Multi-Stimuli-Responsive Organogel Based on Bisthiourea Compounds for The Removal of Selected Organic Dyes
Abstract
The self-assembly of a series of bisthiourea containing amino acid side chains has been studied in a large range of organic solvents. Self-assembly is driven mainly by hydrogen bonding groups of thiourea and amino acids moieties. Of all the synthesized compounds, only bisthiourea with alanine side chains, 3.5 formed thermoreversible gel in 50:3 dichloromethane:water mixture at minimum gel concentration of 0.5%. SEM micrographs of the gel showed the formation of entangled cross-linked fibres. The addition of anions such as Cl¯, F¯ and AcO¯ disrupted the gel network of 3.5 thus inducing the gel-sol transition. To investigate the ability of the bisthiourea to form metallogel, metal ions such as Co2+, Cu2+, Ni2+ and Pb2+ were introduced, however, none of them induce the formation of metallogel. In particular, the gels show good performance in the absorption of bromocresol green and Eriochrome black-T at 75% and 61% efficiency, respectively within 24 hours. The good dye absorption properties of gel 3.5 render the potential of bisthiourea gels as new dye absorption materials, which show significant benefit for water pollution treatment.
References
Bachl, J., Sampedro, D., Mayr, J. & Diaz Diaz, D. (2017). Ultrasonication-enhanced gelation properties of a versatile amphiphilic formamidine-based gelator exhibiting both organogelation and hydrogelation abilities. Physical Chemistry Chemical Physics, 19(34): 22981-22994.
https://doi.org/10.1039/C7CP03529B
Baddi, S., Madugula, S.S., Sarma, D.S., Soujanya, Y. & Palanisamy, A. (2015). Combined experimental and computational study of the gelation of cyclohexane-based bis(acyl-semicarbazides) and the multi-stimuli-responsive properties of their gels. Langmuir, 32(3): 889-899.
https://doi.org/10.1021/acs.langmuir.5b03987
Bai, B., Mao, X., Wei, J., Wei, Z., Wang, H. & Li, M. (2015). Selective anion-responsive organogel based on a gelator containing hydrazide and azobenzene units. Sensors and Actuators B: Chemical, 211: 268-274.
https://doi.org/10.1016/j.snb.2015.01.111
Blažek Bregović, V., Basarić, N. & Mlinarić-Majerski, K. (2015). Anion binding with urea and thiourea derivatives. Coordination Chemistry Reviews, 295: 80-124.
https://doi.org/10.1016/j.ccr.2015.03.011
Cao, X., Zhao, N., Lv, H., Gao, A., Shi, A., & Wu, Y. (2018). 4-Nitrobenzene thiourea self-assembly system and its transformation upon addition of Hg2+ ion: Applications as sensor to fluoride ion. Sensors and Actuators, B: Chemical, 266: 637-644.
https://doi.org/10.1016/j.snb.2018.03.188
Cheng, N., Kang, Q., Xiao, J., Du, N. & Yu, L. (2018). Supramolecular gels: using an amide-functionalized imidazolium-based surfactant. Journal of Colloid and Interface Science, 511: 215-221.
https://doi.org/10.1016/j.jcis.2017.10.009
Chetia, M., Debnath, S., Chowdhury, S. & Chatterjee, S. (2020). Self-assembly and multifunctionality of peptide organogels: Oil spill recovery, dye absorption and synthesis of conducting biomaterials. RSC Advances, 10(9): 5220-5233.
https://doi.org/10.1039/C9RA10395C
Christoff-tempesta, T., Lew, A. & Ortony, J. (2018). Beyond Covalent Crosslinks: Applications of Supramolecular Gels. Gels, 4(2): 1-40.
https://doi.org/10.3390/gels4020040
Dastidar, P., Ganguly, S. & Sarkar, K. (2016). Metallogels from Coordination Complexes, Organometallic, and Coordination Polymers. Chemistry - An Asian Journal, 11(18): 2484-2498.
https://doi.org/10.1002/asia.201600814
De, A. & Mondal, R. (2018). Toxic Metal Sequestration exploiting an unprecedented low-molecular-weight hydrogel-to metallogel transformation. ACS Omega, 3(6): 6022-6030.
https://doi.org/10.1021/acsomega.8b00758
Fakhar, I.M., Yamin, B. & Hasbullah, S.A. (2016). Synthesis and characterization of bis-thiourea having amino acid derivatives. American Institute of Physics, 1784(1): 1-7.
https://doi.org/10.1063/1.4966750
Ha, S., Lee, J., Kim, K.S., Choi, E. J., Nhem, P. & Song, C. (2019). Anion-responsive thiourea-based gel actuator. Chemistry of Materials, 31(15): 5735-5741.
https://doi.org/10.1021/acs.chemmater.9b01715
Han, L., He, Y., An, R., Wang, X., Zhang, Y., Shi, L. & Ran, R. (2019). Mussel-inspired, robust and self-healing nanocomposite hydrogels: Effective reusable absorbents for removal both anionic and cationic dyes. Colloids and Surfaces A, 569: 18-27.
https://doi.org/10.1016/j.colsurfa.2019.02.054
Hooper, A.E., Kennedy, S.R., Jones, C.D. & Steed, J.W. (2016). Gelation by supramolecular dimerization of mono(urea)s. Chemical Communications, 52(1): 198-201.
https://doi.org/10.1039/C5CC06995E
Khan, I., Ur Rahman, N., Ali, A. & Saeed, K. (2019). Adsorption of cobalt onto activated charcoal and its utilization for decolorization of bromocresol green dye. Bulgarian Chemical Communications, 51(4): 488-493.
Kyzas, G. Z., Siafaka, P. I. Pavlidou, E. G., Chrissafis, K. J., & Bikiaris, D. N. (2015). Synthesis and adsorption application of succinyl-grafted chitosan for the simultaneous removal of zinc and cationic dye from binary hazardous mixtures. Chemical Engineering Journal, 259: 438-448.
https://doi.org/10.1016/j.cej.2014.08.019
Li, L., Zhou, N., Kong, H. & He, X. (2019). Controlling the supramolecular polymerization and metallogel formation of Pt(II) complexes via delicate tuning of non-covalent interactions. Polymer Chemistry, 10(40): 5465-5472.
https://doi.org/10.1039/C9PY01299K
Liu, J., Xu, F., Sun, Z., Pan, Y., Tian, J., Lin, H.C. & Li, X. (2016). A supramolecular gel based on a glycosylated amino acid derivative with the properties of gel to crystal transition. Soft Matter, 12(1): 141-148.
https://doi.org/10.1039/C5SM02111A
Liu, Y., Wang, Y., Jin, L., Chen, T. & Yin, B. (2016). MPTTF-containing tripeptide- based organo gels: receptor for 2,4,6-trinitrophenol and multiple stimuli-responsive properties. Soft Matter, 12(3): 934-945.
https://doi.org/10.1039/C5SM02462E
Mondal, S. & Dastidar, P. (2018). Mixed ligand coordination polymers for metallogelation and iodine adsorption. Crystal Growth and Design, 19(1): 470-478.
https://doi.org/10.1021/acs.cgd.8b01547
Okesola, B.O. & Smith, D.K. (2016). Applying low-molecular weight supramolecular gelators in an environmental setting-self-assembled gels as smart materials for pollutant removal. Chemical Society Reviews, 45(15): 4226-4251.
https://doi.org/10.1039/C6CS00124F
Panja, A. & Ghosh, K. (2018). Diaminomalenonitrile -decorated cholesterol -based supra molecular gelator: aggregation, multiple analyte (hydrazine, Hg2+ and Cu2+) detection and dye adsorption. New Journal of Chemistry, 42(16): 13718-13725.
https://doi.org/10.1039/C8NJ02426J
Panja, A., Ghosh, S. & Ghosh, K. (2019). A sulfonyl hydrazine cholesterol conjugate: gelation, anion interaction and its application in dye absorption. New Journal of Chemistry, 42: 10270-10277.
https://doi.org/10.1039/C8NJ05613G
Sengupta, S., Goswami, A. & Mondal, R. (2014). Silver-promoted gelation studies of an unorthodox chelating tripodal pyridine-pyrazole-based ligand: Templated growth of catalytic silver nanoparticles, gas and dye adsorption. New Journal of Chemistry, 38(6): 2470-2479.
https://doi.org/10.1039/c3nj01334k
Staicu, T., Iliş, M., Cîrcu, V. & Micutz, M. (2018). Influence of hydrocarbon moieties of partially fluorinated N-benzoyl thiourea compounds on their gelation properties. A detailed rheological study of complex viscoelastic behavior of decanol/N-benzoyl thiourea mixtures. Journal of Molecular Liquids, 255: 297-312.
https://doi.org/10.1016/j.molliq.2018.01.162
Tatikonda, R., Bhowmik, S., Rissanen, K., Haukka, M. & Cametti, M. (2016). Metallogel formation in aqueous DMSO by perfluoroalkyl decorated terpyridine ligands. Dalton Transactions, 45(32): 12756-12762.
https://doi.org/10.1039/C6DT02008A
Wezenberg, S.J., Croisetu, C.M., Stuart, M.C.A. & Feringa, B.L. (2016). Reversible gel-sol photoswitching with an overcrowded alkene-based bis-urea supergelator. Chemical Science, 7(7): 4341-4346.
https://doi.org/10.1039/C6SC00659K
Yang, Z., Wu, G., Gan, C., Cai, G., Zhang, J. & Ji, H. (2021). Effective adsorption of arsenate, dyes and eugenol from aqueous solutions by cationic supramolecular gel materials. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 616: 126238.
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