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ChemComm
Page 4 of 4
DOI: 10.1039/C7CC01764B
ARTICLE
Journal Name
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Coelho, A. V. Castro, M. Dezotti and G. L. Sant’Anna Jr, J.
Hazard. Mater., 2006, 137, 178.
M. G. Choi, S. Cha, H. Lee, H. L. Jeon and S.‐K. Chang, Chem.
Commun., 2009, 7390.
the “sour” water must be purified and the hydrogen sulfide in
water released into the environment must be below the
olfactory detection limit (~ 15 μM). We obtained samples of
sour water from a local oil refinery. The sour water was diluted
serially in order to obtain a sample with sulfide levels within the
measurable linear range of the probe. Analysis of this diluted
sample yielded a sulfide concentration of 41 ± 3 mM as
measured by Tb‐1.Cu2+. Two independent quantitative assays –
the colourimetric methylene blue assay and an assay employing
a fluorogenic probe AzMC previously developed by our group26
– were also performed to verify our results. These yielded
sulfide concentrations of 40.5 ± 2.3 mM and 40 ± 2.5 mM,
respectively, in excellent agreement with the value derived
using the Tb‐1.Cu2+ probe. Importantly, due to the highly water‐
soluble nature of our lanthanide‐based probe, the addition of
organic solvent to the assay mixture is not required, and unlike
previous azide‐based probes, pre‐incubation is not needed.
These features, coupled with the excellent sensitivity for
sulfide, render the probe superior to many existing
colourimetric and fluorogenic methods for the detection of
sulfide.
10 K. Sasakura, K. Hanaoka, N. Shibuya, Y. Mikami, Y. Kimura, T.
Komatsu, T. Ueno, T. Terai, H. Kimura and T. Nagano, J. Am.
Chem. Soc., 2011, 133, 18003.
11 H. Peng, Y. Cheng, C. Dai, A. L. King, B. L. Predmore, D. J. Lefer
and B. Wang, Angew. Chem. Int. Ed., 2011, 50, 9672.
12 A. R. Lippert, E. J. New and C. J. Chang, J. Am. Chem. Soc., 2011,
133, 10078.
13 F. Yu, P. Li, P. Song, B. Wang, J. Zhao and K. Han, Chem.
Commun., 2012, 48, 2852.
14 C. Yu, X. Li, F. Zeng, F. Zheng and S. Wu, Chem. Commun.,
2013, 49, 403.
15 W. Sun, J. Fan, C. Hu, J. Cao, H. Zhang, X. Xiong, J. Wang, S. Cui,
S. Sun and X. Peng, Chem. Commun., 2013, 49, 3890.
16 S. Chen, Z.‐J. Chen, W. Ren and H.‐W. Ai, J. Am. Chem. Soc.,
2012, 134, 9589.
17 X. Wang, J. Sun, W. Zhang, X. Ma, J. Lv and B. Tang, Chem. Sci.,
2013, 4, 2551‐2556.
18 A. Thibon and V. C. Pierre, Anal. Bioanal. Chem., 2009, 394
,
107.
19 A. Vogler and H. Kunkely, Inorg. Chim. Acta, 2006, 359, 4130.
20 R. M. Izatt, K. Pawlak, J. S. Bradshaw and R. L. Bruening, Chem.
Rev., 1995, 95, 2529.
21 M. L. Cable, D. J. Levine, J. P. Kirby, H. B. Gray and A. Ponce,
Adv. Inorg. Chem., 2011, 63, 1.
22 Z. Liang, T.‐H. Tsoi, C.‐F. Chan, L. Dai, Y. Wu, G. Du, L. Zhu, C.‐
S. Lee, W.‐T. Wong, G.‐L. Law and K.‐L. Wong, Chem. Sci.,
Conclusions
A luminescent lanthanide‐based complex, Tb‐1, has been
synthesised and its bimetallic copper(II) counterpart applied in
the detection of sulfide. Addition of Cu2+ to the complex results
in complete quenching of the luminescent signal, which is then
restored upon exposure to sulfide. The probe responds
selectively to sulfide, with extremely short reaction times and a
detection limit in the nanomolar range. The probe has been
successfully used to measure the amount of sulfide in a real
industrial sour water sample, with the result confirmed by two
independent methods, highlighting the potential for the probe
to be used in environmental/industrial monitoring of sulfide.
2016, 7, 2151.
23 Y.‐W. Yip, G.‐L. Law and W.‐T. Wong, Dalton Trans., 2016, 45
,
928.
24 M. Tropiano and S. Faulkner, Chem. Commun., 2014, 50, 4696.
25 R. Zhang, S. Liu, J. Wang, G. Han, L. Yang, B. Liu, G. Guan and
Z. Zhang, Analyst, 2016, 141, 4919.
26 M. K. Thorson, P. Ung, F. M. Leaver, T. S. Corbin, K. L. Tuck, B.
Graham and A. M. Barrios, Anal. Chim. Acta, 2015, 896, 160.
27 A. M Barrios, M. K. Thorson, K. L. Tuck and B. Graham, Patent
Application number WO 2016028768 A1, The University of
Utah Research Foundation, USA . 2016, 30pp.
28 (a) M. J. Kim, K. M. K. Swamy, K. M. Lee, A. R. Jagdale, Y. Kim,
S.‐J. Kim, K. H. Yoo and J. Yoon, Chem. Commun., 2009,
7215.(b) E. U. Akkaya, M. E. Huston and A. W. Czarnik, J. Am.
Chem. Soc., 1990, 112, 3590.
Acknowledgements
29 W. I. O’Malley, E. H. Abdelkader, M. L. Aulsebrook, R.
Rubbiani, C.‐T. Loh, M. R. Grace, L. Spiccia, G. Gasser, G.
Otting, K. L. Tuck and B. Graham, Inorg. Chem., 2016, 55, 1674.
30 J.‐C. G. Bünzli and C. Piguet, Chem. Soc. Rev., 2005, 34, 1048.
31 This result has been verified by independent measurements
made in the Tuck and Barrios laboratories. Work by Kim and
co‐workers (J.‐Y. Choi, D.‐S. Kim and J.‐Y. Lim, J. Environ. Sci.
Health Part A, 2006, 41, 1155) has conclusively shown that the
while mixing of Cu2+ and HS‐ ions in a 1:1 ratio leads to close
to quantitative precipitation of CuS, the presence of a copper‐
complexing ligand in solution (in their case, nitrilotriacetic
acid or EDTA) reduces the extent of precipitation. The need
for two equivalents of HS‐ to produce a full luminescence
“switch on” effect is therefore not surprising, given the
presence of the copper‐binding DPA‐triazole motif within the
probe.
The authors acknowledge the support of the School of
Chemistry and Monash Institute of Pharmaceutical Sciences,
Monash University. Financial support from the Australian
Research Council is gratefully acknowledged (grant numbers
DP150100383 and FT130100838). M.L.A. is grateful for the
receipt of an Australian Postgraduate Award.
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