Self-assembly of 2, 3-dihydroxycholestane steroids into supramolecular organogels as a soft template for the in-situ generation of silicate nanomaterials
Supramolecular gels are an important and interesting class of soft materials that show great potential for many applications. Most of them have been discovered serendipitously, and understanding the supramolecular self-assembly that leads to the formation of the gel superstructure is the key to the...
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todo:paper_18605397_v9_n_p1826_Edelsztein2023-10-03T16:33:18Z Self-assembly of 2, 3-dihydroxycholestane steroids into supramolecular organogels as a soft template for the in-situ generation of silicate nanomaterials Edelsztein, V.C. Mac Cormack, A.S. Ciarlantini, M. Di Chenna, P.H. Hansen parameters Nanotube Organogel Self-assembly Supramolecular gel Supramolecular gels are an important and interesting class of soft materials that show great potential for many applications. Most of them have been discovered serendipitously, and understanding the supramolecular self-assembly that leads to the formation of the gel superstructure is the key to the directed design of new organogels. We report herein the organogelating property of four stereoisomers of the simple steroid 2, 3-dihydroxycholestane. Only the isomer with the trans-diaxial hydroxy groups had the ability to gelate a broad variety of liquids and, thus, to be a super-organogelator for hydrocarbons. The scope of solvent gelation was analysed with regard to two solvent parameters, namely the Kamlet-Taft and the Hansen solubility parameters. The best correlation was observed with the Hansen approach that revealed the existence of two clear gelation zones. We propose a general model of self-assembly through multiple intermolecular hydrogen bonds between the 1, 2-dihydroxy system, which is based on experimental data and computational simulations revealing the importance of the di-axial orientation of the hydroxy groups for the one-dimensional self-assembly. Under controlled conditions, the fibrillar superstructure of the organogel was successfully used as a template for the in-situ sol-gel polymerization of tetraethoxysilane and the further preparation of silica nanotubes. We propose that the driving forces for templating are hydrogen bonding and electrostatic interactions between the anionic silicate intermediate species and the self-assembled fibrillar network. © 2013 Edelsztein et al. Fil:Edelsztein, V.C. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Di Chenna, P.H. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. JOUR info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar http://hdl.handle.net/20.500.12110/paper_18605397_v9_n_p1826_Edelsztein |
| institution |
Universidad de Buenos Aires |
| institution_str |
I-28 |
| repository_str |
R-134 |
| collection |
Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) |
| topic |
Hansen parameters Nanotube Organogel Self-assembly Supramolecular gel |
| spellingShingle |
Hansen parameters Nanotube Organogel Self-assembly Supramolecular gel Edelsztein, V.C. Mac Cormack, A.S. Ciarlantini, M. Di Chenna, P.H. Self-assembly of 2, 3-dihydroxycholestane steroids into supramolecular organogels as a soft template for the in-situ generation of silicate nanomaterials |
| topic_facet |
Hansen parameters Nanotube Organogel Self-assembly Supramolecular gel |
| description |
Supramolecular gels are an important and interesting class of soft materials that show great potential for many applications. Most of them have been discovered serendipitously, and understanding the supramolecular self-assembly that leads to the formation of the gel superstructure is the key to the directed design of new organogels. We report herein the organogelating property of four stereoisomers of the simple steroid 2, 3-dihydroxycholestane. Only the isomer with the trans-diaxial hydroxy groups had the ability to gelate a broad variety of liquids and, thus, to be a super-organogelator for hydrocarbons. The scope of solvent gelation was analysed with regard to two solvent parameters, namely the Kamlet-Taft and the Hansen solubility parameters. The best correlation was observed with the Hansen approach that revealed the existence of two clear gelation zones. We propose a general model of self-assembly through multiple intermolecular hydrogen bonds between the 1, 2-dihydroxy system, which is based on experimental data and computational simulations revealing the importance of the di-axial orientation of the hydroxy groups for the one-dimensional self-assembly. Under controlled conditions, the fibrillar superstructure of the organogel was successfully used as a template for the in-situ sol-gel polymerization of tetraethoxysilane and the further preparation of silica nanotubes. We propose that the driving forces for templating are hydrogen bonding and electrostatic interactions between the anionic silicate intermediate species and the self-assembled fibrillar network. © 2013 Edelsztein et al. |
| format |
JOUR |
| author |
Edelsztein, V.C. Mac Cormack, A.S. Ciarlantini, M. Di Chenna, P.H. |
| author_facet |
Edelsztein, V.C. Mac Cormack, A.S. Ciarlantini, M. Di Chenna, P.H. |
| author_sort |
Edelsztein, V.C. |
| title |
Self-assembly of 2, 3-dihydroxycholestane steroids into supramolecular organogels as a soft template for the in-situ generation of silicate nanomaterials |
| title_short |
Self-assembly of 2, 3-dihydroxycholestane steroids into supramolecular organogels as a soft template for the in-situ generation of silicate nanomaterials |
| title_full |
Self-assembly of 2, 3-dihydroxycholestane steroids into supramolecular organogels as a soft template for the in-situ generation of silicate nanomaterials |
| title_fullStr |
Self-assembly of 2, 3-dihydroxycholestane steroids into supramolecular organogels as a soft template for the in-situ generation of silicate nanomaterials |
| title_full_unstemmed |
Self-assembly of 2, 3-dihydroxycholestane steroids into supramolecular organogels as a soft template for the in-situ generation of silicate nanomaterials |
| title_sort |
self-assembly of 2, 3-dihydroxycholestane steroids into supramolecular organogels as a soft template for the in-situ generation of silicate nanomaterials |
| url |
http://hdl.handle.net/20.500.12110/paper_18605397_v9_n_p1826_Edelsztein |
| work_keys_str_mv |
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| _version_ |
1807324613647007744 |