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Self-assembly of aromatic biscarbamate gelators: effect of spacer length on the gelation and rheology

  • Original Paper: Supramolecular materials
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Abstract

Low molecular weight biscarbamate organogelators (LMWBGs) with simple molecular structures that could gel different types of organic solvents were synthesized. The LMWBGs were composed of a long hydrophobic tail of linear fatty alcohol (C8–C18) and an aromatic core and could gel organic solvents such as xylene, toluene, NMP, cyclohexanol and chlorobenzene at a concentration of 10–15 mg/mL. Gelation studies indicated that the alkyl chain length residues did not affect the gelation time which was generally around 10–15 min leading to opaque gels in all the solvents. The gels in p-xylene were studied by FTIR spectroscopy and differential scanning calorimetry (DSC) for the nature of the interactions between the gelators and the solvent. FTIR spectroscopic studies revealed that hydrogen bonding and van der Waals interactions were the driving forces for the formation of the gels, while solid-state UV–visible studies revealed the existence of π–π interaction in the xerogel. The gel melting temperatures were found to decrease and then increase with increasing alkyl chain length as observed in DSC. The microscopic observations (FE-SEM) suggested that the gelator molecules self-assembled leading to nano- and microfibres in the turbid gel, and as the alkyl chain length increased, the width of the fibres increased. Rheological studies evinced the viscoelastic nature of the soft gels viscoelasticity increased with increasing gelator concentration, while fluidity increased with increasing chain length. The X-ray diffraction analysis revealed that in the xerogels from p-xylene the molecules aggregated into a layered structure. This study on the influence of alkyl side chains shows that hydrogen bonding and van der Waals interactions play a significant role in the morphology of such self-assembled structures.

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Acknowledgments

Sravan Baddi is indebted to Council of Scientific and Industrial Research (CSIR), India, for Senior Research Fellowship (SRF).

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Authors and Affiliations

  1. Polymers and Functional Materials Division, Indian Institute of Chemical Technology (CSIR-IICT), Hyderabad, India

    Sravan baddi & Aruna Palanisamy

  2. Geochemistry Division, National Geophysical Research Institute (CSIR-NGRI), Hyderabad, India

    D. Srinivasa Sarma

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  1. Sravan baddi
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  2. D. Srinivasa Sarma
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  3. Aruna Palanisamy
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Correspondence to Aruna Palanisamy.

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baddi, S., Sarma, D.S. & Palanisamy, A. Self-assembly of aromatic biscarbamate gelators: effect of spacer length on the gelation and rheology. J Sol-Gel Sci Technol 79, 637–649 (2016). https://doi.org/10.1007/s10971-016-4036-x

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  • DOI: https://doi.org/10.1007/s10971-016-4036-x

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