1

Electronic Supplementary Data

Pyridoxal derived chemosensor: Its application in anion sensing and

molecular logic gate building

Suban K Sahooa,

*, Darshna Sharmaa, Shilpa Bothra

a, Sutapa Mondal Roy

a, Rajender Kumar

a,

Ashok Kumar S Kb, Jitendra P Nandrec, Umesh D Patilc & John F Calland

aDepartment of Applied Chemistry, SV National Institute of Technology (SVNIT), Surat, Gujarat, India

Email: suban_sahoo@rediffmail.com

bSchool of Advanced Sciences, VIT University, Vellore, Tamilnadu, India

cSchool of Chemical Sciences, North Maharashtra University, Jalgaon, Maharashtra, India dSchool of Pharmacy and Pharmaceutical Sciences, The University of Ulster,

Northern Ireland, BT52 1SA

No. Contents Pg No.

1 Fig. S1 – FTIR spectrum of L. 3

2 Fig. S2 – 1H NMR spectrum of L in DMSO-d6. 3

3 Fig. S3 – Mass spectrum of L. 4

4 Fig. S4 – UV-Vis absorption spectra of L (1.0×10-5 M) upon addition of

ten equivalents of different anions such as NO3-, N3

-, ClO4

-, benzoate and

boronate ions in DMSO. Inset showing naked-eye detectable color change of L.

4

5 Fig. S5 – Competitive absorption experiments of L (1.0×10-5

M) for

fluoride and acetate anions in presence of different other anions as mentioned in the text.

5

6 Fig. S6 – Changes in the absorbance spectrum of L (2 mL, 1.0×10-5

M)

upon addition of incremental amounts of AcO- (1.0×10

-4 M) in DMSO.

5

7 Fig. S7 – B-H plot of L with TBAF. 6

8 Fig. S8 – B-H plot of L with TBAAcO. 6

9 Fig. S9 – The stoichiometry analysis for the complexation of L with anions

([F-] = [AcO

-] = 1.0×10

-4 M, Vtotal = 2 mL) by Job’s plot analysis.

7

10 Fig. S10 – Changes in the fluorescence spectra of L (5.0×10-5 M) upon

addition of incremental amounts of AcO- in DMSO.

7

11 Fig. S11 – Competitive fluorescence experiments of L for (a) fluoride anion and

(b) acetate anion in presence of different other anions as mentioned in the text. 8

12 Fig. S12 – 1H NMR spectra (Upfield region) of L in absence and presence of different

equivalents of TBA salts of F- (from top: 3, 1, 0.5 and 0.0 equivalents) in DMSO-d6.

8

13 Fig. S13 – (a) Changes in the absorbance spectrum of L (2 mL, 1.0×10-5

M) upon

addition of incremental amounts of TBAOH (1×10-4 M) in DMSO. (b) UV-Vis absorption

spectra of L (5.0×10-5 M) upon addition of ten equivalents of F- and OH- in DMSO.

9

2

14 Fig. S14 – Changes in the fluorescence spectrum of L (5.0×10-5

M) in presence of

TBAOH (20 µL, 1×10-2 M) in DMSO and DMSO containing 20% water. 9

15 Fig. S15 – Fluorescence spectra of L (5.0×10-5

M) in the presence of two equivalents of

different anions (AcO- and F

-) in DMSO containing 20% H2O.

10

16 Fig. S16 – (a) UV-Vis absorption spectra of L (2 mL in DMSO, 5.0×10-5

M)

at different concentration of NaF (50 µL, in H2O) and visible color change with (b) NaF

and (c) NaAcO.

10

17 Fig. S17 – UV-Vis absorption spectra of L (2 mL, 5.0×10-5

M, in DMSO) at

different concentration of anions (50 µL, in H2O) varies from 100 µM to 1000 µM)

and visible color change with (a) NaF and (b) NaAcO.

11

18 Fig. S18 – (a) UV-Vis absorption spectral changes of L (5.0×10-5

M) upon addition of

commercial toothpaste (S1) and Ayurvedic toothpaste (S2). (b) Naked-eye detection of L

(1×10-5

M) upon addition of commercial toothpaste (S1) and Ayurvedic toothpaste (S2).

11

19 Fig. S19 – UV-Vis absorption spectral and color changes of L in presence of

Ca2+

and AcO-.

11

20 Table S1 – Comparison table for L with the structurally analogous reported receptors. 12

3

Fig. S1 — FTIR spectrum of L.

Fig. S2 — 1H NMR spectrum of L in DMSO-d6.

4

Fig. S3 — Mass spectrum of L.

Fig. S4 — UV-Vis absorption spectra of L (1.0×10-5 M) upon addition of ten equivalents of different anions such as NO3-,

N3-, ClO4

-, benzoate and boronate ions in DMSO. Inset showing naked-eye detectable color change of L.

+Q1: 0.117 to 0.151 min from Sample 4 (Q1MS of HL at +ive mode) of SVNIT.wiff (Turbo Spray) Max. 6.8e6 cps.

100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400 420 440 460 480 500m/z, amu

5.0e5

1.0e6

1.5e6

2.0e6

2.5e6

3.0e6

3.5e6

4.0e6

4.5e6

5.0e6

5.5e6

6.0e6

6.5e6

6.8e6182.1

331.0

149.1

165.1119.1

153.1332.0166.1138.1

102.0286.1245.2123.0 437.2

199.0 468.6112.1 316.1216.1184.1 413.2304.1 430.2270.1154.1 453.2134.1 353.2261.1200.2 485.4368.4246.0177.2 385.3328.1226.2 479.2105.1 299.0 389.3313.1129.3

5

Fig. S5 — Competitive absorption experiments of L (1.0×10-5 M) for fluoride and acetate anions in presence of different

other anions as mentioned in the text.

Fig. S6 — Changes in the absorbance spectrum of L (2 mL, 1.0×10-5 M) upon addition of incremental amounts of

AcO- (1.0×10-4 M) in DMSO.

6

40000 50000 60000 70000 80000 90000 100000

5.5

6.0

6.5

7.0

7.5

8.0

8.5

9.0

1/A

-Ao

1/F

Equation y = a + b*x

Adj. R-Square 0.98207

Value Standard Error

B Intercept 2.95777 0.16114

B Slope 6.15378E-5 2.50474E-6

Fig. S7 — B-H plot of L with TBAF.

50000 60000 70000 80000 90000 100000

4.0

4.5

5.0

5.5

6.0

6.5

1/A

-Ao

1/F

Equation y = a + b*x

Adj. R-Square 0.98809

Value Standard Error

B Intercept 1.66246 0.10643

B Slope 5.00016E-5 1.65431E-6

Fig. S8 — B-H plot of L with TBAAcO.

7

Fig. S9 — The stoichiometry analysis for the complexation of L with anions ([F-] = [AcO-] = 1.0×10-4 M, Vtotal = 2 mL) by

Job’s plot analysis.

Fig. S10 — Changes in the fluorescence spectra of L (5.0×10-5 M) upon addition of incremental amounts

of AcO- in DMSO.

8

Fig. S11 — Competitive fluorescence experiments of L for (a) fluoride anion and (b) acetate anion in presence of different

other anions as mentioned in the text.

Fig. S12 — 1H NMR spectra (Upfield region) of L in absence and presence of different equivalents of TBA salts of F- (from

top: 3, 1, 0.5 and 0.0 equivalents) in DMSO-d6.

9

Fig. S13 — (a) Changes in the absorbance spectrum of L (2 mL, 1.0×10-5 M) upon addition of incremental amounts of

TBAOH (1×10-4 M) in DMSO. (b) UV-Vis absorption spectra of L (5.0×10-5 M) upon addition of ten equivalents of F- and

OH- in DMSO.

Fig. S14 — Changes in the fluorescence spectrum of L (5.0×10-5 M) in presence of TBAOH (20 µL, 1×10-2 M) in DMSO

and DMSO containing 20% water.

10

Fig. S15 — Fluorescence spectra of L (5.0×10-5 M) in the presence of two equivalents of different anions (AcO- and F-) in

DMSO containing 20% H2O.

Fig. S16 — (a) UV-Vis absorption spectra of L (2 mL in DMSO, 5.0×10-5 M) at different concentration of NaF (50 µL, in

H2O) and visible color change with (b) NaF and (c) NaAcO.

11

Fig. S17 — UV-Vis absorption spectra of L (2 mL, 5.0×10-5 M, in DMSO) at different concentration of anions (50 µL, in

H2O) varies from 100 µM to 1000 µM) and visible color change with (a) NaF and (b) NaAcO.

Fig. S18 — (a) UV-Vis absorption spectral changes of L (5.0×10-5 M) upon addition of commercial toothpaste (S1) and

Ayurvedic toothpaste (S2). (b) Naked-eye detection of L (1×10-5 M) upon addition of commercial toothpaste (S1) and

Ayurvedic toothpaste (S2).

Fig. S19 — UV-Vis absorption spectral and color changes of L in presence of Ca2+ and AcO-.

12

Table S1 — Comparison table for L with the structurally analogous reported receptors

Receptors Analytes Medium Mode of sensing/

analytical parameters

Ref.

F- and AcO- DMSO

or

DMSO/H2O

Colorimetric; colourless to red;

λabs = 505 nm;

linearity range: 0.25-8.47 µM

This

work

Fluorescence turn-ON;

λexc/λem = 510 nm/ 640 nm;

LOD: 0.13 µM (F-); 1.10 µM (AcO-)

F- and AcO- H2O:CH3CN:D

MSO = 4:95:1 v

/v

Colourless to intense yellow;

λabs = 455 nm;

LOD: 5 µM(F-) ; 7 µM (AcO-)

[1]

F- and AcO- DMSO:CH3CN

= 5:95, v/v

Colourless to intense yellow;

λabs = 422 nm

[2]

F- DMSO Colourless to yellow;

λabs = 461 nm

Fluorescence turn-ON;

λexc/λem = 396 nm/ 525 nm

[3]

F- DMSO Colourless to yellow;

λabs = 435 nm

Fluorescence turn-ON;

λexc/λem = 390 nm/ 505 nm

[3]

F- and AcO- CH3CN Colourless to yellow;

λabs = 425 nm

[4]

References

1. S. Dalapati, M.A. Alam, S. Jana, S. Karmakar, N. Guchhait, SCA, 102 (2013) 314–318.

2. S. Dalapati, M. A. Alam, S. Jana, N. Guchhait, Journal of Fluorine Chemistry, 132 (2011) 536–540.

3. Qian Li, Y. Guo, J. Xu, S. Shao, Sensors and Actuators B 158 (2011) 427-431.

4. S. Dalapati, M.A. Alam, S. Jana, R. Saha, N. Guchhait, Sensors and Actuators B 162 (2012) 57– 62.