Skip to main content
SpringerLink
Log in

Hydrolysis extraction of diosgenin from Dioscorea nipponica Makino by sulfonated magnetic solid composites

  • Research Paper
  • Published:
Journal of Nanoparticle Research Aims and scope Submit manuscript

Abstract

Extraction of diosgenin from the rhizome of Dioscorea by catalytic hydrolysis over recyclable solid acids is one of the most enviromentally friendly ways for the conversion of biomass into chemicals. In this paper, a magnetic solid acid, Fe3O4@SiO2@NH-(CH2)2-NH2@SO3H with the particle size of about 80 nm, was synthesized by using Fe3O4 (~ 20 nm) as a magnetic core and then coated orderly with tetraethyl orthosilicate (TEOS) and N-{3-(Trimethoxysilyl) propyl} ethylenediamine (TMPED) by sol-gel reactions in water/ethanol solution, followed by the sulfonation of chlorosulfonic acid. The solid acid was characterized by Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), scanning electron microscope (SEM), X-ray diffraction (XRD), vibrating sample magnetometer (VSM), and X-ray photoelectron spectroscopy (XPS). The content of acidic sites on the surface of the solid acid was 1.01 mmol/g, measured by back titration method. The prepared solid acid was used to hydrolyze and extract diosgenin from Dioscorea nipponica Makino (DNM). The results show that the magnetic solid acid has higher hydrolysis activity than 2.5 M hydrochloric acid under same hydrolysis conditions, at 110 °C for 5 h. In addition, the magnetic solid acid can be easily separated from the reaction mixture by the application of a magnet and reused several times without significant activity loss. This work has a potential application value for the extraction of diosgenin from plants.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Scheme 1
Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8

Similar content being viewed by others

References

  • Afradi M, Foroughifar N, Pasdar H, Moghanian H (2016) L-proline N-sulfonic acid-functionalized magnetic nanoparticles: a novel and magnetically reusable catalyst for one-pot synthesis of 3,4-dihydropyrimidine-2-(1H)-thiones under solvent-free conditions. RSC Adv 6:59343–59351

    CAS  Google Scholar 

  • Alemi-Tameh F, Safaei-Ghomi J, Mahmoudi-Hashemi M, Teymuri R (2016) A comparative study on the catalytic activity of Fe3O4@SiO2–SO3H and Fe3O4@SiO2–NH2 nanoparticles for the synthesis of spiro [chromeno [2, 3-c] pyrazole-4, 3′-indoline]-diones under mild conditions. Res Chem Intermediat 42:6391–6406

    CAS  Google Scholar 

  • Che YL, Xu Y, Wang RJ, Chen L (2017) Rapid fluorescence detection of pathogenic bacteria using magnetic enrichment technique combined with magnetophoretic chromatography. Anal Bioanal Chem 409:4709–4718

    CAS  Google Scholar 

  • Deng YH, Cai Y, Sun ZK, Liu J, Liu C, Wei J, Li W, Liu C, Wang Y, Zhao DY (2010) Multifunctional mesoporous composite microspheres with well-designed nanostructure: a highly integrated catalyst system. J Am Chem Soc 132:8466–8473

    CAS  Google Scholar 

  • Elhamifar D, Ramazani Z, Norouzi M, Mirbagheri R (2018) Magnetic iron oxide/phenylsulfonic acid: a novel, efficient and recoverable nanocatalyst for green synthesis of tetrahydrobenzo[b]pyrans under ultrasonic conditions. J Colloid Interf Sci 511:392–401

    CAS  Google Scholar 

  • Elsayed I, Mashaly M, Eltaweel F, Jackson MA, Hassan EB (2018) Dehydration of glucose to 5-hydroxymethylfurfural by a core-shell Fe3O4@SiO2-SO3H magnetic nanoparticle catalyst. Fuel 221:407–416

    CAS  Google Scholar 

  • Fan Z, Zhou L, Xiong TQ, Zhou JS, Li QG, Tan QL, Zhao ZX, Jin J (2015) Antiplatelet aggregation triterpene saponins from the barks of Ilex rotunda. Fitoterapia 101:19–26

    CAS  Google Scholar 

  • Gill CS, Price BA, Jones CW (2007) Sulfonic acid-functionalized silica-coated magnetic nanoparticle catalysts. J Catal 251:145–152

    CAS  Google Scholar 

  • Hu L, Li Z, Wu Z, Lin L, Zhou SY (2016) Catalytic hydrolysis of microcrystalline and rice straw-derived cellulose over a chlorine-doped magnetic carbonaceous solid acid. Ind Crop Prod 84:408–417

    CAS  Google Scholar 

  • Karami K, Najvani SD, Naeini NH, Hervés P (2015) Palladium particles from oxime-derived palladacycle supported on Fe3O4/oleic acid as a catalyst for the copper-free Sonogashira cross-coupling reaction. Chinese J Catal 36:1047–1053

    CAS  Google Scholar 

  • Khorshidi A, Shariati S (2015) Efficient synthesis of 3,3′-bisindoles catalyzed by Fe3O4@MCM-48-OSO3H magnetic core-shell nanoparticles. Chinese J Catal 36:778–784

    CAS  Google Scholar 

  • Koukabi N, Kolvari E, Zolfigol MA, Khazaei A, Shaghasemi BS, Fasahati B (2012) A magnetic particle-supported sulfonic acid catalyst: tuning catalytic activity between homogeneous and heterogeneous catalysis. Adv Synth Catal 354:2001–2008

    CAS  Google Scholar 

  • Lai DM, Deng L, Guo QX, Fu Y (2011a) Hydrolysis of biomass by magnetic solid acid. Energy Environ Sci 4:3552–3557

    CAS  Google Scholar 

  • Lai DM, Deng L, Li J, Liao B, Guo QX, Fu Y (2011b) Hydrolysis of cellulose into glucose by magnetic solid acid. ChemSusChem 4:55–58

    CAS  Google Scholar 

  • Lei L, Zhang W, Gao ZC, Liu L, Yu XD (2018) Preparation of diosgenin from Dioscorea zingiberensis C. H. Wright by stepwise biocatalysis-foam separation-preparative high-performance liquid chromatography (P-HPLC) European Food Research and Technology 244:1447–1452

    CAS  Google Scholar 

  • Le X, Dong ZP, Liu YS, Jin ZC, Huy TD, Le M, Ma JT (2014) Palladium nanoparticles immobilized on core–shell magnetic fibers as a highly efficient and recyclable heterogeneous catalyst for the reduction of 4-nitrophenol and Suzuki coupling reactions. J Mater Chem A 2:19696–19706

    CAS  Google Scholar 

  • Li JQ, Liang XZ (2017) Magnetic solid acid catalyst for biodiesel synthesis from waste oil. Energ Convers Manag 141:126–132

    CAS  Google Scholar 

  • Li PQ, Mou Y, Lu SQ, Sun WB, Lou JF, Yin CH, Zhou LG (2012) Quantitative determination of diosgenin in Dioscorea zingiberensis cell cultures by microplate-spectrophotometry and high-performance liquid chromatography. Afr J Pharm Pharmaco 6:1186–1193

    CAS  Google Scholar 

  • Maleki A, Hajizadeh Z, Firouzi-Haji R (2018) Eco-friendly functionalization of magnetic halloysite nanotube with SO3H for synthesis of dihydropyrimidinones. Micropor Mesopor Mat 259:46–53

    CAS  Google Scholar 

  • Man SL, Gao WY, Zhang YJ, Huang LQ, Liu CX (2010) Chemical study and medical application of saponins as anti-cancer agents. Fitoterapia 81:703–714

    CAS  Google Scholar 

  • Mirfakhraei S, Hekmati M, Eshbala FH, Veisi H (2018) Fe3O4/PEG-SO3H as a heterogeneous and magnetically-recyclable nanocatalyst for the oxidation of sulfides to sulfones or sulfoxides. New J Chem 42:1757–1761

    CAS  Google Scholar 

  • Mirhosseyni MS, Nemati F, Elhampour A (2016) Hollow Fe3O4@DA-SO3H: an efficient and reusable heterogeneous nano-magnetic acid catalyst for synthesis of dihydropyridine and dioxodecahydroacridine derivatives. J Iran Chem Soc 14:791–801

    Google Scholar 

  • Mohammadi R, Kassaee MZ (2013) Sulfochitosan encapsulated nano-Fe3O4 as an efficient and reusable magnetic catalyst for green synthesis of 2-amino-4H-chromen-4-yl phosphonates. J Mol Catal A Chem 380:152–158

    CAS  Google Scholar 

  • Moses T, Papadopoulou KK, Osbourn A (2014) Metabolic and functional diversity of saponins, biosynthetic intermediates and semi-synthetic derivatives. Crit Rev Biochem Mol Biol 49:439–462

    CAS  Google Scholar 

  • Mukherjee S, Sarkar S, Pramanik A (2018) A sustainable synthesis of functionalized pyrrole fused coumarins under solvent-free conditions using magnetic nanocatalyst and a new route to Polyaromatic Indolocoumarins. ChemistrySelect 3:1537–1544

    CAS  Google Scholar 

  • Nasr-Esfahani M, Rafiee Z, Montazerozohori M, Kashi H (2016) A highly efficient magnetic solid acid nanocatalyst for the synthesis of new bulky heterocyclic compounds. RSC Adv 6:47298–47313

    CAS  Google Scholar 

  • Pang X, Huang HZ, Zhao Y, Xiong CQ, Yu LY, Ma BP (2015) Conversion of furostanol saponins into spirostanol saponins improves the yield of diosgenin from Dioscorea zingiberensis by acid hydrolysis. RSC Adv 5:4831–4837

    CAS  Google Scholar 

  • Peng YE, Yang ZH, Wang YX, Liu ZY, Bao JG, Hong Y (2011) Pathways for the steroidal saponins conversion to diosgenin during acid hydrolysis of Dioscorea zingiberensis C. H Wright Chem Eng Res Des 89:2620–2625

    CAS  Google Scholar 

  • Rajkumari K, Kalita J, Das D, Rokhum L (2017) Magnetic Fe3O4@silica sulfuric acid nanoparticles promoted regioselective protection/deprotection of alcohols with dihydropyran under solvent-free conditions. RSC Adv 7:56559–56565

    CAS  Google Scholar 

  • Rothrock JW, Stoudt TH, Garber JD (1955) Isolation of diosgenin by microbiological hydrolysis of saponin. Arch Biochem Biophys 57:151–155

    CAS  Google Scholar 

  • Shang MY, Wang WQ, Zou HZ, Ren GH (2016) Coating Fe3O4 spheres with polypyrrole-Pd composites and their application as recyclable catalysts. Synthetic Met 221:142–148

    CAS  Google Scholar 

  • Shao JG, Xie XC, Xi YJ, Liu XN, Yang YX (2013) Characterization of Fe3O4/SiO2 composite core-shell nanoparticles synthesized in isopropanol medium. Glas Phys Chem 39:329–335

    CAS  Google Scholar 

  • Shariati S, Faraji M, Yamini Y, Rajabi AA (2011) Fe3O4 magnetic nanoparticles modified with sodium dodecyl sulfate for removal of safranin O dye from aqueous solutions. Desalination 270:160–165

    CAS  Google Scholar 

  • Sun LJ, He J, An SS, Zhang JW, Zheng JM, Ren D (2013) Recyclable Fe3O4@SiO2-Ag magnetic nanospheres for the rapid decolorizing of dye pollutants. Chinese J Catal 34:1378–1385

    CAS  Google Scholar 

  • Taheri S, Veisi H, Hekmati M (2017) Application of polydopamine sulfamic acid-functionalized magnetic Fe3O4 nanoparticles (Fe3O4@PDA-SO3H) as a heterogeneous and recyclable nanocatalyst for the formylation of alcohols and amines under solvent-free conditions. New J Chem 41:5075–5081

    CAS  Google Scholar 

  • Tava A, Biazzi E, Mella M, Quadrelli P, Avato P (2017) Artefact formation during acid hydrolysis of saponins from Medicago spp. Phytochemistry 138:116–127

    CAS  Google Scholar 

  • Thombal RS, Jadhav VH (2016a) Application of glucose derived magnetic solid acid for etherification of 5-HMF to 5-EMF, dehydration of sorbitol to isosorbide, and esterification of fatty acids. Tetrahedron Lett 57:4398–4400

    CAS  Google Scholar 

  • Thombal RS, Jadhav VH (2016b) Facile O-glycosylation of glycals using Glu-Fe3O4-SO3H, a magnetic solid acid catalyst. RSC Adv 6:30846–30851

    CAS  Google Scholar 

  • Wang JR, Yau LF, Gao WN, Liu Y, Yick PW, Liu L, Jiang ZH (2014b) Quantitative comparison and metabolite profiling of saponins in different parts of the root of Panax notoginseng. J Agric Food Chem 62:9024–9034

    CAS  Google Scholar 

  • Wang J, Yang KD, Chen J (2004) Determination of Diosgenin by spectrophotometry. Chinese J Anal Lab 23:73–75

    Google Scholar 

  • Wang P, Ma CY, Chen SW, Zhu S, Lou ZX, Wang HX (2014) Conversion of steroid saponins into diosgenin by catalytic hydrolysis using acid-functionalized ionic liquid under microwave irradiation. J Clean Prod 79:265–270

    CAS  Google Scholar 

  • Wang YQ, Zou BF, Gao T, Wu XP, Lou SY, Zhou SM (2012) Synthesis of orange-like Fe3O4/PPy composite microspheres and their excellent Cr(vi) ion removal properties. J Mater Chem 22:9034–9040

    CAS  Google Scholar 

  • Xiong Y, Zhang ZH, Wang X, Liu B, Lin JT (2014) Hydrolysis of cellulose in ionic liquids catalyzed by a magnetically-recoverable solid acid catalyst. Chem Eng J 235:349–355

    CAS  Google Scholar 

  • Yang H, Yin HW, Shen YP, Xia GH, Zhang B, Wu XY, Cai BC, Tam JP (2016) A more ecological and efficient approach for producing diosgenin from Dioscorea zingiberensis tubers via pressurized biphase acid hydrolysis. J Clean Prod 131:10–19

    CAS  Google Scholar 

  • Yan W, Ji L, Hang S, Shun Y (2013) New ionic liquid-based preparative method for diosgenin from Rhizoma dioscoreae nipponicae. Pharmacogn Mag 9:250–254

    CAS  Google Scholar 

  • Yu CJ, Li ZH, Yin HW, Xia GH, Shen YP, Yang H, Jing G, Jia XB (2019) Green production of diosgenin from Discorea nipponica Makino tubers based on pressurized biphase acid hydrolysis via response surface methodology optimization. Green Chem Lett Rev 12:79–88

    CAS  Google Scholar 

  • Zhang CB, Wang HY, Liu FD, Wang L, He H (2013) Magnetic core–shell Fe3O4@C-SO3H nanoparticle catalyst for hydrolysis of cellulose. Cellulose 20:127–134

    CAS  Google Scholar 

  • Zhou JJ, Li YN, Sun HB, Tang ZK, Qi L, Liu L, Ai YJ, Li S, Shao ZX, Liang QL (2017) Porous silica-encapsulated and magnetically recoverable Rh NPs: a highly efficient, stable and green catalyst for catalytic transfer hydrogenation with “slow-release” of stoichiometric hydrazine in water. Green Chem 19:1–7

    Google Scholar 

Download references

Funding

This work was financially supported by Hubei provincial science and technology department (2018ACA158) and the tenth postgraduate education innovation fund of Wuhan Institute of Technology, China (CX2018156).

Author information

Authors and Affiliations

  1. College of Chemistry and Environmental Technology, Wuhan Institute of Technology, Wuhan, 430073, China

    Farong Zhang, Bowei Shen, Wenxiu Jiang, Hui Yuan & Hong Zhou

Authors
  1. Farong Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Bowei Shen
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Wenxiu Jiang
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Hui Yuan
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Hong Zhou
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Hong Zhou.

Ethics declarations

Conflict of interest

The authors declare that they have no conflict of interest.

Additional information

Publisher’s note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Electronic supplementary material

ESM 1

(DOCX 953 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Zhang, F., Shen, B., Jiang, W. et al. Hydrolysis extraction of diosgenin from Dioscorea nipponica Makino by sulfonated magnetic solid composites. J Nanopart Res 21, 269 (2019). https://doi.org/10.1007/s11051-019-4702-3

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s11051-019-4702-3

Keywords

Search

Navigation