1

SUPPORTING IMFORMATION

Hydrazinopyrimidine derived novel Al3+ chemosensor: molecular logic gate and biological

applications

Bhriguram Das,a Satyajit Dey,*a Guru Prasad Maiti,b Ankita bhattacharjee,c Anamika Dharad and

Atanu Janae*

aDepartment of Chemistry, Tamralipta Mahavidyalaya, East Midnapore, West Bengal. Pin No.

721636, Email: satyajitdeyoc@gmail.com

bStephenson Cancer Center, University of Oklahoma Health Sciences Center, Oklahoma City,

Ok-73104, USA.

cDepartment of Ecological Studies, University of Kalyani, Kalyani, Nadia-741235, West

Bengal, India

dDepartment of Chemistry, Jadavpur University, Raja S. C. Mallick Road, Kolkata 700032, India

eDepartment of Chemistry, Indian Institute of Technology Delhi, Hauz Khas, New Delhi 110016,

India. Email: atanujanaic@gmail.com

CONTENTS

SL. NO. Description Page No.

Figure S1 Reaction scheme for the synthesis of chemosensor L 3

Figure S2 1H NMR spectrum of sensor L 4

Figure S3 ESI-MS+ (M/Z) of sensor L 5

Figure S4 IR spectrum of ligand L 6

Electronic Supplementary Material (ESI) for New Journal of Chemistry.This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2018

2

Figure S5 1H NMR of complex 7

Figure S6 Mass spectra of complex. 8

Figure S7 IR spectrum of complex 9

Figure S8 pH effect on fluorescence behavior towards ligand L and L-Al3+ complex

10

Figure S9 Absorption spectral change of towards various metals ions in ethanol and corresponding photographic image under ambient light

11

Figure S10 LOD and LOQ calibration curve. 12

Experimental

Materials and instruments

2-Naphthol (≥ 99.0 %) (a/a), chloroform (≥ 99.0 %), NaOH (≥ 97.0 %), ethyl acetate (98.0 %), silica gel

(60-120 mess), methanol (≥ 99.0 %), high-purity HEPES (99.0 %), Na2EDTA (98.0 %), metal perchlorate

salts and related solvent were purchased from Merck (India)Ltd. and were used without further

purifications. 2-hydroxy-naphlaldehyde and 2,6-dimethyl pyrimidine hydrazine were prepared by using

literature method described elsewhere. Solvents used were of spectroscopic grade for spectral

measurements. Other chemicals were of analytical reagent grade and have been used without further

purification except when specified. 1H NMR was recorded on Brucker 400 MHz instruments using TMS

as internal standard. Chemical shifts δ are expressed in ppm unit and1H–1H coupling constants in Hz.

Mass spectrum were recorded on Qtof Micro YA263 mass spectrometer. Absorbance data obtained from a

UV-Visible spectrometer (model-evolution 201).Fluorescence data were recorded using a xenoflash(PTI)

fluorescence spectrophotometer with excitation wavelength 380 nm for ligand and complex. Anthracene

(φ = 0.27 in ethanol) had been taken as reference compound to measure the fluorescence quantum yield.

Synthesis

(E)-1-((2-(4,6-dimethylpyrimidin-2-yl)hydrazono)methyl)naphthalen-2-ol

3

2-hydroxy-1-naphthaldehyde was prepared according to literature method using Reimer-

Tiemannreaction. A solution of 4,6-dimethyl-2-hydrazinopyrimidine (100mg, 0.72mmol) in ethanol(~15

ml) was added drop wise to a solution containing 2-hydroxy-1-naphthaldehyde (125 mg, 0.72 mmol) in

ethanol(~15 ml) with stirring. The resulting solution was then refluxed for 4 hours. After that volume of

the solution was reduced to one-third of its initial volume to get a faint-yellow precipitate which was

collected by filtration followed by washing thoroughly with cold methanol. The product was purified by

column chromatography separation using ethyl acetate: petroleum ether (8:2; v/v) as eluent (Scheme 1).

The yield of the product was found to be 76%.m.pt: 196-198oC, IH NMR (ESI-Fig. S2)[ 400 MHz,

DMSO-d6]δ(ppm):13.16 (1H, s), 11.49 (1H, s), 9.15 (1H, s), 8.06 (1H, d, J = 8.4 Hz), 7.84-7.88 (2H, m),

7.57 (1H, d, J = 7.6 Hz), 7.40 (1H, d, J = 7.2 Hz), 7.21 (1H, d, J = 8.8 Hz), 6.69 (1H, s), 2.33 (6H, s). MS

(ESI-Fig. S3): m/z=292.13 (calculated), 293.13[M+H]+ (observed). IR(KBr,cm1): (ESI-Fig. S4) 3350,

2921, 2851, 1620, 1598, 1566, 1483, 1401, 1383, 1364, 1315, 1282, 1187, 1158, 1125, 1028.

Figure S1: Reaction Scheme for synthesis of sensor L

N N

OHOH

O

NHH2N

OH

O

OH

NNH

N

N

CHCl3,NaOH,60-700C

H3O+

+ Ethanol

Reflux,4 hrsL

4

Figure S2:1H NMR of the ligand (L) in d6-DMSO

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.511.512.513.514.5f1 (ppm)

BL2 in DMSO

6.19

0.81

0.840.971.001.961.15

1.16

1.08

0.87

2.33

62.

500

6.69

37.

197

7.21

97.

364

7.38

37.

401

7.55

77.

576

7.59

57.

841

7.86

37.

882

8.04

18.

062

9.15

5

11.4

96

13.1

69

5

Figure S3: ESI-MS+ (M/Z) of ligand (L).

6

Figure S4: FT-IR spectrum of ligand (L).

7

Figure S5: 1H NMR of complex

8

Figure S6: Mass spectra of complex.

9

Figure S7: FT-IR spectrum of complex

10

Figure S8: pH effect on fluorescence behavior towards ligand L and L-Al3+ complex

2 4 6 8 10 12

020406080

100120140160180200

Emiss

ion

Inte

nsity

(a.u

.)

pH

L+Al3+

L

11

Figure S9: Absorption spectral change of L (20 µM) towards various metals (50 equivalent) in ethanol (20 µM HEPES buffer, pH 7.2) and corresponding photographic image under ambient light.

350 400 450 5000.0

0.1

0.2

0.3

0.4

0.5

0.6Ab

sorb

ance

(a. u

.)

Wave Length (nm)

Al3+

Cu2+

Zn2+

Cd2+

Mn2+

Ni2+

Co2+

L+ others metal

L Na+ K+ Ba2+ Ca2+ Cd2+ Co2+ Cr3+ Fe3+ Al3+ Mg2+ Mn2+ Ni2+ Cu2+ Zn2+ Hg2+ Pb2+

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Figure S10: LOD and LOQ calibration curve.

0 5 10 15 20 25 300

5000

10000

15000

20000

25000

30000

Emm

isio

n in

tens

ity

[Al3+] x 10-6 M

Equation y = a + Adj. R-Squ 0.9664

Value Standard EB Intercep -351.697 1038.6736B Slope 1120.231 60.12801

LOD=2.7815 x10-6 M=1043.46 ng/mlLOQ=9.2719 x10-6 M=3478.22 ng/ml