Kinetic and isotherm studies of saffron crocin Extraction using 3D graphene oxide-chitosan nanocomposite

Document Type : Complete scientific research article

Authors

1 1Department of Food Materials and Process Design Engineering, Faculty of Food Science, Gorgan University of Agricultural Sciences and Natural Resources, Gorgan, Iran.

2 2 Department of Food Materials and Process Design Engineering, Faculty of Food Science, Gorgan University of Agricultural Sciences and Natural Resources, Gorgan, Iran,

3 3Department of Food Chemistry, Gorgan University of Agricultural Sciences and Natural Resources, Faculty of Food Science, Gorgan University of Agricultural Sciences and Natural Resources, Gorgan, Iran.

4 Department of Food Chemistry, Research Institute of Food Science and Technology, Mashhad, Iran.

5 Pharmaceutical Research Center, School of Pharmacy, Mashhad University of Medical Sciences, Mashhad, Iran.

Abstract

Kinetic and isotherm studies of saffron crocin Extraction using 3D graphene oxide-chitosan nanocomposite
Background and objectives: saffron as the most expensive spice in the world contains compounds called crocins that grant it unique properties. Extraction and purification of this glycosidic compound is one of the major challenges in saffron processing. Graphene oxide (GO) is an excellent adsorbent due to its properties such as flat structure, high surface area, variety of oxygenated functional groups on the surface and the ease and cheapness of its production from graphite. Therefore, in this study, the extraction and purification of saffron crocins were evaluated using 3D nanostructure of GO modified with chitosan biopolymer.
Materials and methods: Graphene oxide synthesis was conducted through improved Hummers method followed by modification with chitosan. 15 ml of crocin solution with different concentration (25, 50, 100 and 200 mg/ml) was mixed with 15mg of nanostructure and under controlled conditions (temperature, pH and stiring rate). In certain intervals (0-200 min), the amount of crocin in solution was determined through reading its absorption at 440 nm. Kinetics (pseudo first and second order models) and isotherms (Langmuir, Freundlich and Dubinin-Radushkevich isotherms) studies of process was investigated. The efficiency of nanostructure in crocin purification was assessed by HPLC at three wavelength of 250, 310 and 440 nm. In order to assess the ability of nanostructure in separation and purification of crocin, saffron extract was used. In order to remove picrocrocin and safranal, dried stigma of saffron was treated in two stages and then extraction was performed using distilled water. The nanostructure was washed with methanol and the extract injected to HPLC.
Results: The best process conditions for crocin isolation were stirring speed = 300 rpm, temperature of 318 K, concentration of 100 mg/l and normal pH of saffron extract. Crocin adsorption was a physiosorption process and followed the pseudo-second-order model and the Freundlich isotherm. HPLC results showed that the purity of the isolated crocin was high and very close to the standard sample.
Conclusion: Instrumental analysis confirmed the formation of graphene oxide/chitosan nanostructures. The effect of process variables including pH, temperature, stirring speed and crocin solution concentration on the separation process efficiency was determined. The adsorption process of crocin on the nanostructures followed a pseudo-second-order model and the adsorption was physical. The results of this study showed that synthesized nanostructures can be well used in the purification process of valuable compounds.
Keywords: Saffron, crocin, purification, graphene oxide/chitosan nanostructure, isotherm.

Keywords


  1. Ai, L., Li, M., and Li, L. 2011. Adsorption of methylene blue from aqueous solution with activated carbon/cobalt ferrite/alginate composite beads: kinetics, isotherms, and thermodynamics. Journal of Chemical & Engineering Data. 56:8.3475-3483.
  2. Amin, B., and Hosseinzadeh, H. 2012. Evaluation of aqueous and ethanolic extracts of saffron, Crocus sativus L., and its constituents, safranal and crocin in allodynia and hyperalgesia induced by chronic constriction injury model of neuropathic pain in rats. Fitoterapia. 83:5.888-895.
  3. Chen, Z., Liu, Y., Fang, L., Jiang, P., and Huang, X. 2019. Role of reduced graphene oxide in dielectric enhancement of ferroelectric polymers composites. Applied Surface Science. 470:3.48-359.
  4. Emadi, F., Amini, A., Gholami, A., and Ghasemi, Y. 2017. Functionalized graphene oxide with chitosan for protein nanocarriers to protect against enzymatic cleavage and retain collagenase activity. Scientific reports. 7: 1.1-13,
  5. Ferrara, L., Naviglio, D., and Gallo, M. 2014. Extraction of bioactive compounds of saffron (Crocus sativus L.) by ultrasound assisted extraction (UAE) and by rapid solid-liquid dynamic extraction (RSLDE). European Scientific Journal. 10:3.
  6. Hadizadeh, F., Mohajeri, S.A., and Seifi, M. 2010. Extraction and purification of crocin from saffron stigmas employing a simple and efficient crystallization method. Pakistan Journal of Biological Sciences. 13:14.691.
  7. Han, D., Yan, L., Chen, W., and Li, W. 2011. Preparation of chitosan/graphene oxide composite film with enhanced mechanical strength in the wet state. Carbohydrate Polymers 83:2.653-658.
  8. Huong, P.T.L., Tu, N., Lan, H., Van Quy, N., Tuan, P.A., Dinh, N.X., Phan, V.N., and Le, A.T. 2018. Functional manganese ferrite/graphene oxide nanocomposites: effects of graphene oxide on the adsorption mechanisms of organic MB dye and inorganic As (v) ions from aqueous solution. RSC advances. 8:22.12376-12389.
  9. Kumar, S., and Koh, J. 2014. Physiochemical and optical properties of chitosan based graphene oxide bionanocomposite. International journal of biological macromolecules. 70.559-564.
  10. Li, P., Gao, Y., Sun, Z., Chang, D., Gao, G., and Dong, A. 2017. Synthesis, characterization, and bactericidal evaluation of chitosan/guanidine functionalized graphene oxide composites. Molecules. 22:1.12.
  11. Majidi, H.J., Babaei, A., Bafrani, Z.A., Shahrampour, D., Zabihi, E., and Jafari, S.M. 2019. Investigating the best strategy to diminish the toxicity and enhance the antibacterial activity of graphene oxide by chitosan addition. Carbohydrate polymers. 225.115220.
  12. Majidi, H.J., Mirzaee, A., Jafari, S.M., Amiri, M., Shahrousvand, M., and Babaei, A. 2019. Fabrication and characterization of graphene oxide-chitosan-zinc oxide ternary nano-hybrids for the corrosion inhibition of mild steel. International journal of biological macromolecules. 148.1190-1200
  13. Marcano, D.C., Kosynkin, D.V., Berlin, J.M., Sinitskii, A., Sun, Z., Slesarev, A., Alemany, L.B., Lu, W., and Tour, J.M. 2010. Improved synthesis of graphene oxide. ACS nano. 4:8.4806-4814.
  14. Mohajeri, S.A., Hosseinzadeh, H., Keyhanfar, F., and Aghamohammadian, J. 2010. Extraction of crocin from saffron (Crocus sativus) using molecularly imprinted polymer solid‐phase extraction. Journal of separation science. 33:15:2302-2309.
  15. Montalvo-Hernández, B., Rito-Palomares, M., and Benavides, J. 2012. Recovery of crocins from saffron stigmas (Crocus sativus) in aqueous two-phase systems. Journal of Chromatography A. 1236.7-15.
  16. Oribayo, O., Feng, X., Rempel, G.L., and Pan, Q. 2017. Synthesis of lignin-based polyurethane/graphene oxide foam and its application as an absorbent for oil spill clean-ups and recovery. Chemical Engineering Journal. 323.191-202.
  17. Pham, V.H., Dang, T.T., Hur, S.H., Kim, E.J., and Chung, J.S. 2012. Highly conductive poly (methyl methacrylate) (PMMA) -reduced graphene oxide composite prepared by self-assembly of PMMA latex and graphene oxide through electrostatic interaction. ACS applied materials & interfaces. 4:5.2630-2636.
  18. Posudievsky, O.Y., Khazieieva, O.A., Koshechko, V.G., and Pokhodenko, V.D. 2012. Preparation of graphene oxide by solvent-free mechanochemical oxidation of graphite. Journal of Materials Chemistry. 22:25.12465-12467.
  19. Rajabi, H., Ghorbani, M., Jafari, S.M., Mahoonak, A.S., and Rajabzadeh, G. 2015. Retention of saffron bioactive components by spray drying encapsulation using maltodextrin, gum Arabic and gelatin as wall materials. Food hydrocolloids. 51.327-337.
  20. Sabzevari, M., Cree, D.E., and Wilson, L.D. 2018. Graphene oxide–chitosan composite material for treatment of a model dye effluent. ACS omega. 3:10.13045-13054.
  21. Sarfarazi, M., Jafari, S.M., Rajabzadeh, G., and Feizi, J. 2019. Development of an environmentally-friendly solvent-free extraction of saffron bioactives using subcritical water. LWT. 114.108428.
  22. Shahzad, A., Miran, W., Rasool, K., Nawaz, M., Jang, J., Lim, S.R., and Lee, D.S. 2017. Heavy metals removal by EDTA-functionalized chitosan graphene oxide nanocomposites. RSC advances. 7:16.9764-9771.
  23. Sui, Z.Y., Cui, Y., Zhu, J.H. and Han, B.H., 2013. Preparation of three-dimensional graphene oxide–polyethylenimine porous materials as dye and gas adsorbents. ACS applied materials & interfaces. 5:18.9172-9179.
  24. Wang, C., Feng, L., Yang, H., Xin, G., Li, W., Zheng, J., Tian, W., and Li, X. 2012. Graphene oxide stabilized polyethylene glycol for heat storage. Physical Chemistry Chemical Physics. 14:38.13233-13238.
  25. Wang, Q., Yang, L., Jia, F., Li, Y., and Song, S. 2018. Removal of Cd (II) from water by using nano-scale molybdenum disulphide sheets as adsorbents. Journal of Molecular Liquids. 263.526-533.
  26. Xu, J., Li, S., Wang, F., Yang, Z., and Liu, H. 2019. Efficient and enhanced adsorption of methylene blue on triethanolamine-modified graphene oxide. Journal of Chemical & Engineering Data. 64:4.1816-1825.
  27. Yadav, M., and Ahmad, S. 2015. Montmorillonite/graphene oxide/chitosan composite: Synthesis, characterization and properties. International journal of biological macromolecules. 79.923-933.
  28. Yang, A., Zhu, Y., and Huang, C.P. 2018. Facile preparation and adsorption performance of graphene oxide-manganese oxide composite for uranium. Scientific reports. 8:1.1-10.
  29. Yang, S.T., Chen, S., Chang, Y., Cao, A., Liu, Y., and Wang, H. 2011. Removal of methylene blue from aqueous solution by graphene oxide. Journal of colloid and interface science. 359:1.24-29.
  30. Yang, X., Tu, Y., Li, L., Shang, S., and Tao, X.M. 2010. Well-dispersed chitosan/graphene oxide nanocomposites. ACS applied materials & interfaces. 2:6.1707-1713.
  31. Zabihi, E., Babaei, A., Shahrampour, D., Arab-Bafrani, Z., Mirshahidi, K.S., and Majidi, H.J. 2019. Facile and rapid in-situ synthesis of chitosan-ZnO nano-hybrids applicable in medical purposes; a novel combination of biomineralization, ultrasound, and bio-safe morphology-conducting agent. International journal of biological macromolecules. 131.107-116.
  32. Zhang, H., Zeng, Y., Yan, F., Chen, F., Zhang, X., Liu, M., and Liu, W. 2004. Semi-preparative isolation of crocins from saffron (Crocus sativus L.). Chromatographia. 59:11-12.691-696.