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Supporting Information
Biginelli-based Organic Nanoprobe for Simultaneous Estimation of Tyramine and 1, 2-
Diaminopropane: application in real samples.
Gaganpreet Kaur,a Tilak Raj,b Navneet Kaura,c* and Narinder Singhb*
aCentre for Nanoscience & Nanotechnology (UIEAST), Panjab University, Chandigarh, 160014,
India. E-mail: [email protected]; Tel: +91-1722534464
bDepartment of Chemistry, Indian Institute of Technology Ropar, Rupnagar, Punjab, India,
140001. E-mail: [email protected]; Fax: +91-1881223395; Tel: +91-1881242176.
cDepartment of Chemistry, Panjab University, Chandigarh, 160014, India. E-mail:
Table of contents
Figure S1. 1H NMR spectrum of compound 1 and its expansion.
Figure S2. 13
C NMR spectrum of compound 1.
Figure S3. ESI Mass spectrum of compound 1.
Figure S4. Plot of variation in size of nanoparticles as a function of concentration of compound
1 in water.
Figure S5. Linear regression graph for Ag (I) titration.
Figure S6. Linear regression graphs for Tyramine titration (A) and linear regression graph for
1,2-Diaminopropane titration (B).
Figure S7. Non-linear regression graphs between Fluorescence Intensity vs. Concentrations of
amines (at higher concentrations).
Figure S8. Fluorescence spectra of nano-aggregates N1 at different concentrations of TBA
perchlorate to evaluate the salt effect.
Figure S9. Fluorescence spectra of nano-aggregates N1 at different pH values.
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 2016
2
Figure S10. Fluorescence intensity v/s pH graphs of A) N1.Ag(I) complex with 50 µM
Tyramine and B) N1.Ag(I) complex with 50 µM 1,2-Diaminopropane.
Figure S11. Plot of fluorescence intensity ratios of N1 and Ag (I) at different concentrations, as
a function of time.
Figure S12. Stability of organic nanoparticles, N1 and the N1.Ag(I) complex over a period of
two weeks.
Figure S13. Fluorescence intensity variation of A) N1 on addition of different metal ions and B)
N1.Ag(I) on addition of different Biogenic amines using five different batches of sensors to
check the reproducibility.
Figure S14. Fluorescence intensity variation of A) N1 on addition of different metal ions and B)
N1.Ag(I) on addition of different Biogenic amines in presence of HEPES buffer, pH 7.4.
Figure S15. Fluorescence intensity v/s wavelength graph of N1.Ag(I) complex with 50 µM each of Tyramine and 50 µM 1, 2-Diaminopropane mixed together.
Table S1: Comparison of current sensor with existing literature.
3
1H-NMR(DMSO, 400MHz)
13 12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
0.00
01
2.46
322.
5088
2.51
292.
5174
2.52
182.
5261
3.36
653.
5812
6.49
336.
8982
6.89
986.
9180
6.93
596.
9379
6.99
536.
9971
7.01
587.
0331
7.03
527.
1388
7.14
097.
1511
7.15
307.
1574
7.15
977.
1695
7.17
177.
2238
7.24
337.
3120
7.33
167.
5589
7.57
837.
6865
7.69
097.
7056
7.71
007.
7248
7.72
918.
2326
8.36
408.
3741
10.7
895
3.03
3.20
1.10
1.36
1.25
1.20
1.33
1.23
1.21
1.18
1.06
1.07
Current Data ParametersNAME Aug28-2015EXPNO 80PROCNO 1
F2 - Acquisition ParametersDate_ 20150828Time 12.16INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zg30TD 65536SOLVENT DMSONS 8DS 2SWH 12019.230 HzFIDRES 0.183399 HzAQ 2.7263477 secRG 456DW 41.600 usecDE 6.00 usecTE 296.9 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 10.90 usecPL1 -3.00 dBSFO1 400.1324710 MHz
F2 - Processing parametersSI 32768SF 400.1299966 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
GK-14BRUKERAVANCE II 400 NMRSpectrometerSAIFPanjab UniversityChandigarh
4
Figure S1. 1H NMR spectrum of compound 1 and its expansion.
6.46.56.66.76.86.97.07.17.27.37.47.57.67.77.87.98.08.18.28.38.48.5 ppm
6.49
33
6.89
826.
8998
6.91
806.
9359
6.93
796.
9953
6.99
717.
0158
7.03
317.
0352
7.13
887.
1409
7.15
117.
1530
7.15
747.
1597
7.16
957.
1717
7.22
387.
2433
7.31
207.
3316
7.55
897.
5783
7.68
657.
6909
7.70
567.
7100
7.72
487.
7291
8.23
26
8.36
408.
3741
1.10
1.36
1.25
1.20
1.33
1.23
1.21
1.18
1.06
Current Data ParametersNAME Aug28-2015EXPNO 80PROCNO 1
F2 - Acquisition ParametersDate_ 20150828Time 12.16INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zg30TD 65536SOLVENT DMSONS 8DS 2SWH 12019.230 HzFIDRES 0.183399 HzAQ 2.7263477 secRG 456DW 41.600 usecDE 6.00 usecTE 296.9 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 10.90 usecPL1 -3.00 dBSFO1 400.1324710 MHz
F2 - Processing parametersSI 32768SF 400.1299966 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
GK-14BRUKERAVANCE II 400 NMRSpectrometerSAIFPanjab UniversityChandigarh
5
Figure S2. 13
C NMR spectrum of compound 1.
13C-NMR, CDCl3, 100 MHz
6
Figure S3. ESI Mass spectrum of compound 1.
Figure S4. Plot of variation in size of nanoparticles as a function of concentration of compound
1 in water.
7
Figure S5. Linear regression graph for Ag (I) titration.
Figure S6. Linear regression graphs for Tyramine titration (A) and linear regression graph for
1,2-Diaminopropane titration (B).
y = -3.7078x + 384.39 R² = 0.995
050
100150200250300350400450
0 10 20 30 40 50 60 70 80Fluo
resc
ence
Inte
nsity
(a.u
.)
Ag (I) concentration (µM)
y = 6.5157x + 122.64 R² = 0.9961
0
100
200
300
400
500
600
0 10 20 30 40 50 60 70Fluo
resc
ence
Inte
nsity
(a.u
.)
Tyr concentration (µM)
A y = 7.5381x + 0.4139
R² = 0.9947
0
100
200
300
400
500
600
0 20 40 60 80Fluo
resc
ence
Inte
nsity
(a.u
.)
1, 2-Dap concentration (µM)
B
8
Figure S7. Non-linear regression graphs between Fluorescence Intensity vs. Concentrations of
amines (at higher concentrations).
Figure S8. Fluorescence spectra of nano-aggregates N1 at different concentrations of (A) TBA
perchlorate to evaluate the salt effect and (B) in presence of NaCl.
0
100
200
300
400
500
600
700
0 20 40 60 80 100 120
Fluo
resc
ence
Inte
nsity
(a.u
.)
Tyr concentration (µM)
A
0
100
200
300
400
500
600
700
0 20 40 60 80 100 120
Fluo
resc
ence
Inte
nsity
(a.u
.)
1, 2-Dap concentration (µM)
B
0
100
200
300
400
500
600
350 450 550 650Flu
ore
sc
en
ce
In
ten
sit
y (a
.u.)
Wavelength (nm)
A
N15 eq.10 eq.50 eq.100 eq.200 eq.
0
100
200
300
400
500
600
350 450 550 650Flu
ore
sc
en
ce
In
ten
sit
y (a
.u.)
Wavelength (nm)
B
N15 eq.10 eq.50 eq.100 eq.200 eq.
9
Figure S9. Fluorescence spectra of nano-aggregates N1 at different pH values.
Figure S10. Fluorescence intensity v/s pH graphs of A) N1.Ag(I) complex with 50 µM Tyramine and B) N1.Ag(I) complex with 50 µM 1,2-Diaminopropane.
200
250
300
350
400
450
500
2 4 6 8 10 12 14Fluo
resc
ence
Inte
nsity
(a.u
.)
pH
A
200
250
300
350
400
450
500
2 4 6 8 10 12 14Fluo
resc
ence
Inte
nsity
(a.u
.)
pH
B
10
Figure S11. Plot of fluorescence intensity ratios of N1 and Ag (I) at different concentrations, as
a function of time.
Figure S12. Stability of organic nanoparticles, N1 and the N1.Ag(I) complex over a period of
two weeks.
0
0.1
0.2
0.3
0.4
0.5
0.6
0 2 4 6 8 10 12
Inte
nsity
Rat
io (a
.u.)
Time (minutes)
N1+10 µM Ag(I)N1+20µM Ag(I)N1+40 µM Ag(I)N1+70 µM Ag(I)
050100150200250300350400450
0 2 4 6 8 10 12 14
Fluo
resc
ence
Inte
nsity
(a.u
.)
Time (in days)
N1N1.Ag(I)
11
Figure S13. Fluorescence intensity variation of A) N1 on addition of different metal ions and B)
N1.Ag(I) on addition of different Biogenic amines using five different batches of sensors to
check the reproducibility.
Figure S14. Fluorescence intensity variation of A) N1 on addition of different metal ions and B)
N1.Ag(I) on addition of different Biogenic amines in presence of HEPES buffer, pH 7.4.
050
100150200250300350400450
N1
Li (I
)N
a (I)
K (I)
Cs
(I)M
g (II
)C
a (II
)Sr
(II)
Ba (I
I)C
r (III
)M
n (II
)Fe
(III)
Co
(II)
Cu
(II)
Zn (I
I)C
d (II
)Pb
(II)
Ag (I
)Fluo
resc
ence
Inte
nsity
(a.u
.) A
050
100150200250300350400450500
N1.
Ag(I)
Spd
Spm Tyr
2,2-
Dpe His
1,2-
Dap
1,4-
Dab
u
1,5-
Dap
e
Fluo
resc
ence
Inte
nsity
(a.u
.)
B
050
100150200250300350400450
N1
Li (I
)N
a (I)
K (I)
Cs
(I)M
g (II
)C
a (II
)Sr
(II)
Ba (I
I)C
r (III
)M
n (II
)Fe
(III)
Co
(II)
Cu
(II)
Zn (I
I)C
d (II
)Pb
(II)
Ag (I
)Fluo
resc
ence
Inte
nsity
(a.u
.)
A
050
100150200250300350400450500
N1.
Ag(I)
Spd
Spm Tyr
2,2-
Dpe His
1,2-
Dap
1,4-
Dab
u
1,5-
Dap
e
Fluo
resc
ence
Inte
nsity
(a.u
.)
B
12
Figure S15. Fluorescence intensity v/s wavelength graph of N1.Ag(I) complex with 50 µM each of Tyramine and 50 µM 1,2-Diaminopropane mixed together.
Determination of detection limit.
The detection limit (DL) of nano-aggregates of 1 for Ag (I) was determined from the following
equation:
Where K = 3; Sb1 is the standard deviation of the blank solution; S is the slope of the calibration
curve. The detection limits of biogenic amines were also determined in a similar fashion.
0
100
200
300
400
500
600
350 400 450 500 550 600
Fluo
resc
ence
Inte
nsity
(a.u
.)
Wavelength (nm)
N1.Ag(I)Tyr+1,2-Dap
13
Table S1: Comparison of current sensor with existing literature.
S. No.
Mode of detection Pretreatment Application to real sample analysis
Detection limit
Reference
1 UV Pretreatment Urine 0.06 µM J. Sep. Sci., 2009, 32, 4143–4147.
2 Matrix -solid -phase-dispersion using HPLC −electrospray−tandemMS
Pretreatment Cheese 0.06 mg/kg
J. Agric. Food Chem. 2005, 53, 3779−3783.
3 UHPLC-MS/MS Pretreatment Anchovy (fish)
Range: 10−750 µg/L
J. Agric. Food Chem. 2012, 60, 5324−5329
4 RP-HPLC coupled with fluorimetry
precolumn dansylation
Wines 0.04 mg/l Food Chem., 2008, 106, 1218–1224
5 Electrochemical sensor based on MWCNT-gold nanoparticle composites
- Yoghurt 57 nM Food Res. Int., 2011, 44, 276–281.
6 Cyclic voltammetry using SWCNT
Pretreatment Fish products
0.62 µM J. Food Eng., 2015, 149, 1–8.
7 Absorption-based Chromogenic Sensing on filter paper
- - 0.02 mM Anal. Chem. 2010, 82, 8402-8405
8 Chameleon dye based, microtitre plate using fluorescence spectroscopy
Pretreatment Fish samples
3.4 µM Analyst, 2011, 136, 4492–4499
9 Micellar liquid chromatography and pulsed amperometric
- Wine 12ng/ml J. Chromatogr. A, 2007, 1156, 288–295.
10 Amperometry Pretreatment Sauerkraut 0.57 µM Sens. Actuators B, 2013, 178, 40– 46
11 Fluorescence Spectroscopy-using easily-engineered nanomaterials
No Milk and Wine
3.91 nM Current study.