substitution on the aggregation of bis-cholesteryl appended 2,6-disubstituted pyridine-based gelators

Meta Fitri Rizkiana, Rathinam Balamurugan, Jui-Hsiang Liu

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

The structurally isomeric, bent core, 2,6-disubstituted pyridine derivatives (PyPC and PyMC) were synthesized, and their gelation ability and aggregation behavior in different solvents were studied using various techniques including electron microscopy (TEM and SEM) and X-ray diffraction analysis (XRD). The PyPC was found to be soluble in most of the organic solvents studied, which may be due to the possible existence of intramolecular hydrogen bonding in PyPC (low angle) that enhanced its solubility. In contrast, PyMC was less soluble, making it a more efficient gelator than PyPC. The results from the morphological studies showed that the xerogel of PyPC in dodecanol exhibited a nanotube morphology (diameter ∼70 nm), whereas PyMC in dodecanol exhibited a fibrous morphology, indicating that the existence of positional isomerism had a profound effect on the aggregation of the molecules in solution. Both right- and left-handed helical structures were observed in all gelators; however, left-handed structures were more predominant. Intermolecular hydrogen bonding as well as π-π stacking cooperatively played an important role in the aggregation of the gelators as evidenced by XRD and temperature-dependent 1H-NMR spectroscopy analyses. Based on these results, aggregation mechanisms were proposed.

Original languageEnglish
Pages (from-to)6068-6075
Number of pages8
JournalNew Journal of Chemistry
Volume39
Issue number8
DOIs
Publication statusPublished - 2015 Aug 1

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Pyridine
Substitution reactions
Dodecanol
Agglomeration
X ray diffraction analysis
Hydrogen bonds
Xerogels
Gelation
Organic solvents
Nanotubes
Electron microscopy
Nuclear magnetic resonance spectroscopy
Solubility
Transmission electron microscopy
Derivatives
Scanning electron microscopy
Molecules
pyridine
Temperature

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Materials Chemistry

Cite this

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title = "The effect of meta versus para substitution on the aggregation of bis-cholesteryl appended 2,6-disubstituted pyridine-based gelators",
abstract = "The structurally isomeric, bent core, 2,6-disubstituted pyridine derivatives (PyPC and PyMC) were synthesized, and their gelation ability and aggregation behavior in different solvents were studied using various techniques including electron microscopy (TEM and SEM) and X-ray diffraction analysis (XRD). The PyPC was found to be soluble in most of the organic solvents studied, which may be due to the possible existence of intramolecular hydrogen bonding in PyPC (low angle) that enhanced its solubility. In contrast, PyMC was less soluble, making it a more efficient gelator than PyPC. The results from the morphological studies showed that the xerogel of PyPC in dodecanol exhibited a nanotube morphology (diameter ∼70 nm), whereas PyMC in dodecanol exhibited a fibrous morphology, indicating that the existence of positional isomerism had a profound effect on the aggregation of the molecules in solution. Both right- and left-handed helical structures were observed in all gelators; however, left-handed structures were more predominant. Intermolecular hydrogen bonding as well as π-π stacking cooperatively played an important role in the aggregation of the gelators as evidenced by XRD and temperature-dependent 1H-NMR spectroscopy analyses. Based on these results, aggregation mechanisms were proposed.",
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The effect of meta versus para substitution on the aggregation of bis-cholesteryl appended 2,6-disubstituted pyridine-based gelators. / Rizkiana, Meta Fitri; Balamurugan, Rathinam; Liu, Jui-Hsiang.

In: New Journal of Chemistry, Vol. 39, No. 8, 01.08.2015, p. 6068-6075.

Research output: Contribution to journalArticle

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