Electronic Supplementary Material (ESI) for J.Fluorescence.
Single chemosensor for double analytes:
spectrophotometric sensing of Cu2+ and fluorogenic
sensing of Al3+ under aqueous conditions
Jie Yang a, Zeli Yuan* a,Guangqing Yua, Shunli Hea, Qinghong Hua, Qing Wua, Bo
Jiang a and Gang Wei*b
a
School of Pharmacy, Zunyi Medical University, Zunyi, Guizhou, 563003,China.Tel.:+86 852 8608579;fax: +86
8528609343;e-mail address:zlyuan@zmc.edu.cn
b
CSIRO Materials Science and Engineering，PO Box 218, Lindfield，NSW 2070，Australia. Tel.:+61 2 9413 7704; e-mail
address: gang.wei@csiro.au
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Table of Contents
General Remarks
General Procedure
References
page
S1
S2-S4
S4
X-Ray data for compound HL (CCDC : 1062532)
S5-S6
spectral data for receptor HL
The data of receptor HL recognized Al3+ and Cu2+
S7-S8
S8-S13
S14-16
The data of DFT calculation
Jie Yang, et al.
S1
General Remarks
1. Materials.
All chemical reagents and solvents were purchased from J&K and used without further purification.
2. Instrumentation
Unless otherwise stated, all reagents were obtained from commercial suppliers and used without further
purification. Solvents employed in this study were of the highest grade and were used as received. The 1H and 13C
NMR spectra were recorded on an Agilent 400 DD2 spectrometer (Agilent, Palo Alto,USA) in DMSO-d6, at
ambient temperature. Chemical shifts (δ) have been expressed in units of parts per million (ppm) relative to TMS,
which was used as an internal reference. High resolution mass spectroscopy (HR-MS) experiments were conducted
on a time-of-flight Micromass LCT PremierXE Spectrometer(Mckinley, NJ, USA). Fluorescence spectra were
generated on a Carry Eclipse spectrophotometer(Agilent, Palo Alto,USA) equipped with quartz cuvettes of 1 cm
path length.Absorption spectra were recorded on a TU-1901 UV-Vis spectrophotometer(PuXi Science and
Technology Development Co., Ltd, Beijing, China). Elemental (C, H, N) analyses were obtained with a Vario
ELIII elemental analyzer(Elementar, WC, Heraeus, Germany). IR spectra were recorded on a Vary FT-IR 1000
FT-IR spectrophotometer(Varian, Palo Alto, USA) as KBr disks over the range of 400–4000 cm–1. The NMR,
HR-MS, FT-IR and physical properties data for each compound have been summarized below for experiment.
The crystal data were collected on CCD SMART APEX diffractometer with graphite-mono chromated Mo Ka
radiation (l¼0.71073 Å) at 293 K, 3135 reflections for HL. Cell refinements and the data reductions were obtained
from SAINT1. Absorption corrections were applied by using multi-scan program SADABS1. Structural solutions
were performed by direct methods and full-matrix least-square refinement based on F2 with the SHELXTL
program packages.2 Anisotropic thermal parameters were applied to all non-hydrogen. All atoms and all hydrogen
atoms of carbon atoms were placed by geometric calculation. Hydrogen atoms on both nitrogen and oxygen atoms
were located in a difference map and were restrained. The SHELXTL2 and Mercury3 programs were used to
prepare materials for publication and the molecular graphics. CCDC-1062532 for HL contain the supplementary
crystallographic data for this paper. These data can be obtained free of charge from. The Cambridge
Crystallographic Data Center via http://www.ccdc. cam.ac.uk /Community /Requestastructure /Pages/
DataRequest.aspx (or from the Cambridge Crystallographic Data Centre, 12Union Road, Cambridge CB21EZ,
U.K.; fax: t44 1223 336 033 or email deposit@ccdc.cam.uk).
Jie Yang, et al.
S2
General Procedure for experiments
1.Synthesis of HL
Scheme 1 Synthesis of chemosensor HL
8-hydroxyjulolidine-9-carboxaldehyde (0.23 g, 1 mmol) and 4-tert-butyl-benzhydrazide
(0.19 g, 1 mmol) in
MeOH (25 mL) in a 50 mL round-bottomed flask were irradiated at 300 W at 60 °C for 15 min. After
cooling the reaction mixture to an ambient temperature, the formed solid was filtered, washed with diethyl ether.
The crude product was purified by recrystallization from methanol to give 0.32 g of HL as a yellow solid (82.0%,
m.p. 116-118°C).1H NMR (DMSO-d6, 400 MHz), δ (ppm): 1.30 (s, 9H),1.84-1.87 (dd, 4H, J=10.8, 5.5 Hz ),
2.60-2.62(dd, 4H, J=14.5, 6.9 Hz), 3.15-3.19 (dd, 4H, J=10.2, 4.9 Hz), 6.71(s, 1H), 7.53-7.55(d, 2H, J=7.6 Hz),
7.83-7.85 (d, 2H, J=8.3 Hz), 8.30 (s, 1H), 11.74 (s, 1H), 11.82 (s, 1H); 13C NMR(DMSO-d6,100 MHz) δ (ppm):
20.24, 20.70, 21.52, 26.54, 30.94, 34.72, 48.85, 49.33, 105.80, 106.28, 112.39, 125.26, 127.34, 128.25, 130.37,
145.59, 150.62, 154.51, 154.66, 162.01; IR (KBr, cm-1) ν: (3416, -OH), (3036, N-H), (1638, C=O), (1552, C=N),
(1305, C-N); Elemental Analysis(Calcd for C24H29N3O2·CH3OH),C 70.82(70.89), H 7.97(7.85), N 9.86(9.92);
＋
HRMS(ESI) calcd for C24H29N3O2 (M＋Na ): 414.2260, found 414.2143.
2. Analysis
Stock solutions (2 mM) of receptor HL and the nitrate salts or chloride (Li+, Na+, K+, Ca2+, Mg2+, Al3+, Mn2+,
Ni2+, Co2+, Cr3+, Zn2+, Cd2+, Cu2+, Ba2+, Pb2+, Ag+, Hg2+, and Fe3+) were prepared in ethanol and water solution
ethanol/water=25%). Solutions of different anions (F-, Cl-, Br-, I-, NO3-, SO32-, SO42-, HSO4-,CO32-, CO3-, HCO3-,
lPO42-, H2PO4-, and AcO-) were prepared in ethanol and water solution(ethanol/water=25%).
3. UV-vis titration measurements of Cu2+-L complex
Test solutions were prepared by placing 10 μL of the HL stock solution into cuvettes and adding 0 - 28μL of
the Cu2+ stock solution (2 mM) prepared above, and diluting the solution to 2 mL with Tris-HCl(pH=7.40) to make
the final concentration of each receptor solution(10 μM) to give 1–14 equiv. After mixing them for a few
seconds, UV-vis spectra were taken at room temperature.
4. Fluorescence titration measurements of Al3+-2L complex
Test solutions were prepared by placing 10 μL of the HL stock solution into cuvettes and adding 0 - 40μL of
Jie Yang, et al.
S3
the Al3+ stock solution (100 mM) prepared above, and diluting the solution to 2 mL with Tris-HCl(pH=7.40) to
make the final concentration of each receptor solution(10 μM) to give 1.0–15.0 equiv. After mixing them for a
few seconds, fluorescence spectra were obtained at room temperature. Both the excitation and emission slit widths
were 5.0 nm.
5. Job plot measurements
For Cu2+, 100, 90, 80, 70, 60, 50, 40, 30, 20, 10 and 0 μL of the HL stock solution (2 mM) were taken and
transferred to vials. Each vial was diluted with tris-HCl buffer to make a total volume of 1.8 mL.Then, 0, 10, 20,
30, 40, 50, 60, 70, 80, 90 and 100 μL of the Cu2+ stock solution(2 mM) were added to each diluted HL solution.
Each vial had a total volume of 2 mL. After shaking them for a minute, UV-vis spectra were obtained at room
temperature.
In the same procedure for Al3+. After mixing them for a few seconds, fluorescence spectra were obtained at
room temperature. Both the excitation and emission slit widths were 5.0 nm.
6. Competitive experiments
Test solutions were prepared by placing 10 μL of the HL stock solution(2 mM) into vials, adding of each ion
stock solution to make 1.0 equiv or 10.0equiv and diluting the solution to 2 mL with Tris-HCl buffer. Then, 10 μ
L of Cu2+ or 100μL Al3+ solution (2 mM) was added into the mixed solution of each ion and receptor HL to make
1.0 equiv or 10.0 equiv. After mixing them for a minute, UV-vis spectra or fluorescence spectra were taken at
room temperature. Both the excitation and emission slit widths were 5.0 nm.
7. pH effect test
Test solutions were prepared by placing 10 μL of the HL stock solution into vials and adding 10μL of the Cu2+
stock solution (2 mM) prepared above. A range of buffers with pH values ranging from 1 to 14 was prepared
by mixing sodium hydroxide solution or hydrochloric acid in Tris-HCl buffer to make the final concentration
of each receptor solution(10 μM). After the solution with a expected pH was obtained, UV-vis spectra were
obtained at room temperature.
In the same procedure for Al3+ except adding 100μL of the Al3+ stock solution (2 mM). After mixing them for
a few seconds, fluorescence spectra were obtained at room temperature. Both the excitation and emission slit
widths were 5.0 nm.
8. 1H NMR titrations
For 1H NMR titrations of receptor HL with Cu2+, five NMR tubes of receptor HL (3.91 mg, 0.01 mmol)
dissolved in DMSO-d6 (700 μL) were prepared and then five different concentrations (0, 0.005, 0.01,
Jie Yang, et al.
S4
0.02, and 0.05 mmol) of CuSO4 or AlCl3 dissolved in D2O were added to each solution of receptor HL. After
shaking them for a minute, 1H NMR spectra were obtained at room temperature.
9 DFT calculation
DFT calculations using the Gaussian suite of programs(Gaussian 09 W) were carried out, which verified the the
coordination modes of 2L- Al3+ and L-Cu2+. To obtain the optimized configurations of 2L- Al3+ and L-Cu2+,
molecular structure optimization and single-point energy calculations were performed at the B3LYP/6-31G(d).
The minimum nature of the structure was confirmed by frequency calculations at the same computational level.
References
1.
Bruker. SMART, SAINT and SADABS; Bruker AXS: Madison, WI, USA, 2003.
2.
G. M. Sheldrick, Acta. Crystallogr., 2008, A64, 112.
Jie Yang, et al.
S6
Original data
1. X-Ray data for receptor HL
Table S1 Crystal data and structure refinement for HL
Formula
HL
Molecular weight
391.50
space group
P2/c
a (A, )
21.6686(19)
b (A, )
9.4210(8)
c (A, )
22.7540(19)
β (°)
103.390(2)
V (Å3)
4518.7(7)
Z
8
Dcalc (g cm-3)
1.151
Goodness-of-fit on F2
1.097
R [I>2δ(I)]
0.0638
wR2 (all data)
0.1604
Table S2 Selected bonds lengths(Å) and angles (°) of HL
Bond lengths
C1-N4
N1-C25
1.437(4)
1.395(9)
O1-C29
1.352(4)
N1-C33
1.388(4)
N1-C25A
1.398(8)
N1-C36
1.440(5)
C2-C3
1.505(5)
N2-C37
1.285(4)
N2-N3
1.381(3)
O2-C38
1.231(4)
C3-C4
1.512(5)
N3-C38
1.341(4)
N4-C9
1.382(4)
N4-C12
1.438(4)
O4-C14
1.241(4)
N5-N6
1.381(3)
N6-C14
C8-C9
1.410(4)
N6 -H6A
0.8600
C7-C8
1.362(4)
C8-C10
1.503(5)
C11-C12
1.468(5)
C13-H13A
0.9300
C18-C19
1.366(5)
111.0(4)
C2-C1-H1A
109.2
C29-O1-H10C
118.9
1.340(4)
Bond angles
C1-C2-C3
Jie Yang, et al.
2
S6
C33 N1 C25A
119.6(6)
C9-N4-C1
120.9(3)
C1-N4-C12
115.8(3)
O3 C5 C4
118.0(3)
C13-N5-N6
115.4(3)
C14-N6-N5
120.5(3)
N4-C9-C4
120.0(4)
N4-C12-C11
113.1(4)
N6-C14-C15
116.5(4)
O1-C29-C28
117.4(4)
N1-C33-C28
120.1(4)
N1-C36-C35A
113.5(9)
O2-C38-N3
121.5(3)
N3-C38-C39
116.4(3)
C35-C36-H36C
74.3
N4-C1-C2-C3
-55.6(5)
C2-C1-N4-C9
37.2(5)
O3-C5-C6-C13
-2.1(5)
C1-N4-C9-C4
-9.7(5)
C1-N4-C9-C8
172.2(3)
C12-N4-C9-C8
9.0(5)
C5-C4-C9-N4
-177.0(3)
C7-C8-C9-N4
176.2(3)
C7-C8-C9-C4
-1.8(5)
C1-N4-C12-C11
168.3(4)
N6-N5-C13-C6
-178.0(3)
N5-N6-C14-C15
-178.3(3)
O4-C14-C15-C20
-154.4(4)
N6-C14-C15-C20
26.3(5)
O1-C29-C30-C31
-179.7(3)
spectral data for receptor HL
Fig. S1 1H NMR of HL in DMSO-d6
Jie Yang, et al.
S7
Fig. S2 13C NMR of HL in DMSO-d6
*
Fig. S3 HRMS(ESI-MS) of HL
The parent ion peaks at m/z 414.2143 is marked with asterisks.
Jie Yang, et al.
S8
Fig. S4 FT-IR of HL
3 The data of receptor HL
Fig. S5
recognized Al3+
and Cu2+
UV-vis spectra of HL (10 μM) before and after addition of various metal ions (100 μM) of Al3+ and
Cu2+ in tris-HCl/-ethanol(9:1,v:v,pH=7.40)buffer
Fig. S6
Fluorescence changes of HL(10 μM)
upon the addition of different metal ions in
tris-HCl/-ethanol(9:1,v:v,pH=7.40) under UV lamp (λex = 365 nm), at room temperature.
Jie Yang, et al.
Fig. S7
S9
A Job plot examined between Cu2+ and HL, indicating the 1:1 Stoichiometry for [L- Cu2+] clearly ) in a
mixture of tris-HCl buffer and ethanol (9/1, v/v, pH=7.40).
Fig. S8
A Job plot examined between Al3+ and HL, indicating the 2: 1 Stoichiometry for [2L- Al3+] clearly in a
mixture of tris-HCl buffer and ethanol (9/1, v/v, pH=7.40).
Jie Yang, et al.
Fig. S9
S10
High resolution mass spectrum of HL (10 μM) upon addition of Cu2+ (10μM) in a mixture of
ethanol/H2O (8:1).
Fig. S10 High resolution mass data of HL (10 μM) upon addition of Cu2+ (10μM) in a mixture of ethanol/H2O
(8:1).
Jie Yang, et al.
S11
8
(Amax-A0)/(A-A0)
Y=1.469X-0.699
(R2=0.9883)
6
Ka=4.7610 M
4
-1
4
2
0
0
1
2
3
4
5
6
1/[Cu2+](X105L·mol-1)
Fig. S11. Benesie-Hildebrand
equation plot of HL, assuming 1:1 stoichiometry for association between HL and
Cu2+ in a mixture of tris-HCl buffer and ethanol (9/1, v/v, pH=7.40)
0.00007
0.00005
-1
[Al ](molL )
0.00006
Y=9.0747E-11X+2.442E-5
R2=0.8934
3+
0.00004
0.00003
0.00002
0.00001
100000
200000 300000
2
(1-)/( )
[Al]3+ =
[𝐿]
500000
1−𝛼
… … (1)
2𝐾[𝐿] 𝑇 𝛼 2
α = [𝐿] = 𝐹
𝑇
400000
𝐹𝑀𝑎𝑥−𝐹
𝑀𝑎𝑥 −𝐹𝑀𝑖𝑛
… … (2)
where K is the association constant of the HL and Al3+.[Al3+] and [L] denote the free concentration of Al3+ ions and the ligand
HL, α is the ratio between the free ligand concentration, [L], and the initial concentration of the ligand, LT. F is the fluorescence
intensity of HL at 427 nm in the presence of different concentrations of Al3+, and Fmin and Fmax are the limiting values of F at zero
Al3+ concentration and at final (plateau) Al3+ concentration, respectively. The curve fitting for the experimental data points was
calculated from eqs 1 and 2 with Ka = 5.71. The good correlation of the measured data with the theoretical predication confirms
the validity of the proposed method.
Fig. S12. Equation plot of HL,Assuming 2:1 stoichiometry for association between HL and Al3+ .
Jie Yang, et al.
S12
0.5
2
Absorbance
Y=0.2717X+0.1945 (R =0.9909)
0.4
0.3
0.2
0.0
0.2
0.4
0.6
2+
0.8
1.0
-1
[Cu ](x10-5mol.L )
Fig. S13. Determination of the detection limit based on absorbance change (at 415 nm) of HL (10 μM) with Cu2+
in Tris-HCl buffer/ethanol (9/1, v/v,pH=7.40)
800
700
Fluorescence
600
Y=188.455X-192.076
2
R =0.9881
500
400
300
200
100
0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0
3+
-5
-1
[Al ](10 molL )
Fig. S14. Determination of the detection limit based on absorbance change (at 415 nm) of HL (10 μM) with Al3+
in Tris-HCl buffer/ethanol (9/1, v/v,pH=7.40).
Jie Yang, et al.
Fig. S15
S13
Fluorescence changes of L-AL3+ complex upon the addition of interfering metal ions in
tris-HCl/-ethanol(9:1,v:v,pH=7.40) under UV lamp (λex = 365 nm), at room temperature
Fluorescence intensity
800
L+Al
600
3+
400
HL
200
0
2
4
6
8
10
12
14
pH
Fig. S16 Fluorescence intensity of HL–Al3+ (HL, 10 μM) after addition of 0.5 equiv. of Al3+ at various ranges of
pH in tris-HCl buffer–ethanol (9/1,v/v,pH=7.40) at room temperature.
HL+Cu2+
0.45
Absorbance
0.40
0.35
0.30
0.25
HL
0.20
0
2
4
6
8
pH
10
12
14
16
Fig. S17 Fluorescence intensity of HL–Al3+ (HL, 10 μM) after addition of 0.5 equiv. of Al3+ at various ranges of
pH in tris-HCl buffer–ethanol (9/1,v/v,pH=7.40) at room temperature.
Jie Yang, et al.
S14
Fig S18 Calculated energy-minimized structures and charge distribution of L-Cu2+
Fig S19 Calculated energy-minimized structures and charge distribution of 2L-Al3+
Jie Yang, et al.
S16
HOMO-1
HOMO-3
HOMO-2
HOMO-4
LUMO+1
LUMO+2
LUMO+3
LUMO+4
Fig S20 Calculated energy-minimized structures of MOS for L-Cu2+
Jie Yang, et al.
S16
HUMO-1
HUMO-2
HUMO-3
HUMO-4
LUMO+1
LUMO+3
LUMO+2
LUMO+4
Fig S 21 Calculated energy-minimized structures of MOS for 2L-Al3+