Bioderived, chiral and stable 1-dimensional light-responsive nanostructures: Interconversion between tubules and twisted ribbons

Andrea Santilli; Andrea Lapi; Jacopo Cautela; Marco D'Abramo; Cheng Giuseppe Chen; Alessandra Del Giudice; Simona Sennato; Domagoj Belić; Victor Hugo Soto Tellini; Karin Schillén; Maria Chiara di Gregorio; Luciano Galantini

doi:10.1016/j.jcis.2022.05.025

Bioderived, chiral and stable 1-dimensional light-responsive nanostructures: Interconversion between tubules and twisted ribbons

J Colloid Interface Sci. 2022 Oct:623:723-734. doi: 10.1016/j.jcis.2022.05.025. Epub 2022 May 10.

Affiliations

¹ Department of Chemistry, Sapienza University of Rome, P.le A. Moro 5, 00185 Rome, Italy.
² Department of Chemistry, Sapienza University of Rome, P.le A. Moro 5, 00185 Rome, Italy; Istituto per i Sistemi Biologici (ISB-CNR), Sede Secondaria di Roma-Meccanismi di Reazione, Dipartimento di Chimica, Università degli Studi di Roma "Sapienza", Italy.
³ CNR-Institute of Complex Systems (ISC)-Sede Sapienza and Physics Department, Sapienza University of Rome, P.le A. Moro 5, Rome, Italy.
⁴ Division of Physical Chemistry, Department of Chemistry, Lund University, P.O. Box 124, 22100 Lund, Sweden; Department of Physics, Josip Juraj Strossmayer University of Osijek, 31000 Osijek, Croatia.
⁵ Escuela de Química, Universidad de Costa Rica, 11501 San José, Costa Rica.
⁶ Division of Physical Chemistry, Department of Chemistry, Lund University, P.O. Box 124, 22100 Lund, Sweden.
⁷ Department of Molecular Chemistry and Materials Science, Weizmann Institute of Science, 7610001 Rehovot, Israel. Electronic address: maria-chiara.di-gregorio@weizmann.ac.il.
⁸ Department of Chemistry, Sapienza University of Rome, P.le A. Moro 5, 00185 Rome, Italy. Electronic address: luciano.galantini@uniroma1.it.

PMID: 35605451
DOI: 10.1016/j.jcis.2022.05.025

Abstract

Hypothesis: Self-assembling molecular structures responding to light stimulus are appealing for applications as sensing and drug delivery. Supramolecular nanotubes have a relevant potential in nanotechnology as they can be used to encapsulate different loads like drugs, biological macromolecules, and nanomaterials. In addition, they are suitable elements for novel supracolloidal materials. Structural responses of supramolecular nanotubes to non-invasive stimuli are very much desired to enable controlled release of the encapsulated guests and to provide these recently developed new materials with an external trigger. Here, we describe the formation of well-defined, single wall tubules that interconvert into twisted ribbons upon UV-light exposure in aqueous environment. The structures are provided by self-assembly of an azobenzene substituted cholic acid, a biological surfactant belonging to the family of bile acids. The azobenzene group allows for the light responsiveness of the molecular packing. Concurrently the steroidal moieties assure both chiral features and extensive hydrophobic interactions for time and temperature resistant aggregates.

Experiments: The molecular packing interconversion was followed by circular dichroism. Microscopy, small angle X-ray scattering and light scattering measurements demonstrated the drastic morphological variation upon irradiation. A model of the molecular arrangement within the tubular walls was suggested based on the circular dichroism spectra simulation.

Findings: Innovatively, the molecular design reported in our work allows for encoding in the same light responsive system multiple desirable features (e.g. bio-origin, temperature resistance and chirality of the aggregates). Such combination of properties, never reported before for a single molecule, might be relevant for the realization of robust, stimuli-responsive bio-vectors.

Keywords: Bile acid; Chirality; Light responsive system; Nanotubes; Self-assembly; Stability.

MeSH terms

Circular Dichroism
Hydrophobic and Hydrophilic Interactions
Nanostructures* / chemistry
Nanotechnology
Nanotubes* / chemistry