2017colorimetric Detection of Cu2+ and Fluorescent Detection

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Article
Colorimetric detection of Cu2+ and fluorescent detection
of PO43- and S2- by a multifunctional chemosensor
Dong Hee Joo, Jin Su Mok, Geon Hwan Bae, Sang Eun Oh, Cheal Kim, and Ji Hye Kang
Ind. Eng. Chem. Res., Just Accepted Manuscript • DOI: 10.1021/acs.iecr.7b01115 • Publication Date (Web): 09 Jul 2017
Downloaded from http://pubs.acs.org on July 15, 2017
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Page 1 of 33 Industrial & Engineering Chemistry Research
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4 Colorimetric detection of Cu2+ and fluorescent detection of PO43- and S2- by a
5 multifunctional chemosensor
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Dong Hee Joo,a Jin Su Mok,a Geon Hwan Bae,a Sang Eun Oh,a Ji Hye Kang*b and Cheal
11 Kim*ab
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a
15 Nowon Institute of Education for The Gifted at Seoultech, Seoul National University of
16 Science and Technology, Seoul 139-743, Korea
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18 b
Department of Fine Chemistry and Department of Interdisciplinary Bio IT Materials, Seoul
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20 National University of Science and Technology, Seoul 139-743, Korea. Fax: +82-2-973-9149;
21 Tel: +82-2-970-6693; E-mail: 5335835k@naver.com (J.H. Kang), chealkim@seoultech.ac.kr
22 (C. Kim).
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26 Abstract
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28 A simple multifunctional chemosensor 1 was synthesized by a combination of N-
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30 aminophthalimide and 8-hydroxyjulolidine-9-carboxaldehyde. The sensor 1 showed a clear
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32 color change toward Cu2+ from pale to deep yellow and significant fluorescence
33 enhancements toward PO43- and S2-. The detection limit (0.14 µM) for Cu2+ ion was below
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35 the World Health Organization (WHO) guideline for drinking water (31.5 µM). The sensor 1
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37 could be used to quantify copper ion in real water samples. In addition, the sensor 1 could
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detect phosphate and sulfide with the fluorescent enhancements in aqueous solution. The
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40 sensing mechanism of Cu2+ by 1 was proposed to be an intramolecular charge transfer (ICT)
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42 and those of PO43- and S2- by 1 were proposed to be a deprotonation process, based on the
43
experimental results and theoretical calculations.
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53 Keywords: colorimetric, fluorescent, copper, phosphate, sulfide, theoretical calculations
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ACS Paragon Plus Environment
Industrial & Engineering Chemistry Research Page 2 of 33
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4 1. Introduction
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6 In recent decades, the development of multifunctional sensors for the detection of two or
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8 more analytes has received considerable attentions due to their simplicity, low cost and
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efficiency in comparison with the previous single-target responsive chemosensors.1–3 Among
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11 diverse approaches for detecting both cations and anions, the colorimetric and fluorogenic
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13 analysis methods have received attention owing to their easy operation, instant response time,
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remote control and multiplicity of measurable parameters.4–8 Thus, the detection of both
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16 metal ions and anions by a multifunctional chemosensor via colorimetric and fluorogenic
17
18 analysis is significantly crucial.
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20 Among the various metal ions, copper ion plays important roles as catalytic cofactor in
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22 various enzymes such as cytochrome c oxidase, tyrosinase and superoxide dismutase.9–14
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24 However, the abnormal intake of Cu2+ can result in liver or kidney damage, gastrointestinal
25 disturbance, dermal or eye irritation and the nerve disorder such as Alzheimer’s disease,
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27 Menke’s disease and Wilson’s disease.15–22 Moreover, copper can be a serious pollution
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29 source in environment because it has been used much in industry and agriculture.23–26
30 Therefore, the development of sensitive probes for Cu2+ is considerably important.
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33 Phosphate (Pi) in biological system is indispensable due to its crucial roles such as essential
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constituents of gene, the pivotal role in energy transduction and bone mineralization.27–31
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36 However, irregular phosphate levels are associated with a number of diseases including
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38 calcification of tissues, muscle weakness, impaired leukocyte and irregularity in bone
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mineralization resulting in rickets or osteomalaciaphosphate.32,33 Nevertheless, the study on
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41 Pi is relatively small compared to that on pyrophosphate (PPi). Accordingly, significant
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43 interests have been recently paid for developing the chemosensors that could recognize Pi.
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45 Sulfide (S2-) is well known as a noxious gas with a rotten egg smell. However, S2- in living
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47 system has a significant effect in a variety of physiological processes such as vasodilation,
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49 cell growth, anti-oxidation, anti-inflammation, anti-apoptosis, neuromodulation of the brain
50 and inhibition of insulin signaling.34–38 Nonetheless, unusual production of sulfide can cause
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52 numerous biochemical problems like Down’s syndrome, Huntington’s and Alzheimer’s
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54 diseases, suffocation, liver cirrhosis and hyperglycemia.39–43 For these reasons, substantial
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1
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4 efforts have been devoted to efficiently detect sulfide.
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Herein, we present on a multifunctional chemosensor 1, obtained by the combination of 8-
8 hydroxyjulolidine-9-carboxaldehyde and N-aminophthalimide. The sensor 1 recognized
9
10 copper ion with an obvious color change from pale to deep yellow and could quantify
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12
concentrations of Cu2+ in real water samples. Also, 1 as fluorescent sensor could be used to
13 detect phosphate and sulfide in aqueous solution. Moreover, the sensing mechanisms of Cu2+,
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15 PO43-, and S2- were explained by theoretical calculations.
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20 2. Experimental
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22 2.1. Materials and instrumentation
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25 All the solvents and reagents (analytical and spectroscopic grade) were purchased from
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Sigma-Aldrich. Absorption spectra were recorded at room temperature using a Perkin Elmer
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28 model Lambda L25 UV/Vis spectrometer. 1H and 13
C NMR spectra were recorded on a
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30 Varian 400 MHz and 100 MHz spectrometer and chemical shifts are recorded in ppm. Electro
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spray ionization mass spectra (ESI-MS) were collected on a Thermo Finnigan (San Jose, CA,
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33 USA) LCQTM Advantage MAX quadrupole ion trap instrument by infusing samples directly
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35 into the source using a manual method. Spray voltage was set at 4.2 kV, and the capillary
36
temperature was at 80 oC. Elemental analysis for carbon, nitrogen, and hydrogen was carried
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38 out by using a MICRO CUBE elemental analyzer (Germany) in Laboratory Center of Seoul
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40 National University of Science and Technology, Korea.
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42 2.2. Synthesis of 1
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45 8-Hydroxyjulolidine-9-carboxaldehyde (0.27 g, 1.2 mmol) and N-aminophthalimide (0.17 g,
46 1 mmol) were dissolved in 10 mL of 1,4-dioxane. Then, three drops of hydrochloric acid
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48 were added into the reaction mixture, which was stirred for 4 h at room temperature until the
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50 precipitate appeared. An orange precipitate was collected by filtration, washed several times
51 with cold ethanol and diethyl ether, and dried in vacuum to obtain the pure orange solid. The
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53 yield: 76%. 1H NMR (400 MHz, DMF-d7, ppm): δ 11.43 (s, 1H), 9.02 (s, 1H), 7.94 (m, 4H),
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55 6.90 (s, 1H), 3.27 (q, 4H), 2.68 (t, J = 6.0 Hz, 4H), 1.91 (m, 4H); 13C NMR (100 MHz, DMF-
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3
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60
1
2
3
4 d7, ppm, 25 °C): δ = 164.48, 163.79, 156.46, 147.17, 134.78, 130.55, 130.19, 123.24, 113.66,
5
6 106.44, 105.46, 49.76, 49.28, 26.84, 21.63, 20.73, 20.23. ESI-MS: m/z calcd for C21H19N3O3
7 + H+, 362.15; found, 362.10. Elemental analysis calcd (%) for C21H19N3O3: C, 69.79; H, 5.30;
8
9 N, 11.63 %; found: C, 69.22; H, 5.41; N, 11.27%.
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2.3. Chromogenic detection for copper ion
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14 2.3.1. UV-vis titration of 1 with Cu2+
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1 (1.8 mg, 0.005 mmol) was dissolved in dimethylformamide (DMF, 1 mL) and 12 µL of
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18 this solution (5 mM) was diluted with 2.988 mL of buffer/DMF solution (3/2, v/v, 10 mM
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20 bis-tris, pH = 7.0) to make the final concentration of 20 µM. Cu(NO3)2·2.5H2O (23.7 mg, 0.1
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mmol) was dissolved in bis-tris buffer (5 mL) and 1.5-13.5 µL of this Cu2+ solution (20 mM)
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23 were transferred to the sensor 1 solution (20 µM) prepared above. After mixing them for a
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25 few seconds, UV-vis spectra were taken at room temperature.
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27 2.3.2. Job plot measurement
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30 1 (1.8 mg, 0.005 mmol) was dissolved in DMF (1 mL) and 300 µL of 1 (5 mM) was diluted
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to 29.7 mL with buffer/DMF solution (3/2, v/v, 10 mM bis-tris, pH = 7.0) to make the final
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33 concentration of 50 µM. 2.7, 2.4, 2.1, 1.8, 1.5, 1.2, 0.9, 0.6 and 0.3 mL of the 1 solution were
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35 taken and transferred to vials. Cu(NO3)2·2.5H2O (0.25 mmol) was dissolved in bis-tris buffer
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(10 mM, 5 mL) and 30 µL of the Cu2+ solution was diluted to 30.0 mL with buffer/DMF
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38 solution (3/2, v/v, 10 mM bis-tris, pH = 7.0) to make the final concentration of 50 µM. 0.3,
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40 0.6, 0.9, 1.2, 1.5, 1.8, 2.1, 2.4 and 2.7 mL of the Cu2+ solution were added to each diluted 1
41
solution. Each vial had a total volume of 3 mL. After mixing them for a few seconds, UV-vis
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43 spectra were taken at room temperature.
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46 2.3.3. Competitive experiment
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48 1 (1.8 mg, 0.005 mmol) was dissolved in DMF (1 mL) and 12 µL of this solution (5 mM)
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50 was diluted with 2.988 mL of buffer/DMF solution (3/2, v/v, 10 mM bis-tris, pH = 7.0) to
51 make the final concentration of 20 µM. MNO3 (M = Ag, Na, K, 0.1 mmol) or M(NO3)2 (M =
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53 Zn, Cu, Cd, Fe, Hg, Co, Ni, Mg, Ca, Pb, Mn, 0.1 mmol) or M(NO3)3 (M = Al, Ga, In, Fe, Cr,
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55 0.1 mmol) was separately dissolved in 10 mM bis-tris buffer (5 mL). 10.5 µL of each metal-
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1
2
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4 ion solution (20 mM) was taken and added to 2.990 mL of the 1 solution (20 µM) to give 3.5
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6 equiv of metal ions. Then, 10.5 µL of Cu2+ solution (20 mM) was added into the mixed
7 solution of each metal ion and 1 to make 3.5 equiv. After mixing them for a few seconds,
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9 UV-vis spectra were taken at room temperature.
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2.4. Fluorogenic detection for PO43- and S2-
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14 2.4.1. UV-vis titrations
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1 (1.8 mg, 0.005 mmol) was dissolved in DMF (1 mL) and 12 µL of this solution (5 mM)
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18 was diluted with 2.988 mL of buffer/DMSO solution (7/3, v/v, 10 mM bis-tris, pH = 7.0) to
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20 make the final concentration of 20 µM. K3PO4 (or Na2S) (3 mmol) was dissolved in bis-tris
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buffer (5 mL) and 1.0-23.0 µL of this PO43- (or 1.0-27.0 µL of the S2-) solution (600 mM)
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23 were transferred to the sensor 1 solution (20 µM) prepared above. After mixing them for a
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25 few seconds, UV-vis spectra were taken at room temperature.
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27 2.4.2. Fluorescence titrations
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30 1 (1.8 mg, 0.005 mmol) was dissolved in DMF (1 mL) and 12 µL of this solution (5 mM)
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was diluted with 2.988 mL of buffer/DMSO solution (7/3, v/v, 10 mM bis-tris, pH = 7.0) to
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33 make the final concentration of 20 µM. K3PO4 (or Na2S) (3 mmol) was dissolved in bis-tris
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35 buffer (5 mL) and 1.0-16.0 µL of this PO43- (or 1.0-20.0 µL of the S2-) solution (600 mM)
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were transferred to the sensor 1 solution (20 µM) prepared above. After mixing them for a
37
38 few seconds, fluorescence spectra were taken at room temperature.
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40
41 2.4.3. Job plot measurements
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43 1 (1.8 mg, 0.005 mmol) was dissolved in DMF (1 mL) and 300 µL of 1 (5 mM) was diluted
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45 to 29.7 mL with buffer/DMSO solution (7/3, v/v, 10 mM bis-tris, pH = 7.0) to make the final
46 concentration of 50 µM. 2.7, 2.4, 2.1, 1.8, 1.5, 1.2, 0.9, 0.6 and 0.3 mL of the 1 solution were
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48 taken and transferred to vials. K3PO4 (or Na2S) (3.0 mmol) was dissolved in bis-tris buffer
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50 (10 mM, 5 mL) and 2.5 µL of the PO43- (or S2-) solution was diluted to 30.0 mL with
51 buffer/DMSO solution (7/3, v/v, 10 mM bis-tris, pH = 7.0) to make the final concentration of
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53 50 µM. 0.3, 0.6, 0.9, 1.2, 1.5, 1.8, 2.1, 2.4 and 2.7 mL of the PO43- (or S2-) solution were
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55 added to each diluted 1 solution. Each vial had a total volume of 3 mL. After mixing them for
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1
2
3
4 a few seconds, UV-vis spectra were taken at room temperature.
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2.4.4. 1H NMR titrations
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9 For 1H NMR titration of sensor 1 with PO43-, three NMR tubes of 1 (3.6 mg, 0.01 mmol)
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11 dissolved in DMF-d7 were prepared and then three different concentrations (0, 0.01 and 0.02
12 mmol) of K3PO4 dissolved in D2O were added to each solution of 1. After shaking them for a
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14 minute, 1H NMR spectra were taken at room temperature.
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2.4.5. Competitive experiments
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19 Tetraethylammonium (TEA) salts of CN-, F-, Cl-, Br- and I- (3 mmol),
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21 tetrabutylammonium (TBA) salts of OAc-, BzO-, N3- and SCN- (3 mmol), sodium salts of
22 NO2-, S2-, HCO3-, CO32- and SO42- (3 mmol) and potassium salt of PO43- (3 mmol) were
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24 separately dissolved in 10 mM bis-tris buffer (5 mL). 18 µL of each anion solution (600
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26 mM) was diluted to 2.955 mL of buffer/DMSO solution (7/3, v/v, 10 mM bis-tris, pH =
27 7.0). 15 µL of the PO43- (or 18 µL of the S2-) solution (600 mM) was added to solutions
28
29 prepared above. Then, 12 µL of the sensor 1 solution (5 mM) was added to the mixed
30
31 solutions to make a total volume of 3 mL. After stirring them for a few seconds,
32 fluorescence spectra were taken at room temperature.
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35 2.5. Theoretical calculations of 1, 1-Cu2+ and 1-
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38 All theoretical calculations were carried out by the density functional theory (DFT) and
39 time-dependent DFT (TD-DFT) method based on the hybrid exchange correlation functional
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41 B3LYP44,45 with the Gaussian 03 program.46 The main atoms were applied by the 6-31G (d, p)
42
43 basis set47,48 and the copper element was employed by the LANL2DZ effective core potential
44 (ECP).49–51 All geometries were completely minimized in the ground states (S0). By using the
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46 Cossi and Barone’s conductor-like polarizable continuum model (CPCM),52,53 we considered
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48 the solvent effect of DMF for the calculations of 1 and 1-Cu2+ complex and DMSO for the
49 calculation of 1-. We calculated the lowest 20 singlet-singlet transitions using TD-DFT
50
51 calculations at the ground state geometries (S0) to examine the transition energies for the
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53 minimized structures of 1, 1-Cu2+ complex and 1-. The GaussSum 2.154 was used to calculate
54 the contribution of molecular orbitals (MO) in electronic transitions.
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1
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6 3. Results and discussion
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8 Sensor 1 was synthesized by coupling N-aminophthalimide and 8-hydroxyjulolidine-9-
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10 carboxaldehyde with 76 % yield in 1,4-dioxane (Scheme 1), and analyzed by 1H NMR (Fig.
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12
S1) and 13C NMR (Fig. S2), ESI-mass spectrometry and elemental analyses.
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14 3.1. Colorimetric and spectral responses of 1 toward Cu2+
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16
The colorimetric sensing properties of sensor 1 were investigated in the presence of 3.5
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18 equiv of various metal ions such as Al3+, Ga3+, In3+, Zn2+, Cd2+, Cu2+, Fe2+, Fe3+, Mg2+, Cr3+,
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20 Hg2+, Ag+, Co2+, Ni2+, Na+, K+, Ca2+, Mn2+ and Pb2+ in buffer/DMF solution (3/2, v/v, 10 mM
21
bis-tris, pH = 7.0). As shown in Fig. 1a, only Cu2+ induced a distinct spectral change, while
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23 other metal ions induced little or small spectral changes. Consistent with the UV-vis spectral
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25 change, the solution color of 1 in the presence of Cu2+ ion changed from pale yellow to deep
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yellow (Fig. 1b), demonstrating that sensor 1 could be used as a “naked-eye” chemosensor
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28 for Cu2+. Counter anion effect of Cu2+ ion was also studied with various anions such as SO42-,
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30 Cl-, and OAc- (Fig. S3). Nearly identical results were observed without respective to the type
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of counter anions. Additionally, we checked the time dependence of sensor 1 to Cu2+ (Fig.
32
33 S4). It took about 10 min for the complete formation of 1-Cu2+ complex.
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35
36 To further examine the sensing properties of 1, UV-vis titration of 1 with Cu2+ ion was
37 performed (Fig. 2). Upon the addition of Cu2+ to a solution of 1, the absorption peak at 383
38
39 nm gradually decreased, whereas the bands at 280 and 422 nm progressively increased with
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41 two clear isosbestic points at 341 and 398 nm. These results suggested that a single species
42 was formed between 1 and copper ion.
43
44
45 To investigate the binding mode of 1 and Cu2+ ion, we carried out the Job plot (Fig. S5)55
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and ESI-mass spectrometry analysis (Fig. S6), which showed the 1:1 stoichiometric ratio for
47
48 the formation of 1-Cu2+ complex. The positive-ion mass spectrum exhibited the formation of
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50 the 1 + Cu2+ + NaCl + 3·H2O – H+ [m/z: 535.10; calcd, 535.05]. In order to further examine
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the interaction between 1 and Cu2+, we conducted 1H NMR titrations of 1 with Cu2+, but it
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53 was not successful due to a paramagnetic character of 1-Cu2+ complex.
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1
2
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4 Based on UV-vis titration data, the binding constant of 1 with Cu2+ was calculated to be 1.6
5
6 × 104 M-1 from Li’s equation (Fig. S7).56 The value is within the range of those (103~1012)
7 previously reported for Cu2+ chemosensors. The detection limit for Cu2+ was determined to
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9 be 0.14 µM (Fig. S8) via 3σ/K,57 which was about 200 times lower than the World Health
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11 Organization (WHO) guideline (31.5 µM) in drinking water.58 Also, a comparison between
12 the present detection limit with the reported ones is presented in Table S1.
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14
15 To check a practical ability of 1 toward Cu2+, sensor 1 was treated with various interfering
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17
cations (Na+, K+, Mg2+, Ca2+, Cr3+, Mn2+, Fe2+, Fe3+, Co2+, Ni2+, Zn2+, Cd2+, Hg2+, Ag+, Al3+,
18 Ga3+, In3+ and Pb2+) including 3.5 equiv of Cu2+ in buffer/DMF solution (3/2, v/v, 10 mM bis-
19
20 tris, pH = 7.0). As shown in Fig. 3, there was no marked change from diverse metal ions
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22
compared with 1-Cu2+. These results indicated that chemosensor 1 could be used as a superior
23 colorimetric sensor for Cu2+ over other relevant species.
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25
26 The pH effect of sensor 1 for detecting Cu2+ was tested in the wide pH range of 2 to 12. As
27 shown in Fig. S9, the absorbance of 1-Cu2+ complex at 422 nm indicated a significant
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29 increase between pH 4 and 11. These results warranted that the chemosensor 1 could be used
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31 as the detector for Cu2+ ion over a broad pH range of 4-11 by the naked eye or UV-vis
32 absorption measurement.
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35 To evaluate the practical use of sensor 1 with Cu2+ in environmental analysis, tap and
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drinking water samples were prepared and analyzed by using the calibration curve of 1
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38 toward Cu2+ (Fig. S10). As shown in Table 1, the satisfactory recoveries and R.S.D. values
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40 were obtained for all samples. This indicated that chemosensor 1 could be suitable and useful
41
42
for detection of Cu2+ ion with good precision and accuracy in real water samples.
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44 To further investigate the colorimetric sensing mechanism of sensor 1 binding to Cu2+, DFT
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46 calculations were performed using the Gaussian 03 program. In order to get the energy-
47 minimized structures of 1 and 1-Cu2+ complex, their geometric optimizations were carried
48
49 out. The main atoms were applied by the B3LYP/6-31G (d, p) method basis set and the Cu
50
51 atom was applied by the LANL2EZ/ECP methods. The energy-optimized structure of 1
52 indicated a slightly distorted structure with the dihedral angle of 2C, 3N, 6C, 7O = -8.551o
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54 (Fig. 4a). 1-Cu2+ complex showed a planer structure with the dihedral angle of 2C, 3N, 6C,
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56
8
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58
59
60
1
2
3
4 7O = -0.224o (Fig. 4b). For further information on electronic transitions of 1 and 1-Cu2+
5
6 complex, TD-DFT calculations were executed at the optimized geometries (S0). The main
7 molecular orbital (MO) contribution of the third lowest excited state of 1 was determined for
8
9 the HOMO → LUMO+1 transition (392.50 nm, Fig. S11). For 1-Cu2+ complex, the main MO
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11 contributions of the sixteenth lowest excited state were determined for the HOMO (α) →
12
LUMO+1 (α) and HOMO (β) → LUMO+2 (β) transitions (409.79 nm, Fig. S12), which
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14 manifested intramolecular charge transfer (ICT) transition from the julolidine group to the
15
16 phthalimide one. As shown in Fig. S13, there was only a red shift (392.50 nm to 409.79 nm)
17
by the chelation of 1 to Cu2+, which is well consistent with the change of UV-vis spectra.
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19 Based on Job plot, ESI-mass spectroscopy analysis and theoretical calculations, we proposed
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21 the structure of a 1:1 complex between 1 and Cu2+ as shown in Scheme 2.
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23
24
25
26 3.2. Fluorescence spectroscopic studies of 1 toward PO43- and S2-
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28 The fluorogenic sensing ability of 1 was studied in the presence of 180 equiv of other
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30 anionic species such as CN-, OAc-, F-, Cl-, Br-, I-, BzO-, N3-, PO43-, NO2-, SCN- and S2- with
31
32 an excitation of 426 nm in buffer/DMSO solution (7/3, v/v, 10 mM bis-tris, pH = 7.0). Sensor
33 1 having no fluorescence intensity at 487 nm exhibited instantly a significant fluorescent
34
35 enhancement with PO43- and S2- while there were no obvious changes in presence of other
36
37 anions (Fig. 5). These results suggested that sensor 1 could have a potential ability of
38 fluorescence chemosensor for PO43- and S2-. Importantly, this is the first example that a single
39
40 chemosensor can detect the three analytes, Cu2+, PO43- and S2-, to the best of our knowledge.
41
42 To investigate the binding affinity of sensor 1 and PO43-, the fluorescence titration was
43
44 performed. As shown in Fig. 6, the emission intensity of 1 at 487 nm exhibited a progressive
45
46 increase up to 150 equiv of PO43-. The photophysical interaction between 1 and PO43- was
47 studied by UV-vis titration experiment (Fig. S14). The UV-vis absorbance gradually
48
49 decreased at 375 nm and steadily increased at 430 nm with a clear isosbestic point at 320 nm.
50
51 This red shift led us to propose that the ICT band of 1 might be enhanced by the
52 deprotonation of the hydroxyl proton by phosphate (Scheme 3).
53
54
55 For further information on the binding mode between 1 and PO43-, the Job plot analysis 55
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9
57
58
59
60
1
2
3
4 was carried out (Fig. S15), which suggested that sensor 1 responded to PO43- with the ratio of
5
6 a 1:1 stoichiometry. Moreover, the negative-ion mass spectrum indicated the formation of the
7 1- + MeOH [m/z: 392.20; calcd, 392.16] (Fig. S16). Furthermore, we performed 1H NMR
8
9 titrations to study the interaction between 1 and PO43-. Upon the addition of PO43- to 1, the
10
11 phenolic proton H8 disappeared and the protons H3 and H4 exhibited slightly up-field shifts
12 (Fig. S17). These results supported the proposal that the hydroxyl group of the julolidine
13
14 moiety might be deprotonated by PO43-. Based on the fluorescence titration data, the
15
16 association constant was estimated to be 5.70 × 102 M-1 from the Benesi-Hildebrand equation
17 (Fig. S18).59
18
19
20 In order to study the practical efficacy of sensor 1 as a fluorogenic chemosensor for PO43-,
21
22
the competition experiments were carried out in the presence of PO43- with various anions
23 such as CN-, OAc-, F-, Cl-, Br-, I-, BzO-, N3-, NO2-, SCN-, S2-, HCO3-, CO32- and SO42- in
24
25 buffer/DMSO solution (7/3, v/v, 10 mM bis-tris, pH = 7.0). As shown in Fig. S19, HCO3- and
26
27
SO42- inhibited 35 % and 25 %, respectively, whereas there was no interference with other
28 anions. These results indicated that sensor 1 could be used as an excellent fluorescent sensor
29
30 for detection of PO43-.
31
32 We investigated the pH dependence of 1 at various pH values for practical application (Fig.
33
34 S20). There was no fluorescence intensity of 1 at pH range of 2-10, whereas the fluorescent
35
36 emission of 1 in the presence of PO43- was significantly enhanced at pH range of 7-10. These
37 results indicated that sensor 1 could detect phosphate at pH range of 7-10.
38
39
40 Next, fluorescence titration was carried out in order to examine interaction properties of
41
42
sensor 1 toward S2- (Fig. 7). Upon the addition of S2-, sensor 1 exhibited a gradual emission
43 enhancement up to 180 equiv. To study the binding properties of 1 toward S2-, UV-vis
44
45 titration experiment was performed (Fig. S21a). If one looks carefully into the UV-vis
46
47
titration, there was a two-step change (0-110 equiv and 120-270 equiv). In the first step (Fig.
48 S21b), the absorbance at 383 nm considerably decreased and the one at 430 nm increased
49
50 with clear isosbestic points at 343 and 406 nm. In the second step (Fig. S21c), the absorbance
51
52
at 377 nm decreased and the one at 430 nm significantly increased with obvious isosbestic
53 points at 320 and 390 nm. The two-step change led us to propose the sensing mechanism of 1
54
55 toward S2- as shown in Scheme 4.
56
10
57
58
59
60
1
2
3
4 In order to understand the binding mode between sensor 1 and S2-, Job plot analysis 55
was
5
6 conducted (Fig. S22). Sensor 1 responded to S2- with the ratio of a 1:1 stoichiometry. In
7 addition, the negative-ion mass spectrum displayed the formation of the 1- + MeOH [m/z:
8
9 392.19; calcd, 392.16] (Fig. S23). Using the fluorescence titration data, the association
10
11 constant was determined to be 6.40 × 102 M-1 from the Benesi-Hildebrand equation (Fig.
12 S24).59
13
14
15 To investigate the competitive ability of 1 toward S2- in the presence of various anions, the
16
17
competition experiments were executed in the solution containing both sulfide and other
18 anions (CN-, OAc-, F-, Cl-, Br-, I-, PO43-, BzO-, N3-, NO2-, SCN-, HCO3-, CO32- and SO42-) in
19
20 buffer/DMSO solution (7/3, v/v, 10 mM bis-tris, pH = 7.0). As shown in Fig. 8, sensor 1 as
21
22
detector of sulfide had no or slight interruption by other anions. Therefore, 1 could be utilized
23 as a fluorogenic sensor for detecting sulfide in the presence of diverse anions. These results
24
25 showed that 1 could be utilized as a fluorogenic sensor for detecting sulfide in the presence of
26
27
diverse anions.
28
29 In order to obtain the information on the sensitivity of sensor 1 at wide pH range, we
30
31 performed pH test (Fig. S25). The fluorescent intensity of 1 exhibited no obvious change at
32 pH range from 2 to 10, while the fluorescent intensity of 1 with S2- showed a significant
33
34 increase at pH range from 3 to 10. These results suggested that 1 could be used as a
35
36 fluorescence sensor for S2- in a wide pH range.
37
38 On the other hand, it is a challenge to distinguish PO43- from S2- by 1. As it has been well
39
40 known that Cu2+ can form a stable complex with S2-, we added Cu2+ ions to 1-PO43- and 1-S2-
41
42
solutions, respectively (Fig. S26). The mixed solution of 1-PO43- with Cu2+ showed color
43 change from deep yellow to green, and the solution color of 1-S2- with Cu2+ changed from
44
45 deep yellow to brown. Therefore, when sensor 1 showed a fluorescence enhancement in the
46
47
presence of an anion, it can be PO43- or S2-. In such a case, the appearance of brown color by
48 the addition of Cu2+ indicates that the anion could be S2-, while it could be PO43- with green
49
50 color.
51
52 In order to obtain insight into the sensing mechanisms and optical properties of 1 for
53
54 detecting phosphate and sulfide, DFT calculations were performed by using Gaussian 03
55
56
11
57
58
59
60
1
2
3
4 program. The B3LYP/6-31G (d, p) method basis set was used for all the atoms. The
5
6 calculated energy-optimized structures of 1 and 1- were shown in Fig. 4. The energy-
7 optimized structure of 1 exhibited a slightly distorted structure with dihedral angles of
8
9 165.851o (1O, 2C, 4C, 5C) (Fig. 4a), whereas 1- indicated a twisted structure between the
10
11 phthalimide and the julolidine groups with a dihedral angle of -107.062o (1O, 2C, 4C, 5C)
12 (Fig. 4c). With TD-DFT calculations, the main transition property of 1 indicated the HOMO
13
14 → LUMO+1 transition (392.50 nm, Fig. S11) and one of 1- showed the HOMO → LUMO+1
15
16 transition (440.63 nm, Fig. S27). These transitions were assigned as the enhanced ICT
17 transition from the julolidine group to the phthalimide one (Fig. S28). There was only
18
19 bathochromic shift (from 392.50 nm to 440.63 nm) by the deprotonation of 1 by PO43- or S2-,
20
21 which is well consistent with the change of UV-vis spectra. These results supported the
22 sensing mechanisms of 1 toward PO43- and S2-, which are proposed in Schemes 3 and 4.
23
24
25
26
27 4. Conclusion
28
29 We have developed a selective chemosensor 1 for the colorimetric detection of copper ion
30
31 and for the fluorescent detection of phosphate and sulfide. Sensor 1 showed the color change
32 from pale to deep yellow in the presence of Cu2+ ion with a 1:1 stoichiometric ratio. The
33
34 detection limit for Cu2+ was 0.14 µM, which was much lower than the drinking water
35
36 guideline (31.5 µM) of WHO. In addition, sensor 1 could apply to quantify Cu2+ in real water
37 samples. The colorimetric sensing mechanism of Cu2+ with 1 was proposed to be ICT
38
39 mechanism by theoretical calculations. Moreover, sensor 1 could detect PO43- and S2- by the
40
41 significant emission enhancement. Importantly, this is the first example that a single
42 chemosensor can detect the three analytes, Cu2+, PO43- and S2-, to the best of our knowledge.
43
44 The deprotonation process of 1 by PO43- and S2- was proposed by ESI-mass analysis, 1H
45
46 NMR titrations and DFT calculations. Therefore, we believe that these results may contribute
47 to the development of a new type of multifunctional chemosensors for multiple analytes
48
49 including metal ions and anions.
50
51
52
53
54 Acknowledgements
55
56
12
57
58
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60
1
2
3
4 Basic Science Research Program through the National Research Foundation of Korea
5
6 (NRF) (NRF-2016M3D3A1A01913239 for the Korea C1 Gas Refinery R&D Center) is
7 gratefully acknowledged. This subject is also supported by Korea Ministry of Environment
8
9 (MOE) as "The Chemical Accident Prevention Technology Development Project". We
10
11 thank Nano-Inorganic Laboratory, Department of Nano & Bio chemistry, Kookmin
12 University to access the Gaussian 03 program packages.
13
14
15
16
17 Supplementary Information
18
19
20 Supplementary data (1H NMR and 13C NMR spectra, time dependence with copper, Job plot
21
and ESI-mass spectroscopy analyses, association constant, detection limit, pH dependence,
22
23 calibration curve with copper, theoretical calculations, UV-vis titrations with phosphate and
24
25 sulfide, 1H NMR titrations with phosphate, competitive selectivity for phosphate and color
26
change of 1 with phosphate and sulfide on addition of copper) associated with this article can
27
28 be found in the online version, at http:// ~.
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44
45
46
47
48
49
50
51
52
53
54
55
56
22
57
58
59
60
1
2
3
4
5
6
7 Table 1. Determination of Cu2+ in water samples.
8
9 Cu(II) added Cu(II) found Recovery R.S.D. (n = 3)
10 Sample
(µmol L-1) (µmol L-1) (%) (%)
11
12 Tap water 0.00 0.00
13 a
14 0.20 0.19 95 0.31
15 Drinking water 0.00 0.00
16
17 0.20a 0.21 105 0.20
18
19 Conditions: [1] = 20 µmol/L in 10 mM bis-tris buffer-DMF solution (3/2, v/v, pH 7.0). a 0.20 µM of Cu2+ ion was artificially
20 added.
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
23
57
58
59
60
1
2
3
4 Figure captions
5
6
7
Figure 1. (a) Absorption spectra of 1 (20 µM) in the presence of diverse cations (3.5 equiv) in
8 buffer/DMF solution (3/2. v/v, 10 mM bis-tris, pH = 7.0). (b) The color changes of 1 (20 µM)
9
10 in the presence of diverse cations (3.5 equiv).
11
12 Figure 2. Absorption spectral changes of 1 (20 µM) upon the addition of different
13
14 concentrations of Cu2+ at room temperature. Inset: Plot of the absorption at 422 nm versus the
15
16 number of equiv of Cu2+ added.
17
18 Figure 3. (a) Competitive selectivity of 1 (20 µM) for Cu2+ (3.5 equiv) in the presence of
19
20 other metal ions (3.5 equiv) in buffer/DMF solution (3/2. v/v, 10 mM bis-tris, pH = 7.0). (b)
21
The competitive color changes of 1 (20 µM) in the absence and presence of other metal ions
22
23 (3.5 equiv).
24
25
26 Figure 4. Energy-optimized structures of (a) 1, (b) 1-Cu2+ complex and (c) 1-.
27
28 Figure 5. Fluorescence spectra of 1 (20 µM) in the presence of different anions (180 equiv)
29
30 in buffer/DMSO solution (7/3, v/v, 10 mM bis-tris, pH = 7.0). Inset: The fluorescence
31
pictures of 1, 1-PO43- and 1-S2- (λex: 426 nm).
32
33
34 Figure 6. Fluorescence spectral changes of 1 (20 µM) upon the addition of different
35
36 concentrations of PO43- at room temperature.
37
38 Figure 7. Fluorescence spectral changes of 1 (20 µM) upon the addition of different
39
40 concentrations of S2- at room temperature.
41
42 Figure 8. Competitive selectivity of 1 (20 µM) toward S2- (180 equiv) in the presence of
43
44 various anions (180 equiv) in buffer/DMSO solution (7/3. v/v, 10 mM bis-tris, pH = 7.0).
45
46
47
48
49
50
51
52
53
54
55
56
24
57
58
59
60
1
2
3
4
5
6 (a)
7
8
9
10
11 0.6 1 and other metal ions
12
13
Cu2+
Absorbance
14
0.4
15
16
17
18 0.2
19 Ag+, Fe2+ and Fe3+
20
21
22 0.0
23 300 400 500
24 Wavelength (nm)
25
26
27 (b)
28
29
30
31
32
33
34
35
36 Fig. 1.
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
25
57
58
59
60
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26 Fig. 2.
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
26
57
58
59
60
1
2
3
4
5
6
7
(a)
8
9
10
11 0.4
12
13
14
15 0.3
Absorbance
16
17
18 0.2
19
20
21
22 0.1
23
24
25
26 0.0 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1
27 Cu2+ - -
3+
- -
3+
-
2+
- - -
3+
- - - - - - - - -
2+
-
2+
Al3+ Ga In Zn2+ Cd Fe2+ Fe Mg2+ Cr3+ Hg2+ Ag+ Co2+ Ni2+ Na+ K+ Ca2+ Mn Pb
28
29
30
31 (b)
32
33
34
35
36
37
38
39
40
41
42 Fig. 3.
43
44
45
46
47
48
49
50
51
52
53
54
55
56
27
57
58
59
60
1
2
3
4
5
6 (a)
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21 (b)
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36 (c)
37
38
39
40
41
42
43
44
45
46
47
48
49 Fig. 4.
50
51
52
53
54
55
56
28
57
58
59
60
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29 Fig. 5.
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
29
57
58
59
60
1
2
3
4
5
6
7
8
9
200 [PO 3-]
Fluorescence Intensity
10 4
11
12
13 150
14
15
16
100
17
18
19
20 50
21
22
23 0
24 450 500 550 600
25
26
Wavelength (nm)
27
28
Fig. 6.
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
30
57
58
59
60
1
2
3
4
5
6
7
8
9 [S2-]
10 200
11
12
13 150
14
15
16 100
17
18
19 50
20
21
22 0
23 450 500 550 600
24
25
Wavelength (nm)
26
27 Fig. 7.
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
31
57
58
59
60
1
2
3
4
5
6
7
8
9
10
11
12 200
13
14
15
16
17
18 100
19
20
21
22
23 0 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1
24 S2- - - - - - - - - - - - - - -
25 - -
CN OAc F
-
Cl- Br- I- - -
PO4 BzO N3 SCN NO2 HCO3 CO3 SO42-
3- - - - 2-
26
27
28
29 Fig. 8.
30
31
32
33
34
35
36
37
38
39
40
41
42
43
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45
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32
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60
1
2
3
4
5
6 Graphical Abstract
7
8
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