Citation: Bing WANG, Qiong WU, JIN-Feng XIA, Xin LI, Dan-Yu JIANG, Qiang LI. Anthrax Biomarker: a Fluorescent Probe for Dipicolinic Acid Using Eu(Ⅲ)-doped Nanosheets[J]. Chinese Journal of Structural Chemistry, ;2020, 39(10): 1788-1794. doi: 10.14102/j.cnki.0254–5861.2011–2707 shu

Anthrax Biomarker: a Fluorescent Probe for Dipicolinic Acid Using Eu(Ⅲ)-doped Nanosheets

Bing WANG ^a ,
Qiong WU ^b ,
JIN-Feng XIA ^c ,
Xin LI ^a ,
Dan-Yu JIANG ^c ,
Qiang LI ^a,,

a.
School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200062, China
b.
Department of Chemistry, Hebei Normal University for Nationalities, Chengde, Hebei 067000, China
c.
Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China

Corresponding author: Qiang LI, qli@chem.ecnu.edu.cn
Received Date: 20 December 2019
Accepted Date: 21 February 2020

Fund Project: the Department of Science and Technology of Hebei Province 17272610

Figures(7)

A novel two-dimensional nanosheet fluorescent probe embedded with rare earth Eu(Ⅲ) was developed to detect dipicolinic acid (DPA), a biomarker of Bacillus anthracis bacterial spores. DPA, a major component of Bacillus anthracis spores which were highly toxic to humans, was not found in other common bacteria. The ability to detect ultra-low concentrations of DPA would therefore be of great significance. Eu(Ⅲ)-doped ytterbium hydroxide nanosheets were obtained by mechanical exfoliation from layered rare-earth hydroxide (LRH) materials. The crystallinities, layered structure and morphology of the as-synthesized nanosheets were studied by power X-ray diffraction, transmission electron microscopy and atomic force microscopy. Eu(Ⅲ) emission increased linearly with DPA addition in the range of 0.1~30 μmol/L. Based on the antenna effect, the detection limit of DPA was 0.078 μmol/L and much lower than the infective dose of Bacillus anthracis in humans of 60 μmol/L. The nanosheet fluorescent probe exhibited good specificity toward DPA, and the interferences with selected aromatic ligands and amino acids were observed to be negligibly small in comparison with that of DPA. Our findings provide a basis for the application of Eu(Ⅲ)-doped nanosheets for accurate, sensitive, and selective monitoring of DPA as a biomarker of anthrax.
- layered compound,
- nanosheets,
- fluorescent probe,
- dipicolinic acid,
- bacterial spores
1. [1]
  Enserink, M. This time it was real: knowledge of anthrax put to the test. Scienc 2001, 294, 490-491 doi: 10.1126/science.294.5542.490
2. [2]
  Yilmaz, M. D.; Oktem, H. A. Eriochrome black T-Eu³⁺ complex as a ratiometric colorimetric and fluorescent probe for the detection of dipicolinic acid, a biomarker of bacterial spores. Anal. Chem. 2018, 90, 4221-4225. doi: 10.1021/acs.analchem.8b00576
3. [3]
  Mock, M.; Fouet, A. Anthrax. Annu. Rev. Microbiol. 2001, 55, 647-671. doi: 10.1146/annurev.micro.55.1.647
4. [4]
  Kumar, G. A. Anthrax: a disease of biowarfare and public health importance. World J. Clin. Cases 2015, 3, 20-33. doi: 10.12998/wjcc.v3.i1.20
5. [5]
  Walt, D. R.; Franz, D. R. Biological warfare detection. Anal. Chem. 2000, 72, 738A-746A. doi: 10.1021/ac003002a
6. [6]
  Wang, Q. X.; Xue, S. F.; Chen, Z. H.; Ma, S. H.; Zhang, S.; Shi, G.; Zhang, M. Dual lanthanide-doped complexes: the development of a time-resolved ratiometric fluorescent probe for anthrax biomarker and a paper-based visual sensor. Biosens. Bioelectron. 2017, 94, 388-393. doi: 10.1016/j.bios.2017.03.027
7. [7]
  Rong, M. C.; Liang, Y. C.; Zhao, D. L.; Chen, B. J.; Pan, C.; Deng, X. Z.; Chen, Y. B.; He, J. A ratiometric fluorescence visual test paper for an anthrax biomarker based on functionalized manganese-doped carbon dots. Sens. Actuators B 2018, 265, 498-505. doi: 10.1016/j.snb.2018.03.094
8. [8]
  Tan, H. L.; Ma, C. J.; Chen, L. L.; Xu, F. G.; Chen, S. H.; Wang, L. Nanoscaled lanthanide/nucleotide coordination polymer for detection of an anthrax biomarker. Sens. Actuators B 2014, 190, 621-626. doi: 10.1016/j.snb.2013.09.024
9. [9]
  Kong, L. B.; Setlow, P.; Li, Y. Q. Analysis of the Raman spectra of Ca⁽²⁺⁾-dipicolinic acid alone and in the bacterial spore core in both aqueous and dehydrated environments. Analyst. 2012, 137, 3683-3689. doi: 10.1039/c2an35468c
10. [10]
  Klonkowski, A.; Lis, S.; Hnatejko, Z.; Czarnobaj, K.; Pietraszkiewicz, M.; Elbanowski, M. Improvement of emission intensity in luminescent materials based on the antenna effect. J. Alloy. Compd. 2000, 300, 55-60.
11. [11]
  Lin, Z. Y.; Qu, Z. B.; Chen, Z. H.; Han, X. Y.; Deng, L. X.; Luo, Q. Y.; Jin, Z. W.; Shi, G. Y.; Zhang, M. The marriage of protein and lanthanide: unveiling a time-resolved fluorescence sensor array regulated by pH toward high throughput assay of metal ions in biofluids. Anal. Chem. 2019, 91, 11170-11177. doi: 10.1021/acs.analchem.9b01879
12. [12]
  Rong, M. C.; Deng, X. Z.; Chi, S.; Huang, L. Z.; Zhou, Y. B.; Shen, Y. N.; Chen, X. Ratiometric fluorometric determination of the anthrax biomarker 2, 6-dipicolinic acid by using europium(Ⅲ)-doped carbon dots in a test stripe. Microchim Acta 2018, 185, 2-10. doi: 10.1007/s00604-017-2585-5
13. [13]
  Zhang, L.; Jiang, D. Y.; Xia, J. F.; Zhang, N.; Li, Q. Fluorescence enhancement of europium-doped yttrium hydroxide nanosheets modified by 2-thenoyltrifluoroacetone. RSC Adv. 2014, 34, 17856-17857.
14. [14]
  Viveros-Andrade, A. G.; Colorado-Peralta, R.; Flores-Alamo, M.; Castillo-Blum, S. E.; Duran-Hernandez, J.; Rivera, J. M. Solvothermal synthesis and spectroscopic characterization of three lanthanide complexes with high luminescent properties [H₂NMe₂]₃[Ln(Ⅲ)(2, 6-pyridinedicarboxylate)₃] (Ln = Sm, Eu, Tb): in the presence of 4, 4-bipyridyl. J. Mol. Struct. 2017, 1145, 10-17. doi: 10.1016/j.molstruc.2017.05.055
15. [15]
  Ming, C. L.; Du, X.; Qin, L.; Cui, G. H. Crystal Structural and fluoresence properties of a two-dimensional cobaltous coordination polymer containing bis(benzimidazole) ligand. J. Struct. Chem. 2014, 55, 927-931. doi: 10.1134/S0022476614050205
16. [16]
  Yu, Y. Y.; Zhang, H. Q. Reduced graphene oxide coupled magnetic CuFe₂O₄-TiO₂ nanoparticles with enhanced photocatalytic activity for methylene blue degradation. Chin. J. Struct. Chem. 2016, 35, 472-480.
17. [17]
  Yilmaz, M. D.; Hsu, S. H.; Reinhoudt, D. N.; Velders, A.; Huskens, H. J. Ratiometric fluorescent detection of an anthrax biomarker at molecular printboards. Angew. Chem. Int. Ed. 2010, 49, 5938-4941. doi: 10.1002/anie.201000540
18. [18]
  Rosen, D. L.; Sharpless, C.; McGown, L. B. Bacterial spore detection and determination by use of terbium dipicolinate photoluminescence. Anal. Chem. 1997, 69, 1082-1085. doi: 10.1021/ac960939w
19. [19]
  Pellegrino, P. M.; Fell, N. F.; Rosen, D. L.; Gillespie, J. B. Bacterial endospore detection using terbium dipicolinate photoluminescence in the presence of chemical and biological materials. Anal. Chem. 1998, 70, 1755-1760. doi: 10.1021/ac971232s
20. [20]
  Xu, J.; Shen, X. K.; Jia, L.; Zhang, M. M.; Zhou, T.; Wei, Y. K. Facile ratiometric fluorapatite nanoprobes for rapid and sensitive bacterial spore biomarker detection. Biosens. Bioelectron. 2017, 87, 991-997. doi: 10.1016/j.bios.2016.09.070
21. [21]
  Ke, L.; Meng, R.; Shan, C.; Jing, C.; Jia, J.; Liu, W. S.; Tang, Y. A novel terbium functionalized micelle nanoprobe for ratiometric fluorescence detection of anthrax spore biomarker. Anal. Chem. 2018, 90, 3600-3607. doi: 10.1021/acs.analchem.8b00050
22. [22]
  Ammann, A. B.; Kolle, L.; Brandl, H. Detection of bacterial endospores in soil by terbium fluorescence. Int. J. Microbiol. 2011, 2011, 1-5.
23. [23]
  Yang, W.; Li, Q.; Zheng, X. H.; Li, X.; Li, X. Luminescent sensing film based on sulfosalicylic acid modified Tb(Ⅲ)-doped yttrium hydroxide nanosheets. J. Adv. Ceram. 2018, 7, 352-361. doi: 10.1007/s40145-018-0285-1
24. [24]
  Siddiqi, Z. A.; Khalid, M. Antimicrobial and SOD activities of novel transition metal complexes of pyridine-2, 6-dicarboxylic acid containing 4-picoline as auxiliary ligand. Eur. J. med. chem. 2010, 45, 264-269. doi: 10.1016/j.ejmech.2009.10.005
25. [25]
  Chen, H.; Xie, Y. J.; Kirillov, A. M.; Liang, L. L.; Yu, M. H.; Liu, W. S.; Tang, Y. A ratiometric fluorescent nanoprobe based on terbium functionalized carbon dots for highly sensitive detection of an anthrax biomarker. Chem. Commun. 2015, 51, 5036-5039. doi: 10.1039/C5CC00757G
26. [26]
  Zhang, Y. H.; Li, B.; Ma, H. P.; Zhang, L. M.; Zheng, Y. X. Rapid and facile ratiometric detection of an anthrax biomarker by regulating energy transfer process in bio-metal-organic framework. Biosens. Bioelectron. 2016, 85, 287-293. doi: 10.1016/j.bios.2016.05.020
27. [27]
  Ma, K.; Wang, H.; Li, X.; Xu, B.; Tian, W. J. Turn-on sensing for Ag⁺ based on aie-active fluorescent probe and cytosine-rich DNA. Anal. Bioanal. Chem. 2015, 407, 2625-2630. doi: 10.1007/s00216-015-8467-y
1. [1]
  Wei GAO , Meiqi SONG , Xuan REN , Jianliang BAI , Jing SU , Jianlong MA , Zhijun WANG . A self-calibrating fluorescent probe for the selective detection and bioimaging of HClO. Chinese Journal of Inorganic Chemistry, 2025, 41(6): 1173-1182. doi: 10.11862/CJIC.20250112
2. [2]
  Lei ZHANG , Cheng HE , Yang JIAO . An azo-based fluorescent probe for the detection of hypoxic tumor cells. Chinese Journal of Inorganic Chemistry, 2025, 41(6): 1162-1172. doi: 10.11862/CJIC.20250081
3. [3]
  Yuan ZHU , Xiaoda ZHANG , Shasha WANG , Peng WEI , Tao YI . Conditionally restricted fluorescent probe for Fe³⁺ and Cu²⁺ based on the naphthalimide structure. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 183-192. doi: 10.11862/CJIC.20240232
4. [4]
  Meirong HAN , Xiaoyang WEI , Sisi FENG , Yuting BAI . A zinc-based metal-organic framework for fluorescence detection of trace Cu²⁺. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1603-1614. doi: 10.11862/CJIC.20240150
5. [5]
  Yang Liu , Leilei Zhang , Kaixuan Liu , Ling-Ling Wu , Hai-Yu Hu . Penicillin G acylase-responsive near-infrared fluorescent probe: Unravelling biofilm regulation and combating bacterial infections. Chinese Chemical Letters, 2024, 35(11): 109759-. doi: 10.1016/j.cclet.2024.109759
6. [6]
  Yi Tao , Jie Pan , Wenting Yin , Qinglong Qiao , Zhaochao Xu . An LPS-targeted fluorescent probe for dynamic super-resolution imaging of Gram-negative bacterial outer membranes. Chinese Chemical Letters, 2026, 37(7): 112611-. doi: 10.1016/j.cclet.2026.112611
7. [7]
  Jinlong YAN , Weina WU , Yuan WANG . A simple Schiff base probe for the fluorescent turn-on detection of hypochlorite and its biological imaging application. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1653-1660. doi: 10.11862/CJIC.20240154
8. [8]
  Yu SU , Xinlian FAN , Yao YIN , Lin WANG . From synthesis to application: Development and prospects of InP quantum dots. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2105-2123. doi: 10.11862/CJIC.20240126
9. [9]
  Jun LUO , Baoshu LIU , Yunchang ZHANG , Bingkai WANG , Beibei GUO , Lan SHE , Tianheng CHEN . Europium(Ⅲ) metal-organic framework as a fluorescent probe for selectively and sensitively sensing Pb²⁺ in aqueous solution. Chinese Journal of Inorganic Chemistry, 2024, 40(12): 2438-2444. doi: 10.11862/CJIC.20240240
10. [10]
  Yingpeng ZHANG , Xingxing LI , Yunshang YANG , Zhidong TENG . A pyrazole-based turn-off fluorescent probe for visual detection of hydrazine. Chinese Journal of Inorganic Chemistry, 2025, 41(7): 1301-1308. doi: 10.11862/CJIC.20250064
11. [11]
  Yuting DU , Jing YUAN , Peiyao DENG . Synthesis and application of a fluorescent probe for the detection of reduced glutathione. Chinese Journal of Inorganic Chemistry, 2025, 41(7): 1331-1337. doi: 10.11862/CJIC.20240461
12. [12]
  Pengli GUAN , Renhu BAI , Xiuling SUN , Bin LIU . Trianiline-derived aggregation-induced emission luminogen probe for lipase detection and cell imaging. Chinese Journal of Inorganic Chemistry, 2025, 41(9): 1817-1826. doi: 10.11862/CJIC.20250058
13. [13]
  Qiang HU , Zhiqi CHEN , Zhong CHEN , Xu WANG , Weina WU . Pyridinium-chalcone-based ClO^- fluorescent probe: Preparation and biological imaging applications. Chinese Journal of Inorganic Chemistry, 2025, 41(9): 1789-1795. doi: 10.11862/CJIC.20250086
14. [14]
  Yanxi LIU , Mengjia XU , Haonan CHEN , Quan LIU , Yuming ZHANG . A fluorescent-colorimetric probe for peroxynitrite-anion-imaging in living cells. Chinese Journal of Inorganic Chemistry, 2025, 41(6): 1112-1122. doi: 10.11862/CJIC.20240423
15. [15]
  Shunping WANG , Chuandong GE , Shuguang QU , Tianduo LI , Shaomin WANG , Qingyuan YANG . Synthesis of a fluorescent probe based on urea-based coordination and Si—O bond cleavage for F^- and Cr(Ⅵ) detection. Chinese Journal of Inorganic Chemistry, 2026, 42(2): 297-308. doi: 10.11862/CJIC.20250214
16. [16]
  Wenrui Jia , Chenghuan Qiao , Dongfang Zhao , Juanshan Du , Yaohua Wu , Yongqi Liang , Qinglian Wu , Xiaochi Feng , Huazhe Wang , Wanqian Guo . Insight into nitrogen-doped biochar prepared from Chinese medicine compound residue for peracetic acid activation in sulfamethoxazole degradation: Electron transfer mechanism. Chinese Chemical Letters, 2025, 36(11): 110886-. doi: 10.1016/j.cclet.2025.110886
17. [17]
  Chuan-Zhi Ni , Ruo-Ming Li , Fang-Qi Zhang , Qu-Ao-Wei Li , Yuan-Yuan Zhu , Jie Zeng , Shuang-Xi Gu . A chiral fluorescent probe for molecular recognition of basic amino acids in solutions and cells. Chinese Chemical Letters, 2024, 35(10): 109862-. doi: 10.1016/j.cclet.2024.109862
18. [18]
  Tao Liu , Xuwei Han , Xueyi Sun , Weijie Zhang , Ke Gao , Runan Min , Yuting Tian , Caixia Yin . An activated fluorescent probe to monitor NO fluctuation in Parkinson’s disease. Chinese Chemical Letters, 2025, 36(3): 110170-. doi: 10.1016/j.cclet.2024.110170
19. [19]
  Qian Pang , Fangjun Huo , Yongkang Yue , Caixia Yin . ONOO⁻ and viscosity dual-response fluorescent probe for arthritis imaging in vivo. Chinese Chemical Letters, 2025, 36(9): 110713-. doi: 10.1016/j.cclet.2024.110713
20. [20]
  Shuairu Wang , Dongsheng Lian , Chuyang Sun , Minghao Xu , Mingming Zhu , Chenxu Yan , Zhiqian Guo . High selective NIR-Ⅱ fluorescent probe for sensing phosgene in plants. Chinese Chemical Letters, 2026, 37(7): 111744-. doi: 10.1016/j.cclet.2025.111744

Get Citation

PDF

XML

Metrics

PDF Downloads(2)
Abstract views(1773)
HTML views(93)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142