In Situ Raman Monitoring of Trace Antibiotics in Different Harsh Water Environments
), Jing Yu1 
()Abstract
In situ surface-enhanced Raman scattering (SERS) is a widely used operando analytical technique, while facing numerous complex factors in applications under aqueous environment, such as low detection sensitivity, poor anti-interference capability, etc., resulting in unreliable detectability. To address these issues, herein a new hydrophobic SERS strategy has been attempted. By comprehensively designing and researching a SERS-active structure of superhydrophobic ZnO/Ag nanowires, we demonstrate that hydrophobicity can not only draw analytes from water onto substrate, but also adjust “hottest spot” from the bottom of the nanowires to the top. As a result, the structure can simultaneously concentrate the dispersed molecules in water and the enhanced electric field in structure into a same zone, while perfecting its own anti-interference ability. The underwater in situ analytical enhancement factor of this platform is as high as 1.67 × 1011, and the operando limited of detection for metronidazole (MNZ) reaches to 10−9 M. Most importantly, we also successfully generalized this structure to various real in situ detection scenarios, including on-site detection of MNZ in corrosive urine, real-time warning of wrong dose of MNZ during intravenous therapy, in situ monitoring of MNZ in flowing wastewater with particulate interference, etc., demonstrating the great application potential of this hydrophobic platform. This work realizes a synergistic promotion for in situ SERS performance under aqueous environment, and also provides a novel view for improving other in situ analytical techniques.
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References
M. Diamant, S. Baruch, E. Kassem, K. Muhsen, D. Samet, M. Leshno, U. Obolski, Nat. Commun. 2021, DOI: https://doi.org/10.1038/s41467-021-21088-5.
K. H. Lee, H. Jang, Y. S. Kim, C. H. Lee, S. H. Cho, M. Kim, H. Son, K. B. Bae, D. V. Dao, Y. S. Jung, I. H. Lee, Adv. Sci. 2021, 8, 2100640.
R. A. Oliveira, V. Cabral, K. B. Xavier, Nat. Microbiol. 2021, 6, 824.
L. L. Qu, Y. Y. Liu, M. K. Liu, G. H. Yang, D. W. Li, H. T. Li, ACS Appl. Mater. Interfaces 2016, 8, 28180.
N. Liang, P. T. Huang, X. H. Hou, Z. Li, L. Tao, L. S. Zhao, Anal. Bioanal. Chem. 2016, 408, 1701.
A. Menelaou, A. A. Somogyi, M. L. Barclay, F. Bochner, J. Chromatogr. B 1999, 731, 261.
J. H. Wang, J. Chromatogr. A 2001, 918, 435.
T. Kokulnathan, S. M. Chen, A. C. S. Appl, Mater. Inter. 2019, 11, 7893.
H. Hao, D. Y. Shi, D. Yang, Z. W. Yang, Z. G. Qiu, W. L. Liu, Z. Q. Shen, J. Yin, H. R. Wang, J. W. Li, H. Wang, M. Jin, J. Hazard. Mater. 2019, 365, 340.
M. Liu, S. Y. Shen, D. Wen, M. R. Li, T. Li, X. J. Chen, Z. Gu, R. Mo, Nano Lett. 2018, 18, 2294.
M. Reyman, M. A. van Houten, R. L. Watson, M. L. J. N. Chu, K. Arp, W. J. de Waal, I. Schiering, F. B. Plotz, R. J. L. Willems, W. van Schaik, E. A. M. Sanders, D. Bogaert, Nat. Commun. 2022, DOI: https://doi.org/10.1038/s41467-022-28525-z.
H. Teymourian, M. Parrilla, J. R. Sempionatto, N. F. Montiel, A. Barfidokht, R. Van Echelpoel, K. De Wael, J. Wang, ACS Sens. 2020, 5, 2679.
X. R. Yang, Z. Chen, W. Zhao, C. X. Liu, X. X. Qian, M. Zhang, G. Y. Wei, E. Khan, Y. H. Ng, Y. S. Ok, Chem. Eng. J. 2021, 405, 126806.
Y. C. Yang, K. Gupta, K. L. Ekinci, Proc. Natl. Acad. Sci. U. S. A. 2020, 117, 10639.
S. Y. Ding, J. Yi, J. F. Li, B. Ren, D. Y. Wu, R. Panneerselvam, Z. Q. Tian, Nat. Rev. Mater. 2016, DOI: https://doi.org/10.1038/natrevmats.2016.21.
K. A. Willets, R. P. Van Duyne, Annu. Rev. Phys. Chem. 2007, 58, 267.
J. Li, H. Liu, S. Chen, X. Liang, Y. Gao, X. Zhao, Z. Li, C. Zhang, F. Lei, J. Yu, J. Phys. Chem. Lett. 2022, 13, 5815.
D. P. dos Santos, M. L. A. Temperini, A. G. Brolo, Acc. Chem. Res. 2019, 52, 456.
J. R. Li, A. Wuethrich, A. I. Sina, H. H. Cheng, Y. L. Wang, A. Behren, P. N. Mainwaring, M. Trau, Nat. Commun. 2021, DOI: https://doi.org/10.1038/s41467-021-27100-2.
J. Yu, Y. Guo, H. J. Wang, S. Su, C. Zhang, B. Y. Man, F. C. Lei, J. Phys. Chem. Lett. 2019, 10, 3676.
J. Yu, M. S. Yang, Z. Li, C. D. Liu, Y. S. Wei, C. Zhang, B. Y. Man, F. C. Lei, Anal. Chem. 2020, 92, 14754.
H. K. Lee, Y. H. Lee, C. S. L. Koh, C. P. Q. Gia, X. M. Han, C. L. Lay, H. Y. F. Sim, Y. C. Kao, Q. An, X. Y. Ling, Chem. Soc. Rev. 2019, 48, 731.
C. C. Li, Y. M. Huang, X. Y. Li, Y. R. Zhang, Q. L. Chen, Z. W. Ye, Z. Alqarni, S. E. J. Bell, Y. K. Xu, J. Mater. Chem. C 2021, 9, 11517.
W. K. Wang, F. Zhao, M. Z. Li, C. P. Zhang, Y. H. Shao, Y. Tian, Angew. Chem. Int. Ed. 2019, 58, 5256.
L. L. Zhang, Y. Guo, R. Hao, Y. F. Shi, H. J. You, H. Nan, Y. Z. Dai, D. J. Liu, D. Y. Lei, J. X. Fang, Nat. Commun. 2021, 12, 1.
C. Q. Han, J. Chen, X. M. Wu, Y. W. Huang, Y. P. Zhao, Talanta 2014, 128, 293.
P. Veerakumar, A. Sangili, S. M. Chen, K. C. Lin, J. Mater. Chem. C 2020, 8, 7575.
M. G. Gong, Z. Yang, X. L. Xu, D. Jasion, S. Mou, H. D. Zhang, Y. Z. Long, S. Q. Ren, J. Mater. Chem. A 2014, 2, 6180.
T. Lee, W. Lee, S. W. Kim, J. J. Kim, B. S. Kim, Adv. Funct. Mater. 2016, 26, 6206.
Y. Liu, A. Das, S. Xu, Z. Y. Lin, C. Xu, Z. L. Wang, A. Rohatgi, C. P. Wong, Adv. Energy Mater. 2012, 2, 47.
F. De Angelis, F. Gentile, F. Mecarini, G. Das, M. Moretti, P. Candeloro, M. L. Coluccio, G. Cojoc, A. Accardo, C. Liberale, R. P. Zaccaria, G. Perozziello, L. Tirinato, A. Toma, G. Cuda, R. Cingolani, E. Di Fabrizio, Nat. Photonics 2011, 5, 683.
J. N. Dong, J. Y. Huang, A. Wang, G. V. Biesold-McGee, X. N. Zhang, S. W. Gao, S. C. Wang, Y. K. Lai, Z. Q. Lin, Nano Energy 2020, 71, 104579.
F. Guo, H. Yang, J. J. Mao, J. Y. Huang, X. Q. Wang, Y. K. Lai, Compos. Commun. 2018, 10, 151.
J. S. Cai, J. Y. Huang, M. Z. Ge, J. Iocozzia, Z. Q. Lin, K. Q. Zhang, Y. K. Lai, Small 2017, 13, 1604240.
B. Bhushan, E. K. Her, Langmuir 2010, 26, 8207.
L. Feng, Y. A. Zhang, J. M. Xi, Y. Zhu, N. Wang, F. Xia, L. Jiang, Langmuir 2008, 24, 4114.
M. J. Cheng, M. M. Song, H. Y. Dong, F. Shi, Small 2015, 11, 1665.
X. F. Gao, X. Yan, X. Yao, L. Xu, K. Zhang, J. H. Zhang, B. Yang, L. Jiang, Adv. Mater. 2007, 19, 2213.
D. Oner, T. J. McCarthy, Langmuir 2000, 16, 7777.
L. Wu, Z. C. Dong, M. X. Kuang, Y. A. Li, F. Y. Li, L. Jiang, Y. L. Song, Adv. Funct. Mater. 2015, 25, 2237.
Z. Yoshimitsu, A. Nakajima, T. Watanabe, K. Hashimoto, Langmuir 2002, 18, 5818.
S. Y. Ding, E. M. You, Z. Q. Tian, M. Moskovits, Chem. Soc. Rev. 2017, 46, 4042.
H. X. Xu, J. Aizpurua, M. Kall, P. Apell, Phys. Rev. E 2000, 62, 4318.
A. Olshtrem, O. Guselnikova, P. Postnikov, A. Trelin, M. Yusubov, Y. Kalachyova, L. Lapcak, M. Cieslar, P. Ulbrich, V. Svorcik, O. Lyutakov, Nanoscale 2020, 12, 14581.
Q. Q. Peng, N. Wang, Y. Zhu, J. Hu, H. Q. Peng, L. Li, B. Z. Zheng, J. Du, D. Xiao, J. Mater. Chem. C 2019, 7, 10465.
D. Murakami, H. Jinnai, A. Takahara, Langmuir 2014, 30, 2061.
H. Y. Wu, B. T. Cunningham, Nanoscale 2014, 6, 5162.
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