Journal of Materials Science

, Volume 51, Issue 18, pp 8529–8542 | Cite as

Steroid-based A(LS)3-type gelators: probing the design criteria in creating soft materials

  • Hai-Kuan Yang
  • Xiao-Xiao Wang
  • He Xiao
  • Zhi-Nan Ma
Original Paper


A new series of low molecular weight gelators, namely compounds 1–4, have been synthesized and investigated the gelation ability in various organic solvents for the purpose of probing the rational design criteria in creating optimized steroid-based A(LS)3-type gelators. To generate compounds 1–4, we designed identical cholesterol moieties and amide bonds, and fine-tuned the structures of functionalized linkers or aromatic units. The gelation ability indicated that compounds 1 and 4 were poor gelators, and compound 2 was an efficient gelator for some aromatic solvents, while compound 3 was a highly efficient gelator. To facilitate understanding the reason of this phenomenon, a close investigation of the supramolecular structures in the xerogels of compounds 1–4 was carried out using TEM and AFM characterizations. The investigation showed that a slight change in the molecular structure of gelator could greatly affect the gelation ability as well as the morphology of the supramolecular self-assembly. Especially, it was highlighted that an appropriate aromatic unit as a backbone of gelator and a flexible linker were welcomed in order to obtain an effective A(LS)3 type gelator. The formation mechanism of organogels has also been proposed. Moreover, we explained from a molecular level why the gelling ability as well as thermal stability of organogels formed by compound 3 or 2 was better than that formed by compound 1 or 4. The results described herein possibly provide the rational design criteria in creating optimized steroid-based A(LS)3-type gelators toward functional gels with unusual properties.


Atomic Force Microscopy Aromatic Unit Xerogel Sample Lower Polarity Solvent Gelator Molecule 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.



We greatly appreciate the financial support of the Open Research Fund of Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), Nankai University; the National Natural Science Foundation of China 21503195; and the Natural Science Foundation of Shanxi 2015021044.

Supplementary material

10853_2016_114_MOESM1_ESM.doc (9.6 mb)
Supplementary material 1 (DOC 9836 kb)


  1. 1.
    Lin NB, Liu XY (2015) Correlation between hierarchical structure of crystal networks and macroscopic performance of mesoscopic soft materials and engineering principles. Chem Soc Rev 44:7881–7915CrossRefGoogle Scholar
  2. 2.
    Yu GC, Yan XZ, Han CY, Huang FH (2013) Characterization of supramolecular gels. Chem Soc Rev 42:6697–6722CrossRefGoogle Scholar
  3. 3.
    Buerklea LE, Rowan SJ (2012) Supramolecular gels formed from multi-component low molecular weight species. Chem Soc Rev 41:6089–6102CrossRefGoogle Scholar
  4. 4.
    Steed JW (2012) Supramolecular gel chemistry: developments over the last decade. Chem Commun 47:1379–1383CrossRefGoogle Scholar
  5. 5.
    Pritchard CD, O’Shea TM, Siegwart DJ, Calo E, Anderson DG, Reynolds FM, Thomas JA, Slotkin JR, Woodard EJ, Langer R (2011) An injectable thiol-acrylate poly(ethylene glycol) hydrogel for sustained release of methylprednisolone sodium succinate. Biomaterials 32:587–597CrossRefGoogle Scholar
  6. 6.
    Goto H, Zhang HQ, Yashima E (2003) Chiral stimuli-responsive gels: helicity induction in poly(phenylacetylene) gels bearing a carboxyl group with chiral amines. J Am Chem Soc 125:2516–2523CrossRefGoogle Scholar
  7. 7.
    Sugiyasu K, Fujita N, Shinkai S (2005) Fluorescent organogels as templates for sol-gel transcription toward creation of optical nanofibers. J Mater Chem 15:2747–2754CrossRefGoogle Scholar
  8. 8.
    Yang D, Liu CX, Zhang L, Liu MH (2014) Visualized discrimination of ATP from ADP and AMP through collapse of supramolecular gels. Chem Commun 50:12688–12690CrossRefGoogle Scholar
  9. 9.
    Yang XY, Zhang GX, Zhang DQ (2012) Stimuli responsive gels based on low molecular weight gelators. J Mater Chem 22:38–50CrossRefGoogle Scholar
  10. 10.
    Barman S, Garg JA, Blacque O, Venkatesan K, Berke H (2012) Triptycene based luminescent metal-organic gels for chemosensing. Chem Commun 48:11127–11129CrossRefGoogle Scholar
  11. 11.
    Banerjee S, Kandanelli R, Bhowmik S, Maitra U (2011) Self-organization of multiple components in a steroidal hydrogel matrix: design, construction and studies on novel tunable luminescent gels and xerogels. Soft Matter 7:8207–8215CrossRefGoogle Scholar
  12. 12.
    Mukhopadhyay P, Iwashita Y, Shirakawa M, Kawano S, Fujita N, Shinkai S (2006) Spontaneous colorimetric sensing of the positional isomers of dihydroxynaphthalene in a 1D organogel matrix. Angew Chem Int Ed 45:1592–1595CrossRefGoogle Scholar
  13. 13.
    Murata K, Aoki M, Suzuki T, Harada T, Kawabata H, Komri T, Olrseto F, Ueda K, Shinkai S (1994) Thermal and light control of the sol-gel phase transition in cholesterol-based organic gels. Novel helical aggregation modes as detected by circular dichroism and electron microscopic observation. J Am Chem Soc 116:6664–6676CrossRefGoogle Scholar
  14. 14.
    Hanabusa K, Matsumoto Y, Miki T, Koyama T, Shirai H (1994) Cyclo(dipeptide)s as low-molecular-mass gelling agents to harden organic fluids. J Chem Soc Chem Commun. 11:1401–1402CrossRefGoogle Scholar
  15. 15.
    van Esch J, Schoonbeek F, de Loos M, Kooijman H, Spek AL, Kellogg RM, Feringa BL (1999) Cyclic bis-urea compounds as gelators for organic solvents. Chem Eur J 5:937–950CrossRefGoogle Scholar
  16. 16.
    Hafkamp RJH, Kokke BPA, Danke IM, Geurts HPM, Rowan AE, Feiters MC, Nolte RJM (1997) Organogel formation and molecular imprinting by functionalized gluconamides and their metal complexes. Chem Commun 6:545–546CrossRefGoogle Scholar
  17. 17.
    Lin YC, Weiss RG (1987) Liquid-crystalline solvents as mechanistic probes. 24. A novel gelator of organic liquids and the properties of its gels. Macromolecules 20:414–417CrossRefGoogle Scholar
  18. 18.
    Lin YC, Kachar B, Weiss RG (1989) Liquid-crystalline solvents as mechanistic probes. Part 37. Novel family of gelators of organic fluids and the structure of their gels. J Am Chem Soc 111:5542–5551CrossRefGoogle Scholar
  19. 19.
    Svobodová H, Noponen V, Kolehmainen E, Sievänen E (2012) Recent advances in steroidal supramolecular gels. RSC Adv 2:4985–5007CrossRefGoogle Scholar
  20. 20.
    Tu T, Fang W, Bao X, Li X, Dötz KH (2011) Visual chiral recognition through enantioselective metallogel collapsing: synthesis, characterization, and application of platinum–steroid low-molecular-mass gelators. Angew Chem Int Ed 50:6601–6605CrossRefGoogle Scholar
  21. 21.
    Gansäuer A, Winkler I, Klawonn T, Nolte RJM, Feiters MC, Börner HG, Hentschel J, Dötz KH (2009) Novel organometallic gelators with enhanced amphiphilic character: structure − property correlations, principles for design, and diversity of gelation. Organometallics 28:1377–1382CrossRefGoogle Scholar
  22. 22.
    Dawn A, Shiraki T, Haraguchi S, Tamaru S, Shinkai S (2011) What kind of “soft materials” can we design from molecular gels ? Chem Asian J 6:266–282CrossRefGoogle Scholar
  23. 23.
    Wang C, Chen Q, Sun F, Zhang DQ, Zhang GX, Huang YY, Zhao R, Zhu DB (2010) Multistimuli responsive organogels based on a new gelator featuring tetrathiafulvalene and azobenzene groups: reversible tuning of the gel-sol transition by redox reactions and light irradiation. J Am Chem Soc 132:3092–3096CrossRefGoogle Scholar
  24. 24.
    Vijayakumar C, Praveen VK, Ajayaghosh A (2009) RGB emission through controlled donor self-assembly and modulation of excitation energy transfer: a novel strategy to white-light-emitting organogels. Adv Mater 21:2059–2063CrossRefGoogle Scholar
  25. 25.
    Ajayaghosh A, Praveen V, Vijayakumar C, George S (2007) Molecular wire encapsulated into π organogels: efficient supramolecular light-harvesting antennae with color-tunable emission. Angew Chem Int Ed 46:6260–6265CrossRefGoogle Scholar
  26. 26.
    Sugiyasu K, Fujita N, Shinkai S (2004) Visible-light-harvesting organogel composed of cholesterol-based perylene derivatives. Angew Chem Int Ed 43:1229–1233CrossRefGoogle Scholar
  27. 27.
    Yan JL, Liu J, Lei HR, Kang Y, Zhao C, Fang Y (2015) Ferrocene-containing thixotropic molecular gels: creation and a novel strategy for water purification. J Colloid Interface Sci 448:374–379CrossRefGoogle Scholar
  28. 28.
    Balamurugan R, Wu KM, Chien CC, Liu JH (2014) Structure-property relationships of symmetrical and asymmetrical azobenzene derivatives as gelators and their self-assemblies. Soft Matter 10:8963–8970CrossRefGoogle Scholar
  29. 29.
    Cai XQ, Liu KQ, Yan JL, Zhang HL, Hou XY, Liu Z, Fang Y (2012) Calix[4]arene-based supramolecular gels with unprecedented rheological properties. Soft Matter 8:3756–3761CrossRefGoogle Scholar
  30. 30.
    Sun HB, Liu SJ, Zhao Q, Huang W (2015) Multiple-stimuli responsive luminescent gels based on cholesterol containing benzothiadiazole fluorophores. Chin J Chem 10:1140–1144CrossRefGoogle Scholar
  31. 31.
    Hou Q, Wang S, Zang L, Wang X, Jiang S (2009) Hydrogen-bonding A(LS)2-type low-molecular-mass gelator and its thermotropic mesomorphic behavior. J Colloid Interface Sci 338:463–467CrossRefGoogle Scholar
  32. 32.
    Dutta S, Kar T, Mandal D, Das PK (2013) Structure and properties of cholesterol-based hydrogelators with varying hydrophilic terminals: biocompatibility and development of antibacterial soft nanocomposites. Langmuir 29:316–327CrossRefGoogle Scholar
  33. 33.
    Devi M, Dhir A, Pooja Pradeep CP (2014) New triangular steroid-based A(LS)3 type gelators for selective fluoride sensing application. RSC Adv 4:27098–27105CrossRefGoogle Scholar
  34. 34.
    Jiao TF, Gao FQ, Wang YJ, Zhou JX, Gao FM, Luo XZ (2012) Supramolecular gel and nanostructures of bolaform and trigonal cholesteryl derivatives with different aromatic spacers. Curr Nanosci 8:111–116CrossRefGoogle Scholar
  35. 35.
    Xue M, Gao D, Chen X, Liu K, Fang Y (2011) New dimeric cholesteryl-based A(LS)2 gelators with remarkable gelling abilities: organogel formation at room temperature. J Colloid Interface Sci 361:556–564CrossRefGoogle Scholar
  36. 36.
    Eldridge JE, Ferry JD (1954) Studies of the crosslinking process in gelatin gels. III. Dependence of melting point on concentration and molecular weight. J Phys Chem 58:992–995CrossRefGoogle Scholar
  37. 37.
    Adhikari B, Nanda J, Banerjee A (2011) Pyrene-containing peptide-based fluorescent organogels: inclusion of graphene into the organogel. Chem-Eur J 17:11488–11496CrossRefGoogle Scholar
  38. 38.
    He PL, Liu J, Liu KQ, Ding LP, Yan JL, Gao D, Fang Y (2010) Preparation of novel organometallic derivatives of cholesterol and their gel-formation properties. Colloids and surfaces a: physicochem. Colloids Surf A Physicochem Eng Aspects 362:127–134CrossRefGoogle Scholar
  39. 39.
    Kato T (2010) From nanostructured liquid crystals to polymer-based electrolytes. Angew Chem Int Ed 49:7847–7848CrossRefGoogle Scholar
  40. 40.
    Lan Y, Corradini MG, Weiss RG, Raghavanc SR, Rogers MA (2015) To gel or not to gel: correlating molecular gelation with solvent parameters. Chem Soc Rev 44:6035–6058CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media New York 2016

Authors and Affiliations

  • Hai-Kuan Yang
    • 1
  • Xiao-Xiao Wang
    • 1
  • He Xiao
    • 1
  • Zhi-Nan Ma
    • 1
  1. 1.The Department of Chemistry, School of ScienceNorth University of ChinaTaiyuanPeople’s Republic of China

Personalised recommendations