Abstract
A magnetically responsive composite was prepared for improved solid-phase extraction of salmon sperm DNA sodium salt. It consists of chitosan-modified Fe3O4-magnetized multi-walled carbon nanotubes coated with a poly(ethylene glycol) based deep eutectic solvent. The sorbent was characterized by X-ray diffraction, vibrating sample magnetometry, Fourier transform infrared spectrometry, thermogravimetric analysis and transmission electron microscopy. The effects of the concentration of DNA, ionic strength, pH value, temperature and extraction time on extraction performance were optimized. Compared to plain Fe3O4, the new sorbent displays a superior DNA extraction capacity of 178 mg·g−1. It also displays favorable selectivity for DNA over bovine hemoglobin. Regeneration studies show that (a) 79% of DNA can be eluted from loaded sorbent by using 1 M NaCl, and that (b) the conformation of DNA remains unchanged as evidenced by CD spectra. The sorbent can be recycled six times without significant loss of extraction capacity. It was applied to the extraction of DNA from bovine whole blood prior to DNA quantitation by agarose gel electrophoresis. The results show this new sorbent to be a viable material for separation of DNA that excels by its low cost, high loading capacity and ease of regeneration.
![](http://media.springernature.com/lw685/springer-static/image/art%3A10.1007%2Fs00604-017-2444-4/MediaObjects/604_2017_2444_Figa_HTML.gif)
Chitosan (CS)-modified magnetic multi-walled carbon nanotubes were coated with a poly(ethylene glycol)-based deep eutectic solvent (DES) to obtain a new material (referred to as DES-mCS/MWCNTs) for solid-phase extraction of DNA. It exhibits excellent magnetic response, high loading capacity and good reusability.
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs00604-017-2444-4/MediaObjects/604_2017_2444_Sch1_HTML.gif)
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs00604-017-2444-4/MediaObjects/604_2017_2444_Fig1_HTML.gif)
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs00604-017-2444-4/MediaObjects/604_2017_2444_Fig2_HTML.gif)
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs00604-017-2444-4/MediaObjects/604_2017_2444_Fig3_HTML.gif)
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs00604-017-2444-4/MediaObjects/604_2017_2444_Fig4_HTML.gif)
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs00604-017-2444-4/MediaObjects/604_2017_2444_Fig5_HTML.gif)
Similar content being viewed by others
References
Demeke T, Jenkins GR (2010) Influence of DNA extraction methods, PCR inhibitors and quantification methods on real-time PCR assay of biotechnology-derived traits. Anal Bioanal Chem 396:1977–1990. doi:10.1007/s00216-009-3150-9
Aziz-Zanjani MO, Mehdinia A (2014) A review on procedures for the preparation of coatings for solid phase microextraction. Microchim Acta 181:1169–1190. doi:10.1007/s00604-014-1265-y
Hu LL, Hu B, Shen LM, Zhang DD, Chen XW, Wang JH (2015) Polyethyleneimine-iron phosphate nanocomposite as a promising adsorbent for the isolation of DNA. Talanta 132:857–863. doi:10.1016/j.talanta.2014.10.047
Iijima S (1991) Helical microtubules of graphitic carbon. Nature 354:56–58. doi:10.1038/354056a0
Yang SX, Wang LY, Zhang XD, Yang WJ, Song GL (2015) Enhanced adsorption of Congo red dye by functionalized carbon nanotube/mixed metal oxides nanocomposites derived from layered double hydroxide precursor. Chem Eng J 275:315–321. doi:10.1016/j.cej.2015.04.049
Chen J, Wang YZ, Huang YH, Xu KJ, Li N, Wen Q, Zhou YG (2015) Magnetic multiwall carbon nanotubes modified with dual hydroxy functional ionic liquid for the solid-phase extraction of protein. Analyst 140:3474–3483. doi:10.1039/c5an00201j
Kumar P, Sengupta A, Deb AKS, Dasgupta K, Ali SM (2016) Sorption behaviour of Pu4+ and PuO2 2+ on amido amine-functionalized carbon nanotubes: experimental and computational study. RSC Adv 6:107011–107020. doi:10.1039/C6RA24184K
Fei B, Lu HF, Hu ZG, **n JH (2006) Solubilization, purification and functionalization of carbon nanotubes using polyoxometalate. Nanotechnology 17:1589. doi:10.1088/0957-4484/17/6/010
Seligra PG, Lamanna M, Famá L (2015) Promising PLA-functionalized MWCNT composites to use in nanotechnology. Polym Compos 37:3066–3072. doi:10.1002/pc.23504
Li LL, Luo CN, Li XJ, Duan HM, Wang XJ (2014) Preparation of magnetic ionic liquid/chitosan/graphene oxide composite and application for water treatment. Int J Biol Macromol 66:172–178. doi:10.1016/j.ijbiomac.2014.02.031
Zhang LF, **a W, Liu X, Zhang WQ (2015) Synthesis of titanium cross-linked chitosan composite for efficient adsorption and detoxification of hexavalent chromium from water. J Mater Chem A 3:331–340. doi:10.1039/c4ta05194g
Rungrotmongkol T, Arsawang U, Iamsamai C, Vongachariya A, Dubas ST, Ruktanonchai U, Soottitantawat A, Hannongbua S (2011) Increased dispersion and solubility of carbon nanotubes noncovalently modified by the polysaccharide biopolymer, chitosan: MD simulations. Chem Phys Lett 507:134–137. doi:10.1016/j.cplett.2011.03.066
Chatterjee S, Lee MW, Woo SH (2010) Adsorption of congo red by chitosan hydrogel beads impregnated with carbon nanotubes. Bioresour Technol 101:1800–1806. doi:10.1016/j.biortech.2009.10.051
Li CY, Yang KQ, Zhang YY, Tang H, Yan F, Tan L, **e QJ, Yao SZ (2011) Highly biocompatible multi-walled carbon nanotube-chitosan nanoparticle hybrids as protein carriers. Acta Biomater 7:3070–3077. doi:10.1016/j.actbio.2011.05.005
Zhan YK, Pan LK, Nie CY, Li HB, Sun Z (2011) Carbon nanotube–chitosan composite electrodes for electrochemical removal of Cu(II) ions. J Alloys Compd 509:5667–5671. doi:10.1016/j.jallcom.2011.02.118
Xu KJ, Wang YZ, Huang YH, Li N, Wen Q (2015) A green deep eutectic solvent-based aqueous two-phase system for protein extracting. Anal Chim Acta 864:9–20. doi:10.1016/j.aca.2015.01.026
Zhang HM, Wang YZ, Xu KJ, Li N, Wen Q, Yang Q, Zhou YG (2016) Ternary and binary deep eutectic solvents as a novel extraction medium for protein partitioning. Anal Methods 8:8196–8207. doi:10.1039/c6ay01860b
Li N, Wang YZ, Xu KJ, Wen Q, Ding XQ, Zhang HM, Yang Q (2016) High-performance of deep eutectic solvent based aqueous bi-phasic systems for the extraction of DNA. RSC Adv 6:84406–84414. doi:10.1039/c6ra17689e
Dai YT, Witkamp GJ, Verpoorte R, Choi YH (2013) Natural deep eutectic solvents as new potential media for green technology. Anal Chim Acta 766:61–68. doi:10.1016/j.aca.2012.12.019
Duan L, Dou LL, Guo L, Li P, Liu EH (2016) Comprehensive evaluation of deep eutectic solvents in extraction of bioactive natural products. ACS Sustain Chem Eng 4:2405–2411. doi:10.1021/acssuschemeng.6b00091
Huang YH, Wang YZ, Pan Q, Wang Y, Ding XQ, Xu KJ, Li N, Wen Q (2015) Magnetic graphene oxide modified with choline chloride-based deep eutectic solvent for the solid-phase extraction of protein. Anal Chim Acta 877:90–99. doi:10.1016/j.aca.2015.03.048
Liu YJ, Wang YZ, Dai QZ, Zhou YG (2016) Magnetic deep eutectic solvents molecularly imprinted polymers for the selective recognition and separation of protein. Anal Chim Acta 936:168–178. doi:10.1016/j.aca.2016.07.003
Zhu HY, Fu YQ, Jiang R, Yao J, Liu L, Chen YW, **ao L, Zeng G (2013) Preparation, characterization and adsorption properties of chitosan modified magnetic graphitized multi-walled carbon nanotubes for highly effective removal of a carcinogenic dye from aqueous solution. Appl Surf Sci 285:865–873. doi:10.1016/j.apsusc.2013.09.003
Wang S, Zhai YY, Gao Q, Luo WJ, **a H, Zhou CG (2013) Highly efficient removal of acid red 18 from aqueous solution by magnetically retrievable chitosan/carbon nanotube: batch study, isotherms, kinetics, and thermodynamics. J Chem Eng Data 59:39–51. doi:10.1021/je400700c
Wang HY, Wang JJ, Zhang SB (2011) Binding Gibbs energy of ionic liquids to calf thymus DNA: a fluorescence spectroscopy study. Phys Chem Chem Phys 13:3906–3910. doi:10.1039/C0CP01815E
Cao MW, Deng ML, Wang XL, Wang YL (2008) Decompaction of cationic gemini surfactant-induced DNA condensates by β-cyclodextrin or anionic surfactant. J Phys Chem B 112:13648–13654. doi:10.1021/jp803244f
Jumbri K, Ahmad H, Abdulmalek E, Rahman MBA (2016) Binding energy and biophysical properties of ionic liquid-DNA complex: understanding the role of hydrophobic interactions. J Mol Liq 223:1197–1203. doi:10.1016/j.molliq.2016.09.040
Liu JW (2012) Adsorption of DNA onto gold nanoparticles and graphene oxide: surface science and applications. Phys Chem Chem Phys 14:10485–10496. doi:10.1039/c2cp41186e
Li X, Zhang JX, Gu HC (2011) Adsorption and desorption behaviors of DNA with magnetic mesoporous silica nanoparticles. Langmuir 27:6099–6106. doi:10.1021/la104653s
Chen XW, Mao QX, Liu JW, Wang JH (2012) Isolation/separation of plasmid DNA using hemoglobin modified magnetic nanocomposites as solid-phase adsorbent. Talanta 100:107–112. doi:10.1016/j.talanta.2012.07.095
Ghaemi M, Absalan G (2014) Study on the adsorption of DNA on Fe3O4 nanoparticles and on ionic liquid-modified Fe3O4 nanoparticles. Microchim Acta 181:45–53. doi:10.1007/s00604-013-1040-5
Kose K (2016) Nucleotide incorporated magnetic microparticles for isolation of DNA. Process Biochem 51:1644–1649. doi:10.1016/j.procbio.2016.07.021
Tang RH, Yang H, Choi JR, Gong Y, Hu J, Wen T, Li XJ, Xu B, Mei QB, Xu F (2017) Paper-based device with on-chip reagent storage for rapid extraction of DNA from biological samples. Microchim Acta 184:2141–2150. doi:10.1007/s00604-017-2225-0
Acknowledgements
The authors greatly appreciate the financial supports by the National Natural Science Foundation of China (No.21375035; No.21675048) and the Foundation for Innovative Research Groups of NSFC (Grant 21521063).
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
The author(s) declare that they have no competing interests.
Electronic supplementary material
ESM 1
(DOCX 22.7 mb)
Rights and permissions
About this article
Cite this article
Xu, K., Wang, Y., Zhang, H. et al. Solid-phase extraction of DNA by using a composite prepared from multiwalled carbon nanotubes, chitosan, Fe3O4 and a poly(ethylene glycol)-based deep eutectic solvent. Microchim Acta 184, 4133–4140 (2017). https://doi.org/10.1007/s00604-017-2444-4
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s00604-017-2444-4