Abstract
This work demonstrates the power of graphene and graphene oxide (GO) as stationary phases for high performance liquid chromatography (HPLC) based elemental speciation analysis combined with detection by inductively coupled plasma mass spectrometry (ICP-MS). Inorganic mercuric and organomercuric compounds coordinate with 2-thiosalicylic acid (TSA) to form Hg-TSA complexes. These complexes are retained by GO owing to its strong π electron stacking capability for TSA. Separation of the four mercury species tested was achieved within 12 min with resolutions of 1.8–3.4. Similarly, inorganic anionic species of arsenic and selenium, and organoarsenicals are electrostatically attracted by aromatic quaternary ammonium cations in the mobile phases. Organoarsenicals also can be separated by using long alkyl quaternary ammonium compounds. Aromatic quaternary ammonium compounds possess particularly high affinity to GO because of strong π interaction. This leads to effective retention of the As/Se anions. A comparison between graphene and GO as stationary phases for HPLC separation of mercury and arsenic species demonstrates negligible difference. Arsenic species are separated within 32 min, and selenium species are achieved within 20 min. The mobile phase also allows efficient separation of iodate, iodide, bromate, bromide, chromic acid and chromate. Analysis of a certified fish tissue by HPLC-ICP-MS using the GO@SiO2 column demonstrates its feasibility for routine elemental analysis. Good agreement is found between experimental results and certified values, with recoveries ranging between 92 and 96%.
References
Chang DW, Baek JB (2017) Charge transport in graphene oxide. Nano Today 17:38–53
Farooqui UR, Ahmad AL, Hamid NA (2018) Graphene oxide: a promising membrane material for fuel cells. Renew Sust Energ Rev 82:714–733
Shiraz HG, Tavakoli O (2017) Investigation of graphene-based systems for hydrogen storage. Renew Sust Energ Rev 74:104–109
Xiang Q, Cheng B, Yu J (2015) Graphene-based photocatalysts for solar-fuel generation. Angew Chem Int Ed 54(39):11350–11366
Nagar R, Vinayan BP, Samantaray SS, Ramaprabhu S (2017) Recent advances in hydrogen storage using catalytically and chemically modified graphene nanocomposites. J Mater Chem A 5(44):22897–22912
Ozer LY, Garlisi C, Oladipo H, Pagliaro M, Sharief SA, Yusuf A, Almheiri S, Palmisano G (2017) Inorganic semiconductors-graphene composites in photo (electro)catalysis: synthetic strategies, interaction mechanisms and applications. J Photochem Photobiol C 33:132–164
Mohammadi O, Golestanzadeh M, Abdouss M (2017) Recent advances in organic reactions catalyzed by graphene oxide and sulfonated graphene as heterogeneous nanocatalysts: a review. New J Chem 41(20):11471–11497
Reina G, Miguel Gonzalez-Dominguez J, Criado A, Vazquez E, Bianco A, Prato M (2017) Promises, facts and challenges for graphene in biomedical applications. Chem Soc Rev 46(15):4400–4416
Georgakilas V, Tiwari JN, Kemp KC, Perman JA, Bourlinos AB, Kim KS, Zboril R (2016) Noncovalent functionalization of graphene and graphene oxide for energy materials, biosensing, catalytic, and biomedical applications. Chem Rev 116(9):5464–5519
Tang LAL, Wang J, Loh KP (2010) Graphene-based SELDI probe with ultrahigh extraction and sensitivity for DNA oligomer. J Am Chem Soc 132(32):10976–10977
Gulbakan B, Yasun E, Shukoor MI, Zhu Z, You M, Tan X, Sanchez H, Powell DH, Dai H, Tan W (2010) A dual platform for selective analyte enrichment and ionization in mass spectrometry using aptamer-conjugated graphene oxide. J Am Chem Soc 132(49):17408–17410
Wang X, Liu B, Lu Q, Qu Q (2014) Graphene-based materials: fabrication and application for adsorption in analytical chemistry. J Chromatogr A 1362:1–15
Liu Q, Shi J, Sun J, Wang T, Zeng L, Jiang G (2011) Graphene and graphene oxide sheets supported on silica as versatile and high-performance adsorbents for solid-phase extraction. Angew Chem 123(26):6035–6039
Chen J, Zou J, Zeng J, Song X, Ji J, Wang Y, Ha J, Chen X (2010) Preparation and evaluation of graphene-coated solid-phase microextraction fiber. Anal Chim Acta 678(1):44–49
Zhang S, Du Z, Li G (2011) Layer-by-layer fabrication of chemical-bonded graphene coating for solid-phase microextraction. Anal Chem 83(19):7531–7541
Zhai H, Su Z, Chen Z, Liu Z, Yuan K, Huang L (2015) Molecularly imprinted coated graphene oxide solid-phase extraction monolithic capillary column for selective extraction and sensitive determination of phloxine B in coffee bean. Anal Chim Acta 865:16–21
Su S, Chen B, He M, Hu B (2014) Graphene oxide–silica composite coating hollow fiber solid phase microextraction online coupled with inductively coupled plasma mass spectrometry for the determination of trace heavy metals in environmental water samples. Talanta 123:1–9
Mo J, Zhou L, Li X, Li Q, Wang L, Wang Z (2017) On-line separation and pre-concentration on a mesoporous silica-grafted graphene oxide adsorbent coupled with solution cathode glow discharge-atomic emission spectrometry for the determination of lead. Microchem J 130:353–359
Zhang Y, Zhong C, Zhang Q, Chen B, He M, Hu B (2015) Graphene oxide–TiO2 composite as a novel adsorbent for the preconcentration of heavy metals and rare earth elements in environmental samples followed by on-line inductively coupled plasma optical emission spectrometry detection. RSC Adv 5(8):5996–6005
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
Sereshti H, Farahani MV, Baghdadi M (2016) Trace determination of chromium (VI) in environmental water samples using innovative thermally reduced graphene (TRG) modified SiO2 adsorbent for solid phase extraction and UV–vis spectrophotometry. Talanta 146:662–669
Nazari S, Mehri A, Hassannia AS (2017) Fe3O4-modified graphene oxide as a sorbent for sequential magnetic solid phase extraction and dispersive liquid phase microextraction of thallium. Microchim Acta 184(9):3239–3246
Kojidi MH, Aliakbar A (2017) A graphene oxide based poly (2, 6-diaminopyridine) composite for solid-phase extraction of Cd (II) prior to its determination by FAAS. Microchim Acta 184(8):2855–2860
Qu Q, Shen Y, Gu C, Gu Z, Gu Q, Wang C, Hu X (2012) Capillary column coated with graphene oxide as stationary phase for gas chromatography. Anal Chim Acta 757:83–87
Gao X, Mo R, Ji Y (2015) Preparation and characterization of tentacle-type polymer stationary phase modified with graphene oxide for open-tubular capillary electrochromatography. J Chromatogr A 1400:19–26
Xu Y, Niu X, Dong Y, Zhang H, Li X, Chen H, Chen X (2013) Preparation and characterization of open-tubular capillary column modified with graphene oxide nanosheets for the separation of small organic molecules. J Chromatogr A 1284:180–187
Zhang J, Zhang W, Bao T, Chen Z (2014) Enhancement of capillary electrochromatographic separation performance by conductive polymer in a layer-by-layer fabricated graphene stationary phase. J Chromatogr A 1339:192–199
Qu Q, Gu C, Hu X (2012) Capillary coated with graphene and graphene oxide sheets as stationary phase for capillary electrochromatography and capillary liquid chromatography. Anal Chem 84(20):8880–8890
Ye N, Li J, Xie Y, Liu C (2013) Graphene oxide coated capillary for chiral separation by CE. Electrophoresis 34(6):841–845
Zhao H, Wang Y, Cheng H, Shen Y (2016) Graphene oxide decorated monolithic column as stationary phase for capillary electrochromatography. J Chromatogr A 1452:27–35
Wang MM, Yan XP (2012) Fabrication of graphene oxide nanosheets incorporated monolithic column via one-step room temperature polymerization for capillary electrochromatography. Anal Chem 84(1):39–44
Zhang X, Chen S, Han Q, Ding M (2013) Preparation and retention mechanism study of graphene and graphene oxide bonded silica microspheres as stationary phases for high performance liquid chromatography. J Chromatogr A 1307:135–143
Zhao H, Wang Y, Zhang D, Cheng H, Wang Y (2018) Electrochromatographic performance of graphene and graphene oxide modified silica particles packed capillary columns. Electrophoresis 39(7):933–940
Templeton DM, Fujishiro H (2017) Terminology of elemental speciation – an IUPAC perspective. Coord Chem Rev 352:424–431
Clough R, Harrington CF, Hill SJ, Madrid Y, Tyson JF (2017) Atomic spectrometry update: review of advances in elemental speciation. J Anal At Spectrom 32(7):1239–1282
Li Y, Yan XP, Dong LM, Wang SW, Jiang Y, Jiang DQ (2005) Development of an ambient temperature post-column oxidation system for high-performance liquid chromatography on-line coupled with cold vapor atomic fluorescence spectrometry for mercury speciation in seafood. J Anal At Spectrom 20(5):467–472
Shade CW, Hudson RJ (2005) Determination of MeHg in environmental sample matrices using Hg− Thiourea complex ion chromatography with on-line cold vapor generation and atomic fluorescence spectrometric detection. Environ Sci Technol 39(13):4974–4982
Cheng H, Chen X, Shen L, Wang Y, Xu Z, Liu J (2018) Ion-pairing reversed-phase chromatography coupled to inductively coupled plasma mass spectrometry as a tool to determine mercurial species in freshwater fish. J Chromatogr A 1531:104–111
Chen X, Han C, Cheng H, Wang Y, Liu J, Xu Z, Hu L (2013) Rapid speciation analysis of mercury in seawater and marine fish by cation exchange chromatography hyphenated with inductively coupled plasma mass spectrometry. J Chromatogr A 1314:86–93
Chen X, Han C, Cheng H, Liu J, Xu Z, Yin X (2013) Determination of mercurial species in fish by inductively coupled plasma mass spectrometry with anion exchange chromatographic separation. Anal Chim Acta 796:7–13
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The authors acknowledge the financial support from the National Natural Science Foundation of China under project Nos. 21675037 and 21405030.
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Cheng, H., Zhang, W., Wang, Y. et al. Graphene oxide as a stationary phase for speciation of inorganic and organic species of mercury, arsenic and selenium using HPLC with ICP-MS detection. Microchim Acta 185, 425 (2018). https://doi.org/10.1007/s00604-018-2960-x
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DOI: https://doi.org/10.1007/s00604-018-2960-x