摘要

利用表面增强拉曼光谱（SERS）和静电富集（EP）相结合的技术，实现了水环境中磺胺甲基嘧啶、丁胺卡那霉素、恩诺沙星和环丙沙星的有效富集和快速痕量探测。实验结果表明，与非静电富集SERS探测相比较，磺胺甲基嘧啶和丁胺卡那霉素的特征峰强度提高了大约10倍，恩诺沙星和环丙沙星的特征峰强度提高了2~3倍；4种抗生素的最低检测浓度分别为1.9×10-8，1.7×10-8，5.5×10-8 ，6.0×10-8 mol·L-1；当被检测目标的浓度较低时，特征峰强度与探测浓度具有良好的线性关系。EP-SERS技术可有效提高水环境中抗生素的检测灵敏度。

Abstract

The effective accumulation and the rapid trace detection of sulfadiazine, amikacin, enrofloxacin and ciprofloxacin are realized by the hyphenated technology of surface enhanced Raman spectroscopy (SERS) and electrostatic preconcentration (EP). The experimental results show that, if compared with those by the non-EP-SERS detection, the characteristic peak intensities of sulfadiazine and amikacin are increased by about 10 times, and the characteristic peak intensities of enrofloxacin and ciprofloxacin are increased by 2-3 times. The minimum detectable concentrations of the 4 kinds of antibiotics are 1.9×10-8, 1.7×10-8, 5.5×10-8 and 6.0×10-8 mol·L-1, respectively. A good linear relationship between the characteristic peak intensity and detection concentration appears when the concentration of detected targets is relatively low. The detection sensitivity of antibiotics in aqueous can be improved effectively by using the EP-SERS technology.

补充资料

中图分类号：O433

DOI：10.3788/cjl201845.0207028

所属栏目：“生物医学光子学新技术及进展”专题

基金项目：国家自然科学基金（41476081）、山东省重点研发计划（2016GSF115020）、山东省自然科学基金（BS2013HZ006，ZR2011DQ010

收稿日期：2017-09-13

修改稿日期：2017-10-30

网络出版日期：--

作者单位    点击查看

联系人作者：马君(majun@ouc.edu.cn)

备注：马海宽（1989—），男，硕士研究生，主要从事光谱技术及其应用方面的研究。E-mail: dzmahaikuan@163.com

【1】Kumar K, Thompson A, Singh A K, et al. Enzyme-linked immunosorbent assay for ultratrace determination of antibiotics in aqueous samples［J］. Journal of Environmental Quality, 2004, 33(1): 250-256.

【2】Sacher F, Lange F T, Brauch H J, et al. Pharmaceuticals in groundwaters: Analytical methods and results of a monitoring program in Baden-Württemberg, Germany［J］. Journal of Chromatography A, 2001, 938(1/2): 199-210.

【3】Wan W N, Chen X, Ju X H, et al. Simultaneous determination of residual antibiotics in livestock manure by solid phase extraction-ultra-high performance liquid chromatography tantem mass spectrometry［J］. Chinese Journal of Analytical Chemistry, 2013, 41(7): 993-999.
万位宁, 陈熹, 居学海, 等. 固相萃取-超高效液相色谱串联质谱法同时检测禽畜粪便中多种抗生素残留［J］. 分析化学, 2013, 41(7): 993-999.

【4】Qi Y J, Liu F. Analysis of antibiotics in groundwater: A review［J］. Rock and Mineral analysis, 2014, 33(1): 1-11.
祁彦洁, 刘菲. 地下水中抗生素污染检测分析研究进展［J］. 岩矿测试, 2014, 33(1): 1-11.

【5】Ren B, Li J F, Huang Y F, et al. Electrochemical surface-enhanced Raman spectroscopy: Current status and perspective［J］. Electrochemistry, 2010, 16(3): 305-316.
任斌, 李剑锋, 黄逸凡, 等. 电化学表面增强拉曼光谱—现状和展望［J］. 电化学, 2010, 16(3): 305-316.

【6】Liu S P, Zhu H F, Chen N, et al. Surface enhanced Raman scattering spectrum analysis of nude mouse serum with Au nanoparticles active substrate［J］. Chinese Journal of Lasers, 2012, 39(5): 0504004.
刘书朋, 朱鸿飞, 陈娜, 等. 金颗粒为活性基底的裸鼠血清表面增强拉曼散射光谱分析［J］. 中国激光, 2012, 39(5): 0504004.

【7】Yang F, Zhong Y, Zhou H K, et al. Detection of years of dried tangerine peels based on surface-enhanced Raman spectroscopy［J］. Laser & Optoelectronics Progress, 2017, 54(3): 033001.
杨方, 钟莹, 周鸿昆, 等. 基于表面增强拉曼光谱技术的陈皮年份检测［J］. 激光与光电子学进展, 2017, 54(3): 033001.

【8】Zhao C, Li R, Yang H N, et al. Measurement of platelet-derived growth factor-BB in urine samples based on surface-enhanced Raman spectroscopy［J］. Chinese Journal of Lasers, 2017, 44(8): 0811002.
赵畅, 李蓉, 杨荟楠, 等. 基于表面增强拉曼光谱测量尿液样本中血小板衍生生长因子-BB［J］. 中国激光, 2017, 44(8): 0811002.

【9】Li C Y, Lai K Q, Zhang Y Y, et al. Use of surface-enhanced Raman spectroscopy for the test of residuals of prohibited and restricted drugs in fish muscle［J］. Acta Chimica Sinica, 2013, 71(2): 221-226.
李春颖, 赖克强, 张源园, 等. 表面增强拉曼光谱检测鱼肉中禁用和限用药物研究［J］. 化学学报, 2013, 71(2): 221-226.

【10】Han C Q, Chen J, Wu X M, et al. Detection of metronidazole and ronidazole from environmental samples by surface enhanced Raman spectroscopy［J］. Talanta, 2014, 128: 293-298.

【11】Andreou C, Mirsafavi R, Moskovits M, et al. Detection of low concentrations of ampicillin in milk［J］. Analyst, 2015, 140(15): 5003-5005.

【12】Ma J, Kong D D, Han X H, et al. Detection of antibiotics in water using silver colloid films as substrate of surface-enhanced Raman scattering［J］. Spectroscopy and Spectral Analysis, 2013, 33(10): 2688-2693.
马君, 孔德地, 韩晓红, 等. 应用银溶胶膜探测水中抗生素的表面增强拉曼光谱研究［J］. 光谱学与光谱分析, 2013, 33(10): 2688-2693.

【13】Li D, Li D W, Fossey J S, et al. Portable surface-enhanced Raman scattering sensor for rapid detection of aniline and phenol derivatives by on-site electrostatic preconcentration［J］. Analytical Chemistry, 2010, 82(22): 9299-9305.

【14】Lee P C, Meisel D. Adsorption and surface-enhanced Raman of dyes on silver and gold sols［J］. Journal of Physical Chemistry, 1982, 86(17): 3391-3395.

【15】Li Q Q, Du Y P, Xu Y, et al. Rapid and sensitive detection of pesticides by surface-enhanced Raman spectroscopy technique based on glycidyl methacrylate-ethylene dimethacrylate (GMA-EDMA) porous material［J］. Chinese Chemical Letters, 2013, 24(4): 332-334.

【16】Yang J L, Li R P, Wang L W, et al. Raman enhancement study on Au@SiO2 nanoparticles with different Au core sizes［J］. Chinese Journal of Lasers, 2016, 43(2): 0215001.
杨晶亮, 李若平, 王立卫, 等. 不同金颗粒尺寸的Au@SiO2纳米粒子拉曼增强研究［J］. 中国激光, 2016, 43(2): 0215001.

【17】Boreen A L, Arnold W A, McNeill K. Triplet-sensitized photodegradation of sulfa drugs containing six-membered heterocyclic groups: Identification of an SO2 extrusion photoproduct［J］. Environmental Science & Technology, 2005, 39(10): 3630-3638.

【18】Li T, Tang Y L, Ling Z G, et al. Influence of external electric field on the molecular structure and electronic spectrum of paranitrochlorobenzene［J］. Acta Physica Sinica, 2013, 62(10): 103103.
李涛, 唐延林, 凌智钢, 等. 外电场对对硝基氯苯分子结构与电子光谱影响的研究［J］. 物理学报, 2013, 62(10): 103103.

【19】Cao X P, Sun C Q, Thamann T J. A study of sulfamerazine single crystals using atomic force microscopy, transmission light microscopy, and Raman spectroscopy［J］. Journal of Pharmaceutical Sciences, 2005, 94(9): 1881-1892.

【20】Sutherland W S, Laserna J J, Angebranndt M J, et al. Surface-enhanced Raman analysis of sulfa drugs on colloidal silver dispersion［J］. Analytical Chemistry, 1990, 62(7): 689-693.

【21】Zhang Y Y, Huang Y Q, Zhai F L, et al. Analyses of enrofloxacin, furazolidone and malachite green in fish products with surface-enhanced Raman spectroscopy［J］.Food Chemistry, 2012, 135(2): 845-850.

【22】Fu R R, Liu G Q, Jia C, et al. Fabrication of silver nanoplate hierarchical turreted ordered array and its application in trace analyses［J］. Chemical Communications, 2015, 51(30): 6609-6612.

【23】Pavel I, Szeghalmi A, Moigno D, et al. Theoretical and pH dependent surface enhanced Raman spectroscopy study on caffeine［J］. Biopolymers, 2003, 72(1): 25-37.

【24】He L L, Lin M S, Li H, et al. Surface-enhanced Raman spectroscopy coupled with dendritic silver nanosubstrate for detection of restricted antibiotics［J］.Journal of Raman Spectroscopy, 2010, 41(7): 739-744.

【25】Skoulika S G, Georgiou C A. Rapid quantitative determination of ciprofloxacin in pharmaceuticals by use of solid-state FT-Raman spectroscopy［J］. Applied Spectroscopy, 2001, 55(9): 1259-1265.

引用该论文

Ma Haikuan,Zhang Xu,Zhong Shilei,Shi Xiaofeng,Ma Lizhen,Ma Jun. Detection of Antibiotics Based on Hyphenated Technique of Electrostatic-Preconcentration and Surface-Enhanced-Raman-Spectroscopy[J]. Chinese Journal of Lasers, 2018, 45(2): 0207028

马海宽,张旭,钟石磊,史晓凤,马丽珍,马君. 基于静电富集-表面增强拉曼光谱联用技术的抗生素检测[J]. 中国激光, 2018, 45(2): 0207028

被引情况

【1】陈阳,严霞,张旭,史晓凤,马君. 基于支持向量机算法的多环芳烃表面增强拉曼光谱的定量分析. 中国激光, 2019, 46(3): 311005--1