Abstract
New hydrogels having high water content, ∼96 wt%, composed of cationic surfactants, alkyltrimethylammonium bromides (C n TAB, n = 12, 14, 16, and 18), and a small dye molecule, sodium azobzenzene 4,4′-dicarboxylic acid (AzoNa2), was firstly obtained. The three-dimensional network structures of hydrogels were determined by transmission electron microscopy images, scanning electron microscopy images, 1H nuclear magnetic resonance, and small-angle X-ray scattering measurements. The mechanism of hydrogel formation was also illustrated. The rheological data were obtained to investigate the mechanical strength of hydrogels, which were turned out to be strong mechanical strength (∼104 Pa) materials. We found that the strength of the hydrogel depends on the fiber density, which can be controlled by changing the proportion of the two compounds, concentration of surfactants, temperature, and the chain length of the surfactant. Interestingly, the hydrogels were found to have a multiple-stimulus response property. A reversible thermal, UV–vis, or a chemical response was investigated in the mixtures of cationic surfactants and azoic salt for the first time. These findings may find potential applications such as sensors, actuators, shape memories, and drug delivery systems, etc.
Similar content being viewed by others
References
Terech P, Weiss RG (1997) Low molecular mass gelators of organic liquids and the properties of their gels. Chem Rev 97:3133–3159
Estroff LA, Hamilton AD (2004) Water gelation by small organic molecules. Chem Rev 104:1201–1217
Fuhrhop JH, Helfrich W (1993) Fluid and solid fibers made of lipid molecular bilayers. Chem Rev 93:1565–1582
Trickett K, Eastoe J (2008) Surfactant-based gels. Adv Colloid Interface Sci 144:66–74
van Esch JH, Feringa BL (2000) New functional materials based on self-assembling organogels: from serendipity towards design. Angew Chem Int Ed 39:2263–2266
Gronwald O, Snip E, Shinkai S (2002) Gelators for organic liquids based on self-assembly: a new facet of supramolecular and combinatorial chemistry. Curr Opin Colloid Interface Sci 7:148–156
Sangeetha NM, Maitra U (2005) Supramolecular gels: functions and uses. Chem Soc Rev 34:821–836
George M, Weiss RG (2006) Molecular organogels soft matter comprised of low-molecular-mass organic gelators and organic liquids. Acc Chem Res 39:489–497
Mackenzie JD, Bescher EP (2007) Chemical routes in the synthesis of nanomaterials using the sol–gel process. Acc Chem Res 40:810–818
Cai W, Wang G, Du P, Wang R, Jiang X, Li Z (2008) Foldamer organogels: a circular dichroism study of glucose-mediated dynamic helicity induction and amplification. J Am Chem Soc 130:13450–13459
Suzuki M, Yumoto M, Shirai H, Hanabusa K (2008) Supramolecular gels formed by amphiphilic low-molecular-weight gelators of Nα, Nε-diacyl-l-lysine derivatives. Chem Eur J 14:2133–2144
Yu L, Ding J (2008) Injectable hydrogels as unique biomedical materials. Chem Soc Rev 37:1473–1481
Cravotto G, Cintas P (2009) Molecular self-assembly and patterning induced by sound waves: the case of gelation. Chem Soc Rev 38:2684–2697
Suzuki M, Hanabusa K (2009) L-lysine-based low-molecular-weight gelators. Chem Soc Rev 38:967–975
Xue P, Lu R, Yang X, Zhao L, Xu F, Liu Y, Zhang H, Nomoto H, Takafuji M, Ihara H (2009) Self-assembly of a chiral lipid gelator controlled by solvent and speed of gelation. Chem Eur J 15:9824–9835
Wang C, Zhang D, Zhu D (2005) A low-molecular-mass gelator with an electroactive tetrathiafulvalene group: tuning the gel formation by charge-transfer interaction and oxidation. J Am Chem Soc 127:16372–16373
Wang C, Sun F, Zhang D, Zhang G, Zhu D (2010) Cholesterol-substituted tetrathiafulvalene (TTF) compound: formation of organogel and supramolecular chirality. Chin J Chem 28:622–626
Jeppesen JO, Perkins J, Becher J, Stoddart JF (2001) Slow shuttling in an amphiphilic bistable [2]rotaxane incorporating a tetrathiafulvalene unit. Angew Chem Int Ed 40:1216
Balzani V, Credi A, Mattersteig G, Matthews OA, Raymo FM, Stoddart JF, Venturi M, White AJP, Williams DJ (2000) Switching of pseudorotaxanes and catenanes incorporating a tetrathiafulvalene unit by redox and chemical inputs. J Org Chem 65:1924–1936
Zhao Y, Aprahamian I, Trabolsi A, Erina N, Stoddart JF (2008) Organogel formation by a cholesterol-stoppered bistable [2]rotaxane and its dumbbell precursor. J Am Chem Soc 130:6348–6350
Wang C, Chen Q, Sun F, Zhang D, Zhang G, Huang Y, Zhao R, Zhu D (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 132:3092–3096
Kitamura T, Nakaso S, Mizoshita N, Tochigi Y, Shimomura T, Moriyama M, Ito K, Kato T (2005) Electroactive supramolecular self-assembled fibers comprised of doped tetrathiafulvalene-based gelators. J Am Chem Soc 127:14769–14775
Kitahara T, Shirakawa M, Kawano S, Beginn U, Fujita N, Shinkai S (2005) Creation of a mixed-valence state from one-dimensionally aligned TTF utilizing the self-assembling nature of a low molecular-weight gel. J Am Chem Soc 127:14980–14981
Puigmarti-Luis J, Laukhina EE, Laukhin VN, del Pino AP, Mestres N, Vidal-Gancedo J, Rovira C, Amabilino DB (2009) Rich phase behavior in a supramolecular conducting material derived from an organogelator. Adv Funct Mater 19:934–941
Puigmarti-Luis J, Laukhin V, del Pino AP, Vidal-Gancedo J, Rovira C, Laukhina E, Amabilino DB (2006) Supramolecular conducting nanowires from organogels. Angew Chem Int Ed 46:238–241
Akutagawa T, Kakiuchi K, Hasegawa T, Noro S, Nakamura T, Hasegawa H, Mashiko S, Becher J (2005) Molecularly assembled nanostructures of a redox-active organogelator. Angew Chem Int Ed 44:7283–7287
Liu J, He P, Yan J, Fang X, Peng J, Liu K, Fang Y (2008) An organometallic super-gelator with multiple-stimulus responsive properties. Adv Mater 20:2508
Kawano S, Fujita N, Shinkai S (2004) A coordination gelator that shows a reversible chromatic change and sol–gel phase-transition behavior upon oxidative/reductive stimuli. J Am Chem Soc 126:8592–8593
Tsuchiya K, Orihara Y, Kondo Y, Yoshino N, Ohkubo T, Sakai H, Abe M (2004) Control of viscoelasticity using redox reaction. J Am Chem Soc 126:12282–12283
Koumura N, Kudo M, Tamaoki N (2004) Photocontrolled gel-to-sol-to-gel phase transitioning of meta-substituted azobenzene bisurethanes through the breaking and reforming of hydrogen bonds. Langmuir 20:9897–9900
Yagai S, Iwashima T, Kishikawa K, Nakahara S, Karatsu T, Kitamura A (2006) Photoresponsive self-assembly and self-organization of hydrogen-bonded supramolecular tapes. Chem Eur J 12:3984–3994
Yagai S, Nakajima T, Kishikawa K, Kohmoto S, Karatsu T, Kitamura A (2005) Hierarchical organization of photoresponsive hydrogen-bonded rosettes. J Am Chem Soc 127:11134–11139
Kim JH, Seo M, Kim YJ, Kim SY (2009) Rapid and reversible gel–sol transition of self-assembled gels induced by photoisomerization of dendritic azobenzenes. Langmuir 25:1761–1766
Ji Y, Kuang G, Jia X, Chen E, Wang B, Li W, Wei Y, Lei J (2007) Photoreversible dendritic organogel. Chem Commun 4233–4235
Moriyama M, Mizoshita N, Yokota T, Kishimoto K, Kato T (2003) Photoresponsive anisotropic soft solids: liquid-crystalline physical gels based on a chiral photochromic gelator. Adv Mater 15:1335–1338
Moriyama M, Mizoshita N, Kato T (2006) Novel low-molecular-weight gelators based on azobenzene containing L-amino acids. Bull Chem Soc Jpn 79:962–964
Miljanić S, Frkanec L, Meić Z, Žinić M (2005) Photoinduced gelation by stilbene oxalyl amide compounds. Langmuir 21:2754–2760
Miljanić S, Frkanec L, Meić Z, Žinić M (2006) Gelation ability of novel oxamide-based derivatives bearing a stilbene as a photo-responsive unit. Eur J Org Chem 1323–1334
Eastoe J, Sanchez-Dominguez M, Wyatt P, Heenan RK. A photo-responsive organogel. Chem Commun 2608–2609.
Kumar NSS, Varghese S, Narayan G, Das S (2006) Hierarchical self-assembly of donor-acceptor-substituted butadiene amphiphiles into photoresponsive vesicles and gels. Angew Chem Int Ed 45:6317–6321
Abe M, Kishida T, Fujita N, Sada K, Shinkai S (2003) Binary organogelators which show light and temperature responsiveness. Org Biomol Chem 1:2744–2747
Wang C, Zhang D, Xiang J, Zhu D (2007) New organogels based on an anthracene derivative with one urea group and its photodimer: fluorescence enhancement after gelation. Langmuir 23:9195–9200
Ahmed SA, Sallenave X, Fages F, Mieden-Gundert G, Müller WM, Müller U, Vögtle F, Pozzo JL (2002) Multiaddressable self-assembling organogelators based on 2H-chromene and N-Acyl-1, ω-amino acid units. Langmuir 18:7096–7101
Qiu Z, Yu H, Li J, Wang Y, Zhang Y (2009) Spiropyran-linked dipeptide forms supramolecular hydrogel with dual responses to light and to ligand–receptor interaction. Chem Commun 3342–3344
Chen Q, Feng Y, Zhang D, Zhang G, Fan Q, Sun S, Zhu D (2010) Light-triggered self-assembly of a spiropyran-functionalized dendron into nano-/micrometer-sized particles and photoresponsive organogel with switchable fluorescence. Adv Funct Mater 20:36–42
de Jong JJD, Lucas LN, Kellogg RM, van Esch JH, Feringa BL (2004) Reversible optical transcription of supramolecular chirality into molecular chirality. Science 304:278–281
Wang S, Shen W, Feng YL, Tian H (2006) A multiple switching bisthienylethene and its photochromic fluorescent organogelator. Chem Commun 1497–1499
Ma M, Kuang Y, Gao Y, Zhang Y, Gao P, Xu B (2010) Aromatic–aromatic interactions induce the self-assembly of pentapeptidic derivatives in water to form nanofibers and supramolecular hydrogels. J Am Chem Soc 132:2719–2728
Gao Y, Kuang Y, Guo Z, Guo Z, Krauss IJ, Xu B (2009) Enzyme-instructed molecular self-assembly confers nanofibers and a supramolecular hydrogel of taxol derivative. J Am Chem Soc 131:13576–13577
Chen Q, Zhang D, Zhang G, Zhu D (2009) New cholesterol-based gelators with maleimide unit and the relevant Michael adducts: chemoresponsive organogels. Langmuir 25:11436–11441
George M, Weiss RG (2001) Chemically reversible organogels: aliphatic amines as “latent” gelators with carbon dioxide. J Am Chem Soc 123:10393–10394
Shirakawa M, Fujita N, Shinkai S (2003) [60]Fullerene-motivated organogel formation in a porphyrin derivative bearing programmed hydrogen-bonding sites. J Am Chem Soc 125:9902–9903
Yang J (2002) Viscoelastic wormlike micelles and their applications. Curr Opin Colloid Interface Sci 7:276–281
Gradzielski M, Bergmeier M, Muller M, Hoffmann H (1997) Novel gel phase: a cubic phase of densely packed monodisperse, unilamellar vesicles. J Phys Chem B 101:1719–1722
Gradzielski M, Muller M, Bergmeier M, Hoffmann H, Hoinkis E (1999) Structural and macroscopic characterization of a gel phase of densely packed monodisperse, unilamellar vesicles. J Phys Chem B 103:1416–1424
Li L, Yi Y, Dong J, Li X (2010) Azobenzene dye induced micelle to vesicle transition in cationic surfactant aqueous solutions. J Colloid Interface Sci 343:504–509
Oh H, Ketner AM, Heymann R, Kesselman E, Danino D, Falvey DE, Raghavan SR (2013) A simple route to fluid with photo-switchable viscosities based on a reversible transition between vesicles and wormlike micelles. Soft Matter 9:5025–5033
Matsumura A, Sakai K, Sakai H, Abe M (2011) Photoinduced increase in surfactant solution viscosity using azobenzene dicarboxylate for molecular switching. J Oleo Sci 60:203–207
Basit H, Pal A, Sen S, Bhattacharya S (2008) Two-component hydrogels comprising fatty acids and amines: structure, properties, and application as a template for the synthesis of metal nanoparticles. Chem Eur J 14:6534–6545
Simmons BA, Taylor CE, Landis FA, John VT, McPherson GL, Schwartz DK, Moore R (2001) Microstructure determination of AOT + phenol organogels utilizing small-angle X-ray scattering and atomic force microscopy. J Am Chem Soc 123:2414–2421
Stokes RJ, Evans DF (1997) Fundamentals of interfacial engineering. Wiley-VCH, New York
Acknowledgments
This work was financially supported by the NSFC (grant no. 21033005 and 21273136), the National Basic Research Program of China (973 program, 2009CB930103).
Author information
Authors and Affiliations
Corresponding author
Appendix A. Supplementary data
Below is the link to the electronic supplementary material.
ESM 1
Supporting material includes TEM images, SAXS data, SAXRD data, and photos of samples response to chemicals. Supplementary data associated with this article can be found in the online version (doi: ) (DOC 9261 kb)
Rights and permissions
About this article
Cite this article
Wang, D., Hao, J. Multiple-stimulus-responsive hydrogels of cationic surfactants and azoic salt mixtures. Colloid Polym Sci 291, 2935–2946 (2013). https://doi.org/10.1007/s00396-013-3036-4
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s00396-013-3036-4