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Electronic Supplementary Information

“A colorimetric and fluorescent turn-on chemosensor operative in

aqueous media for Zn2+ based on a multifunctionalized

spirobenzopyran derivative”

Jian-Fa Zhu, Han Yuan, Wing-Hong Chan* and Albert W. M. Lee Department of Chemistry, Hong Kong Baptist University, Kowloon Tong, Hong Kong

SAR, China

Fax: +852 3411 7348; Tel: +852 3411 7076; Email: whchan@hkbu.edu.hk Figure S1

UV-vis spectra of SPQN (10 μM) upon the titration of

Cu2+ (0 – 10 equiv) in buffer solution (50 mM HEPES, 50% ethanol, pH = 7.4)

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Figure S2 Fluorescence intensity of SPQN (10 μM) at various pH

values in ethanol/water (2:8, v/v) solution in the absence and presence of Zn2+ (5 equiv)

S3

Figure S3 Job’s plot by fluorescence method of the complex between SPQN and Zn2+

S4

Figure S4 Fluorescence spectra (λex = 515 nm) of 10 μM SPQN

upon the titration of Pb2+ (0 – 10.0 equiv) in buffer solution (50 mM, HEPES, 50% ethanol, pH = 7.4); inset: fluorescence intensity ratio as a function of Pb2+ concentration

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Figure S5 Plot of fluorescence intensity changes of SPQN(10μM) by

adding (a) 1 equiv of Zn2+; (b) (a) + 1 equiv of EDTA; (c) (b) + 1 equiv of Zn2+

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Figure S6 MADLI-TOF HRMS spectrum of SPQN-Zn2+ showing [M + Zn – H]+ peak at 609.2233

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Figure S7 The overlapping of the emissive peak of the quinoline moiety of SPQN (λex = 326 nm) and the absorption peak of SPQN-Zn2+ complex

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Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2010

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Figure S8 Fluorescence spectra (λex = 326 nm) of SPQN (10 μM) in

buffer solution (50 mM, HEPES, 50% ethanol, pH = 7.4) in the presence of different concentration of Zn2+ (exceeding 1 equiv)

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Figure S9-11 Spectral data of compound 3 (1H NMR; 13C NMR; HRMS) S7 Figure S12-14 Spectral data of compound 4 (1H NMR; 13C NMR; HRMS) S8 Figure S15-17 Spectral data of compound 5 (1H NMR; 13C NMR; HRMS) S9 Figure S18-20 Spectral data of compound 7 (1H NMR; 13C NMR; HRMS) S10 Figure S21-23 Spectral data of SPQN (1H NMR; 13C NMR; HRMS) S11

Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2010

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Fig. S1 UV-vis spectra of SPQN (10 μM) upon the titration of Cu2+ (0 – 2

equiv) in buffer solution (50 mM HEPES, 50% ethanol, pH = 7.4)

300 400 500 6000.0

0.1

0.2

0.3

0.4

0.5

0.6

0.000000 0.000005 0.000010 0.000015 0.000020

0.00

0.05

0.10

0.15

0.20

0.25

0.30Ab

s

[Zn2+]

Abs

Wavelength(nm)

0

2 equiv Cu2+

2 4 6 8 10 12

0

50000

100000

150000

200000

250000

300000

350000

Fluo

resc

ent i

nten

sity

pH

SPQN-5ZnSPQN

Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2010

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Fig. S2 Fluorescence intensity of SPQN (10 μM) at various pH values in

ethanol/water (2:8, v/v) solution in the absence and presence of Zn2+ (5 equiv).

Fig. S3 Job’s plot by fluorescence method of the complex between SPQN and

Zn2+.

0.0 0.2 0.4 0.6 0.8 1.0

0

100000

200000

300000

400000

500000

600000

700000

Fluo

resc

ent I

nten

sity

[Zn]/([Zn]+[SPQN])

600 650 700 750

20000

40000

60000

80000

100000

120000

140000

0 2 4 6 8 100.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5

5.0

Cg/Ch

F/F0

Fluo

resc

ent I

nten

sity

Wavelength(nm)

0

10.0 equiv Pb2+

Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2010

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Fig. S4 Fluorescence spectra (λex = 515 nm) of 10 μM SPQN upon the

titration of Pb2+ (0 – 10.0 equiv) in buffer solution (50 mM, HEPES, 50% ethanol, pH = 7.4); inset: fluorescence intensity ratio as a function of Pb2+ concentration

Fig. S5 Plot of fluorescence intensity changes of SPQN(10μM) by adding (a) 1 equiv

of Zn2+; (b) (a) + 1 equiv of EDTA; (c) (b) + 1 equiv of Zn2+

560 630 7000

200000

400000

600000

Fluo

resc

ent i

nten

sity

Wavelength(nm)

a

b

c

Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2010

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Fig. S6 MADLI-TOF HRMS spectrum of SPQN-Zn2+ showing [M + Zn – H]+ peak at 609.2233 Fig. S7 The overlapping of the emissive peak of the quinoline moiety of SPQN (λex = 326 nm) and the absorption peak of SPQN-Zn2+ complex

100000

200000

Fluo

resc

ent i

nten

sity

1.0

5.0 equiv Zn2+

300 400 500 600 700 8000

100000

200000

300000

400000

500000

Fluo

resc

ent I

nten

sity

Wavelength(nm)

Abs

0.00

0.05

0.10

0.15

0.20

0.25

0.30

Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2010

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Fig. S8 Fluorescence spectra (λex = 326 nm) of SPQN (10 μM) in buffer solution (50

mM, HEPES, 50% ethanol, pH = 7.4) in the presence of different concentration of Zn2+ (exceeding 1 equiv)

Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2010

S8

Fig. S9-11 Spectral data of compound 3 (1H NMR; 13C NMR; HRMS)

Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2010

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Fig. S12-14 Spectral data of compound 4 (1H NMR; 13C NMR; HRMS)

Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2010

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Fig. S15-17 Spectral data of compound 5 (1H NMR; 13C NMR; HRMS)

Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2010

S11

Fig. S18-20 Spectral data of compound 7 (1H NMR; 13C NMR; HRMS)

Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2010

S12

Fig. S21-23 Spectral data of compound 5 (1H NMR; 13C NMR; HRMS)

Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2010