Abstract
A scorpion-shaped di-NBD (4-substituted-7-nitrobenzoxadiazole) derivative of cholesterol (Chol-2NBD) was designed and synthesized. The gelation behaviors of the compound in a series of single and mixed liquids were tested. It was shown that the compound is an effective gelator for mixture liquids of THF and benzene at room temperature. Furthermore, FT-IR and temperature-/concentration-dependent 1H NMR spectroscopy studies revealed that hydrogen bonding and π-π stacking among the molecules of Chol-2NBD are two main driving forces for the physical gelation of the mixture liquids. Interestingly, as observed in the gelation test and confirmed by rheological studies, the Chol-2NBD-THF/benzene gel systems, at least the one with 2:8 of the volume ratio of THF to benzene, are mechanically stable, but very sensitive to the stimulus of shear stress, which means that the gel changes into a liquid upon shaking. More interestingly, the liquid returns to gel instantly once the shear stress is removed. This phase transition process could be repeated for many times at room temperature. In addition, primary tests demonstrated that the fluorescence emission of Chol-2NBD is significantly quenched by the presence of water, ammonia water, or ammonia gas, but the emission recovers after evaporation of them. Further detailed investigation is under progress.
Similar content being viewed by others
References
Flory PJ. Introduction lecture. Faraday Discuss Chem Soc, 1974, 57: 7–18
Ajayaghosh A, Chithra P, Varghese R. Self-assembly of tripodal squaraines: cation-assisted expression of molecular chirality and change from spherical to helical morphology. Angew Chem Int Ed, 2007, 46: 230–233
Wei TB, Dang JP, Lin Q, Yao H, Liu Y, Zhang WQ, Ming JJ, Zhang YM. Novel smart supramolecular metallo-hydrogel that could selectively recognize and effectively remove Pb2+ in aqueous solution. Sci China Chem, 2012, 55: 2554–2561
George M, Weiss RG. Molecular organogels. Soft matter comprised of low-molecular-mass organic gelators and organic liquids. Acc Chem Res, 2006, 39: 489–497
Yang XY, Zhang DQ, Zhang GX, Zhu DB. Tetrathiafulvalene (TTF)-based gelators: stimuli responsive gels and conducting nanostructures. Sci China Chem, 2011, 54: 596–602
Sangeetha NM, Maitra U. Supramolecular gels: functions and uses. Chem Soc Rev, 2005, 34: 821–836
Rozner S, Garti N. The activity and absorption relationship of cholesterol and phytosterols. Colloids Surf A, 2006, 282-283: 435–456
Duan PF, Li YG, Jiang J, Wang TY, Liu MH. Towards a universal organogelator: a general mixing approach to fabricate various organic compounds into organogels. Sci China Chem, 2011, 54: 1051–1063
Ajayaghosh A, Praveen VK. p-Organogels of self-assembled p-phenylenevinylenes: soft materials with distinct size, shape and functions. Acc Chem Res, 2007, 40: 644–656
Maeda H, Haketa Y, Nakanishi T. Aryl-substituted C3-bridged oligopyrroles as anion receptors for formation of supramolecular organogels. J Am Chem Soc, 2007, 129: 13661–13674
Zhu GY, Dordick JS. Solvent effect on organogel formation by low molecular weight molecules. Chem Mater, 2006, 18: 5988–5995
Hirst AR, Coates IA, Boucheteau TR, Miravet JF, Escuder B, Castelletto V, Hamley IW, Smith DK. Low-molecular-weight gelators: elucidating the principles of gelation based on gelator solubility and a cooperative self-assembly model. J Am Chem Soc, 2008, 130: 9113–9121
Ihara H, Sakurai T, Yamada T, Hashimoto T, Takafuji M, Sagawa T, Hachisako H. Chirality control of self-assembling organogels from a lipophilic L-glutamide derivative with metal chlorides. Langmuir, 2002, 18: 7120–7123
Liu KQ, He PL, Fang Y. Progress in the studies of low-molecular mass gelators. Sci China Chem, 2011, 54: 575–586
Lloyd GO, Steed JW. Anion-tuning of supramolecular gel properties. Nat Chem, 2009, 1: 437–442
Steed JW, Atwood JL. Supramolecular Chemistry. 2nd ed. Chippenham, UK: John Wiley and Sons, 2009
Hirst AR, Escuder B, Miravet JF, Smith DK. High-tech applications of self-assembling supramolecular nanostructured gel-phase materials: from regenerative medicine to electronic devices. Angew Chem Int Ed, 2008, 47: 8002–8018
Lehn JM. Toward complex matter: supramolecular chemistry and self-organization. Proc Nati Acad Sci USA, 2002, 99: 4763–4768
Lehn JM. From supramolecular chemistry towards constitutional dynamic chemistry and adaptive chemistry. Chem Soc Rev, 2007, 36: 151–160
Noh E, Park S, Kang S, Lee JY, Jung JH. Remarkable reinforcement of a supramolecular gel constructed by heteroditopic [18]-crown-6-based molecular recognition. Chem Eur J, 2013, 19: 2620–2627
Vemula PK, Li J, John G. Enzyme catalysis: tool to make and break amygdalin hydrogelators from renewable resources: a delivery model for hydrophobic drugs. J Am Chem Soc, 2006, 128: 8932–8938
Lee KY, Mooney DJ. Hydrogels for tissue engineering. Chem Rev, 2001, 101: 1869–1880
Gao P, Zhan CL, Liu MH. Controlled synthesis of double- and multiwall silver nanotubes with template organogel from a bolaamphiphile. Langmuir, 2006, 22: 775–779
McQuade DT, Pullen AE, Swager TM. Conjugated polymer-based chemical sensors. Chem Rev, 2000, 100: 2537–2574
Du P, Chen GS, Jiang M. Electrochemically sensitive supra-crosslink and its corresponding hydrogel. Sci China Chem, 2012, 55: 836–843
Ahmed SA, Sallenave X, Fages F, Mieden-Gundert G, Müller WM, Pozzo JL. Multiaddressable self-assembling organogelators based on 2H-chromene and N-acyl-1,ω-amino acid units. Langmuir, 2002, 18: 7096–7101
Meng YB, Yang YJ. Gelation of the organic liquid electrolytes and the conductivities as gel electrolytes. Electrochem Commun, 2007, 9: 1428–1433
Daly R, Kotova O, Boese M, Gunnlaugsson T, Boland JJ. Chemical nano-gardens: growth of salt nanowires from supramolecular self-assembly gels. ACS Nano, 2013, 7: 4838–4845
Kakuta T, Takashima Y, Harada A. Highly elastic supramolecular hydrogels using host-guest inclusion complexes with cyclodextrins. Macromolecules, 2013, 46: 4575–4579
Roy B, Bairi P, Chakraborty P, Nandi AK. Stimuli-responsive, thixotropic bicomponent hydrogel of melamine-Zn(II)-orotate complex. Supramol Chem, 2013, 25: 335–343
Wang H, Wang Z, Yi X, Long J, Liu J, Yang Z. Anti-degradation of a recombinant complex protein by incoporation in small molecular hydrogels. Chem Commun, 2011, 47: 955–957
Liu H, Hu Y, Wang H, Wang J, Kong D, Wang L, Chen L, Yang Z. A thixotropic molecular hydrogel selectively enhances Flk1 expression in differentiated murine embryonic stem cells. Soft Matter, 2011, 7: 5430–5436
Yan C, Altunbas A, Yucel T, Nagarkar RP, Schneider JP, Pochan DJ. Injectable solid hydrogel: mechanism of shear-thinning and immediate recovery of injectable β-hairpin peptide hydrogels. Soft Matter, 2010, 6: 5143–5156
Pek YS, Wan ACA, Shekaran A, Zhuo L, Ying JY. A thixotropic nanocomposite gel for three-dimensional cell culture. Nat Nanotechnol, 2008, 3: 671–675
Pek YS, Wan ACA, Ying JY. The effect of matrix stiffness on mesenchymal stem cell differentiation in a 3D thixotropic gel. Biomaterials, 2010, 31: 385–391
Fang WW, Sun ZM, Tu T. Novel supramolecular thixotropic metallohydrogels consisting of rare metal-organic nanoparticles: synthesis, characterization, and mechanism of aggregation. J Phys Chem C, 2013, 117: 25185–25194
Hoshizawa H, Minemura Y, Yoshikawa K, Suzuki M, Hanabusa K. Thixotropic hydrogelators based on a cyclo(dipeptide) derivative. Langmuir, 2013, 29: 14666–14673
Nanda J, Biswas A, Banerjee A. Single amino acid based thixotropic hydrogel formation and pH-dependent morphological change of gel nanofibers. Soft Matter, 2013, 9: 4198–4208
Xu ZY, Peng JX, Yan N, Yu H, Zhang SS, Liu KQ, Fang Y. Simple design but marvelous performances: molecular gels of superior strength and self-healing properties. Soft Matter, 2013, 9: 1091–1099
Sawant PD, Liu XY. Formation and novel thermomechanical processing of biocompatible soft materials. Chem Mater, 2002, 14: 3793–3798
Weng ZY, Gao YP, Zhang JK, Dong XW, Liu T. Synthesis and biological evaluation of novel n-[3-(4-phenylpip-erazin-1-yl)-propyl]-carboxamide derivatives. J Chem Res, 2011, 35: 43–46
Yan JL, Liu J, Sun YH, Jing P, He PL, Gao D, and Fang Y. Oligo(FcDC-co-CholDEA) with ferrocene in the main chain and cholesterol as a pendant group: preparation and unusual properties. J Phys Chem B, 2010, 114: 13116–13120
Tamaki M, Han GX, Hruby VJ. Practical and efficient synthesis of orthogonally protected constrained 4-guanidinoprolines. J Org Chem, 2001, 66: 1038–1042
Li YG, Liu KQ, Liu J, Peng JX, Feng XL, Fang Y. Amino acid derivatives of cholesterol as “latent” organogelators with hydrogen chloride as a protonation reagent. Langmuir, 2006, 22: 7016–7020
Yu GC, Yan XZ, Han CY, Huang FH. Characterization of supramolecular gels. Chem Soc Rev, 2013, 42: 6697–6722
Yang M, Zhang Z, Yuan F, Wang W, Hess S, Lienkamp K, Lieberwirth I, Wegner G. Self-assembled structures in organogels of amphiphilic diblock codendrimers. Chem Eur J, 2008, 14: 3330–3337
Nebot VJ, Armengol J, Smets J, Prieto SF, Escuder B, Miravet JF. Molecular hydrogels from bolaform amino acid derivatives: a structure-properties study based on the thermodynamics of gel solubilization. Chem Eur J, 2012, 18: 4063–4072
Author information
Authors and Affiliations
Corresponding author
Electronic supplementary material
Rights and permissions
About this article
Cite this article
Hu, B., Liu, K., Chen, X. et al. Preparation of a scorpion-shaped di-NBD derivative of cholesterol and its thixotropic property. Sci. China Chem. 57, 1544–1551 (2014). https://doi.org/10.1007/s11426-014-5135-6
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11426-014-5135-6