腐植酸与环丙沙星结合机制的多维光谱学解析研究

doi:10.6023/A21080408

摘要/Abstract

本工作研究了水环境中残留喹诺酮类抗生素环丙沙星(ciprofloxacin, CIP)与溶解有机物(dissolved organic matter, DOM)腐植酸(humic acid, HA)的结合作用机理. 采用三维荧光、傅里叶红外光谱、二维相关光谱和液体核磁共振氢谱等技术进行表征分析. 结果表明, CIP和HA的结合作用会产生明显的荧光淬灭现象, 且在6 h后结合开始趋于平衡. 结合作用与HA表面的羟基、羧基以及酮基等官能团相关, 而CIP分子哌嗪环上的H质子是参与结合的主要位点. 此外, 影响因素实验表明, 离子强度(ionic strength, IS)对结合作用影响较小, 而pH对其影响较大, 且在pH=5时荧光淬灭率最高. 荧光淬灭率与金属离子价态呈现正相关. 通过研究水体中CIP和HA的相互作用, 对于监测研究天然水体中残留抗生素的迁移和转化提供理论依据.

关键词: 环丙沙星, 溶解有机物, 结合作用, 多维光谱, 机理研究

In this paper, the mechanism of the binding interaction between residual ciprofloxacin (CIP) and dissolved organic matter humic acid (HA) in natural water environment was systematically investigated. Various spectral analysis technologies, including the three-dimensional excitation-emission matrix spectra, fourier transform infrared (FTIR) spectra, two-dimensional correlation spectra (2D-COS) and liquid nuclear magnetic resonance (¹H NMR) spectra techniques, were adopted to reveal the mechanism of the binding interaction between CIP and HA. The results suggested that the binding interaction between CIP and HA resulted in significant fluorescence quenching, and the binding interaction tended to balance after 6 h monitored by ultraviolet (UV) differential spectroscopy. Based on the FTIR analysis, the hydroxyl, carboxyl and ketone groups of HA were the main contributors to the binding interaction, and the results of 2D-COS indicated that the ketone groups preferentially participated in binding interaction compared to carboxyl groups. The H protons on the piperazine ring of CIP were identified as the main binding sites by the ¹H NMR, and the comparison of fluorescence quenching rate of other fluoroquinolone antibiotics (norfloxacin and levofloxacin) with similar structures also verified that the piperazine ring played a crucial role in binding interaction. Additionally, the influence of ionic strength (IS, range 0.001—0.1) on the binding interaction was ignorable compared with pH. The fluorescence quenching rates increased firstly and then decreased with the increase of pH (range 3—11), and the fluorescence quenching rate was up to 70% at pH 5. Moreover, the fluorescence quenching rates were positively correlated with the valence state of metal ions (order of influence followed: Al³⁺>Zn²⁺, Co²⁺, NH₄⁺, Ca²⁺>Mn²⁺, Na⁺, K⁺). This study provides the theoretical basis and effective detection technologies for monitoring the migration and transformation of residual antibiotics in the natural water environment.

Key words: ciprofloxacin, dissolved organic matter, binding interaction, multi-spectroscopic, mechanism

引用此文

杨波, 张永丽, 郭洪光. 腐植酸与环丙沙星结合机制的多维光谱学解析研究[J]. 化学学报, 2021, 79(12): 1494-1501.

Bo Yang, Yongli Zhang, Hongguang Guo. Multi-spectroscopic Investigation on Mechanism of Binding Interaction between Humic Acid and Ciprofloxacin[J]. Acta Chimica Sinica, 2021, 79(12): 1494-1501.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

图/表 9

图1. (a) HA, CIP以及HA/CIP随时间变化的紫外可见吸收光谱; (b) HA/CIP体系随时间变化的紫外吸光度差值([CIP]=0.5 mg/L, [HA]=2.5 mg/L)

Figure 1. (a) The UV-vis absorption spectra of HA, CIP and HA/CIP vs. time; (b) the difference in UV-visible absorbance of HA/CIP over time ([CIP]=0.5 mg/L, [HA]=2.5 mg/L)

图2. 三维荧光谱图: (a) 0.5 mg/L CIP; (b) 1 mg/L HA; (c) 0.5 mg/L CIP+1 mg/L HA; (d) 0.5 mg/L CIP+2 mg/L HA

Figure 2. Excitation-emission matrix spectra: (a) 0.5 mg/L CIP; (b) 1 mg/L HA; (c) 0.5 mg/L CIP+1 mg/L HA; (d) 0.5 mg/L CIP+2 mg/L HA

图3. (a) HA投量和(b) CIP浓度对荧光淬灭率的影响(a: [CIP]=0.25 mg/L, [HA]=0.1~4.5 mg/L; b: [CIP]=0.25~1.5 mg/L, [HA]=2.5 mg/L)

Figure 3. Effect of (a) HA dosages and (b) CIP concentrations on the fluorescence quenching (a: [CIP]=0.25 mg/L, [HA]=0.1—4.5 mg/L; b: [CIP]=0.25—1.5 mg/L, [HA]=2.5 mg/L)

图4. (a) IS和(b) pH对荧光淬灭率的影响([CIP]=0.25 mg/L, [HA]=1.25 mg/L)

Figure 4. (a) Effect of IS and (b) pH on the fluorescence quenching rate ([CIP]=0.25 mg/L, [HA]=1.25 mg/L)

图5. (a) 金属离子对CIP和HA荧光强度的影响; (b) 金属离子对荧光淬灭率的影响([CIP]=0.25 mg/L, [HA]=2.5 mg/L)

Figure 5. (a) Effect of various metal ions on the fluorescence intensity of both CIP and HA; (b) effect of various metal ions on the fluorescence quenching ([CIP]=0.25 mg/L, [HA]=2.5 mg/L)

图6. 不同m(HA)∶m(CIP)比例在(a) 4000~800 cm-1和(b) 1800~800 cm-1范围内的FTIR图; (c) 2D-COS同步谱; (d) 2D-COS异步谱 ([CIP]=0~2.5 mg/L, [HA]=2.5 mg/L)

Figure 6. The FTIR spectra of various m(HA)∶m(CIP) at the range of (a) 4000—800 cm-1 and (b) 1800—800 cm-1; (c) synchronous and (d) asynchronous maps of 2D-COS ([CIP]=0—2.5 mg/L, [HA]=2.5 mg/L)

ṽ/cm^-1	1444	1375	1252	1074
1631	–(+)	+(–)	+(+)	–(–)
1444		–(+)	–(–)	+(+)
1375			+(+)	–(–)
1252				–(+)
1074

表1. 2D-COS同步异步谱中交叉相关峰符号

Table 1. Sign of each cross-peak in the synchronous and asynchronous maps from 2D-COS

图7. (a) 不同m(CIP)∶m(HA)比例的核磁共振氢谱; (b) 不同CIP分子H质子的绝对化学位移([CIP]=2 mg/mL, [HA]=0~4 mg/mL)

Figure 7. (a) The 1H NMR of various m(CIP)∶m(HA); (b) the absolute chemical shift of various H protons of CIP ([CIP]=2 mg/mL, [HA]=0—4 mg/mL)

图8. 不同种类的氟喹诺酮类抗生素荧光淬灭率比较([CIP]=[NOR]=[LEVO]=0.25 mg/L, [HA]=3 mg/L)

Figure 8. Comparison of fluorescence quenching rates of different fluoroquinolone antibiotics ([CIP]=[NOR]=[LEVO]=0.25 mg/L, [HA]=3 mg/L)

参考文献 29

[1]	Guo, H.-G.; Gao, N.-Y.; Yang, Y.; Zhang, Y.-L. Chem. Eng. J. 2016, 292, 82. doi: 10.1016/j.cej.2016.01.009
[2]	Kim, T.-K.; Kim, T.; Park, H.; Lee, I.; Jo, A.; Choi, K.; Zoh, K.-D. Chem. Eng. J. 2020, 394, 124803. doi: 10.1016/j.cej.2020.124803
[3]	Philippe, A.; Schaumann, G.-E. Environ. Sci. Technol. 2014, 48, 8946. doi: 10.1021/es502342r pmid: 25082801
[4]	Wei, J.; Tu, C.; Yuan, G.-D.; Zhou, Y.-Q.; Wang, H. L.; Lu, J. Sci. Total. Environ. 2020, 701, 134919. doi: 10.1016/j.scitotenv.2019.134919
[5]	Wang, L.; Liang, N.; Li, H.; Yang, Y.; Zhang, D.; Liao, S.-H.; Pan, B. Environ. Pollut. 2015, 196, 379. pmid: 25463736
[6]	Lyu, Y.; Yu, J.; Guo, M.-H.; Wang, K.; Yu, Z.-X.; Zhang, L.-X.; Zhang, Y.; Chen, L.-L. Chemosphere 2021, 263, 128044. doi: 10.1016/j.chemosphere.2020.128044
[7]	Zhang, W.-J.; Su, Y.; Xu, K.-X.; Shi, T.; Liu, J. Acta Chim. Sinica 2010, 68, 2574 (in Chinese).
	( 张婉洁, 苏洋, 徐可欣, 石婷, 刘瑾, 化学学报, 2010, 68, 2574.)
[8]	Xu, J.; Yu, H.-Q.; Sheng, G.-P. J. Hazard. Mater. 2016, 302, 262. doi: 10.1016/j.jhazmat.2015.09.058
[9]	Yan, M.-Q.; Lu, Y.-J.; Gao, Y.; Benedetti, M.-F.; Korshin, G.-V. Environ. Sci. Technol. 2015, 49, 8323. doi: 10.1021/acs.est.5b00003
[10]	Wang, J.; Liu, Z.-F.; Liu, S.-P.; Shen, W. Acta Chim. Sinica 2008, 66, 1337 (in Chinese).
	( 王剑, 刘忠芳, 刘绍璞, 申伟, 化学学报, 2008, 66, 1337.)
[11]	Lu, R.; Sheng, G.-P.; Liang, Y.; Li, W.-H.; Tong, Z.-H.; Chen, W.; Yu, H.-Q.; Weber, R.; Aliyeva, G.; Vijgen, J. Environ. Sci. Pollut. R. 2013, 20, 2220. doi: 10.1007/s11356-012-1087-6
[12]	Pan, B.; Liu, Y.; Xiao, D.; Wu, F.-C.; Wu, M.; Zhang, D.; Xing, B.-S. Environ. Pollut. 2012, 161, 192. doi: 10.1016/j.envpol.2011.10.026 pmid: 22230085
[13]	Wang, L.; Li, H.; Zhang, D.; Wu, M.; Pan, B.; Xing, B.-S. Water Res. 2017, 122, 337. doi: S0043-1354(17)30484-0 pmid: 28618358
[14]	Wang, R.-Z.; Yang, S.-K.; Fang, J.; Wang, Z.-Z.; Chen, Y.-Y.; Zhang, D.; Yang, C.-Y. Int. J. Env. Res. Pub. He. 2018, 15, 1458. doi: 10.3390/ijerph15071458
[15]	Li, Y.; Jiang, Y.-C.; Jiang, P.-P.; Du, S.-Y.; Jiang, J.-S.; Leng, Y. Acta Chim. Sinica 2019, 77, 66 (in Chinese). doi: 10.6023/A18070301
	( 李月, 姜宇晨, 蒋平平, 杜盛郁, 姜就胜, 冷炎, 化学学报, 2019, 77, 66.) doi: 10.6023/A18070301
[16]	Zhao, X.-T.; Hu, Z.-Z.; Yang, X.; Cai, X.-W.; Wang, Z.-W.; Xie, X.-Y. Environ. Pollut. 2019, 248, 815. doi: 10.1016/j.envpol.2019.02.077
[17]	Pan, B.; Qiu, M.-Y.; Wu, M.; Zhang, D.; Peng, H.-B.; Wu, D.; Xing, B.-S. Environ. Pollut. 2012, 161, 76. doi: 10.1016/j.envpol.2011.09.040 pmid: 22230071
[18]	Ren, D.; Huang, B.; Yang, B.-Q.; Pan, X.-J.; Dionysiou, D.-D. J. Hazard. Mater. 2017, 327, 197. doi: 10.1016/j.jhazmat.2016.12.054
[19]	Lei, K.; Han, X.-J.; Fu, G.; Zhao, J.; Yang, L.-B. Environ. Monit. Assess. 2014, 186, 8857. doi: 10.1007/s10661-014-4049-2
[20]	Yang, B.; Wang, C.-J.; Cheng, X.; Zhang, Y.-L.; Li, W.; Wang, J.-Q.; Tian, Z.-X.; Chu, W.-H.; Kroshin, G.-V.; Guo, H.-G. Water Res. 2021, 202, 117379. doi: 10.1016/j.watres.2021.117379 pmid: 34246001
[21]	Xiong, J. Ph.D. Dissertation, Huazhong Agricultural University, Wuhan, 2015 (in Chinese).
	( 熊娟, 博士论文, 华中农业大学, 武汉, 2015.)
[22]	Chen, W.-R.; Huang, C.-H. Environ. Sci. Technol. 2009, 43, 401. doi: 10.1021/es802295r
[23]	Yang, B.; Zhang, Y.-L. Acta Chim. Sinica 2019, 77, 1017 (in Chinese). doi: 10.6023/A19060203
	( 杨波, 张永丽, 化学学报, 2019, 77, 1017.) doi: 10.6023/A19060203
[24]	Yan, W.; Zhang, J.-F.; Jing, C.-Y. J. Colloid. Interf. Sci. 2013, 390, 196. doi: 10.1016/j.jcis.2012.09.039
[25]	Xu, H.-C.; Yan, M.-Q.; Li, W.-T.; Jiang, H.-L.; Guo, L.-D. Water Res. 2018, 144, 435. doi: 10.1016/j.watres.2018.07.062
[26]	Noda, I. Macromol. Symp. 2014, 339, 17. doi: 10.1002/masy.201300129
[27]	Garro Linck, Y.; Chattah, A.-K.; Graf, R.; Romañuk, C.-B.; Olivera, M.-E.; Manzo, R.-H.; Monti, G.-A.; Spiess, H.-W. Phys. Chem. Chem. Phys. 2011, 13, 6590. doi: 10.1039/c0cp02919j pmid: 21384011
[28]	Bedard, M.; Giffear, K.-A.; Ponton, L.; Sienerth, K.-D.; Del Gaizo Moore, V. Biophys. Chem. 2014, 189, 1. doi: 10.1016/j.bpc.2014.02.001 pmid: 24583968
[29]	Xu, J.; Hu, Y.-Y.; Li, X.-Y.; Chen, J.-J.; Sheng, G.-P. Environ. Pollut. 2018, 243, 752. doi: 10.1016/j.envpol.2018.09.002