a pyridomethene-bf complex-based chemosensor …s1 a pyridomethene-bf 2 complex-based chemosensor...
TRANSCRIPT
S1
A pyridomethene-BF2 complex-based chemosensor for detection of
hydrazine
Yan-Duo Lin and Tahsin J. Chow*,a
a Institute of Chemistry, Academia Sinica, Taipei 115 Taiwan
Supporting Information
Contents:
S1 Table of Contents
S2, S3, S4 1H, 13C, and 19F NMR spectra of 3.
S5, S6, S7 1H, 13C, and 19F NMR spectra of PBF2.
S8 Figure S7. Time-dependent absorption spectra of sensor PBF2 (1 x 10-5 M) upon the addition of hydrazine (10 equiv) in a mixture of acetate buffer (pH 4.0, 10 mM) and DMSO (1/9, v/v). The arrows indicate the change of incubation time 0 to 8 mins.
S9 Figure S8. Normalized absorption spectra of PBF2 in cyclohexane, toluene, THF, ethyl acetate, dichloromethane, and acetonitrile.
S10 Figure S9. (a) Absorption and (b) fluorescence spectra of PBF2 (1 x 10-5 M in a mixture of acetate buffer (pH 4.0, 10 mM) and DMSO (1/9, v/v)) in the presence of hydrazine and ions (F-, Cl-, Br-, I-, CN-, ClO4
-, H2PO4-, HSO4
-, NO3-, CH3CO2
-, Li+, Na+, K+, Cs+, Ag+, Ba2+, Ca2+, Mg2+, Co2+, Cu2+, Pb2+, Zn2+, Y3+).
S11 Figure S10. The fluorescence intensity of sensor PBF2 (1 x 10-5 M) incubated with hydrazine (2 x 10-4 M) for 0-8 min.
S12 Figure S11. The simulated absorption spectra of sensor PBF2 (black line) and PBF2-NH2 (red line).
S13 Figure S12. IR spectra of probe PBF2 (upper line), PBF2 upon addition of hydrazine (bottom line).
S14 Figure S13. 1H NMR spectra for a continuous change of PBF2 to PBF2-NH2.
S15 Figures S14 and S15. The absorption and emission spectra of PBF2 upon the addition of n-propylamine.
S16 Figure S16. Changes of spectral intensity at different pH.
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S2
Figure S1. 1H NMR spectrum of 3
NNC
NB
F
F
S
OHC
3
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S3
Figure S2. 13C NMR spectrum of 3
NNC
NB
F
F
S
OHC
3
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S4
Figure S3. 19F NMR spectrum of 3
NNC
NB
F
F
S
OHC
3
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S5
98
76
54
32
1pp
m
1.31171.32581.3399
2.4998
3.1340
4.30874.32284.33704.3510
7.27247.28567.29907.56457.58277.60017.89117.89928.06648.08088.08848.09648.26308.28148.39868.5483
3.05
2.04
1.002.020.992.041.051.032.00
NAME tschow130411
EXPNO 1
PROCNO 1
Date_ 20130411
Time 18.18
INSTRUM spect
PROBHD 5 mm PABBO BB/
PULPROG zg30
TD 32768
SOLVENT DMSO
NS 128
DS 2
SWH 5241.090 Hz
FIDRES 0.159945 Hz
AQ 3.1261172 sec
RG 812.7
DW 95.400 usec
DE 6.50 usec
TE 332.9 K
D1 1.00000000 sec
TD0 1
======== CHANNEL f1 ========
NUC1 1H
P1 11.40 usec
PL1 -5.00 dB
SFO1 500.1325007 MHz
SI 16384
SF 500.1300060 MHz
WDW EM
SSB 0
LB 0.30 Hz
GB 0
PC 1.00
Figure S4. 1H NMR spectrum of PBF2
NNC
NB
F
F
S
EtOOC
CN
PBF 2
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S6
180
160
140
120
100
8060
4020
ppm
13.6642
39.001539.168539.335339.502239.669239.836240.0032
61.8102
69.8137
97.6931115.4582117.0036117.4221119.3757119.8913120.6588125.7765134.4756134.5341137.1437138.1752140.9587141.2015146.2745146.9905148.4353148.7651161.7282
NAME tschow130411
EXPNO 2
PROCNO 1
Date_ 20130412
Time 9.43
INSTRUM spect
PROBHD 5 mm PABBO BB/
PULPROG zg0dc
TD 32768
SOLVENT CDCl3
NS 15282
DS 2
SWH 28901.734 Hz
FIDRES 0.882011 Hz
AQ 0.5669364 sec
RG 13004
DW 17.300 usec
DE 6.50 usec
TE 333.0 K
D1 3.00000000 sec
d11 0.03000000 sec
TD0 1
======== CHANNEL f1 ========
NUC1 13C
P0 4.00 usec
PL1 3.00 dB
SFO1 125.7716224 MHz
======== CHANNEL f2 ========
CPDPRG2 waltz16
NUC2 1H
PCPD2 90.00 usec
PL2 -5.00 dB
PL12 14.60 dB
SFO2 500.1320000 MHz
SI 32768
SF 125.7578899 MHz
WDW EM
SSB 0
LB 2.00 Hz
GB 0
PC 1.00
Figure S5. 13C NMR spectrum of PBF2
NNC
NB
F
F
S
EtOOC
CN
PBF 2
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S7
-100
-110
-120
-130
-140
-150
-160
-170
ppm
-137.6822-137.6184-137.5555-137.4912
NAME tschow130411
EXPNO 3
PROCNO 1
Date_ 20130411
Time 18.03
INSTRUM spect
PROBHD 5 mm PABBO BB/
PULPROG zgfhigqn
TD 131072
SOLVENT CDCl3
NS 32
DS 2
SWH 46948.355 Hz
FIDRES 0.358188 Hz
AQ 1.3959668 sec
RG 2048
DW 10.650 usec
DE 6.50 usec
TE 333.2 K
D1 1.00000000 sec
d11 0.03000000 sec
d12 0.00002000 sec
TD0 1
======== CHANNEL f1 ========
NUC1 19F
P1 13.60 usec
PL1 -5.00 dB
SFO1 470.5264790 MHz
======== CHANNEL f2 ========
CPDPRG2 waltz16
NUC2 1H
PCPD2 90.00 usec
PL2 -5.00 dB
PL12 14.60 dB
SFO2 500.1320000 MHz
SI 65536
SF 470.5923620 MHz
WDW EM
SSB 0
LB 0.30 Hz
GB 0
PC 1.00
Figure S6. 19F NMR spectrum of PBF2
NNC
NB
F
F
S
EtOOC
CN
PBF 2
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S8
Figure S7. Time-dependent absorption spectra of sensor PBF2 (1 x 10-5 M) upon the addition
of hydrazine (10 equiv) in a mixture of acetate buffer (pH 4.0, 10 mM) and DMSO (1/9, v/v).
The arrows indicate the change of incubation time 0 to 8 min.
300 400 500 6000.0
0.1
0.2
0.3
0.4
0.5
0.6
8 min
0 min
8 min
0 min
Abso
rban
ce
Wavelength (nm)
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S9
300 400 500 6000.0
0.2
0.4
0.6
0.8
1.0
Norm
aliz
ed A
bsor
banc
e
Wavelength (nm)
c-Hex toluene THF DCM EA MeCN
Figure S8. Normalized absorption spectra of PBF2 in cyclohexane, toluene, THF, ethyl acetate, dichloromethane, and acetonitrile.
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S10
350 400 450 500 550 600 6500.0
0.1
0.2
0.3
0.4
0.5
0.6(a)
PBF2+ other ions
PBF2 + hydrazine + other ions
Abso
rban
ce
Wavelength (nm)
400 500 600 700 800 9000
2000
4000
6000
8000(b)
PBF2 + other ions
PBF2 + hydrazine+other ions
Fluo
resc
ence
Inte
nsity
Wavelength (nm)
Figure S9. (a) Absorption and (b) fluorescence spectra of PBF2 (1 x 10-5 M in a mixture of acetate buffer (pH 4.0, 10 mM) and DMSO (1/9, v/v)) in the presence of hydrazine and ions (F-, Cl-, Br-, I-, CN-, ClO4
-, H2PO4-, HSO4
-, NO3-, CH3CO2
-, Li+, Na+, K+, Cs+, Ag+, Ba2+, Ca2+, Mg2+, Co2+, Cu2+, Pb2+, Zn2+, Y3+).
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S11
500 600 700 800 9000
1000
2000
3000
4000
5000
6000 8 min
0 min
8 min
0 min
Fluo
resc
ence
Inte
nsity
Wavelength (nm)
Figure S10. The fluorescence intensity of sensor PBF2 (1 x 10-5 M) incubated with hydrazine (2 x 10-4 M) for 0-8 min.
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S12
200 400 600 8000
10000
20000
30000
40000
Abso
rbilit
y
Wavelength (nm)
PBF2 PBF2-NH2
Figure. S11 The simulated absorption spectra of sensor PBF2 (black line) and PBF2-NH2 (red line).
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S13
Figure S12. IR spectra of probe PBF2 (upper line), and PBF2 upon addition of hydrazine (bottom line).
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S14
6.46.66.87.07.27.47.67.88.08.28.48.68.8 ppm
PBF2
PBF2 + 0.2 eq
PBF2 + 0.5 eq
PBF2 + 0.7 eq
PBF2 + 1 eq
Figure S13. 1H NMR spectra for a continuous change of PBF2 to PBF2-NH2.
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S15
300 350 400 450 500 550 600 6500.0
0.1
0.2
0.3
0.4
0.5
0.6Ab
sorb
ance
Wavelength (nm)
0 4 eq 8 eq 12 eq 16 eq 20 eq 24 eq 30 eq
Figure S14. Change of absorption spectrum of PBF2 (1 × 10-5 M) upon the addition of n-propylamine (0~30 equiv at 4.0 equiv interval) in a mixed solvent of an acetate buffer (pH 4.0, 10 mM) and DMSO (1/9, v/v).
400 500 600 700 800 9000
2000
4000
6000
Fluo
resc
ence
Inte
nsity
Wavelength (nm)
0 4 eq 8 eq 12 eq 16 eq 20 eq 24 eq 30 eq
Figure S15. Fluorescence titration spectra of PBF2 (1 x 10-5 M in a mixture of acetate buffer (pH 4.0, 10 mM) and DMSO (1/9, v/v)) solution with different concentrations of n-propylamine (0~30 equiv at 4.0 equiv interval).
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S16
2 4 6 80.0
0.1
0.2
0.3
0.4
0.5
0.6
Abso
rban
ce
pH
PBF2 PBF2+ 20 eq hydrazine
Figure S16. Changes of spectral intensity at different pH. The absorption intensity (490 nm) of PBF2 (1 x 10-5 M) solutions in a mixture of acetate buffer (pH 4.0, 10 mM) and DMSO (1/9, v/v) with and without hydrazine (20 equiv.).
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