Electronic Supplementary Information】 Selective fluoride ... · Selective fluoride sensing using organic-inorganic hybrid nanomaterials containing anthraquinone Eunjeong Kim,a Hyun

S 1

【 Electronic Supplementary Information】

Selective fluoride sensing using organic-inorganic hybrid nanomaterials containing anthraquinone

Eunjeong Kim,a Hyun Jung Kim,b Doo Ri Bae,a Soo Jin Lee,a Eun Jin Cho,c Moo Ryeong Seo,a Jong Seung Kim*b and Jong Hwa Jung*a

a Department of Chemistry and Research Institute of Natural Science, Gyeongsang National

University, Chinju 660-701, S. Korea. Fax No.: +82-55-758-6027; E-mail:

[email protected]. b Department of Chemistry, Korea University, Seoul 136-701, S. Korea.

c Department of Materials Science and Engineering, KAIST, Daejeon 305-701, S. Korea

Table of Contents: Title and table of contents ····································································································· S1

Fig. S1 Thermogravimetric analysis data of (a) AFMS and (b) AFSP ································· S2

Fig. S2 IR spectra of (a) mesoporous silica and (b) AFMS ·················································· S3

Fig. S3 The nitrogen adsorption-desorption isotherms of AFSP·········································· S4

Fig. S4 Fluorescent spectra of (A) receptor 1 and (B) mesoporous silica···························· S5

Fig. S5 Fluorescent spectra of anthraquinone by the addition of fluorodie ion ···················· S6

Fig. S6 Fluorescent spectra of AFSP ··················································································· S7

Fig. S7 IR spectra of (a) AFMS and (b) F--loaded AFMS····················································· S8

Fig. S8 EDX spectrum of AFMS loaded F- ··········································································· S9

Fig. S9 Fluorescent spectra of AFMS by addition of basic anions······································· S10

Fig. S10 Immobilization method of receptor 1 onto glass slide ············································ S11 Fig. S11 Fluorescent spectra of AFMS by addition of tetrabutylammonium

fluoride in the presence of other anions in water ····················································· S12

Fig. S12 Calibration curve of fluoride ion against intensity of AFMS by addition of tetrabutylammonium fluoride···························································· S13 Table S1 Fluorescence changes (I/Io) of AFMS upon addition of various anions ················ S14

Table S2 Fluorescence changes (I/Io) of 1 upon addition of various anions ························ S14

Supplementary Material (ESI) for New Journal of ChemistryThis journal is (c) The Royal Society of Chemistry and

The Centre National de la Recherche Scientifique, 2008

S 2

Fig. S1 Thermogravimetric analysis data of (a) AFMS and (b) AFSP.

200 400 600 80075

80

85

90

95

100

a

b

22.1 %

Wei

ght (

%)

Temperature (oC)

5.3 %



S 3

Fig. S2 IR spectra of (a) mesoporous silica and (b) AFMS.

4000 3500 3000 1500 1000 500

b

a

1080

15401640

167029332980

3434

3480

Wavenumber (cm-1)

Tran

smitt

ance

1633



S 4

0.0 0.2 0.4 0.6 0.8 1.00

50

100

150

200

250

300

Qua

ntity

Ads

orbe

d (c

m3 /g

STP

)

Relative Pressure (P/P0)

Fig. S3 The nitrogen adsorption-desorption isotherms of AFSP.



S 5

Fig. S4 Fluorescent spectra of (A) receptor 1 (0.2 mM) and (B) mesoporous silica (5.0 mg) by

addition of tetrabutylammonium anions (20.0 equiv) in water: (a) none, (b)HSO4-, (c)Br-, (d)Cl-, (e) I-

and (f) F-.

450 500 550 600 650 7000

100

200

300

400

f

edcba

Inte

nsity

Wavelength (nm)

edcba

250 300 350 4000

100

200

300

400

f

B

Inte

nsity

Wavelength (nm)

A

250 300 350 4000

5

10

15

20BA



S 6

Fig. S5 Fluorescent spectra of anthraquinone (1.0 x 10-3 M) by the addition of anions (5.0 equiv) in

acetonitrile.

450 500 550 600 6500

1

2

3

4

5

6

7

Inte

nsity

Wavelength(nm)

Anthraquinone,

F-, Br-, Cl-, I-, HSO4-



S 7

Fig. S6 Fluorescent spectra of AFSP (5.0 mg) by addition of tetrabutylammonium anions (20.0 equiv)

in water.

550 600 650 7000

50

100

150

200

250

300

350

400

550 600 6500

2

4

6

8

10

12AFSPHSO4

-

Br-

Cl- I-

F-

Inte

nsity

Wavelength (nm)

Inte

nsity

Wavelength (nm)



S 8

Fig. S7 IR spectra of (a) free-AFMS and (b) F--loaded AFMS.

4000 3500 3000 2000 1500 1000 500

N-H1540

HN NHO

Wavenumber (cm-1)

Tran

smitt

ance

(%)

F-

C=O1638

N-H1555

C=O1645



S 9

Fig. S8 EDX spectrum of F- loaded AFMS.

0 5 10 15 20Energy (keV)

0

2

4

6

8cps

C

N

O

F

Si

Cu



S 10

Fig. S9 Fluorescent spectra of AFMS (0.3 mg) by the addition of basic anions (5.0 equiv) in water.

500 550 600 650 7000

2

4

6

8

10

12

14

Inte

nsity

Wavelength(nm)

(a) without anions (b) tetrabutylamonium hydroxide (c) sodium benzolate

(d) sodium acetate



S 11

Fig. S10 Immobilization method of receptor 1 onto glass slide.



S 12

Fig. S11 Fluorescent spectra of AFMS by addition of tetrabutylammonium fluoride in the presence of

other anions (20 equiv.) in water.

500 550 600 650 7000

50

100

150

200

250

Inte

nsity

Wavelength (nm)

AFMS+anions (HSO4

-,Cl-,Br-,I-)AFMS+anions+0.2eq AFMS+anions+0.4eq AFMS+anions+0.5eq



S 13

Fig. S12 Calibration curve of concentration of fluoride ion against intensity of AFMS.

0.0 2.5 5.0 7.5 10.00

5

10

15

20

25

Inte

nsity

Concentration of F- [μM]



S 14

Table S1 Fluorescence changes (I/Io) of AFMS upon addition of various anions.

Fluorescence Change(I/Io)

λem(nm) F- Cl- Br- I- HSO4-

450 0.37 0.88 0.91 0.88 0.91

Condition: AFMS (5.0 mg) in H2O, excitation at 420 nm; anions, 20.0 equiv in H2O. Io:

fluorescence emission intensity of AFMS; I: fluorescence emission intensity of AFMS in the

presence of anions.

Table S2 Fluorescence changes (I/Io) of receptor 1 upon addition of various anions.

Fluorescence Change(I/Io)

λem(nm) F- Cl- Br- I- HSO4-

425 0.04 0.95 0.96 0.97 0.96

Condition: receptor 1, 0.2 mM in H2O, excitation at 420 nm; anions, 20.0 equiv in H2O. Io:

fluorescence emission intensity of receptor 1; I: fluorescence emission intensity of receptor 1 in the

presence of anions.



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Electronic Supplementary Information】 Selective fluoride ... · Selective fluoride sensing using organic-inorganic hybrid nanomaterials containing anthraquinone Eunjeong Kim,a Hyun