Microchimica Acta

, 186:464 | Cite as

p-Phenylenediamine-modified graphene oxide as a sorbent for solid-phase extraction of phenylurea herbicides, nitroimidazoles, chlorophenols, phenylurea insecticides and phthalates

  • Liying Guo
  • Lin Hao
  • Tian Gao
  • Chun WangEmail author
  • Qiuhua WuEmail author
  • Zhi Wang
Original Paper


Graphene oxide was covalently modified with p-phenylenediamine via a diazonium reaction. The resulting material was employed as a sorbent for the solid-phase extraction of six phenylurea herbicides (metoxuron, monuron, chlortoluron, isoproturon, monolinuron, and buturon) from environmental water and lettuce leafs. Some key factors that influence the extraction efficiency were studied, including sample loading rate, sample pH, and desorption conditions. Following desorption with acetonitrile, the analytes were quantified by HPLC with UV detection. Under optimized conditions, response to phenylurea herbicides is linear in the 2.0–100 ng mL−1 concentration range for water samples, and 5.0–100 ng g−1 for leaf lettuces. The limits of detection are 0.10–0.25 ng mL−1 for water samples, and 1.5–2.5 ng g−1 for leaf lettuces. The sorbent was also applied to the preconcentration of organic compounds including nitroimidazoles, chlorophenols, phenylurea insecticides and phthalates. This shows that this sorbent has a large potential for the enrichment of organic pollutants.

Graphical abstract

A graphene oxide/p-phenylenediamine (GO@PA) composite was prepared via a simple and environmentally-friendly diazonium reaction between p-phenylenediamine diazonium salt and graphene oxide. It was used as the solid phase extraction (SPE) adsorbent to extract phenylurea herbicides with the extraction efficiency higher than that of commercial C18, multi-walled carbon nanotube and polystyrene polymer. The SPE method was combined with HPLC for simultaneous determination of six phenylurea herbicides in environment water and vegetable samples.


High performance liquid chromatography Amination modification Diazonium reaction Surface chemistry Leaf lettuces 



Financial supports from the National Natural Science Foundation of China (31571925, 31671930), the Natural Science Foundation of Hebei Province (B2016204136, B2016204146, B2017204025, C2018204076), Preferential Foundation for the Introduction of Overseas Scholars by Hebei Province (CL201713), the Natural Science Foundation of Hebei Agricultural University (LG201607, LG201610, ZD201703, LG201712) are gratefully acknowledged.

Compliance with ethical standards

The author(s) declare that they have no competing interests.

Ethical approval

This article does not contain any studies with human or animal subjects.

Informed consent

Not applicable.

Supplementary material

604_2019_3606_MOESM1_ESM.doc (2.3 mb)
ESM 1 (DOC 2340 kb)


  1. 1.
    Farajzadeh MA, Mohebbi A, Feriduni B (2016) Development of continuous dispersive liquid-liquid microextraction performed in home-made device for extraction and preconcentration of aryloxyphenoxy-propionate herbicides from aqueous samples followed by gas chromatography-flame ionization detection. Anal Chim Acta 920:1–9. CrossRefPubMedGoogle Scholar
  2. 2.
    Nélieu S, Bonnemoy F, Bonnet JL, Lefeuvre L, Baudiffier D, Heydorff M, Quéméneur A, Azam D, Ducrot PH, Lagadic L, Bohatier J, Einhorn J (2010) Ecotoxicological effects of diuron and chlorotoluron nitrate-induced photodegradation products: monospecific and aquatic mesocosm-integrated studies. Environ Toxicol Chem 29:2644–2652. CrossRefPubMedGoogle Scholar
  3. 3.
    Baskeyfield DEH, Davis F, Magan N, Tothill IE (2011) A membrane-based immunosensor for the analysis of the herbicide isoproturon. Anal Chim Acta 699:223–231. CrossRefPubMedGoogle Scholar
  4. 4.
    Sapozhnikova Y, Wirth E, Singhasemanon N, Bacey J, Fulton M (2008) Distribution of antifouling biocides in California marinas. J Environ Monit 10:1069–1075. CrossRefPubMedGoogle Scholar
  5. 5.
    Gatidou G, Thomaidis NS, Zhou JL (2007) Fate of Irgarol 1051, diuron and their main metabolites in two UK marine systems after restrictions in antifouling paints. Environ Int 33:70–77. CrossRefPubMedGoogle Scholar
  6. 6.
    Abbot J, Marohasy J (2011) Has the herbicide Diuron caused mangrove dieback? A re-examination of the evidence. Hum Ecol Risk Assess 17:1077–1094. CrossRefGoogle Scholar
  7. 7.
    de Lima F, Gozzi F, Fiorucci AR, Cardoso CAL, Arruda GJ, Ferreira VS (2011) Determination of linuron in water and vegetable samples using stripping voltammetry with a carbon paste electrode. Talanta 83:1763–1768. CrossRefPubMedGoogle Scholar
  8. 8.
    Liu X, Wang C, Wu Q, Wang Z (2015) Metal-organic framework-templated synthesis of magnetic nanoporous carbon as an efficient absorbent for enrichment of phenylurea herbicides. Anal Chim Acta 870:67–74. CrossRefPubMedGoogle Scholar
  9. 9.
    Su M, Jia L, Wu X, Sun H (2018) Residue investigation of some phenylureas and tebuthiuron herbicides in vegetables by ultra-performance liquid chromatography coupled with integrated selective accelerated solvent extraction-clean up in situ. J Sci Food Agric 98:4845–4853. CrossRefPubMedGoogle Scholar
  10. 10.
    Escuderos-Morenas ML, Santos-Delgado MJ, Rubio-Barroso S, Polo-Dı́ez LM (2003) Direct determination of monolinuron, linuron and chlorbromuron residues in potato samples by gas chromatography with nitrogen–phosphorus detection. J Chromatogr A 1011:143–153. CrossRefPubMedGoogle Scholar
  11. 11.
    Rodriguez-Mozaz S, Lopez de Alda MJ, Barceló D (2007) Advantages and limitations of on-line solid phase extraction coupled to liquid chromatography–mass spectrometry technologies versus biosensors for monitoring of emerging contaminants in water. J Chromatogr A 1152:97–115. CrossRefPubMedGoogle Scholar
  12. 12.
    Adelhelm C, Niessner R, Poschl U, Letzel T (2008) Analysis of large oxygenated and nitrated polycyclic aromatic hydrocarbons formed under simulated diesel engine exhaust conditions (by compound fingerprints with SPE/LC-API-MS). Anal Bioanal Chem 391:2599–2608. CrossRefPubMedPubMedCentralGoogle Scholar
  13. 13.
    Płotka-Wasylka J, Szczepańska N, De la Guardia M, Namieśnik J (2016) Modern trends in solid phase extraction: new sorbent media. Trends Anal Chem 77:23–43. CrossRefGoogle Scholar
  14. 14.
    Jiménez-Soto JM, Cárdenas S, Valcárcel M (2009) Evaluation of carbon nanocones/disks as sorbent material for solid-phase extraction. J Chromatogr A 1216:5626–5633. CrossRefPubMedGoogle Scholar
  15. 15.
    Muñoz J, Gallego M, Valcárcel M (2004) Solid-phase extraction–gas chromatography–mass spectrometry using a fullerene sorbent for the determination of inorganic mercury(II), methylmercury(I) and ethylmercury(I) in surface waters at sub-ng/ml levels. J Chromatogr A 1055:185–190. CrossRefPubMedGoogle Scholar
  16. 16.
    Savio M, Parodi B, Martinez LD, Smichowski P, Gil RA (2011) On-line solid phase extraction of Ni and Pb using carbon nanotubes and modified carbon nanotubes coupled to ETAAS. Talanta 85:245–251. CrossRefPubMedGoogle Scholar
  17. 17.
    Wang Y, Gao S, Zang X, Li J, Ma J (2012) Graphene-based solid-phase extraction combined with flame atomic absorption spectrometry for a sensitive determination of trace amounts of lead in environmental water and vegetable samples. Anal Chim Acta 716:112–118. CrossRefPubMedGoogle Scholar
  18. 18.
    Wu Q, Wang C, Liu Z, Wu C, Zeng X, Wen J, Wang Z (2009) Dispersive solid-phase extraction followed by dispersive liquid-liquid microextraction for the determination of some sulfonylurea herbicides in soil by high-performance liquid chromatography. J Chromatogr A 1216:5504–5510. CrossRefPubMedGoogle Scholar
  19. 19.
    Singh V, Joung D, Zhai L, Das S, Khondaker SI, Seal S (2011) Graphene based materials: past, present and future. Prog Mater Sci 56:1178–1271. CrossRefGoogle Scholar
  20. 20.
    Sitko R, Zawisza B, Malicka E (2013) Graphene as a new sorbent in analytical chemistry. Trac-Trend Anal Chem 51:33–43. CrossRefGoogle Scholar
  21. 21.
    Reddy KR, Sin BC, Ryu KS, Kim J-C, Chung H, Lee Y (2009) Conducting polymer functionalized multi-walled carbon nanotubes with noble metal nanoparticles: synthesis, morphological characteristics and electrical properties. Synth Met 159:595–603. CrossRefGoogle Scholar
  22. 22.
    Peng W, Li H, Liu Y, Song S (2017) A review on heavy metal ions adsorption from water by graphene oxide and its composites. J Mol Liq 230:496–504. CrossRefGoogle Scholar
  23. 23.
    Lee J, Kim J, Kim S, Min D-H (2016) Biosensors based on graphene oxide and its biomedical application. Adv Drug Deliv Rev 105:275–287. CrossRefPubMedGoogle Scholar
  24. 24.
    Zhao G, Ren X, Gao X, Tan X, Li J, Chen C, Huang Y, Wang X (2011) Removal of Pb(II) ions from aqueous solutions on few-layered graphene oxide nanosheets. Dalton Trans 40:10945–10952. CrossRefPubMedGoogle Scholar
  25. 25.
    Sun Y, Wang Q, Chen C, Tan X, Wang X (2012) Interaction between Eu(III) and graphene oxide nanosheets investigated by batch and extended X-ray absorption fine structure spectroscopy and by modeling techniques. Environ Sci Technol 46:6020–6027. CrossRefPubMedGoogle Scholar
  26. 26.
    Ghanem A, Adly FG, Sokerik Y, Antwi NY, Shenashen MA, El-Safty SA (2017) Trimethyl- β -cyclodextrin-encapsulated monolithic capillary columns: preparation, characterization and chiral nano-LC application. Talanta 169:239–248. CrossRefPubMedGoogle Scholar
  27. 27.
    Compton OC, Dikin DA, Putz KW, Brinson LC, Nguyen ST (2010) Electrically conductive "alkylated" graphene paper via chemical reduction of amine-functionalized graphene oxide paper. Adv Mater 22:892–896. CrossRefPubMedGoogle Scholar
  28. 28.
    Fang F, Kong L, Huang J, Wu S, Zhang K, Wang X, Sun B, Jin Z, Wang J, Huang XJ, Liu J (2014) Removal of cobalt ions from aqueous solution by an amination graphene oxide nanocomposite. J Hazard Mater 270:1–10. CrossRefPubMedGoogle Scholar
  29. 29.
    Sun M, Tang R, Wu Q, Wang C, Wang Z (2013) Graphene reinforced hollow fiber liquid-phase microextraction for the determination of phthalates in water, juice and milk samples by HPLC. Anal Methods-UK 5:5694. CrossRefGoogle Scholar
  30. 30.
    Wang W, Ma R, Wu Q, Wang C, Wang Z (2013) Fabrication of magnetic microsphere-confined graphene for the preconcentration of some phthalate esters from environmental water and soybean milk samples followed by their determination by HPLC. Talanta 109:133–140. CrossRefPubMedGoogle Scholar
  31. 31.
    De la Peña AM, Mahedero MC, Bautista-Sánchez A (2003) Monitoring of phenylurea and propanil herbicides in river water by solid-phase-extraction high performance liquid chromatography with photoinduced-fluorimetric detection. Talanta 60:279–285. CrossRefPubMedGoogle Scholar
  32. 32.
    Lin H-H, Sung Y-H, Huang S-D (2003) Solid-phase microextraction coupled with high-performance liquid chromatography for the determination of phenylurea herbicides in aqueous samples. J Chromatogr A 1012:57–66. CrossRefPubMedGoogle Scholar
  33. 33.
    Gao S, You J, Zheng X, Wang Y, Ren R, Zhang R, Bai Y, Zhang H (2010) Determination of phenylurea and triazine herbicides in milk by microwave assisted ionic liquid microextraction high-performance liquid chromatography. Talanta 82:1371–1377. CrossRefPubMedGoogle Scholar
  34. 34.
    Chou T-Y, Lin S-L, Fuh M-R (2009) Determination of phenylurea herbicides in aqueous samples using partitioned dispersive liquid–liquid microextraction. Talanta 80:493–498. CrossRefPubMedGoogle Scholar

Copyright information

© Springer-Verlag GmbH Austria, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Department of Chemistry, College of ScienceHebei Agricultural UniversityBaodingChina

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