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Instant hydrogel formation of terpyridine-based complexes
triggered by DNA via non-covalent interaction
Lijun Geng, Xudong Yu*, Yajuan Li, Yanqiu Wang, Yongquan Wu, Jujie Ren, Fengfeng Xue, Tao Yi
Lijun Geng, Xudong Yu*, Yajuan Li, Yanqiu Wang, Jujie Ren
College of Science, Hebei University of Science and Technology,Yuhua Road 70, Shijiazhuang 050080, China
E-mail: chemyxd@163.com (X. Yu)
Yongquan Wu
School of Chemistry and Chemical Engineering, Gannan Normal University, Ganzhou, Jiangxi 341000, China
Fengfeng Xue, Tao Yi
Department of Chemistry, and Collaborative Innovation Center of Chemistry for Energy Materials, Fudan University, 220 Handan Road, Shanghai 200433, China
Electronic Supplementary Material (ESI) for Nanoscale.This journal is © The Royal Society of Chemistry 2019
2
1. Synthesis of ligand TEG, Zn(II)(TE)I2 , Zn(II)(TEG)L, and Cd(II)(TEG)Cl2.
N
N
N
Br
+N
O
Br2
CHO
N
N
NHN
NH3
1
NH2
NH2
H2N
2 (TE)
+
N
N
N
NH
HN
O
OH
OH
OH
OHOH
OO
OH
OHOH
HO
4 (TEG)
ZnL
N
N
N
NH
HN
O
OH
OH
OH
OHOHZnL
5a-5h (Zn(II)(TEG)L)
N
N
NHN NH2
Zn
ZnI2
II
3 (Zn(II)(TE)I2)
L=F-, Cl-, Br-, I-, AcO-, SO42-, NO3
-, C6H11O7-
Scheme S1. The synthesis procedure of TEG and Zn2+-based complexes.
The synthesis of 1 and 2(TE) could be seen in literature 1 and 2, respectively.
Synthesis of Zn(II)(TE)I2:
The solution of Compound TE (0.73 g, 2 mmol) dissolved in methanol (20 mL) was
added to a stirring solution of ZnI2 (1.27 g, 4 mmol) dissolved in methanol (10 mL)
and continued stirring at room temperature for 3h. The resulting product was filtered
and the solid was washed with methanol to give a yellow powder (0.96 g, yield: 70%).
Mp: > 250°C. 1H NMR (500 MHz, DMSO-d6): 9.16-8.92 (m, 6H), 8.42-8.36 (m, 2H),
8.22 (d, J = 8.5 Hz, 1H), 7.96-7.81 (m, 4H), 6.85 (d, J = 9.0 Hz, 1H), 3.48 (t, J = 5.0
Hz, 2H), 3.34 (t, J = 5.5 Hz, 2H). 13C NMR (125 MHz, DMSO-d6): 58.51, 60.48,
112.86, 118.22, 122.66, 123.35, 127.70, 129.80, 141.41, 147.77, 148.40, 149.09,
3
151.28, 154.61. MS calc. for [C23H21I2N5Zn+Na]+: 711.9; Found: 712.1. Element
Anal. Calcd for C23H21I2N5Zn, C, 40.23; H, 3.08; N, 10.20 %. Found: C, 40.16; H,
3.01; N, 10.13 %.
Synthesis of TEG:
Compound TE (1 g, 2.7 mmol) and D-(+)-Gluconic acid δ-lactone (477 mg, 2.7 mmol)
were refluxed in ethanol (60 mL) for 14 h. The separated solid was filtered and
recrystallized in water to give a pale yellow solid (0.66 g, 45%). Mp: 201-202°C. 1H
NMR (500 MHz, DMSO-d6): 8.78 (d, J = 4.0 Hz, 2H), 8.68 (s, 1H), 8.66 (s, 3H),
8.06-8.03 (m, 2H), 7.75 (d, J = 4.0 Hz, 2H), 7.55-7.52 (m, 2H), 6.81 (d, J = 8.0 Hz,
2H), 6.22 (t, J = 5.5 Hz, 1H), 4.06 (d, J = 3.5 Hz, 2H), 3.98 (s, 1H), 3.62 (d, J = 9.5
Hz, 1H), 3.54 (s, 2H), 3.44-3.36 (m, 9H), 3.22 (d, J = 6.0 Hz, 2H). 13C NMR (125
MHz, DMSO-d6): 40.85, 45.60, 66.65, 73.42, 74.77, 75.57, 76.81, 115.71, 119.45,
124.12, 127.60, 140.65, 152.55, 158.64, 176.27. MS calc. for [C29H31N5O6+H]+:
546.2; Found: 546.1. Element Anal. Calcd for C29H31N5O6, C, 63.84; H, 5.73; N,
12.84 %. Found: C, 63.72; H, 5.65; N, 12.71 %.
Synthesis of Zn(II)(TEG)L
5a. Zn(II)(TEG)F2
The solution of ZnF2 (132 mg, 1.3 mmol) dissolved in water (10 mL) was added to a
stirring solution of compound TEG (0.7 g, 1.3 mmol) dissolved in 2-methoxyethanol
(30 mL) and continued stirring at room temperature for 5 h. The resulting product was
filtered and the solid was washed with water and 2-methoxyethanol to give a yellow
powder;Yield: 0.64 g (76%). Mp: > 250°C. 1H NMR (500 MHz, DMSO-d6): 8.38-
8.05 (m, 2H), 7.48-6.80 (m, 10H), 6.27-5.91 (m, 2H), 4.38 (s, 1H), 4.16 (s, 1H), 3.93-
3.89 (m, 4H), 3.71-3.62 (m, 3H), 3.22-2.80 (m, 3H), 2.24 (s, 1H). MS calc. for
[C29H31F2N5O6Zn+K]+: 688.1; Found: 688.8. Element Anal. Calcd for
C29H31F2N5O6Zn, C, 53.67; H, 4.81; N, 10.79 %. Found: C, 53.78; H, 4.70; N, 10.65
%.
Compound 5b and 5c were synthesized as the same procedure given for compound
5b. Zn(II)(TEG)(SO4)
ZnSO4 (375 mg, 1.3 mmol), water (15 mL), Yield: 0.75 g (82%). Mp: > 250°C. 1H
NMR (500 MHz, DMSO-d6): 8.56-8.54 (m, 4H), 7.75-7.32 (m, 4H), 6.98-6.95 (m,
4H), 6.73-6.70 (m, 2H), 5.81-5.78 (m, 2H), 4.37 (t, J = 3.5 Hz, 1H), 4.15 (s, 1H),
3.86-3.71 (m, 4H), 3.40-3.31 (m, 2H), 2.95 (s, 1H). MS calc. for [C29H31N5O10SZn-
4
ZnSO4 +Na]+: 568.2; Found: 568.5. Element Anal. Calcd for C29H31N5O10SZn, C,
49.26; H, 4.42; N, 9.91 %. Found: C, 49.13; H, 4.30; N, 9.86 %.
5c. Zn(II)(TEG)(C6H11O7)2
Zinc gluconate (577 mg, 1.3 mmol), water (15 mL), Yield: 0.95 g (73%). Mp: >
250°C. 1H NMR (500 MHz, DMSO-d6): 8.46-8.43 (m, 4H), 7.72-7.46 (m, 8H), 6.27-
6.25 (m, 2H), 4.35 (s, 1H), 4.11-4.09 (m, 2H), 3.84-3.65 (m, 6H), 3.45 (t, J = 7.5 Hz,
3H), 3.18-3.16 (m, 3H), 2.86-2.85 (m, 1H). MS calc. for [C41H53N5O20Zn-
ZnC12H22O14+Na]+: 568.2; Found: 568.5. Element Anal. Calcd for C41H53N5O20Zn, C,
49.18; H, 5.34; N, 6.99 %. Found: C, 49.27; H, 5.26; N, 6.82 %.
5d. Zn(II)(TEG)Cl2
The solution of ZnCl2 (177 mg, 1.3 mmol) dissolved in methanol (8 mL) was added to
a stirring solution of compound TEG (700 mg, 1.3 mmol) dissolved in 2-
methoxyethanol (30 mL) and continued stirring at room temperature for 6h. The
resulting product was filtered and the solid was washed with methanol and 2-
methoxyethanol to give an orange powder; Yield: 0.62 g (70%). Mp: > 250°C. 1H
NMR (500 MHz, DMSO-d6): 8.91 (s, 4H), 8.81 (d, J = 4.0 Hz, 2H), 8.30 (t, J = 7.0
Hz, 2H), 8.15 (d, J = 8.0 Hz, 2H), 7.95 (t, J = 6.0 Hz, 1H), 7.85 (t, J = 6.0 Hz, 2H),
6.81 (d, J = 8.0 Hz, 2H), 6.53 (s, 1H), 5.48 (d, J = 5.0 Hz, 1H), 4.58 (d, J = 5.0 Hz,
1H), 4.54 (d, J = 5.5 Hz, 1H), 4.50 (d, J = 7.0 Hz, 1H), 4.37 (t, J = 5.5 Hz, 1H), 4.06
(t, J = 4.5 Hz, 1H), 3.99-3.97 (m, 1H), 3.63-3.59 (m, 1H), 3.54-3.47 (m, 3H), 3.42-
3.40 (m, 1H), 3.25 (t, J = 7.0 Hz, 3H). 13C NMR (125 MHz, D2O): 40.90, 65.45, 73.21,
73.95, 75.01, 120.19, 118.91, 118.15, 177.43. MS calc. for [C29H31Cl2N5O6Zn+Na]+:
702.1; Found: 702.2. Element Anal. Calcd for C29H31Cl2N5O6Zn: C, 51.08; H, 4.58; N,
10.27 %. Found: C, 51.23; H, 4.63; N, 10.13 %.
For compounds 5e-5h the same procedure as for compounder 5d was used.
5e. Zn(II)(TEG)Br2
ZnBr2 (293 mg, 1.3 mmol), reaction solvent: methanol (15 mL), yield: 0.8 g (80%).
Mp: > 250°C. 1H NMR (500 MHz, DMSO-d6): 8.83 (d, J = 4.0 Hz, 6H), 8.24 (s, 2H),
8.09 (t, J = 5.0 Hz, 2H), 7.98-7.84 (m, 4H), 6.74 (d, J = 7.5 Hz, 2H), 6.53 (s, 1H),
5.51 (d, J = 5.0 Hz, 1H), 4.61 (d, J = 5.0 Hz, 1H), 4.57 (d, J = 5.0 Hz, 1H), 4.52 (d, J
= 7.5 Hz, 1H), 4.39 (t, J = 6.0 Hz, 1H), 4.06 (t, J = 4.0 Hz, 1H), 3.98 (t, J = 3.5 Hz,
1H), 3.62-3.47 (m, 4H), 3.22 (t, J = 6.0 Hz, 3H). 13C NMR (125 MHz, DMSO-d6):
37.52, 42.11, 63.41, 70.24, 71.55, 72.32, 73.56, 73.91, 111.94, 116.99, 122.18, 126.90,
129.12, 146.99, 148.35, 151.38, 153.86, 173.11. MS calc. for [C29H31Br2N5O6Zn+H]+:
5
771.8; Found: 772.0. Element Anal. Calcd for C29H31Br2N5O6Zn, C, 45.19; H, 4.05; N,
9.09 %. Found: C, 45.32; H, 4.16; N, 8.97 %.
5f. Zn(II)(TEG)I2
ZnI2 (413 mg, 1.3 mmol), reaction solvent: methanol (10 mL), yield: 0.78 g (70%).
Mp: > 250°C. 1H NMR (500 MHz, DMSO-d6): 9.20 (s, 1H), 9.13 (d, J = 8.0 Hz, 1H),
9.01-8.90 (m, 4H), 8.40-8.16 (m, 5H), 7.93-7.90 (m, 3H), 7.47 (t, J = 6.0 Hz, 1H),
6.92 (d, J = 8.5 Hz, 1H), 6.83 (d, J = 8.5 Hz, 1H), 5.48 (s, 1H), 4.57-4.50 (m, 4H),
4.38-4.35 (m, 1H), 4.06 (d, J = 3.5 Hz, 1H), 3.98 (s, 1H), 3.61-3.46 (m, 6H). 13C
NMR (125 MHz, DMSO-d6): 37.47, 42.07, 63.37, 70.21, 71.51, 72.27, 73.50, 112.03,
117.30, 122.47, 127.05, 129.24, 147.43, 148.17, 151.43, 154.09, 173.07. MS calc. for
[C29H31I2N5O6Zn+H]+: 866.0; Found: 865.9. Element Anal. Calcd for
C29H31I2N5O6Zn, C, 40.28; H, 3.61; N, 8.10 %. Found: C, 40.41; H, 3.54; N, 8.23 %.
5g. Zn(II)(TEG)(NO3)2
Zn(NO3)2 (386 mg, 1.3 mmol), reaction solvent: methanol (4 mL), yield: 0.65 g (68%).
Mp: > 250°C. 1H NMR (500 MHz, DMSO-d6): 9.20 (s, 1H), 9.12 (d, J = 8.0 Hz, 1H),
9.03 (d, J = 8.0 Hz, 1H), 8.97 (s, 1H), 8.87 (s, 1H), 8.45-8.39 (m, 1H), 8.33-8.23(m,
3H), 8.16(d, J = 8.5 Hz, 1H), 8.01-7.90 (m, 3H), 7.47 (t, J = 7.0 Hz, 1H), 6.93-6.84
(m, 2H), 6.66-6.56 (m, 1H), 5.53-5.50 (m, 1H), 4.62-4.34 (m, 5H), 4.07-4.04 (m, 1H),
3.97 (s, 1H), 3.62-3.46 (m, 4H), 3.31-3.24 (m, 2H). 13C NMR (125 MHz, DMSO-d6):
37.57, 42.14, 63.44, 70.28, 71.57, 72.31, 73.54, 112.22, 117.65, 118.26, 121.47,
123.20, 127.38, 129.61, 147.67, 148.74, 149.07, 151.77, 155.05, 173.21. MS calc. for
[C29H31N7O12Zn-ZnN2O6+Na]+: 568.2; Found: 568.4. Element Anal. Calcd for
C29H31N7O12Zn, C, 47.39; H, 4.25; N, 13.34 %. Found: C, 47.52; H, 4.17; N, 13.29 %.
5h. Zn(II)(TEG)(AcO)2
Zn(AcO)2 (285 mg, 1.3 mmol), reaction solvent: methanol (15 mL), yield: 0.54 g
(57%). Mp: > 250°C. 1H NMR (500 MHz, DMSO-d6): 9.20 (s, 1H), 9.13 (d, J = 8.0
Hz, 1H), 9.01-8.90 (m, 4H), 8.40-8.16 (m, 5H),7.93-7.90 (m, 3H), 7.47(t, J = 6.0 Hz,
1H), 6.92 (d, J = 8.5 Hz, 1H), 6.83 (d, J = 8.5 Hz, 1H), 5.48 (s, 1H), 4.57-4.35 (m,
4H), 4.36 (t, J = 5.5 Hz, 1H), 4.06 (d, J = 3.5 Hz, 1H), 3.98 (s, 1H), 3.61-3.46 (m, 6H). 13C NMR (125 MHz, D2O): 41.21, 60.53, 62.74, 74.05, 75.69, 76.75, 111.51, 114.82,
122.49, 123.20, 129.67, 149.10, 153.32, 175.64. MS calc. for [C33H37N5O10Zn-H] -:
726.2; Found: 726.3. Element Anal. Calcd for C33H37N5O10Zn, C, 54.36; H, 5.12; N,
9.61 %. Found: C, 54.45; H, 5.01; N, 9.57 %.
6
Cd(II)(TEG)Cl2
The solution of CdCl2 (296mg, 1.3 mmol) dissolved in water (10 mL) was added to a
stirring solution of compound TEG (0.7 g, 1.3 mmol) dissolved in 2-methoxyethanol
(30 mL) and continued stirring at room temperature for 4 h. The resulting product was
filtered and the solid was washed with water and 2-methoxyethanol to give a yellow
powder; Yield: 0.68 g (72%). Mp: > 250°C. 1H NMR (500 MHz, DMSO-d6): 8.71 (d,
J =8.0 Hz, 2H), 8.67 (d, J =4.0 Hz, 2H), 8.61 (s, 2H), 8.13 (t, J = 7.5 Hz, 2H), 7.96 (d,
J =6.5 Hz, 3H), 7.75 (t, J = 6.0 Hz, 2H), 6.61 (d, J = 8.0 Hz, 2H), 6.38 (s, 1H), 5.51 (d,
J = 4.5Hz, 1H), 4.61- 4.52 (m, 4H), 3.50-3.46 (m, 4H), 3.35-3.32 (m, 6H). 13C NMR
(125 MHz, DMSO-d6): 39.65, 40.32, 70.69, 72.01, 72.79, 74.02, 74.36, 112.35,
118.09, 123.42, 127.14, 129.31, 149.55, 151.52, 173.53. MS calc. for
[C29H31Cl2N5O6Cd-Cl]+: 693.6; Found: 694.2. Element Anal. Calcd for
C29H31CdCl2N5O6, C, 47.79; H, 4.29; N, 9.61 %. Found: C, 47.71; H, 4.26; N, 9.65 %.
2. Other experiment data
480 520 560 600 6400
2000
4000
6000
Inte
nsity
Wavelengtn/nm
Figure S1 Fluorescent titrations of Zn(II)(TEG)I2 (10-5 M) upon the addition of DNA
in tris buffer (pH = 7.4) with λex= 454 nm (base pairs: 0-42 equiv.).
7
0.0 0.2 0.4 0.6 0.8 1.0
1200
1600
2000
2400
Inte
nsity
[DNA]/[DNA+Zn(II)(TEG)I2]
Figure S2 The Job’s plot curves of Zn(II)(TEG)I2 with DNA in water.
0.0 200.0k 400.0k 600.0k 800.0k 1.0M 1.2M 1.4M0.0
2.0x10-4
4.0x10-4
6.0x10-4
8.0x10-4
1.0x10-3
1.2x10-3
1.4x10-3 D Linear Fit of D
1/(I-
I 0)
1/[DNA]
Equation y = a + b*x
Weight No Weighting
Residual Sum of Squares
1.34939E-8
Adj. R-Square 0.98743Value Standard Error
D Intercept 2.11044E-4 1.55109E-5D Slope 8.78756E-10 3.30238E-11
Figure S3 The linear fitting curve of fluorescence change of Zn(II)(TEG)I2 (10-5M)
with the addition of DNA.
Detection limit of Zn(II)(TEG)I2 toward DNA by fluorescence intensity changes at
555nm
8
n 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15Intensity(Xn
)
591.8
591.0
592.1
594.6
592.7
592.8
592.8
590.2
593.1
592.2
591.4
590.6
591.3
589.7
591.2
n 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30Intensity( Xn )
592.7
593.6
594.1
592.8
591.3
591.7
591.9
593.3
591.9
595.1
595.7
596.6
596.0
595.5
594.7
X average = 592.8 σ = 1.764 L = 8.114 K = 4.2×104
R = 0.9874 ε = 2.0 ×1013 the detection limit: 4.06×10-13
480 520 560 600 640 6800
500
1000
1500
2000
2500
Inte
nsity
Wavelenth/nm200 250 300 350 400 450 500 550
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
Abso
rban
ce
Wavelengtn/nm
a b
Figure S4 a) Fluorescent titrations of Zn(II)(TEG)(AcO)2 (10-5 M) upon the addition
of DNA in water (base pairs: 0-75 equiv.); b) UV-vis titrations of
Zn(II)(TEG)(AcO)2 (10-6 M) upon the addition of DNA.
480 520 560 600 6400
1000
2000
3000
4000
5000
6000
7000
Inte
nsity
Wavelength/nm
Figure S5 Fluorescent emission spectra for the titration of Zn(II)(TEG)(AcO)2 (10-5 M)
upon the addition of DNA in tris buffer λex = 454 nm (base pairs: 0-62 equiv.).
9
550 600 650 700 7500
500
1000
1500
2000
Inte
nsity
Wavelength/nm
0μM 5μM 15μM 22.5μM
Figure S6 The fluorescence changes of DNA/ethidium bromide hybrid (base pairs: 20
μM, ethidium bromide: 10 μM) upon the gradual addition of Zn(II)(TEG)I2.
400 450 500 550 600 6500
200
400
600
800
1000
1200
Inte
nsity
Wavelength/nm
TEG TEG+DNA
450 500 550 600 6500
400
800
1200
Inte
nsity
Wavelength/nm
2 2+DNA
a b
c
400 500 600 7000
100
200
300
400
500
600
Inte
nsity
Wavelengtn/nm
Figure S7 a) Fluorescent titrations of Zn(II)(TE)I2 (10-5 M) solution upon the addition
of DNA(base pairs: 0-128 equiv.) (λex = 454 nm); b) TEG solution (10-5 M) upon the
addition of DNA (10-4 M), λex = 340 nm; c) TE solution (10-5 M) upon the addition of
DNA (10-4 M), λex = 390 nm.
10
-0.4 -0.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2-6.0x10-6
-4.0x10-6
-2.0x10-6
0.0
2.0x10-6
4.0x10-6
6.0x10-6
8.0x10-6
i/A
E/VFigure S8 CV curves Zn(II)(TEG)I2 (10-5 M) in the presence of DNA (base pairs: 0-
83.2 equiv.).
-0.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2-1.0x10-5
-5.0x10-6
0.0
5.0x10-6
1.0x10-5
1.5x10-5
E/V
i/A
Figure S9 CV curves Zn(II)(TE)I2 (10-5 M) in the presence of DNA (base pairs: 0-249
equiv.).
11
300 400 500 600-10-8-6-4-202468
10
Ellip
ticity
Wavelength/nm
Figure S10 CD spectral changes of DNA (base pairs: 1.65×10-4 M) with the addition
of Zn(II)(TEG)I2 (0- 3.61equv.) in water.
300 400 500-10
-8
-6
-4
-2
0
2
4
6
8
CD/m
deg
Wavelength/ nm 300 400 500-8
-6
-4
-2
0
2
4
6
8
CD/m
deg
Wavelengtn/nm
a b
Figure S11 CD spectral changes of DNA (base pairs: 1.65×10-4 M) with the addition
of Zn2+ complexes in tris buffer (pH = 7.4), for a): Zn(II)(TEG)I2 (0-2.87 equiv. ); for
b): Zn(II)(TEG)(AcO)2 (0-2.32 equiv. ) .
500 550 600 650 700 7500
100
200
300
400
Inte
nsity
Wavelength/nm500 550 600 650 700 750
0
20
40
60
80
100
120
140
160
180
Inte
nsity
Wavelength/nm
a b
Figure S12 The fluoresent titrations of Zn(II)(TEG)I2 (10-5 M) upon the addition of
ss-DNA. a) poly(AT)10 (0-1.38 equiv.); b) poly(GC)10 (0-1.13 equiv.).
12
0 200 400 600 800 1000 1200
50
100
150
200
250 (GC)10
(AT)10
Inte
nsity
[base pairs] /nM
Figure S13 The fluorescent intensity value changes of Zn(II)(TEG)I2 at 540 nm in the
presence of ss-DNA.
Table S1 The gelation properties of Zn(II)(TEG)L(25 mg mL-1) with DNA (1 equiv.
base pairs).
Zn2+ metal Complex H-C +DNAa Sonication +DNAb
Zn(II)(TEG)F2 S G I I
Zn(II)(TEG)Cl2 G G I G
Zn(II)(TEG)Br2 G G I G
Zn(II)(TEG)I2 G P I G
Zn(II)(TEG)(NO3)2 S P I I
Zn(II)(TEG)(AcO)2 S G I I
Zn(II)(TEG)(C6H11O7)2 S G I I
Zn(II)(TEG)SO4 S P S PNote: P: precipitate; S: solution; G: gel; I: insoluble; H–C: heating–cooling process. a) Assembly
of Zn2+ metal Complex/DNA hybrid (R=1:1) obtained by heating-cooling process; b) Assembly of
Zn2+ metal Complex/DNA hybrid (R=1:1, R: molecular ratio of Zn2+ metal complex and DNA
base pairs) treated by ultrasound.
13
Table S2 The gelation properties of TEG (25 mg mL-1) with DNA (1 equiv. base pairs)
in the presence of other different metal ions (1 equiv.). Note: Cd(II)(TEG)Cl2 was
synthesized and characterized.
Metal ions R.T. U
NaNO3 S P
KNO3 I I
AgNO3 S P
BaCl2 I S
Mg( (NO3)2 I I
SrCl2 I S
Fe (NO3)3 I I
Al (NO3)3 I I
Bi (NO3)3 I I
Cd(II)(TEG)Cl2 I INote: P: precipitate; S: solution; G: gel; I: insoluble; R. T.: room temperature.
2000 1500 1000 5000
40
80
120
160
200
2000 1500 1000 500
Tran
smitt
ance
(%)
Wavenumber (cm-1)
1226.91277.5
1238.4
1243.6
642.4
Zn(II)(TEG)AcO2 powder Zn(II)(TEG)AcO2/DNA hydrogel DNA powder
612.1639.2
Figure S14 The FT-IR spectra of Zn(II)(TEG)(AcO)2 powder, hydrogel of
Zn(II)(TEG)(AcO)2 /DNA hybrids (base pairs: 1 equiv), DNA powder.
14
250 300 350 400 450 500 550
-30
-20
-10
0
10
20
CD/m
deg
Wavelength/nm
Figure S15 CD spectral changes of DNA (base pairs: 1.65×10-4 M) with the addition
of Zn(II)(TEG)I2 (0-3.24 equiv.) in phosphate buffer saline (pH = 7.4).
a b
Figure S16 TEM images of Zn(II)(TEG)L assembly; a) solution of
Zn(II)(TEG)(AcO)2 after evaporation; b) suspension of Zn(II)(TEG)I2. Scale bar: 100
nm, 1 μm.
15
-0.2 0.0 0.2 0.4 0.6 0.8 1.0-4.0x10-4
-3.0x10-4
-2.0x10-4
-1.0x10-4
0.0
1.0x10-4
2.0x10-4
3.0x10-4
i/A
E/V
Zn(II)(TEG)I2/DNA gel
200 300 400 500 600 700-40
-20
0
20
40
60
80
100
Ellip
ticity
Wavelength/nm
Zn(II)(TEG)I2/DNA gel Zn(II)(TEG)(AcO)2/DNA gel
200 300 400 5000.0
0.5
1.0
1.5
2.0
2.5 Solution of Zn(II)(TEG)I2 Zn(II)(TEG)I2/DNA gel
Abso
rban
ce
Wavelength/nm300 400 500 600 700
0.10
0.15
0.20
0.25
0.30
Abso
rban
ce
Wavelength/nm
gel of Zn(II)(TEG)I2/DNA hybrid
a b
c d
Figure S17 a) Uv-vis spectra of Zn(II)(TEG)I2 solution (10-6 M) and gel of
Zn(II)(TEG)I2 /DNA hybrid (Zn(II)(TEG)I2: 25 mg/mL, base pairs: 1.75×10-2 M); b)
Uv-Vis spectra of Zn(II)(TEG)I2 /DNA gel; c) CD spectra of Zn2+ metal
complex/DNA hybrid hydrogels (Zn2+ complex: 25 mg/mL, base pairs:1 equiv.) ; d)
CV curve of Zn(II)(TEG)I2/DNA hybrid hydrogel.
500 550 600 650 700 750 8000
100
200
300
400
500
600
700
Zn(II)(TEG)(AcO)2 sol Zn(II)(TEG)(AcO)2/DNA hydrogel
Inte
nsity
Wavelength/nm450 500 550 600 650 700 750 800
0
200
400
600
800
Zn(II)(TEG)I2 suspension Zn(II)(TEG)I2/DNA hydrogel
Inte
nsity
Wavelength/nm
a b
Figure S18 a) Fluorescent emission spectra for Zn(II)(TEG)I2 suspension (25 mg/mL)
and gel of Zn(II)(TEG)I2 /DNA hybrid (base pairs: 1.75×10-2 M); b) Fluorescent
emission spectra of Zn(II)(TEG)(AcO)2 solution (25 mg/mL) and gel of
Zn(II)(TEG)(AcO)2/DNA hybrid (base pairs: 3.5×10-2 M). For
Zn(II)(TEG)(AcO)2/DNA hydrogel: 24 fold at λex = 577 nm; for Zn(II)(TEG)I2/DNA
hydrogel: 41 fold at λex = 587 nm.
16
5 10 15 20 250
20
40
60
80
100
2θ
Inte
nsity
Zn(II)(TEG)(AcO)2 powder Zn(II)(TEG)(AcO)2/DNA hydrogel
2.02
1.14 0.78
0.600.52
0.50
0.460.42
0.40
1.94 1.200.54
0.46 0.384.04
Figure S19 XRD data of Zn(II)(TEG)(AcO)2 powder and xerogel of
Zn(II)(TEG)(AcO)2/DNA hybrid (base pairs: 1 equiv.).
5 10 15 20 250
20
40
60
80
100
2θ
0.942.10
0.440.78
Inte
nsity
Zn(II)(TG)I2+DNA hydrogel Zn(II)(TG)I2 powder
2.10 0.50
0.40
0.78
0.44 0.400.94
Figure S20 XRD data of Zn(II)(TEG)I2 powder and xerogel of Zn(II)(TEG)I2/DNA
hybrid (base pairs: 0.6 equiv.).
17
5 10 15 20 250
20
40
60
80
100
2θ
Inte
nsity
Figure 21 XRD data of DNA powder.
a b
Figure S22 Photos of the a) Zn(II)(TEG)I2/(AT)10 hybrid gel (base pairs: 1 equiv.); b)
Zn(II)(TEG)I2/(GC)10 hybrid gel (base pairs: 1 equiv.).
a b
Figure S23 TEM images of Zn(II)(TEG)I2/poly(AT)10 hybrid gel. Scale bar: 2 µm, 1
18
µm.
Figure 24 TEM images of Zn(II)(TEG)I2/(CG)10 hybrid gel. Scale bar: 2 µm, 1 µm.
0.1 1 101
10
100
1000
10000
Zn(II)(TEG)(AcO)2/DNA gel G' G"
Zn(II)(TEG)I2/DNA gel G' G''
Zn(II)(TEG)I2gel+DNA G' G''
Stor
age M
odul
us G
'(Pa)
Loss
Mod
ulus
G''(P
a)
Frequency f (Hz)
a
b0.1 1 10
1
10
Zn(II)(TEG)I2 hydrogel
G' G''
Stor
age M
odul
us G
'(Pa)
Loss
Mod
ulus
G''(P
a)
Frequency f (Hz)
19
Figure S25. a) Frequency sweep experiments of G′ and G″ for Zn(II)(TEG)I2
hydrogel gel with strain at 0.1%; b) Frequency sweep experiments of G′ and G″
for DNA hydrogels with Zn(II)(TEG)I2, Zn(II)(TEG)(AcO)2 with strain at 0.1%.
Table S3 The gradually gelation paths of DNA and DNA analogues in the presence of
different Zn2+ metal complexes (Zn2+ complexes: 25 mg/mL, DNA or DNA analogues
L: 1equiv. ).
Zn(II)(TEG)(C6H11O7)2
Zn(II)(TEG)SO4
Zn(II)(TEG)(NO3)2
Zn(II)(TEG)(AcO)2
R.T.
U R.T. U R.T. U R.T. U
AMP S OG P OG P P S OG
ADP OG S OG P TG S P P
ATP OG P P P P OG OG TG
st-DNA
OG I P P P I OG I
(GC)10 S S S S S S S S
(AT)10 S S S S S S S S
FAD P P P P P P S S
NADP S S P P P P S S
Note: U: ultrasound; P: precipitate; S: solution; I: insoluble; OG: opaque gel; TG: transparent gel. R. T.
room temperature.
20
Table S4 The gelation properties of DNA and DNA analogues in the presence of
different Zn2+ metal complexes (Zn2+ complexes: 25 mg/mL, DNA or DNA analogues
L: 1equiv.).
Zn(II)(TEG)F2
Zn(II)(TEG)I2
Zn(II)(TEG)Cl2
Zn(II)(TEG)Br2
R.T. U R.T. U R.T. U R.T. U
AMP S OG I P I OG I OG
ADP P OG I OG I OG I OG
ATP OG OG I P I P I P
st-DNA
OG I I OG I OG I OG
(GC)10 OG OG I OG I OG I P
(AT)10 S S I OG I OG I OG
FAD OG S I P I OG I I
NADP S S I P I I I OG
Note: U: ultrasound; P: precipitate; S: solution; I: insoluble; OG: opaque gel; TG: transparent gel; R. T.
room temperature.
21
Table S5 The subsequent and gradual gelation pathways for selective recognition of DNA
and DNA analogues and photos of these gels.
order
AMP ADP ATP st-DNA
(GC)1
0
(AT)10
FAD NADP
1 Zn(II)(TEG)(C6H11
O7)2 S
2 Zn(II)(TEG)SO4
3 Zn(II)(TEG)(NO3)2
S
4 Zn(II)(TEG)(AcO)2
5 Zn(II)(TEG)F2S
6 Zn(II)(TEG)I2
7 Zn(II)(TEG)Cl2
S
8 Zn(II)(TEG)Br2
Table S6 The gelation properties of Zn2+ complexes in the presence of different kinds of
ds-DNA.
Zn(II)(TEG)F2 Zn(II)(TEG)Cl2 Zn(II)(TEG)Br2 Zn(II)(TEG)I2
R.T. U R.T. U R.T. U R.T. U
stDNA OG I I OG I OG I OG
hsDNA S OG I OG I OG I I
ctDNA Sa I I I I I I I
Note: U: ultrasound; P: precipitate; S: solution; I: insoluble; OG: opaque gel; TG: transparent gel; R. T.
room temperature. a: Zn(II)(TEG)F2 was soluble and DNA was insoluble.
22
a b c
Figure S26 CLSM images of MCF-7 cells incubated for 30 min at 37 °C in PBS buffer (10
μM) of Zn(II)(TEG)I2. a) The bright image; b) The dark image for Zn(II)(TEG)I2, (λex=405
nm, emission collected: 500-600 nm); c) The overlay image of a) and b).
a b c
Figure S27 Fluorescent CLSM images of MCF-7 cells incubated for 30 min at 37 °C in tris
buffer (10 μM) of Zn(II)(TE)I2. (a) Bright field; b) The dark image for Zn(II)(TE)I2,
(λex=405 nm, emission collected: 500-600 nm); c) The overlay image of a) and b).
0 5 10 15 20 250
20
40
60
80
100
Via
bilit
y(%
)
C M)
Zn(II)(TEG)I2
Figure S28 Cell viability value (%) of Zn(II)(TEG)I2 by the MTT method.
23
0 5 10 15 20 250
20
40
60
80
100
Via
bilit
y(%
)
C M)
Zn(II)(TE)I2
Figure S29 Cell viability value (%) of Zn(II)(TE)I2 by the MTT method.
a
c
b
d
Figure S30 The co-stained experiments of Zn(II)(TEG)I2 with DAPI. MCF-7 cells
were incubated for 30 min at 37 °C with 1 in PBS buffer (10 μm) of Zn(II)(TEG)I2,
24
and then the cells were stained with DAPI for 30 min. a) The bright image; b) The
dark image for Zn(II)(TEG)I2, (λex=405 nm, emission collected: 500-600 nm); c) The
dark image for DAPI, (λex =405 nm, emission collected: 450-490 nm); d) The overlay
image of a), b), and c).
References[1] X. Piao, Y. Zou, J. C. Wu, T. Yi, Org. Lett. 2009, 11, 3818-3821.
[2] L. J. Geng, Y. J. Li, Z.Y. Wang, Y. Q. Wang, G. L Feng, X. L. Pang, X. D. Yu,
Soft Matter 2015, 11, 8100-8104.
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