Multi-spectroscopic Investigation on Mechanism of Binding Interaction between Humic Acid and Ciprofloxacin

doi:10.6023/A21080408

Abstract

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

Cite this article

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.

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Fig. & Tab. 9

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)

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

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)

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

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

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

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)

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

References 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

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