{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,4,16]],"date-time":"2026-04-16T08:06:32Z","timestamp":1776326792690,"version":"3.50.1"},"reference-count":54,"publisher":"MDPI AG","issue":"9","license":[{"start":{"date-parts":[[2019,4,28]],"date-time":"2019-04-28T00:00:00Z","timestamp":1556409600000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100001809","name":"National Natural Science Foundation of China","doi-asserted-by":"publisher","award":["21527813, 21477166, 21677182 and 21737006"],"award-info":[{"award-number":["21527813, 21477166, 21677182 and 21737006"]}],"id":[{"id":"10.13039\/501100001809","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100003453","name":"Natural Science Foundation of Guangdong Province","doi-asserted-by":"publisher","award":["S2013030013474"],"award-info":[{"award-number":["S2013030013474"]}],"id":[{"id":"10.13039\/501100003453","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>In this study, the detection and quantification of multiple classes of antibiotics in water matrices are proposed using a lab-made solid phase microextraction (SPME) fiber coupled with high-performance liquid chromatography-tandem mass spectrometry (LC-MS\/MS). The lab-made fiber was prepared using a graphene oxide (G), carbon nanotubes (C), and tin dioxide (T) composite, namely GCT, with polyacrylonitrile (PAN) as supporting material. The detected antibiotics were enrofloxacin, sulfathiazole, erythromycin, and trimethoprim. The custom-made fiber was found to be superior compared with a commercial C18 fiber. The excellent reproducibility and lower intra-fiber relative standard deviations (RSDs 1.8% to 6.8%) and inter-fiber RSDs (4.5% to 8.8%) made it an ideal candidate for the detection of traces of antibiotics in real environmental samples. The proposed validated method provides a satisfactory limit of detection and good linear ranges with higher (&gt;0.99) coefficient of determination in the aqueous system. Application of the method was made in different real water systems such as river, pond and tap water using the standard spiking method. Excellent sensitivity, reproducibility, lower amount of sample detection and higher recovery was found in a real water sample. Therefore, the extraction method was successfully applied to the detection and quantification of multiple classes of antibiotics in different aqueous systems with satisfactory results.<\/jats:p>","DOI":"10.3390\/molecules24091670","type":"journal-article","created":{"date-parts":[[2019,4,29]],"date-time":"2019-04-29T02:57:32Z","timestamp":1556506652000},"page":"1670","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":17,"title":["Carbon and Tin-Based Polyacrylonitrile Hybrid Architecture Solid Phase Microextraction Fiber for the Detection and Quantification of Antibiotic Compounds in Aqueous Environmental Systems"],"prefix":"10.3390","volume":"24","author":[{"given":"Sandip","family":"Mondal","sequence":"first","affiliation":[{"name":"MOE Key Laboratory of Bioinorganic and Synthetic Chemistry\/KLGHEI of Environment and Energy Chemistry, School of Chemistry, Sun Yat-sen University, Guangzhou 510275, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Jialing","family":"Jiang","sequence":"additional","affiliation":[{"name":"MOE Key Laboratory of Bioinorganic and Synthetic Chemistry\/KLGHEI of Environment and Energy Chemistry, School of Chemistry, Sun Yat-sen University, Guangzhou 510275, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Yin","family":"Li","sequence":"additional","affiliation":[{"name":"MOE Key Laboratory of Bioinorganic and Synthetic Chemistry\/KLGHEI of Environment and Energy Chemistry, School of Chemistry, Sun Yat-sen University, Guangzhou 510275, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Gangfeng","family":"Ouyang","sequence":"additional","affiliation":[{"name":"MOE Key Laboratory of Bioinorganic and Synthetic Chemistry\/KLGHEI of Environment and Energy Chemistry, School of Chemistry, Sun Yat-sen University, Guangzhou 510275, China"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"1968","published-online":{"date-parts":[[2019,4,28]]},"reference":[{"key":"ref_1","unstructured":"Ficai, A., and Grumezescu, A.M. (2017). Chapter 1-Antimicrobials: Meeting the Challenges of Antibiotic Resistance Through Nanotechnology. Nanostructures for Antimicrobial Therapy, Elsevier."},{"key":"ref_2","doi-asserted-by":"crossref","unstructured":"Aarestrup, F.M. (2015). The livestock reservoir for antimicrobial resistance: A personal view on changing patterns of risks, effects of interventions and the way forward. Philos. Trans. R. Soc. Lond. B Biol. Sci., 370.","DOI":"10.1098\/rstb.2014.0085"},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"26","DOI":"10.1016\/j.cej.2011.09.127","article-title":"Studies on the removal of tetracycline by multi-walled carbon nanotubes","volume":"178","author":"Zhang","year":"2011","journal-title":"Chem. Eng. J."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"5326","DOI":"10.1038\/srep05326","article-title":"Adsorption of tetracycline from aqueous solutions onto multi-walled carbon nanotubes with different oxygen contents","volume":"4","author":"Yu","year":"2014","journal-title":"Sci. Rep."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"292","DOI":"10.1016\/j.envint.2010.10.002","article-title":"Disposal practices for unused medications around the world","volume":"37","author":"Tong","year":"2011","journal-title":"Environ. Int."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"641","DOI":"10.1016\/j.envres.2010.06.008","article-title":"Influence of water and food consumption on inadvertent antibiotics intake among general population","volume":"110","author":"Ji","year":"2010","journal-title":"Environ. Res."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"1509","DOI":"10.1021\/ac015588m","article-title":"Determination of Persistent Tetracycline Residues in Soil Fertilized with Liquid Manure by High-Performance Liquid Chromatography with Electrospray Ionization Tandem Mass Spectrometry","volume":"74","author":"Hamscher","year":"2002","journal-title":"Anal. Chem."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"52","DOI":"10.1016\/j.jece.2017.11.059","article-title":"Antibiotic resistance and wastewater: Correlation, impact and critical human health challenges","volume":"6","author":"Kumar","year":"2018","journal-title":"J. Environ. Chem. Eng."},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"1298","DOI":"10.1021\/acs.chemrestox.6b00122","article-title":"Embryonic Stage-Dependent Teratogenicity of Ketamine in Zebrafish (Danio rerio)","volume":"29","author":"Serafim","year":"2016","journal-title":"Chem. Res. Toxicol."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"188","DOI":"10.1016\/j.cej.2018.06.110","article-title":"Facile fabrication of ascorbic acid reduced graphene oxide-modified electrodes toward electroanalytical determination of sulfamethoxazole in aqueous environments","volume":"352","author":"Chen","year":"2018","journal-title":"Chem. Eng. J."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"168","DOI":"10.1016\/j.scitotenv.2018.12.258","article-title":"Occurrence and distribution of pharmaceutical and personal care products, artificial sweeteners, and pesticides in groundwater from an agricultural area in Korea","volume":"659","author":"Lee","year":"2019","journal-title":"Sci. Total Environ."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"946","DOI":"10.1016\/j.scitotenv.2018.11.449","article-title":"Occurrence, distribution and ecological risks of antibiotics and pesticides in coastal waters around Liaodong Peninsula, China","volume":"656","author":"Xie","year":"2019","journal-title":"Sci. Total Environ."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"448","DOI":"10.1016\/j.envint.2018.12.065","article-title":"Antibiotics bioremediation: Perspectives on its ecotoxicity and resistance","volume":"124","author":"Kumar","year":"2019","journal-title":"Environ. Int."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"417","DOI":"10.1128\/MMBR.00016-10","article-title":"Origins and evolution of antibiotic resistance","volume":"74","author":"Davies","year":"2010","journal-title":"Microbiol. Mol. Biol. Rev."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"260","DOI":"10.1016\/j.copbio.2008.05.006","article-title":"Antibiotics and antibiotic resistance in water environments","volume":"19","author":"Baquero","year":"2008","journal-title":"Curr. Opin. Biotechnol."},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"29","DOI":"10.1016\/j.aca.2016.12.038","article-title":"High-throughput untargeted screening of veterinary drug residues and metabolites in tilapia using high resolution orbitrap mass spectrometry","volume":"957","author":"Jia","year":"2017","journal-title":"Anal. Chim. Acta"},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"168","DOI":"10.1016\/S0140-6736(15)00474-2","article-title":"Access to effective antimicrobials: a worldwide challenge","volume":"387","author":"Laxminarayan","year":"2016","journal-title":"Lancet"},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"499","DOI":"10.1016\/0006-291X(69)90943-7","article-title":"Comparative studies on the mechanism of action of lincomycin, streptomycin, and erythromycin","volume":"37","author":"Igarashi","year":"1969","journal-title":"Biochem. Biophys. Res. Commun."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"35","DOI":"10.1093\/jac\/dkn147","article-title":"Trimethoprim and enterococci in urinary tract infections: New perspectives on an old issue","volume":"62","author":"Wisell","year":"2008","journal-title":"J. Antimicrob. Chemoth."},{"key":"ref_20","doi-asserted-by":"crossref","unstructured":"Papich, M.G. (2016). Enrofloxacin. Saunders Handbook of Veterinary Drugs, W.B. Saunders. [4th ed.].","DOI":"10.1016\/B978-0-323-24485-5.00240-0"},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"77","DOI":"10.1016\/j.etap.2014.11.007","article-title":"Sulfathiazole: Analytical methods for quantification in seawater and macroalgae","volume":"39","author":"Leston","year":"2015","journal-title":"Environ. Toxicol. Pharmacol."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"593","DOI":"10.1016\/j.jpba.2016.07.022","article-title":"Enhancement for trace analysis of sulfonamide antibiotics in water matrices using bar adsorptive microextraction (BA\u03bcE)","volume":"129","author":"Ide","year":"2016","journal-title":"J. Pharm. Biomed. Anal."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"80","DOI":"10.1016\/j.aca.2011.11.036","article-title":"Development of a dispersive liquid\u2013liquid microextraction method for the determination of fluoroquinolones in chicken liver by high performance liquid chromatography","volume":"730","author":"Moema","year":"2012","journal-title":"Anal. Chimi. Acta"},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"2873","DOI":"10.1021\/jf060068j","article-title":"Determination of Five Macrolide Antibiotic Residues in Raw Milk Using Liquid Chromatography\u2212Electrospray Ionization Tandem Mass Spectrometry","volume":"54","author":"Wang","year":"2006","journal-title":"J. Agric. Food Chem."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"8099","DOI":"10.1007\/s00216-016-9913-1","article-title":"Simultaneous determination of 12 pharmaceuticals in water samples by ultrasound-assisted dispersive liquid\u2013liquid microextraction coupled with ultra-high performance liquid chromatography with tandem mass spectrometry","volume":"408","author":"Guan","year":"2016","journal-title":"Anal. Bioanal. Chem."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"629","DOI":"10.1365\/s10337-008-0753-9","article-title":"LC Determination of Chloramphenicol in Honey Using Dispersive Liquid\u2013Liquid Microextraction","volume":"68","author":"Chen","year":"2008","journal-title":"Chromatographia"},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"977","DOI":"10.1016\/j.chemosphere.2006.07.037","article-title":"Determination of antibiotic compounds in water by on-line SPE-LC\/MSD","volume":"66","author":"Choi","year":"2007","journal-title":"Chemosphere"},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"2647","DOI":"10.1021\/acs.jafc.6b00748","article-title":"Determination of Tetracycline Antibiotic Residues in Honey and Milk by Miniaturized Solid Phase Extraction Using Chitosan-Modified Graphitized Multiwalled Carbon Nanotubes","volume":"64","author":"Xu","year":"2016","journal-title":"J. Agric. Food Chem."},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"62","DOI":"10.1016\/j.aca.2018.09.060","article-title":"Solid-phase microextraction of antibiotics from fish muscle by using MIL-101(Cr)NH2-polyacrylonitrile fiber and their identification by liquid chromatography-tandem mass spectrometry","volume":"1047","author":"Mondal","year":"2019","journal-title":"Anal. Chim. Acta"},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"1","DOI":"10.1016\/j.chroma.2006.07.011","article-title":"Determination of sulfonamide antibiotics in wastewater: A comparison of solid phase microextraction and solid phase extraction methods","volume":"1131","author":"Balakrishnan","year":"2006","journal-title":"J. Chromatogr. A"},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"302","DOI":"10.1021\/acs.analchem.7b04502","article-title":"Advances in Solid Phase Microextraction and Perspective on Future Directions","volume":"90","author":"Gionfriddo","year":"2018","journal-title":"Anal. Chem."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"115","DOI":"10.1002\/jssc.201401032","article-title":"Determination of tetracycline antibiotics in fatty food samples by selective pressurized liquid extraction coupled with high-performance liquid chromatography and tandem mass spectrometry","volume":"38","author":"Jiao","year":"2015","journal-title":"J. Sep. Sci."},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"1703","DOI":"10.1016\/j.foodcont.2010.05.004","article-title":"Determination of macrolide and lincosamide antibiotics by pressurised liquid extraction and liquid chromatography-tandem mass spectrometry in meat and milk","volume":"21","author":"Juan","year":"2010","journal-title":"Food Control"},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"4953","DOI":"10.1007\/s00216-016-9590-0","article-title":"Simultaneous analysis of 45 pharmaceuticals and personal care products in sludge by matrix solid-phase dispersion and liquid chromatography tandem mass spectrometry","volume":"408","author":"Li","year":"2016","journal-title":"Anal. Bioanal. Chem."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"553","DOI":"10.1016\/j.foodchem.2012.02.120","article-title":"Matrix solid-phase dispersion method for the determination of macrolide antibiotics in sheep\u2019s milk","volume":"134","year":"2012","journal-title":"Food Chem."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"713","DOI":"10.1002\/jssc.201700798","article-title":"Determination of multiple antibiotics in leafy vegetables using QuEChERS\u2013UHPLC\u2013MS\/MS","volume":"41","author":"Yu","year":"2018","journal-title":"J. Sep. Sci."},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"2857","DOI":"10.1007\/s12161-018-1252-8","article-title":"Determination of Antibiotics in Vegetables Using QuEChERS-Based Method and Liquid Chromatography-Quadrupole Linear Ion Trap Mass Spectrometry","volume":"11","author":"He","year":"2018","journal-title":"Food Anal. Methods"},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"20","DOI":"10.1016\/S1369-7021(06)71788-6","article-title":"Graphene: carbon in two dimensions","volume":"10","author":"Katsnelson","year":"2007","journal-title":"Mater. Today"},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"241","DOI":"10.3390\/chemosensors3040241","article-title":"Selectivity of Catalytically Modified Tin Dioxide to CO and NH3 Gas Mixtures","volume":"3","author":"Marikutsa","year":"2015","journal-title":"Chemosensors"},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"235","DOI":"10.1016\/j.jhazmat.2016.02.045","article-title":"Adsorption behavior and mechanism of chloramphenicols, sulfonamides, and non-antibiotic pharmaceuticals on multi-walled carbon nanotubes","volume":"310","author":"Zhao","year":"2016","journal-title":"J. Hazard. Mater."},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"1487","DOI":"10.1039\/C5SC03992D","article-title":"A novel probe based on phenylboronic acid functionalized carbon nanotubes for ultrasensitive carbohydrate determination in biofluids and semi-solid biotissues","volume":"7","author":"Chen","year":"2016","journal-title":"Chem. Sci."},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"5618","DOI":"10.1002\/anie.201006896","article-title":"In Vivo Solid-Phase Microextraction in Metabolomics: Opportunities for the Direct Investigation of Biological Systems","volume":"50","author":"Vuckovic","year":"2011","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_43","doi-asserted-by":"crossref","first-page":"1944","DOI":"10.1021\/ac102614v","article-title":"Systematic Evaluation of Solid-Phase Microextraction Coatings for Untargeted Metabolomic Profiling of Biological Fluids by Liquid Chromatography\u2212Mass Spectrometry","volume":"83","author":"Vuckovic","year":"2011","journal-title":"Anal. Chem."},{"key":"ref_44","doi-asserted-by":"crossref","first-page":"12124","DOI":"10.1002\/anie.201304538","article-title":"Solid-Phase Microextraction: A Complementary In Vivo Sampling Method to Microdialysis","volume":"52","author":"Cudjoe","year":"2013","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_45","doi-asserted-by":"crossref","first-page":"17963","DOI":"10.1021\/acsami.5b04673","article-title":"One-Pot Synthesis of Three-Dimensional Graphene\/Carbon Nanotube\/SnO2 Hybrid Architectures with Enhanced Lithium Storage Properties","volume":"7","author":"Zhang","year":"2015","journal-title":"ACS Appl. Mater. Interfaces"},{"key":"ref_46","doi-asserted-by":"crossref","first-page":"158","DOI":"10.1016\/j.ecoleng.2016.03.022","article-title":"Biosorptive uptake of ibuprofen by chemically modified Parthenium hysterophorus derived biochar: Equilibrium, kinetics, thermodynamics and modeling","volume":"92","author":"Mondal","year":"2016","journal-title":"Ecol. Eng."},{"key":"ref_47","doi-asserted-by":"crossref","first-page":"561","DOI":"10.1016\/j.talanta.2018.02.062","article-title":"Zinc(II)-based metal\u2013organic nanotubes coating for high sensitive solid phase microextraction of nitro-polycyclic aromatic hydrocarbons","volume":"186","author":"Wang","year":"2018","journal-title":"Talanta"},{"key":"ref_48","doi-asserted-by":"crossref","first-page":"40","DOI":"10.1016\/j.chroma.2016.12.010","article-title":"Preparation of three-dimensional mesoporous polymer in situ polymerization solid phase microextraction fiber and its application to the determination of seven chlorophenols","volume":"1479","author":"Wang","year":"2017","journal-title":"J. Chromatogr. A"},{"key":"ref_49","doi-asserted-by":"crossref","first-page":"368","DOI":"10.1016\/j.molliq.2017.03.091","article-title":"Salting-out and salting-in effects of organic compounds and applications of the salting-out effect of Pentasodium phytate in different extraction processes","volume":"236","author":"Grundl","year":"2017","journal-title":"J. Mol. Liq."},{"key":"ref_50","doi-asserted-by":"crossref","first-page":"1","DOI":"10.1016\/j.chroma.2016.01.051","article-title":"In situ solvothermal synthesis of metal\u2013organic framework coated fiber for highly sensitive solid-phase microextraction of polycyclic aromatic hydrocarbons","volume":"1436","author":"Gao","year":"2016","journal-title":"J. Chromatogr. A"},{"key":"ref_51","doi-asserted-by":"crossref","first-page":"2530","DOI":"10.1021\/ac00111a006","article-title":"Solid Phase Microextraction Coupled to High-Performance Liquid Chromatography","volume":"67","author":"Chen","year":"1995","journal-title":"Anal. Chem."},{"key":"ref_52","doi-asserted-by":"crossref","first-page":"1081","DOI":"10.1016\/S0731-7085(98)00074-0","article-title":"Solid phase micro extraction coupled with semi-microcolumn high performance liquid chromatography for the analysis of benzodiazepines in human urine","volume":"17","author":"Jinno","year":"1998","journal-title":"J. Pharm. Biomed. Anal."},{"key":"ref_53","doi-asserted-by":"crossref","first-page":"550","DOI":"10.1016\/j.talanta.2017.07.066","article-title":"Rapid in vivo determination of fluoroquinolones in cultured puffer fish (Takifugu obscurus) muscle by solid-phase microextraction coupled with liquid chromatography-tandem mass spectrometry","volume":"175","author":"Tang","year":"2017","journal-title":"Talanta"},{"key":"ref_54","doi-asserted-by":"crossref","unstructured":"Khan, R., Ben Aissa, S., Sherazi, A.T., Catanante, G., Hayat, A., and Marty, L.J. (2019). Development of an Impedimetric Aptasensor for Label Free Detection of Patulin in Apple Juice. Molecules, 24.","DOI":"10.3390\/molecules24061017"}],"container-title":["Molecules"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1420-3049\/24\/9\/1670\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,11]],"date-time":"2025-10-11T12:47:48Z","timestamp":1760186868000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1420-3049\/24\/9\/1670"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2019,4,28]]},"references-count":54,"journal-issue":{"issue":"9","published-online":{"date-parts":[[2019,5]]}},"alternative-id":["molecules24091670"],"URL":"https:\/\/doi.org\/10.3390\/molecules24091670","relation":{},"ISSN":["1420-3049"],"issn-type":[{"value":"1420-3049","type":"electronic"}],"subject":[],"published":{"date-parts":[[2019,4,28]]}}}