Electronic Supplementary Information (ESI)
A mesoporous silica supported Hg2+ chemodosimeter
Bing Leng, Jianbing Jiang and He Tian*
Key Laboratory for Advanced Materials and Institute of Fine Chemicals, East China
University of Science & Technology, Shanghai 200237, P.R. China
E-mail: tianhe@ecust.edu.cn (He Tian);
Fax: +86-21-64252288; Tel: +86-21-64252756
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Captions:
Materials
Characterization
Preparation of compound 1
Preparation of compound 2
Preparation of compound 3
Fig. S1 The color change and fluorescence emission response of 1 (10 μM) upon addition of 2 equiv. of Hg2+
in ethanol-water (1:1, V/V) solution. Left to right: 1, 1 and Hg2+, the emission of 1 and emission of 1 and
Hg2+ (irradiated at 365 nm using UV lamp)
Fig. S2 The (a) colorimetric response and (b) emission ratiometric response of CFMS towards Hg2+ ion in
water (irradiated at 365 nm using UV lamp)
Fig. S3 Absorbance spectra (a) and Fluorescent spectra (b) of mesoporous silica before and after the addition
of Hg2+
Fig. S4 (a) Color and (b) fluorescence changes of water suspensions of CFMS in the absence and presence
of Hg2+ and other cations (Na+, Mg2+, Pb2+, Zn2+, Cu2+, Cd2+, Co2+, Ni2+ and Mn2+) (irradiated at 365 nm
using UV lamp)
Literature Cited
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Materials
Cetyltrimethylammonium bromide (CTAB), tetraethylorthosilicate (TEOS) and Hg(ClO4)2·3H2O were
purchased from Sigma-Aldrich and used as received. All other reagents were of analytical purity and used
without
further
treatment.
Butylisothiocyanate,
3-(triethoxysilyl)propylisothiocyanate1,2,
and
4-(aminoethylene) amino-N-butyl-1, 8-naphthalimide3,4 were prepared based on known methods.
Characterization
1H
NMR and 13C NMR spectra in CDCl3 were recorded on Brucker AM-400 or 500 spectrometers with
tetramethylsilane (TMS) as the internal standard. Mass spectra (MS) were recorded on HITACHI-80 and
4700-Propeotics analyzers. UV-Vis absorption spectra were performed on a Varian Cray 500
spectrophotometer and fluorescence spectra were recorded on a Varian Cray Eclipse fluorescence
spectrophotometer. X-ray powder diffraction (XRD) patterns of all samples were recorded on a Rigaku
D/MAX-2550 diffractometer using Cu Kα radiation within the scattering angle 2θ range of 0.5°–10°,
typically run at a voltage of 40 kV and current of 100 mA. Nitrogen adsorption–desorption isotherms were
measured at 77 K on a Micromeritics ASAP 2010 apparatus. The transmission electron microscopy (TEM)
images of the samples were acquired on a JEOL 2100F transmission electron microscope. The infrared
spectroscopy was made using a Nicolet 380 spectrometer (KBr pellet technique).
Preparation of compound 1
1 was prepared by a similar procedure as 3 from 4-(aminoethylene)amino-N-butyl-1,8-naphthalimide and
butylisothiocyanate and purified by column chromatography on silica using 9 : 1 CH2Cl2–EtOAc as eluent to
afford the product as yellow solid. Yield 80 %. 1H NMR (500 MHz, CDCl3) (ppm): 0.90 (t, 3H, J = 7.4 Hz,
CH3), 0.96 (t, 3H, J = 7.4 Hz, CH3), 1.40 (m, 4H, CH2CH3, CH2CH3), 1.59 (m, 2H, CH2CH2CH3), 1.69 (m,
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2H, CH2CH2CH3), 3.38 (m, 4H, NCH2), 4.15 (t, 2H, J = 7.5 Hz , NCH2), 4.21 (m, 2H, NCH2), 6.28 ( m, 2H,
naphthalene-H, NH), 6.69 ( s, 1H, NH), 7.58 ( s, 1H, NH), 7.62 (t, 1H, J = 7.78 Hz, J = 7.92 Hz,
naphthalene-H), 8.25 (d, 1H, J = 8.29 Hz, naphthalene-H), 8.49 (d, 1H, J = 8.32 Hz, naphthalene-H), 8.55 (d,
1H, J =7.25 Hz, naphthalene-H).
13C
NMR (100 MHz, CDCl3) (ppm): 14.33, 14.56, 20.70, 21.12, 30.37,
31.05, 31.54, 40.71, 43.52, 47.16, 103.92, 110.13, 121.12, 123.21, 125.62, 129.05, 130.44, 132.07, 135.06,
151.19, 165.41, 168.53, 186.80. HRMS (EI): calculated for C23H30N4O2S [M+] 426.2089; found 426.2091.
Preparation of compound 2
To a solution of 1 (0.5 g, 1.17 mmol) in 20 mL of ethanol was added 1.1 g (2.43 mmol) of
Hg(ClO4)2·3H2O with magnetic stirring at room temperature. After 20 min reaction the solution was filtered.
The filtrate was concentrated and the residue was purified by column chromatography on silica using 9 : 1
CH2Cl2–EtOAc as eluent to yield 0.42 g of 2. Yield 91%. 1H NMR (500 MHz, CDCl3) (ppm): 0.90 (m, 6H,
CH3), 1.32 (m, 4H, CH2CH3), 1.50 (m, 2H, CH2CH2CH3), 1.60 (m, 2H, CH2CH2CH3), 3.49 (m, 2H, NCH2),
3.79 (m, 2H, NCH2), 4.27 (m, 4H, NCH2), 6.39 (s, 1H, NH), 7.94 (m, 2H, naphthalene-H), 8.40 (m, 3H,
naphthalene-H). 13C NMR (100 MHz, CDCl3) (ppm): 14.25, 14.39, 20.46, 20.83, 30.51, 31.23, 40.79, 43.22,
44.66, 53.50, 122.96, 123.51, 128.04, 129.24, 129.39, 129.59, 129.97, 132.25, 133.11, 138.51, 158.75,
163.21, 163.82. HRMS (EI): calculated for C23H28N4O2 [M+] 392.2212; found 392.2213.
Preparation of compound 3
4-(Aminoethylene)amino-N-butyl-1,8-naphthalimide (1.15 g, 3.7 mmol) was dissolved in 30 mL of
anhydrous tetrahydrofuran (THF). The solution was cooled to -10 °C and then a solution of
3-(Triethoxysilyl)propylisothiocyanate (1.0 g, 3.8 mmol) in 10 mL of THF was slowly added under stirring.
After 0.5 h at this temperature, the resultant yellow reaction mixture was allowed to warm gently to room
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temperature and stirred overnight. The solvent was then evaporated under reduced pressure. The residue was
purified by column chromatography on silica using 9:1 CH2Cl2–EtOAc as eluent to yield 1.64 g of 3 as
yellow solid. Yield 77%. 1H NMR (500 MHz, CDCl3) (ppm): 0.65 (t, 2H, J = 7.5 Hz, SiCH2), 0.98 (t, 3H, J
= 7.4 Hz, CH3), 1.20 (t, 9H, J = 7.0 Hz, (OCH2CH3)3), 1.42 (m, 2H, CH2CH3), 1.72 (m, 4H, CH2CH2CH3,
CH2CH2Si), 3.40 (m, 4H, NCH2), 3.80 (q, 6H, J = 7.0 Hz, (OCH2CH3)3), 4.15 (t, 2H, J = 7.6 Hz, NCH2),
4.25 (m, 2H, NCH2), 6.43 (m, 2H, naphthalene-H, NH), 6.69 (s, 1H, NH), 7.62 (m, 2H, naphthalene-H, NH),
8.35 (d, 1H, J = 8.3 Hz, naphthalene-H), 8.50 (d, 1H, J = 8.34 Hz, naphthalene-H), 8.56 (d, 1H, J = 7.31 Hz,
naphthalene-H). 13C NMR (100 MHz, CDCl3) (ppm): 8.15, 14.30, 18.95, 20.65, 23.64, 30.34, 39.40, 42.88,
43.47, 47.27, 59.25, 103.94, 109.65, 121.12, 122.91, 125.57, 129.41, 130.51, 133.40, 135.26, 151.44, 165.06,
165.12, 184.00. HRMS (ESI): calculated for C28H42N4O5SSi [M+ + H] 575.2723; found 575.2726.
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Fig. S1 The color change and fluorescence emission response of 1 (10 μM) upon addition of 2 equiv. of Hg2+
in ethanol-water (1:1, V/V) solution. Left to right: 1, 1 and Hg2+, the emission of 1 and emission of 1 and
Hg2+ (irradiated at 365 nm using UV lamp).
Fig. S2 The (a) colorimetric response and (b) emission ratiometric response of CFMS towards Hg2+ ion in
water (irradiated at 365 nm using UV lamp).
Fig. S3 (a) Color and (b) fluorescence changes of water suspensions of CFMS in the absence and presence
of Hg2+ and other cations (Na+, Mg2+, Pb2+, Zn2+, Cu2+, Cd2+, Co2+, Ni2+ and Mn2+) (irradiated at 365 nm
using UV lamp).
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Literature Cited
1. Wong R, Dolman S J. Isothiocyanates from Tosyl Chloride Mediated Decomposition of in Situ Generated
Dithiocarbamic Acid Salts J Org Chem 2007; 72: 3969-3971.
2. Munch H, Hansen J S, Pittelkow M, Christensen J B, Boas U. A new efficient synthesis of isothiocyanates
from amines using di-tert-butyl dicarbonate. Tetrahedron Lett. 2008; 49: 3117-3119.
3. Chang S, Utecht R E, Lewis D E. Synthesis and bromination of 4-alkylamino-N-alkyl-1,8-naphthalimides.
Dyes Pigm. 1999; 43: 83-94.
4. Tian H, Xu T, Zhao Y, Chen K. Two-path photo-induced electron transfer in naphthalimide-based model
compound. J Chem Soc, Perkin Trans 2. 1999; 545-550.
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