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Chiral self-assembly and water effect on a supramolecular organogel stable towards aqueous interfaces

  • Invited Paper: Supramolecular materials
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Abstract

Herein, we report on the stabilizing effect of water and the chiral self-assembly mode of a cholesterol-based low-molecular-weight supramolecular organogelator. Dynamic rheology experiments performed on gels prepared in methanol and methanol–water mixtures showed an enhanced strength and rigidity in the presence of water, in line with the thermal stability previously observed. Morphological characterization experiments (scanning electron microscopy and X-ray powder diffraction) were performed on aerogels obtained after solvent extraction with supercritical CO2. Concentration- and temperature-dependent proton nuclear magnetic resonance and electronic circular dichroism experiments confirmed that the molecules of gelator self-assemble with a dominant right-handed helicity through intermolecular hydrogen bond interactions between the carbamate groups, and that the addition of water does not affect either the mode of assembly or the chirality of the supramolecular structure. Computational simulation experiments allowed us to propose a mode of self-assembly compatible with the experimental results, which involves a unidimensional head-to-tail stacking of molecules. A methanolic gel was successfully used as a molecular template for the in situ hydrolytic sol-gel polymerization of tetraethyl orthosilicate giving rise to silica nanotubes with an internal diameter of 7 nm.

Highlights

  • Water effect on a low-molecular-weight gel based on cholesterol and a benzyloxycarbamate group.

  • Water increases the thermostability, strength, and rigidity of a supramolecular organogel.

  • Intermolecular H-bonding interactions are involved in the 1D chiral self-assembly.

  • The organogel was used as a template for in situ sol-gel polymerization of TEOS into silica nanotubes.

  • The presence of water does not affect the mode of self-assembly.

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Acknowledgements

We acknowledge the institutions that supported this project: Universidad de Buenos Aires and Consejo Nacional de Investigaciones Científicas y Técnicas.

Funding

This work was supported by Universidad de Buenos Aires, Argentina (grant 20020150100121BA) and Consejo Nacional de Investigaciones Científicas y Técnicas, Argentina (grant PIP 11220110100778).

Author information

Authors and Affiliations

  1. Consejo Nacional de Investigaciones Científicas y Técnicas, Unidad de Microanálisis y Métodos Físicos Aplicados a la Química Orgánica (UMYMFOR), Departamento de Química Orgánica, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Ciudad Universitaria, Pabellón 2, C1428EG, Buenos Aires, Argentina

    Evelyn L. Bonifazi, Andrea S. Mac Cormack & Pablo H. Di Chenna

  2. Consejo Nacional de Investigaciones Científicas y Técnicas, Instituto de Tecnología de Alimentos y Procesos Químicos (ITAPROQ) Departamento de Industrias, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Ciudad Universitaria, C1428EGA, Buenos Aires, Argentina

    Verónica M. Busch

  3. Comisión Nacional de Energía Atómica (CNEA), Gerencia Química, Centro Atómico Constituyentes, Av. Gral. Paz 1499, San Martín, B1650KNA, Buenos Aires, Argentina

    M. Laura Japas

  4. Escuela de Ciencia y Tecnología, Universidad Nacional de San Martín, Martín de Irigoyen 3100, 1650 San Martín, Buenos Aires, Argentina

    M. Laura Japas

  5. Dipartimento di Chimica e Chimica Industriale, Università di Pisa, Via Moruzzi 13, 56124, Pisa, Italy

    Lorenzo Di Bari

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  1. Evelyn L. Bonifazi
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  2. Andrea S. Mac Cormack
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  3. Verónica M. Busch
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  4. M. Laura Japas
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  5. Lorenzo Di Bari
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Correspondence to Pablo H. Di Chenna.

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Bonifazi, E.L., Mac Cormack, A.S., Busch, V.M. et al. Chiral self-assembly and water effect on a supramolecular organogel stable towards aqueous interfaces. J Sol-Gel Sci Technol 102, 30–40 (2022). https://doi.org/10.1007/s10971-021-05550-w

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