DOI: 10.1039/C9CC09240D
ChemComm
CREATED USING THE RSC COMMUNICATION TEMPLATE (VER. 2.1) - SEE WWW.RSC.ORG/ELECTRONICFILES FOR DETAILS
4
K. A. Anderson, Mercury analysis in environmental samples by cold
vapor techniques, in: Encyclopedia of Analytical Chemistry, Wiley,
New York, 2006.
J. M. Lo, J. C. Yu, F. I. Hutchison, C. M. Wai, Anal. Chem., 1982,
54, 2536.
a) E. M. Nolan and S. J. Lippard, Chem. Rev., 2008, 108, 3443; b) Y.
Yang, Q. Zhao, W. Feng, F. Li, Chem. Rev., 2013, 113, 192; c) H. N.
Kim, W. X. Ren, J. S. Kim, J. Yoon, Chem. Soc. Rev., 2012, 41,
3210.
equiv.) of methylmercury induced a little enhancement of the
emission in this condition. We optimized some conditions (the
concentration probe, pH, slit size, and buffering agents) for the
reactivity of 1 for methylmercury. 1 showed considerable turn-on
response to the low concentrations (0~3 equiv.) of methylmercury
within 5 mins and a linear relationship between the emission
intensity and the concentration of methylmercury was obtained
for a wide concentration ranging from 0 to 8 µM (0~1600 ppb).
The detection limit for methylmercury was below 1 µM (200
ppb). Considering the limits (500-1000 ppb) for organic mercury
species in food,18 1 had an enough sensitivity and fast response
for the detection of contaminated methylmercury in food.
5
6
7
For some examples of Hg2+-selective fluorescent probes, see: a) X.
Zhang, Y. Xiao, X. Qian, Angew. Chem. Int. Ed., 2008, 47, 8025; b) J.
Liu and Y. Lu, Angew. Chem. Int. Ed., 2007, 46, 7587. c) Y. K. Yang, K.
J. Yook, J. Tae, J. Am. Chem. Soc., 2005, 127, 16760; d) I. Samb, J.
Bell, P. Y. Toullec, V. Michelet, I. Leray, Org. Lett., 2011, 13, 1182; e)
S. Ando and K. Koide, J. Am. Chem. Soc., 2011, 133, 2556; f) M. H.
Lee, S. W. Lee, S. H. Kim, C. Kang, J. S. Kim, Org. Lett., 2009, 11,
2101; g) Z. Ruan, C. Li, J. R. Li, J. Qin, Z. Li, Sci. Rep., 2015, 5, 15987;
h) P. Samanta, A. V. Desai, S. Sharma, P. Chandra, S. K. Ghosh, Inorg.
Chem., 2018, 57, 2360; i) H. Yang, C. Han, X. Zhu, Y. Liu, K. Y. Zhang,
S. Liu, Q. Zhao, F. Li, W. Huang, Adv. Funct. Mater., 2016, 26, 1945; j)
M. Deng, D. Gong, S. C. Han, X. Zhu, A. Iqbal, W. Liu, W. Qin, H. Guo,
Sens. Actuator B-Chem., 2017, 243, 195; k) M. Santra, B. Roy, K. H.
Ahn, Org. Lett., 2011, 13, 3422; l) L. N. Neupane, G. W. Hwang K.-H.
Lee, Biosens. Bioelectron., 2017, 92, 179; m) D.-H. Kim, J. Seong, H.
Lee, K.-H. Lee, Sens. Actuators, B, 2014, 196, 421; n) H. S. Hewage
and E. V. Anslyn, J. Am. Chem. Soc., 2009, 131, 13099; o) C. Song, W.
Yang, N. Zhou, R. Qian, Y. Zhang K. Lou, R. Wang, W. Wang, Chem.
Commun., 2015, 51, 4443; p) Z. Wang, J. H. Lee, Y. Lu, Chem.
Commun., 2008, 6005; q) Z. Ruan, Y. Shan, Y. Gong, C. Wang, F. Ye,
Y. Qiu, Z. Liang, Z. Li, J. Mater. Chem. C, 2018, 6, 773; r) Y. Shan, W.
Yao, Z. Liang, L. Zhu, S. Yang, Z. Ruan, Dyes and Pigments, 2018,
156, 1.
For some examples of fluorescent probes for methylmercury, see: a)
M. Santra, D. Ryu, A. Chatterjee, S. K. Ko, I. Shin, K. H. Ahn,
Chem. Commun., 2009, 2115; b) Y. Liu, M. Chen, T. Cao, Y. Sun,
C. Li, Q. Liu, T. Yang, L. Yao, W. Feng, F. Li, J. Am. Chem. Soc.,
2013, 135, 9869; c) Y. K. Yang, S. K. Ko, I. Shin, J. Tae, Org.
Biomol, Chem., 2009, 7, 4590; d) X. Chen, K. H. Baek, Y. Kim, S. J.
Kim, I. Shin, J. Yoon, Tetrahedron, 2010, 66, 4016.
a) K. Torssell, Acta Chem. Scand., 1959, 13, 115; b) F. R. Bean and
J. R. Johnson, J. Am. Chem. Soc., 1932, 54, 711; c) R. C. Larock,
Organomercury Compounds in Organic Synthesis; Springer-Verlag:
Berlin, 1985; 12, 15-16.
To confirm the irreversible reaction between
1
and
methylmercury, we analyzed the product(s) of 1 with CH3HgCl
using HPLC-mass spectrometer with C18 column. In this case, we
used distilled water including 2% CH3CN as a solvent for the
convenience purification. According to HPLC-MS analysis, the
peak corresponding to 1 disappeared and new major peak
corresponding to arylmethylmercury at 542.10 (m/z) was
observed (Figure S18-S19). This result suggested that 1 reacted
irreversibly with CH3Hg+, resulting in the production of
arylmethyl mercury compound (3). The product could explain the
reason why 1 exhibited a saturation of fluorescent change about
at 1.0 equiv. of CH3HgCl. We measured the absorption/emission
band shifts of 3 depending on solvents of different polarity (Table
S2). The emission maximum of 3 was slightly red-shifted in more
polar solvent, which supported that the exchange of the boronic
acid to methylmercury might enhance the intramolecular charge-
transfer in the molecule.
The potential application in intracellular detection of Hg2+ and
CH3Hg+ using the fluorescent probe was studied (Figure S20).
The probe penetrated biological membranes of the cells and
detected intracellular Hg2+ and CH3Hg+ by turn-on response,
which supported that the displacement reaction of the arylboronic
acid with mercury species worked well in the cellular
environment and the reaction-based probe could be applied for
probing the mercury species in cells.
In the present study, we showed that the displacement reaction
of arylboronic acid with mercury species was very useful for the
development of novel fluorescent probes for inorganic mercury
species as well as methylmercury. The fluorescent probe based on
the displacement reaction of arylboronic acid with mercury
species showed remarkable sensing properties for Hg2+ as well as
methylmercury such as high sensitivity, high selectivity, fast
response at room temperature, operations in purely aqueous
solutions, and large fluorescent signal change. Unlike the other
reaction-based probes for Hg2+ and methylmercury, 1 detected
Hg2+ as well as methylmercury by formation of a covalent adduct
of the probe with the mercury species. Considering the recent
increase of contamination of inorganic and organic mercury
species, this result will promote to develop new sensing and
removing systems for inorganic and organic mercury species
based on the displacement reaction of arylboronic acid
derivatives.
8
9
10
11
a) A. Sarafraz-Yazdi, E. Fatehyan, A. Amiri, J. Chromatogr. Sci.,
2014, 52, 81; b) A. S. Yazdi, S. Banihashemi, Z. Es’haghi,
Chromatographia, 2010, 71, 1049.
a) J. C. Koziar and D. O. Cowan, Acc. Chem. Res., 1978, 11, 334; b)
H. Masuhara, H. Shioyama, T. Saito, K. Hamada, S. Yasoshima, N.
Mataga, J. Phys. Chem., 1984, 88, 5868; c) P. Svejda, A. H. Maki,
R. R. Anderson, J. Am. Chem. Soc., 1978, 100, 7138.
M. G. Choi, D. H. Ryu, H. L. Jeon, S. Cha, J. Cho, H. H. Joo, K. S.
Hong, C. Lee, S. Ahn, S. K. Chang, Org. Lett., 2008, 10, 3717.
M. Matsushita, M. M. Meijler, P. Wirsching, R. A. Lerner, K. D.
Janda, Org. Lett., 2005, 7, 4943.
S. W. Lee, S. Y. Lee, S. H. Lee, Tetrahedron Lett., 2019, 60,
151048.
12
13
14
15
16
X. Guo, J. Huang, Y. Wei, Q. Zeng, L. Wang, J. Hazard. Mater.,
2020, 381, 120969.
a) C. R. Lohani, L. N. Neupane, J. M. Kim, K. H. Lee, Sens.
Actuator B-Chem., 2012, 161, 1088; b) C. R. Lohani, J. M. Kim, K.
H. Lee, Tetrahedron, 2011, 67, 4130; c) D. H. Kim, J. Seong, H.
Lee, K. H. Lee, Sens. Actuator B-Chem., 2014, 196, 421; d) H. Li, Y.
Li, Y. Dang, L. Ma, Y. Wu, G. Hou, L. Wu, Chem. Commun., 2009,
4453.
This work was supported by the Inha University Research Grant.
Notes and references
17
18
W. H. Melhuish, J. Phys. Chem., 1961, 65, 229.
1
W. F. Fitzgerald, C. H. Lamborg, C. R. Hammerschmidt, Chem.
Rev., 2007, 107, 641.
T. W. Clarkson, L. Magos, Crit. Rev. Toxicol. 2006, 36, 609.
EPA, 2001. U.S., Mercury Update: Impact on Fish Advisories. U.S.
Environmental Protection Agent (EPA) Fact Sheet EPA-823-F-01-
011; EPA, Office of water: Washington, DC.
(a) Y.-S. Hong, Y. Kim, K. Lee, J. Prev. Med. Pub. Health, 2012,
45, 353; (b) H. C. Vieira, F. Morgado, A. M. V. M. Soares, S. N.
Abreu, Environ. Sci. Pollut. Res., 2015, 22, 9595.
2
3
4| [journal], [year], [vol], 00–00
This journal is © The Royal Society of Chemistry [year]