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Corresponding Author(s)

杜娟（1986—），女，江西农业大学副教授，博士。E-mail: Juandu0708@jxau.edu.cn

Abstract

Objective: This study provided a new research direction for the detection of ofloxacin content. Methods: Using biomass reduction method to formulate a reduced graphene oxide-gold composite nanomaterials (rGO-AuNPs) , which had high surface enhanced Raman scattering (SERS) activity. The successful synthesis of rGO-AuNPs was demonstrated by ultraviolet visible spectroscopy, transmission electron microscopy and scanning electron microscopy, respectively. The Raman enhancement factor (EF) of rGO-AuNPs was measured and calculated. Based on the SERS hot spot effect and the specific binding ability of nucleic acid aptamer, ofloxacin content detection system was established, the detection conditions were optimized, the standard curve was established, and apply it to OFL detection in pond water sample. Results: rGO-AuNPs composite nanomaterials was successfully synthesized by using Lilium casa blanca petals biomass as reductants. Gold nanoparticles were observed on reduced graphene oxide sheets and the EF was 3.88×107. Additionally, SERS intensity had a good linear relationship with ofloxacin mass concentration in the range of 1 to 500 ng/mL, and the limit of detection was 0.3 ng/mL. The recovery was 96.28% to 102.84%, and the relative standard deviation was less than 10%. Conclusion: The synthesized rGO-AuNPs had high SERS activity and a positive application prospects in ofloxacin detection.

Publication Date

10-20-2023

First Page

48

Last Page

54

DOI

10.13652/j.spjx.1003.5788.2022.80989

References

[1] FAN M, ANDRADE G F, BROLO A G. A review on recent advances in the applications of surface-enhanced Raman scattering in analytical chemistry[J]. Analytica Chimica Acta, 2020, 1 097: 1-29.
[2] QIAN Z, CHENG Y, ZHOU X, et al. Fabrication of graphene oxide/Ag hybrids and their surface-enhanced Raman scattering characteristics[J]. Journal of Colloid and Interface Science, 2013, 397: 103-107.
[3] SHI Q, HUANG J, SUN Y, et al. Utilization of a lateral flow colloidal gold immunoassay strip based on surface-enhanced Raman spectroscopy for ultrasensitive detection of antibiotics in milk[J]. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2018, 197: 107-113.
[4] DESANTIS C J, PEVERLY A A, PETERS D G, et al. Octopods versus concave nanocrystals:Control of morphology by manipulating the kinetics of seeded growth via co-reduction[J]. Nano Letters, 2011, 11（5）: 2 164-2 168.
[5] FAN M, ANDRADE G F S, BROLO A G. A review on the fabrication of substrates for surface enhanced Raman spectroscopy and their applications in analytical chemistry[J]. Analytica Chimica Acta, 2011, 693（1/2）: 7-25.
[6] HRELESCU C, SAU T K, ROGACH A L, et al. Selective excitation of individual plasmonic hotspots at the tips of single gold nanostars[J]. Nano Letters, 2011, 11（2）: 402-407.
[7] LI I L, CHEN S F, ZHAI J P. The Raman spectrum of graphene oxide decorated with different metal nanoparticles[J]. SPIE Proceedings, 2015, 9 673: 184-188.
[8] LU Y, MAO J, WANG Z, et al. Facile synthesis of porous hexapod Ag@ AgCl dual catalysts for in situ SERS monitoring of 4-nitrothiophenol reduction[J]. Catalysts, 2020, 10（7）: 746.
[9] SOLEYMANI A R, RAFIGH S M, HEKMATI M. Green synthesis of RGO/Ag: As evidence for the production of uniform mono-dispersed nanospheres using microfluidization[J]. Applied Surface Science, 2020, 518: 146264.
[10] HE J, SONG G, WANG X, etal. Multifunctional magnetic Fe3O4/GO/Ag composite microspheres for SERS detection and catalytic degradation of methylene blue and ciprofloxacin[J]. Journal of Alloys and Compounds, 2022, 893: 162226.
[11] GU C, MAN S Q, TANG J, et al. Preparation of a monolayer array of silica@gold core-shell nanoparticles as a SERS Substrate[J]. Optik-International Journal for Light and Electron Optics, 2020, 221: 165274.
[12] CHEN Y, LIU H, LI X, et al. Development of RGO@MoS2@Ag ternary nanocomposites with tunable geometry structure for recyclable SERS detection[J]. Sensors and Actuators B: Chemical, 2021, 339: 129856.
[13] YANG S, XUE B, LI Y, et al. Controllable Ag-rGO heterostructure for highly thermal conductivity in layer-by-layer nanocellulose hybrid films[J]. Chemical Engineering Journal, 2020, 383: 123072.
[14] MURPHY S, HUANG L, KAMAT P V. Reducedgraphene oxide-silver nanoparticle composite as an active SERS material[J]. Journal of Physical Chemistry C, 2013, 117（9）: 4 740-4 747.
[15] XIE L, LING X, FANG Y, et al. Graphene as a substrate to suppress fluorescencein resonance Raman spectroscopy[J]. Journal of the American Chemical Society, 2009, 131（29）: 9 890-9 891.
[16] DARABDHARA G, DAS M R, SINGH S P, et al. Ag and Au nanoparticles/reduced graphene oxide composite materials:Synthesis and application in diagnostics and therapeutics[J]. Advances in Colloid and Interface Science, 2019, 271: 101991.
[17] ZHOU X, WANG L, SHEN G, et al. Colorimetric determination of ofloxacin using unmodified aptamers and the aggregation of gold nanoparticles[J]. Microchimica Acta, 2018, 185（7）: 1-9.
[18] 马婧怡, 田冰, 王鑫, 等. 基于核酸适配体检测动物性食品中卡那霉素残留研究进展[J]. 食品与机械, 2021, 37（12）: 188-196. MA J Y, TIAN B, WANG X, et al. Research progress in aptasensors for the detection of kanamycin residues in animal-derived foods[J]. Food & Machinery, 2021, 37（12）: 188-196.
[19] 班晶晶, 刘贵珊, 何建国, 等. 基于表面增强拉曼光谱与二维相关光谱法检测鸡肉中恩诺沙星残留[J]. 食品与机械, 2020, 36（7）: 55-58. BAN J J, LIU G S, HE J G, et al. Detection of Enrofloxacin residues in chicken based on surface enhanced Raman spectroscopy and two-dimensional correlation spectroscopy[J]. Food & Machinery, 2020, 36（7）: 55-58.
[20] WANG H, ZHANG Z, CHEN C, et al. Fullerene carbon dot catalytic amplification-aptamer assay platform for ultratrace As3＋ utilizing SERS/RRS/Abs trifunctional Au nanoprobes[J]. Journal of Hazardous Materials, 2021, 403: 123633.
[21] 张辉, 叶华, 吴世嘉, 等. 核酸适配体及其在食品安全领域中的应用研究进展[J]. 食品与机械, 2016, 32（10）: 194-199. ZHANG H, YE H, WU S J, et al. Progress on application of aptamers on food safety detection[J]. Food & Machinery, 2016, 32（10）: 194-199.
[22] 高林晨萌, 叶华, 黄圣博, 等. 核酸适配体在食品危害物多靶标检测中的应用进展[J]. 食品与机械, 2021, 37（4）: 217-225. GAO L C M, YE H, HUANG S B, et al. Recent advances in simultaneous detection of food hazards based on aptasensor[J]. Food & Machinery, 2021, 37（4）: 217-225.
[23] 赵晗, 于丽佳, 吴志生, 等. 基于核酸适配体调控噻菁染料聚集体构建铅离子检测方法[J]. 食品与机械, 2021, 37（1）: 73-78. ZHAO H, YU L J, WU Z S, et al. Construction of lead （II） ion detection method based on regulation of thiacyanine self-assembly by nucleic acid aptamer[J]. Food & Machinery, 2021, 37（1）: 73-78.
[24] FENG N, ZHANG L, SHEN J, et al. SERS molecular-ruler based DNA aptamer single-molecule and its application to multi-level optical storage[J]. Chemical Engineering Journal, 2022, 433: 133666.
[25] LIU Y, TIAN H, CHEN X, et al. Indirect surface-enhanced Raman scattering assay of insulin-like growth factor 2 receptor protein by combining the aptamer modified goldsubstrate and silver nanoprobes[J]. Microchimica Acta, 2020, 187（3）: 1-9.
[26] MUHAMMAD M, HUANG Q. A review of aptamer-based SERS biosensors: Design strategies and applications[J]. Talanta, 2021, 227: 122188.
[27] LI H, WANG W, ANG B, et al. Green biosynthesis of gold nanoparticles by Lilium casa blanca petals and evaluation of catalytic activity[J]. Micro & Nano Letters, 2019, 14（10）: 1 069-1 074.
[28] REINEMANN C, VON FRITSCH U F, RUDOLPH S, et al. Generation and characterization of quinolone-specific DNA aptamers suitable for water monitoring[J]. Biosensors and Bioelectronics, 2016, 77: 1 039-1 047.
[29] PAN X, LI L, LIN H, et al. A graphene oxide-gold nanostar hybrid based-paper biosensor for label-free SERS detection of serum bilirubin for diagnosis of jaundice[J]. Biosensors and Bioelectronics, 2019, 145: 111713.
[30] DU H Y, LI H M, XU G D, et al. Lilium casa blanca petals mediated silver nanoparticles with antioxidant and surface enhanced Raman scattering activities[J]. Food Bioscience, 2020, 38: 100792.
[31] 张泸文, 余婉松, 夏苏捷, 等. 基于表面增强拉曼光谱的养殖水中五氯酚残留检测[J]. 食品与机械, 2019, 35（12）: 82-86. ZHANG L W, YU W S, XIA S J, et al. Detection of pentachlorophenol in fishery water using surface-enhanced Raman spectroscopy[J]. Food & Machinery, 2019, 35（12）: 82-86.
[32] SINGH J P, NANDI T, GHOSH S K. Structure-property relationship of silver decorated functionalized reduced graphene oxide based nanofluids: Optical and thermophysical aspects and applications[J]. Applied Surface Science, 2021, 542: 148410.
[33] MASCARENHAS F C, SYKAM N, SELVAKUMAR M, et al. Green reduction of graphene oxide using Indian gooseberry （amla） extract for gas sensing applications[J]. Journal of Environmental Chemical Engineering, 2020, 8（2）: 103712.
[34] AIN Q T, HAQ S H. Simple-chemical synthetic route for the preparation of Ag nanoparticles supported on reduced graphene oxide[J]. Materials Express, 2020, 10（6）: 909-914.
[35] DU P, ZHANG X, YIN H, et al. In situ surface-enhanced Raman scattering monitoring of reduction of 4-nitrothiophenol on bifunctional metallic nanostructure[J]. Japanese Journal of Applied Physics, 2018, 57（3）: 030308.
[36] LING Y, XIE W C, WANG W L, et al. Direct observation of 4-nitrophenyl disulfide produced from p-nitrothiophenol in air by Raman spectroscopy[J]. Journal of Raman Spectroscopy, 2018, 49（3）: 520-525.
[37] FU W L, ZHEN S J, HUANG C Z. Controllable preparation of graphene oxide/metal nanoparticle hybrids as surface-enhanced Raman scattering substrates for 6-mercaptopurine detection[J]. RSC Advances, 2014, 4（31）: 16 327-16 332.
[38] FEI L, ZHANG S H, CAO H J, et al. Protein-decorated reduced oxide graphene composite and its application to SERS[J]. ACS Applied Materials & Interfaces, 2012, 4（6）: 3 278-3 284.
[39] KRISHNAN S K, CHIPATECUA GODOY Y. Deep eutectic solvent-assisted synthesis of Au nanostars supported on graphene oxide as an efficient substrate for SERS-based molecular sensing[J]. ACS omega, 2019, 5（3）: 1 384-1 393.
[40] ZHANG Z, TIAN Y, HUANG P, et al. Using target-specific aptamers to enhance the peroxidase-like activity of gold nanoclusters for colorimetric detection of tetracycline antibiotics[J]. Talanta, 2020, 208: 120342.
[41] PARK T H, GALPERIN M. Charge-transfer contribution to surface-enhanced Raman scattering in a molecular junction: Time-dependent correlations[J]. Physical Review B, 2011, 84（7）: 075447.
[42] XU H, AIZPURUA J, KLL M, et al. Electromagnetic contributions to single-molecule sensitivity in surface-enhanced Raman scattering[J]. Physical Review E, 2000, 62（3）: 4 318.
[43] KIRTLEY J, JHA S, TSANG J. Surface plasmon model of surface enhanced Raman scattering[J]. Solid State Communications, 1980, 35（7）: 509-512.
[44] LIU H, HAO C, NAN Z, et al. Fabrication of graphene oxide and sliver nanoparticle hybrids for fluorescence quenching of DNA labeled by methylene blue[J]. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2020, 243: 118802.
[45] PENG H, PAN B, WU M, et al. Adsorption of ofloxacin on carbon nanotubes: Solubility, pH and cosolvent effects[J]. Journal of Hazardous Materials, 2012, 211: 342-348.

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