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Supplementary Information
A red-emitting fluorescent probe for detecting Hg2+ in aqueous medium, living cells and organism with a large Stokes shiftLei Yang,a‡ Yuanan Su,a‡ Yani Geng,a Haiqing Xiong,a Jinliang Han,a Qian Fanga and Xiangzhi Songa*
a College of Chemistry & Chemical Engineering, Central South University, Changsha, Hunan Province, P. R. China, 410083.
* To whom correspondence should be addressed. Fax: +86-731-88836954; Tel: +86-731-88836954; E-mail: song@rowland.harvard.edu
‡ These authors contributed equally to this work.
Table S1 ....................................................................................................................................................................2Table S2 ....................................................................................................................................................................3Fig. S1 .......................................................................................................................................................................4Fig. S2 .......................................................................................................................................................................4Fig. S3 .......................................................................................................................................................................5Fig. S4 .......................................................................................................................................................................5Fig. S5 .......................................................................................................................................................................6Fig. S6 .......................................................................................................................................................................6Fig. S7 .......................................................................................................................................................................7Fig. S8 .......................................................................................................................................................................7Fig. S9 .......................................................................................................................................................................8Fig. S10 .....................................................................................................................................................................8Fig. S11 .....................................................................................................................................................................9Fig. S12 .....................................................................................................................................................................9Fig. S13 ...................................................................................................................................................................10Fig. S14 ...................................................................................................................................................................10Fig. S15 ...................................................................................................................................................................11Fig. S16 ...................................................................................................................................................................11
Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry.This journal is © The Royal Society of Chemistry 2018
2
Table S1 Comparison of Fluorescent Probes for Hg2+.
Probeλex/λem (nm)
Stokes shift (nm)
Detection limit (nM)
Analytical applications
Literature
O
N
O
NH2
N N
HOOC
520/573 53 97River water,
pond water and living cells
Analytica Chimica Acta,
2016, 934, 218-225
N O S
N
S 487/511 24 1700 NoChem.
Commun., 2009, 3560-3562
O
N
S
N
S
HO OH
509/529 20 39 Living cellsTalanta, 2017, 170, 103–110
S
SS
S O 370/418 48 50 NoChem.
Commun., 2005, 2161–2163
O
N
O
N N
N
N
NHS
S
HN
NH
SNH
520/583 63 304Pond water and
tap water
Dyes and Pigments, 2016,
127, 94-99
S
NO
HNO
365/500 135 100 NoOrg. Lett., 2011, 13, 3422-3425
S SN N
N N
380/458 78 80 NoOrg. Lett., 2012, 14, 6084-6087
O O
NCCN
NC
560/613 53 10River water and
living cells
Sensors and Actuators B,
2014, 191, 605–611
O
N
S
NH
NH
534/566 32 39 Living cellsChem.
Commun., 2010, 46, 3529–3531
3
NO O
NH2
420/480 66 50 NoOrg. Lett., 2010, 22, 5310-5313
N
N O
CN
CN 475/625 150 7.1Water samples, living cells and
organismThis work
Table S2 Determination of Hg2+ in water samples.Sample HgCl2 spiked (μM) HgCl2 recovered (μM) Recovery (%)
0 not detected2 2.07 ± 0.03 1034 3.82 ± 0.12 956 5.78 ± 0.13 968 7.78 ± 0.09 9710 10.50 ± 0.07 10512 12.61 ± 0.21 10514 13.48 ± 0.19 9616 16.51 ± 0.14 10318 17.74 ± 0.19 99
Tap water
20 19.48 ± 0.03 970 not detected2 2.24 ± 0.09 1094 3.82 ± 0.05 966 5.69 ± 0.12 958 7.76 ± 0.20 9710 10.18 ± 0.16 10212 12.64 ± 0.19 10514 13.95 ± 0.22 10016 16.37 ± 0.06 10218 17.47 ± 0.08 97
Yangtze River water
20 19.90 ± 0.15 990 not detected2 1.82 ± 0.13 914 3.81 ± 0.21 956 5.48 ± 0.19 918 7.69 ± 0.07 9610 10.23 ± 0.06 10212 12.36 ± 0.08 10314 13.75 ± 0.11 9816 16.34 ± 0.12 10218 17.92 ± 0.07 99
Xiang River water
20 19.86 ± 0.20 99
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Fig. S1 Absorption spectra of Probe 1 (10.0 µM) in the presence/absence of Hg2+ (5.0 equiv.) in HEPES buffer (20 mM, pH=7.4, containing 30% EtOH) incubation at room temperature for 60 min. Inset: photographs of Probe 1 without (left) and with (right) 5.0 equiv. of Hg2+.
Fig. S2 Absorption (black) and emission spectra (red) of dye 5 (10.0 µM) in HEPES buffer (20 mM, pH=7.4, containing 30% EtOH).
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Fig. S3 Absorbance at 495 nm of Probe 1 (10.0 µM) versus the concentration of Hg2+ in HEPES buffer (20 mM, pH=7.4, containing 30% EtOH). Inset: the linear relationship between the absorbance of the solution of Probe 1 and Hg2+ concentration (0.0-25.0 µM).
Fig. S4 1H NMR spectrum of compound 3 in CDCl3.
N
N
CHO
OBr
6
Fig. S5 13C NMR spectrum of compound 3 in CDCl3.
301.1410 340.0672
363.05671+
381.0297
mercury\mercury 1: +MS, 0.1-0.2min #3-10
0.0
0.5
1.0
1.5
2.0
2.5
6x10Intens.
300 325 350 375 400 425 450 475 500 m/z
Fig. S6 HRMS spectrum of compound 3.
N
N
CHO
OBr
N
N
CHO
OBr
7
Fig. S7 1H NMR spectrum of compound 4 in CDCl3.
Fig. S8 13C NMR spectrum of compound 4 in CDCl3.
N
N
CHO
O
N
N
CHO
O
8
283.12811+
296.2421
340.26831+
360.30961+
384.2944
mercury\mercury 2: +MS, 0.1-0.3min #5-17
0.00
0.25
0.50
0.75
1.00
1.25
1.50
7x10Intens.
200 225 250 275 300 325 350 375 400 m/z
Fig. S9 HRMS spectrum of compound 4.
Fig. S10 1H NMR spectrum of Probe 1 in CDCl3.
N
N O
CN
CN
N
N
CHO
O
9
Fig. S11 13C NMR spectrum of Probe 1 in CDCl3.
306.23851+
308.1309
309.1344
310.1378
316.1922
mercury\mercury probe: +MS, 0.1-0.2min #4-13
0
2
4
6
5x10Intens.
306 308 310 312 314 316 m/z
Fig. S12 HRMS spectrum of compound Probe 1.
N
N O
CN
CN
N
N O
CN
CN
10
Fig. S13 Plot of the natural log of fluorescence intensity change for Probe 1 (10.0 µM) with Hg2+ (5.0 equiv.) as a function of the reaction time in HEPES buffer (20 mM, pH=7.4, containing 30% EtOH). kobs = 0.04579 min-1.
Fig. S14 1H NMR spectrum of the reaction product between Probe 1 and Hg2+ in CDCl3.
N
N
O
CN
CNN
N
O
CN
Probe 1 Dye 5
HgCl2NH
11
17:36:45 11-Jul-20154-1
m/z220 230 240 250 260 270 280 290 300 310 320 330 340
%
0
100LZX-88 5 (0.094) AM (Cen,4, 80.00, Ht,5000.0,0.00,1.00); Sm (Mn, 2x3.00); Cm (1:31) TOF MS ES+
1.49e3283.1557
274.2751
246.2435218.2111
284.1557
318.3021284.3288302.3060
285.1549 330.3371
Fig. S15 HRMS spectrum of the reaction product between Probe 1 and Hg2+.
Fig. S16 Cytotoxicity assay of Probe 1 at different concentration for HeLa cells.
N
N
O
CN
CNN
N
O
CN
Probe 1 Dye 5
HgCl2NH
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