Abstract
In the present work, stable organogels and hydrogels could be formed by dimeric-dehydrocholic acid derivative (DDAD) in different solvents. Compared with the organogels, the hydrogels formed by DDAD were found to be thermal reversible and had higher gel-to-solution transition temperature. The supramolecular structures in the organogels and hydrogels were further studied by using transmission electron microscopy (TEM) and atomic force microscopy (AFM). TEM and AFM images of the supramolecular gels showed that the solvent effects played a crucial role in morphological structures. Specifically, the organogel had a three-dimensional porous network structure. While, the hydrogel had a supramolecular structure made up of long fibers. Fourier transformation infrared spectroscopy (FT-IR) showed that multiple hydrogen bonds among the gelator molecules were the main driving forces in gel formation. On this base, the solvent effects on the gelation abilities and thermal stability were discussed. Thus, the present study provides a solvent-induced self-assembly approach and contributes substantially to the development of the supramolecular gels as soft materials.
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References
Steed JW (2010) Anion-tuned supramolecular gels: a natural evolution from urea supramolecular chemistry. Chem Soc Rev 39:3686–3699. https://doi.org/10.1039/B926219A
Jungst T, Smolan W, Schacht K, Scheibel T, Groll J (2016) Strategies and molecular design criteria for 3D printable hydrogels. Chem Rev 116:1496–1539. https://doi.org/10.1021/acs.chemrev.5b00303
Narayana YSLV, Chandrasekar R (2011) Triple emission from organic/inorganic hybrid nanovesicles in a single excitation. ChemPhysChem 12:2391–2396. https://doi.org/10.1002/cphc.201100426
Lorenzo MLD, Cocca M, Gentile G, Avella M, Gutierrez D, Pirriera MD, Kennedy M, Ahmed H, Doran J (2013) Thermoreversible luminescent organogels doped with Eu(TTA)3phen complex. J Colloid Interface Sci 398:95–102. https://doi.org/10.1016/j.jcis.2013.02.012
Xiao TX, Wang LY (2018) Recent advances of functional gels controlled by pillar[n]arene-based host-guest interactions. Tetrahedron Lett 59:1172–1182. https://doi.org/10.1016/j.tetlet.2018.02.028
Li F, Palaniswamy G, de Jong MR, Åslund A, Konradsson P, Marcelis ATM, Sudhölter EJR, Cohen Stuart MA, Leermakers FAM (2010) Nanowires formed by the co-assembly of a negatively charged low-molecular weight gelator and a zwitterionic polythiophene. ChemPhysChem 11:1956–1960. https://doi.org/10.1002/cphc.200900946
Mallia VA, Samai S, Weiss RG (2016) Cholesterol and dihydrocholesterol are simple steroidal molecular gelators: how one double bond controls the structure and mechanotropic properties of their gels. ChemistrySelect 1:4965–4972. https://doi.org/10.1002/slct.201601012
de Fávere VT, Hinze WL (2009) Evaluation of the potential of chitosan hydrogels to extract polar organic species from nonpolar organic solvents: application to the extraction of aminopyridines from hexane. J Colloid Interface Sci 330:38–44. https://doi.org/10.1016/j.jcis.2008.10.035
Yang HK, Zhao H, Yang PR, Huang CH (2017) How do molecular structures affect gelation properties of supramolecular gels? Insights from low-molecular-weight gelators with different aromatic cores and alkyl chain lengths. Colloids Surf A Physicochem Eng Asp 535:242–250. https://doi.org/10.1016/j.colsurfa.2017.09.044
Li Q, Li RH, Lan HC, Lu YX, Li YQ, Xiao SZ, Yi T (2017) Halogen effect on non-conventional organogel assisted by balanced π-π interaction. ChemistrySelect 2:5421–5426. https://doi.org/10.1002/slct.201700760
Krishnan BP, Sureshan KM (2016) A molecular-level study of metamorphosis and strengthening of gels by spontaneous polymorphic transitions. ChemPhysChem 17:3062–3067. https://doi.org/10.1002/cphc.201600590
Kim DJ, Kwon JE, Park SK (2018) Fully reversible multistate fluorescence switching: organogel system consisting of luminescent cyanostilbene and turn-on diarylethene. Adv Funct Mater 28:1706213. https://doi.org/10.1002/adfm.201706213
Chang DD, Yan WH, Han D, Wang QC, Zou L (2018) A photo-switchable dual-modality linear supramolecular polymer based on host-guest interaction of cyclodextrin and pseudorotaxane. Dyes Pigm 149:188–192. https://doi.org/10.1016/j.dyepig.2017.09.064
Sahoo JK, Braegelman AS, Webber MJ (2018) Immunoengineering with supramolecular peptide biomaterials. J Indian Inst Sci 98:69–79. https://doi.org/10.1007/s41745-018-0060-x
Sahoo JK, Nazareth C, VandenBerga MA, Webber MJ (2017) Self-assembly of amphiphilic tripeptides with sequence-dependent nanostructure. Biomater Sci 5:1526–1530. https://doi.org/10.1039/C7BM00304H
You D, Min XY, Liu LL, Ren Z, Xiao X, Pavlostathis SG, Luo JM, Luo XB (2018) New insight on the adsorption capacity of metallogels for antimonite and antimonate removal: from experimental to theoretical study. J Hazard Mater 346:218–225. https://doi.org/10.1016/j.jhazmat.2017.12.035
Gao F, Sheng Y, Song YH, Zou HF (2018) Sol-gel synthesis of silica composited flower-like microspheres using trivalent europium tartrate as a template. J Solgel Sci Technol 85:470–479. https://doi.org/10.1007/s10971-017-4551-4
Döring A, Birnbaum W, Kuckling D (2013) Responsive hydrogels-structurally and dimensionally optimized smart frameworks for applications in catalysis, micro-system technology and material science. Chem Soc Rev 42:7391–7420. https://doi.org/10.1039/C3CS60031A
Yang Q, Lv J, Li PY (2018) A pH-responsive self-healing gel with crosslinking of cucurbituril (CB[n]) via hydrogen bonding. Chem Lett 47:192–195. https://doi.org/10.1246/cl.170886
Zhao Q, Chen Y, Lie Y (2018) A polysaccharide/tetraphenylethylene-mediated blue-light emissive and injectable supramolecular hydrogel. Chinese Chem Lett 29:84–86. https://doi.org/10.1016/j.cclet.2017.07.024
Hao L, Yegin C, Talari JV, Oh JK, Zhang M, Sari MM, Zhang LH, Min Y, Akbulut M, Jiang B (2018) Thermo-responsive gels based on supramolecular assembly of an amidoamine and citric acid. Soft Matter 14:432–439. https://doi.org/10.1039/C7SM01592E
Wang L, Hui X, Geng HM, Ye L, Zhang AY, Shao ZQ, Feng ZG (2017) Synthesis and gelation capability of mono- and disubstituted cyclo(L-Glu-L-Glu) derivatives with tyramine, tyrosine and phenylalanine. Colloid Polym Sci 295:1549–1561. https://doi.org/10.1007/s00396-017-4120-y
Wang JY, Han YC (2011) Tuning the stop bands of inverse opal hydrogels with double network structure by controlling the solvent and pH. J Colloid Interface Sci 353:498–505. https://doi.org/10.1016/j.jcis.2010.10.002
Khimani M, Verma G, Kumar S, Hassan PA, Aswal VK, Bahadur P (2015) PH induced tuning of size, charge and viscoelastic behavior of aqueous micellar solution of pluronic P104-anthranilic acid mixtures: a scattering, rheology and NMR study. Colloids Surf A Physicochem Eng Asp 470:202–210. https://doi.org/10.1016/j.colsurfa.2015.01.051
Wei HL, Yao K, Chu HJ, Li ZC, Zhu J, Shen YM, Zhao ZX, Feng YL (2012) Click synthesis of the thermo- and pH-sensitive hydrogels containing β-cyclodextrins. J Mater Sci 47:332–340. https://doi.org/10.1007/s10853-011-5802-3
Ran X, Wang HT, Zhang P, Bai BL, Zhao CX, Yu ZX, Li M (2011) Photo-induced fiber-vesicle morphological change in an organogel based on an azophenyl hydrazide derivative. Soft Matter 7:8561–8566. https://doi.org/10.1039/C1SM05566F
Wu YP, Wu S, Zou G, Zhang QJ (2011) Solvent effects on structure, photoresponse and speed of gelation of a dicholesterol-linked azobenzene organogel. Soft Matter 7:9177–9183. https://doi.org/10.1039/C1SM06240A
Travaglini L, D’Annibale A, Schillén K, Olsson U, Sennato S, Pavela NV, Galantini L (2012) Amino acid-bile acid based molecules: extremely narrow surfactant nanotubes formed by a phenylalanine-substituted cholic acid. Chem Commun 48:12011–12013. https://doi.org/10.1039/C2CC36030F
Cao XH, Liu X, Chen LM, Mao YY, Lan HC, Yi T (2015) Photoisomerization-induced morphology and transparency transition in an azobenzene based two-component organogel system. J Colloid Interface Sci 458:187–193. https://doi.org/10.1016/j.jcis.2015.07.047
Li ZL, Hao AY, Hao JC (2014) Formation of heat-triggered supramolecular organogel in which β-cyclodextrin as sole gelator. Colloids Surf A Physicochem Eng Asp 441:8–15. https://doi.org/10.1016/j.colsurfa.2013.08.078
Wei J, Chai Q, He LH, Bai BL, Wang HT, Li M (2016) An anthracene-based organogel with colorimetric fluoride-responsive and fluorescence-enhanced properties. Tetrahedron 72:3073–3076. https://doi.org/10.1016/j.tet.2016.04.035
Xing PY, Sun T, Li SY, Hao AY, Su J, Hou YH (2013) An instant-formative heat-set organogel induced by small organic molecules at a high temperature. Colloids Surf A Physicochem Eng Asp 421:44–50. https://doi.org/10.1016/j.colsurfa.2012.12.052
Yang HK, Ren LJ, Wu H, Wang W (2016) Self-assembly of the polyoxometalate-cholesterol conjugate into microrods or nanoribbons regulated by thermodynamics. New J Chem 40:954–961. https://doi.org/10.1039/C5NJ02271A
Liu J, Yan JL, Yuan XW, Liu KQ, Peng JX, Fang Y (2008) A novel low-molecular-mass gelator with a redox active ferrocenyl group: tuning gel formation by oxidation. J Colloid Interface Sci 318:397–404. https://doi.org/10.1016/j.jcis.2007.10.005
Wang YQ, Wang ZY, Xu ZC, Yu XD, Zhao K, Li YJ, Pang XL (2016) Ultrasound-accelerated organogel: application for visual discrimination of Hg2+ from Ag+. Org Biomol Chem 14:2218–2222. https://doi.org/10.1039/C5OB02261D
Li YG, Wang TY, Liu MH (2007) Ultrasound induced formation of organogel from a glutamic dendron. Tetrahedron 63:7468–7473. https://doi.org/10.1016/j.tet.2007.02.070
Adhikari B, Kraatz HB (2014) Redox-triggered changes in the self-assembly of a ferrocene-peptide conjugate. Chem Commun 50:5551–5553. https://doi.org/10.1039/C3CC49268K
Delbecq F, Kaneko N, Endo H, Kawai T (2012) Solvation effects with a photoresponsive two-component 12-hydroxystearic acid-azobenzene additive organogel. J Colloid Interface Sci 384:94–98. https://doi.org/10.1016/j.jcis.2012.06.045
Xing PY, Chu XX, Li SY, Hou YH, Ma MF, Yang JS, Hao AY (2013) Self-recovering β-cyclodextrin gel controlled by good/poor solvent environments. RSC Adv 3:22087. https://doi.org/10.1039/C3RA42587H
Svobodová H, Nonappa LM, Wimmer Z, Kolehmainen E (2012) A steroid-based gelator of A(LS)2 type: tuning gel properties by metal coordination. Soft Matter 8:7840. https://doi.org/10.1039/C2SM25259G
Chakrabarty A, Maitra U, Das AD (2012) Metal cholate hydrogels: versatile supramolecular systems for nanoparticle embedded soft hybrid materials. J Mater Chem 22:18268. https://doi.org/10.1039/C2JM34016J
Fathalla M, Strutt NL, Sampath S, Katsiev K, Hartlieb KJ, Bakr OM, Stoddart FJ (2015) Porphyrinic supramolecular daisy chains incorporating pillar[5]arene-viologen host-guest interactions. Chem Commun 51:10455–10458. https://doi.org/10.1039/C5CC03717D
Wang H, Zhang JY, Zhang WP, Yang YJ (2009) Host-guest interactions of 5-fluorouracil in supramolecular organogels. Eur J Pharm Biopharm 73:357–360. https://doi.org/10.1016/j.ejpb.2009.07.005
Cao XH, Zhang MM, Liu KY, Mao YY, Lan HC, Liu B, Yi T (2012) Formation and regulation of supramolecular chirality in organogel via addition of tartaric acid. Chin Sci Bull 33:4272–4277. https://doi.org/10.1007/s11434-012-5436-0
Xin FF, Zhang HC, Hao BX, Sun T, Kong L, Li YM, Hou YH, Li SY, Zhang Y, Hao AY (2012) Controllable transformation from sensitive and reversible heat-set organogel to stable gel induced by sodium acetate. Colloids Surf A Physicochem Eng Asp 410:18–22. https://doi.org/10.1016/j.colsurfa.2012.06.008
Kuosmanen R, Puttreddy R, Willman RM, Äijäläinen I, Galandáková A, Ulrichová J, Salo H, Rissanen K, Sievänen E (2016) Biocompatible hydrogelators based on bile acid ethyl amides. Steroids 108:7–16. https://doi.org/10.1016/j.steroids.2016.02.014
Svobodová H, Noponen V, Kolehmainen E, Sievänen E (2012) Recent advances in steroidal supramolecular gels. RSC Adv 2:4985. https://doi.org/10.1039/C2RA01343F
Laishram R, Maitra U (2018) Bile salt-derived Eu3+ organogel and hydrogel: Water-enhanced luminescence of Eu3+ in a gel matrix. ChemistrySelect 3:519–523. https://doi.org/10.1002/slct.201701013
Löfman M, Koivukorpi J, Noponen V, Salo H, Sievänen E (2011) Bile acid alkylamide derivatives as low molecular weight organogelators: systematic gelation studies and qualitative structural analysis of the systems. J Colloid Interface Sci 360:633–644. https://doi.org/10.1016/j.jcis.2011.04.112
Willemen HM, Vermonden T, Marcelis ATM, Sudhölter EJR (2002) Alkyl derivatives of cholic acid as organogelators: one-component and two-component gels. Langmuir 18:7102–7106. https://doi.org/10.1021/la025514l
Maitra U, Kumar PV, Chandra N, D’Souza LJ, Prasanna MD, Raju AR (1999) First donor-acceptor interaction promoted gelation of organic fluids. Chem Commun 7:595–596. https://doi.org/10.1039/A809821B
Chakrabarty A, Maitra U, Devi Das A (2012) Metal cholate hydrogels: versatile supramolecular systems for nanoparticle embedded soft hybrid materials. J Mater Chem 22:18268–18274. https://doi.org/10.1039/C2JM34016J
Yang HK, Qi P, Zhao H (2018) A novel hydrogelator based on dimeric-dehydrocholic acid derivative. Colloid Polym Sci 296:1071–1078. https://doi.org/10.1007/s00396-018-4324-9
Eldridge JE, Ferry JD (1954) Studies of the cross-linking process in gelatin gels. III. Dependence of melting point on concentration and molecular weight. J Phys Chem 58:992–995. https://doi.org/10.1021/j150521a013
Funding
We greatly appreciate the financial support of the Scientific and Technological Innovation Plan of Higher Education Institutions of Shanxi Province (No. 2021L609), the Fundamental Research Program of Shanxi Province (No. 202203021211102), and National Natural Science Foundation of China (No. 21802127).
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Ruicong Wang: funding acquisition, conceptualization, methodology, and writing original draft. Xiaoting Hao: data curation, investigation, and experiment. Haikuan Yang: funding acquisition, supervision, writing — review and editing. All authors contributed to the general discussion. All authors have read and agreed to the published version of the manuscript.
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Wang, R., Hao, X. & Yang, H. Using a solvent-induced self-assembly approach to fabricate and tune the organogels and hydrogels. Colloid Polym Sci 302, 163–171 (2024). https://doi.org/10.1007/s00396-023-05186-y
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DOI: https://doi.org/10.1007/s00396-023-05186-y