Hemimicelles/admicelles supported on magnetic graphene sheets for enhanced magnetic solid-phase extraction.

In this work, superparamagnetic nanoparticle-decorated graphene (MG) sheets were synthesized and used as support for hemimicelles/admicelles for solid-phase extraction (SPE) of different compounds from environmental water samples for the first time. The MG sheets were facilely synthesized by a one-step, one-pot redox reaction between graphene oxide and Fe(II). Due to the large surface area and unique nanosheet morphology, MG served as an excellent nano-scaled support material for hemimicelles and admicelles, exhibiting higher loading capacity than conventional materials and pure Fe₃O₄ nanoparticles. The MG sheets could be negatively or positively charged depending on solution pH, allowing the extraction to be conducted in different modes. In cationic mode, cetyltrimethylammonium bromide (CTAB) was used as micelle-forming reagent, and perfluoroalkyl and polyfluoroalkyl substances (PFASs) and alkylphenols were used as model analytes. In anionic mode, sodium dodecyl sulfate (SDS) was used as micelle-forming reagent and alkyltrimethylammonium salts were selected as analytes. In both modes, the formation processes of hemimicelles/admicelles on MG sheets were studied and the extraction conditions were optimized. For PFASs, the analytical sensitivity was enhanced by 50-113-fold by the extraction, and the method detection limits (MDLs) ranged from 0.15 to 0.50 ng/L. For alkyltrimethylammonium salts, the MDLs were in the range of 1.4-8.0 ng/L. In both modes, good recoveries (56.3-93.9%) and reproducibility (run-to-run RSDs<9.3%) were obtained. The results from this work show a potential new role of graphene in analytical sample preparation.

[1]  Andre K. Geim,et al.  The rise of graphene. , 2007, Nature materials.

[2]  Jie Huang,et al.  Controlled assembly of Fe3O4 magnetic nanoparticles on graphene oxide. , 2011, Nanoscale.

[3]  Kian Ping Loh,et al.  Graphene-based SELDI probe with ultrahigh extraction and sensitivity for DNA oligomer. , 2010, Journal of the American Chemical Society.

[4]  G. Jiang,et al.  Determination of perfluorinated compounds in wastewater and river water samples by mixed hemimicelle-based solid-phase extraction before liquid chromatography-electrospray tandem mass spectrometry detection. , 2007, Journal of chromatography. A.

[5]  W. Hu,et al.  Sulfonated Graphene for Persistent Aromatic Pollutant Management , 2011, Advanced materials.

[6]  Guibin Jiang,et al.  Graphene-assisted matrix solid-phase dispersion for extraction of polybrominated diphenyl ethers and their methoxylated and hydroxylated analogs from environmental samples. , 2011, Analytica chimica acta.

[7]  Jerald L Schnoor,et al.  Detection of perfluorooctane surfactants in Great Lakes water. , 2004, Environmental science & technology.

[8]  Guangying Zhao,et al.  Preparation of a graphene-based magnetic nanocomposite for the extraction of carbamate pesticides from environmental water samples. , 2011, Journal of chromatography. A.

[9]  P. Lam,et al.  Perfluorooctanesulfonate and related fluorochemicals in the Amur tiger (Panthera tigris altaica) from China. , 2008, Environmental science & technology.

[10]  Jingjun Ma,et al.  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. , 2012, Analytica chimica acta.

[11]  L. Dai,et al.  Oxidizing metal ions with graphene oxide: the in situ formation of magnetic nanoparticles on self-reduced graphene sheets for multifunctional applications. , 2011, Chemical communications.

[12]  Kai-Uwe Goss,et al.  The pKa values of PFOA and other highly fluorinated carboxylic acids. , 2008, Environmental science & technology.

[13]  Shuhong Yu,et al.  Water-soluble magnetic-functionalized reduced graphene oxide sheets: in situ synthesis and magnetic resonance imaging applications. , 2010, Small.

[14]  Hian Kee Lee,et al.  Plunger-in-needle solid-phase microextraction with graphene-based sol-gel coating as sorbent for determination of polybrominated diphenyl ethers. , 2011, Journal of chromatography. A.

[15]  Fumio Okada,et al.  Determination of perfluorooctane sulfonate, perfluorooctanoate and perfluorooctane sulfonylamide in human plasma by column-switching liquid chromatography-electrospray mass spectrometry coupled with solid-phase extraction. , 2004, Journal of chromatography. B, Analytical technologies in the biomedical and life sciences.

[16]  Qian Liu,et al.  Graphene and graphene oxide sheets supported on silica as versatile and high-performance adsorbents for solid-phase extraction. , 2011, Angewandte Chemie.

[17]  Jinbin Liu,et al.  Toward a universal "adhesive nanosheet" for the assembly of multiple nanoparticles based on a protein-induced reduction/decoration of graphene oxide. , 2010, Journal of the American Chemical Society.

[18]  Shigeo Fujii,et al.  Perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) in sewage treatment plants. , 2009, Water research.

[19]  Young Chun,et al.  Water-dispersible magnetite-reduced graphene oxide composites for arsenic removal. , 2010, ACS nano.

[20]  G. Ozin,et al.  Graphene oxide-periodic mesoporous silica sandwich nanocomposites with vertically oriented channels. , 2010, ACS nano.

[21]  Xi Chen,et al.  Preparation and evaluation of graphene-coated solid-phase microextraction fiber. , 2010, Analytica chimica acta.

[22]  Q. Zhang,et al.  Surface assembly of graphene oxide nanosheets on SiO2 particles for the selective isolation of hemoglobin. , 2011, Chemistry.

[23]  Yali Shi,et al.  Cetyltrimethylammonium Bromide-coated magnetic nanoparticles for the preconcentration of phenolic compounds from environmental water samples. , 2008, Environmental science & technology.

[24]  Klaus Müllen,et al.  Graphene-based nanosheets with a sandwich structure. , 2010, Angewandte Chemie.

[25]  S. Rubio,et al.  Supramolecular assemblies for extracting organic compounds , 2003 .

[26]  Anne Marie Vinggaard,et al.  Endocrine-Disrupting Potential of Bisphenol A, Bisphenol A Dimethacrylate, 4-n-Nonylphenol, and 4-n-Octylphenol in Vitro: New Data and a Brief Review , 2007, Environmental health perspectives.

[27]  N. He,et al.  Synthesis and characterization of a novel magnetic carrier with its composition of Fe3O4/carbon using hydrothermal reaction , 2006 .

[28]  S. Rubio,et al.  Solid-phase extraction of amphiphiles based on mixed hemimicelle/admicelle formation: application to the concentration of benzalkonium surfactants in sewage and river water. , 2003, Analytical chemistry.

[29]  Philippe Lambin,et al.  Graphene: nanoscale processing and recent applications. , 2012, Nanoscale.

[30]  Hongwei Ma,et al.  One Step Synthesis of Graphene Oxide−Magnetic Nanoparticle Composite , 2010 .

[31]  N. Yamashita,et al.  Species-specific concentrations of perfluoroalkyl contaminants in farm and pet animals in Japan. , 2008, Chemosphere.

[32]  Ke-Jing Huang,et al.  Spectrofluorimetric determination of glutathione in human plasma by solid-phase extraction using graphene as adsorbent. , 2011, Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy.

[33]  Zhiping Luo,et al.  One-pot synthesis of magnetic graphene nanocomposites decorated with core@double-shell nanoparticles for fast chromium removal. , 2012, Environmental science & technology.

[34]  E. Conte,et al.  Analytical applications of admicelle and hemimicelle solid phase extraction of organic analytes , 2010 .

[35]  Qiang Gao,et al.  Magnetic retrieval of graphene: extraction of sulfonamide antibiotics from environmental water samples. , 2011, Journal of chromatography. A.

[36]  P. Eriksson,et al.  Neonatal exposure to perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) causes neurobehavioural defects in adult mice. , 2008, Neurotoxicology.

[37]  Shaojun Guo,et al.  Graphene nanosheet: synthesis, molecular engineering, thin film, hybrids, and energy and analytical applications. , 2011, Chemical Society reviews.

[38]  Kian Ping Loh,et al.  Hydrothermal Dehydration for the “Green” Reduction of Exfoliated Graphene Oxide to Graphene and Demonstration of Tunable Optical Limiting Properties , 2009 .

[39]  Guibin Jiang,et al.  Preparation of graphene-encapsulated magnetic microspheres for protein/peptide enrichment and MALDI-TOF MS analysis. , 2012, Chemical communications.

[40]  G. Jiang,et al.  Application of graphene in analytical sample preparation , 2012 .

[41]  Yan Li,et al.  Adsorption and removal of tetracycline antibiotics from aqueous solution by graphene oxide. , 2012, Journal of colloid and interface science.

[42]  R. Ruoff,et al.  Graphene-based ultracapacitors. , 2008, Nano letters.

[43]  Guibin Jiang,et al.  Evaluation of graphene as an advantageous adsorbent for solid-phase extraction with chlorophenols as model analytes. , 2011, Journal of chromatography. A.

[44]  Chun Li,et al.  Flexible graphene films via the filtration of water-soluble noncovalent functionalized graphene sheets. , 2008, Journal of the American Chemical Society.