Abstract:
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.
Registro:
Documento: |
Artículo
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Título: | Self-assembly of 2, 3-dihydroxycholestane steroids into supramolecular organogels as a soft template for the in-situ generation of silicate nanomaterials |
Autor: | Edelsztein, V.C.; Mac Cormack, A.S.; Ciarlantini, M.; Di Chenna, P.H. |
Filiación: | Departamento de Química Orgánica and UMYMFOR (CONICET-FCEN), Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Ciudad Universitaria, Pabellón II, Buenos Aires, C1428EGA, Argentina
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Palabras clave: | Hansen parameters; Nanotube; Organogel; Self-assembly; Supramolecular gel |
Año: | 2013
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Volumen: | 9
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Página de inicio: | 1826
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Página de fin: | 1836
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DOI: |
http://dx.doi.org/10.3762/bjoc.9.213 |
Título revista: | Beilstein Journal of Organic Chemistry
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Título revista abreviado: | Beilstein J. Org. Chem.
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ISSN: | 18605397
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CODEN: | BJOCB
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Registro: | https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_18605397_v9_n_p1826_Edelsztein |
Referencias:
- Shahmburo, A., Biewer, M.C., (2002) Chem. Mater, 14, pp. 3745-3750. , doi:10.1021/cm020421a
- Llusar, M., Sanchez, C., Inorganic and hybrid nanofibrous materials templated with organogelators (2008) Chemistry of Materials, 20 (3), pp. 782-820. , DOI 10.1021/cm702141e
- Wang, X., Zhou, L., Wang, H., Luo, Q., Xu, J., Liu, J., (2011) J. Colloid Interface Sci., 353, pp. 412-419. , doi:10.1016/j.jcis.2010.09.089
- Prathap, A., Sureshman, K.M., (2012) Chem. Commun., 48, pp. 5250-5252. , doi:10.1039/c2cc31631e
- Shibata, Y., Kato, T., Kado, T., Shiratuchi, R., Takashima, R., Kaneto, W., Hayase, S., (2003) Chem. Commun., pp. 2730-2731. , doi:10.1039/b305368g
- Ajayaghosh, A., Praveen, V.K., Vijayakumar, C., (2008) Chem. Soc. Rev., 37, pp. 109-122. , doi:10.1039/b704456a
- Li, Y., Liu, J., Du, G., Yan, H., Wang, H., Zhang, H., An, W., Hao, J., (2010) J. Phys. Chem. B, 114, pp. 10321-10326. , doi:10.1021/jp1017373
- Murata, K., Aoki, M., Suzuki, T., Harada, T., Kawabata, H., Komori, T., Ohseto, F., Shinkai, S., (1994) J. Am. Chem. Soc., 116, pp. 6664-6676. , doi:10.1021/ja00094a023
- Yu, X., Liu, Q., Wu, J., Zhang, M., Cao, X., Zhang, S., Wang, Q., Yi, T., (2010) Chem.-Eur. J., 16, pp. 9099-9106. , doi:10.1002/chem.201000187
- Maitra, U., Chakrabarty, A., (2011) Beilstein J. Org. Chem., 7, pp. 304-309. , doi:10.3762/bjoc.7.40
- Chen, J., Wu, W., McNeil, A.J., (2012) Chem. Commun., 48, pp. 7310-7312. , doi:10.1039/c2cc33486k
- Díaz Díaz, D., Kühbeck, D., Koopmans, R., (2011) J. Chem. Soc. Rev., 40, pp. 427-448. , doi:10.1039/c005401c
- Weiss, R.G., Terech, P., (2006) Molecular Gels: Materials with Self-Assembled Fibrillar Networks, , Springer: The Netherlands
- Desiraju, G.R., (1995) Angew. Chem., Int. Ed. Engl., 34, pp. 2311-2327. , doi:10.1002/anie.199523111
- Sahoo, P., Chakraborty, I., Dastidar, P., (2012) Soft Matter, 8, pp. 2595-2598. , doi:10.1039/c2sm06957a
- Adalder, T.K., Adarsh, N.N., Sankolli, R., Dastidar, P., (2010) Beilstein J. Org. Chem., 6, pp. 848-858. , doi:10.3762/bjoc.6.100
- Hirst, A.R., Coates, I.A., Boucheteau, T.R., Miravet, J.F., Escuder, B., Castelletto, V., Hamley, I.W., Smith, D.K., Low-molecular-weight gelators: Elucidating the principles of gelation based on gelator solubility and a cooperative self-assembly model (2008) Journal of the American Chemical Society, 130 (28), pp. 9113-9121. , DOI 10.1021/ja801804c
- Raynal, M., Bouteiller, L., (2011) Chem. Commun., 47, pp. 8271-8273. , doi:10.1039/c1cc13244j
- Gao, J., Wu, S., Rogers, M.A., (2012) J. Mater. Chem., 22, pp. 12651-12658. , doi:10.1039/c2jm32056h
- Edwards, W., Lagadec, C.A., Smith, D.K., (2011) Soft Matter, 7, pp. 110-117. , doi:10.1039/c0sm00843e
- Löfman, M., Koivukorpi, J., Noponen, V., Salo, H., Sievänen, E., (2011) J. Colloid Interface Sci., 360, pp. 633-644. , doi:10.1016/j.jcis.2011.04.112
- Zinic, M., Vögtle, F., Fages, F., Gelation with small molecules (1989) J. Am. Chem. Soc., 111, pp. 5542-5551. , Fages, F., Ed.; Weiss, R. G. doi:10.1021/ja00197a005
- Svobodová, H., Noponen, V., Kolehmainen, E., Sievänen, E., (2012) RSC Adv., 2, pp. 4985-5007. , doi:10.1039/c2ra01343f
- Edelsztein, V.C., Burton, G., Di Chenna, P.H., (2010) Tetrahedron, 66, pp. 2162-2167. , doi:10.1016/j.tet.2010.01.065
- Edelsztein, V.C., Jares-Erijman, E.A., Müllen, K., Di Chenna, P.H., Spagnuolo, C.C., (2012) J. Mater. Chem., 22, pp. 21857-21861. , doi:10.1039/c2jm34891h
- Silva, M.M.C., Riva, S., Sa E Melo, M.L., Regioselective enzymatic acylation of vicinal diols of steroids (2005) Tetrahedron, 61 (12), pp. 3065-3073. , DOI 10.1016/j.tet.2005.01.104
- Jursic, B.S., Upadhyay, S.K., Creech, C.C., Neumann, D.M., (2010) Bioorg. Med. Chem. Lett., 24, pp. 7372-7375. , doi:10.1016/j.bmcl.2010.10.044
- Kamlet, M.J., Abboud, J.L.M., Abraham, M.H., Taft, R.W., (1983) J. Org. Chem., 48, pp. 2877-2887. , doi:10.1021/jo00165a018
- Martin, C.R., Kohli, P., The emerging field of nanotube biotechnology (2003) Nature Reviews Drug Discovery, 2 (1), pp. 29-37. , DOI 10.1038/nrd988
- Bae, S.W., Tan, W., Hong, J.-I., (2012) Chem. Commun., 48, pp. 2270-2282. , doi:10.1039/c2cc16306c
- Raghavan, S.R., Cipriano, B.H., Gel formation: Phase diagrams using table top rheology and calorimetry (2006) Molecular Gels: Materials with Self-Assembled Fibrillar Networks, , Weiss, R. G.; Terech, P., Eds.; Springer Verlag: The Netherlands
Citas:
---------- APA ----------
Edelsztein, V.C., Mac Cormack, A.S., Ciarlantini, M. & Di Chenna, P.H.
(2013)
. Self-assembly of 2, 3-dihydroxycholestane steroids into supramolecular organogels as a soft template for the in-situ generation of silicate nanomaterials. Beilstein Journal of Organic Chemistry, 9, 1826-1836.
http://dx.doi.org/10.3762/bjoc.9.213---------- CHICAGO ----------
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"
. Beilstein Journal of Organic Chemistry 9
(2013) : 1826-1836.
http://dx.doi.org/10.3762/bjoc.9.213---------- MLA ----------
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"
. Beilstein Journal of Organic Chemistry, vol. 9, 2013, pp. 1826-1836.
http://dx.doi.org/10.3762/bjoc.9.213---------- VANCOUVER ----------
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. Beilstein J. Org. Chem. 2013;9:1826-1836.
http://dx.doi.org/10.3762/bjoc.9.213