a pyridomethene-bf complex-based chemosensor …s1 a pyridomethene-bf 2 complex-based chemosensor...

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

[email protected]

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.

Electronic Supplementary Material (ESI) for RSC AdvancesThis journal is © The Royal Society of Chemistry 2013

mailto:[email protected]

mailto:[email protected]

S2

Figure S1. 1H NMR spectrum of 3

NNC

NB

F

F

S

OHC

3


S3

Figure S2. 13C NMR spectrum of 3

NNC

NB

F

F

S

OHC

3


S4

Figure S3. 19F NMR spectrum of 3

NNC

NB

F

F

S

OHC

3


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


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


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


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


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


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)


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.


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+).


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.


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).


S13

Figure S12. IR spectra of probe PBF2 (upper line), and PBF2 upon addition of hydrazine (bottom line).


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.


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).


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.).


a pyridomethene-bf complex-based chemosensor …s1 a pyridomethene-bf 2 complex-based chemosensor...

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