Post on 17-Oct-2021
General Papers Arkivoc 2017, v, S1-S15
Page S1 ©ARKAT USA, Inc
Supplementary Material
New "turn-off" fluorescence sensors to detect vapors of nitro-explosives on the basis of 4,6-bis[5-(heteroaryl)thiophen-2-yl] substituted 5-(4-tert-
butylphenyl)pyrimidines
Egor V. Verbitskiy,a,b Anna A. Baranova,b Yuliya A. Yakovleva,b Roman D. Chuvashov,b Konstantin O. Khokhlov,b Ekaterina M. Dinastiya,a Gennady L. Rusinov,a,b leg N. Chupakhin,a,b
Valery N. Charushina,b
a Postovsky Institute of Organic Synthesis, Ural Branch of the Russian Academy of Sciences, S. Kovalevskoy Str., 22, Ekaterinburg, 620990, Russia
bUral Federal University, Mira St. 19, Ekaterinburg, 620002, Russia E-mail: Verbitsky@ios.uran.ru
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Fluo
resc
ence
Inte
nsity
(a.u
.)
wavelength (nm)
7c
Figure S1. Solid-state fluorescence spectra of compound 7c.
General Papers Arkivoc 2017, v, S1-S15
Page S2 ©ARKAT USA, Inc
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coun
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(c)
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coun
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(d)
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coun
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(e)
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(f)
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(g)
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coun
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(h)
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coun
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(i)
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wagelength (nm)
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(j)
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coun
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wagelength (nm)
0 mol/L 5x10-7 mol/L 1x10-6 mol/L 2x10-6 mol/L 4x10-6 mol/L 6x10-6 mol/L 8x10-6 mol/L 1x10-5 mol/L
(k)
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(l)
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(m)
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(n)
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(o)
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ts
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0 mol/L 5x10-7 mol/L 1x10-6 mol/L 2x10-6 mol/L 4x10-6 mol/L 6x10-6 mol/L 8x10-6 mol/L 1x10-5 mol/L
Figure S2. Fluorescence quenching studies of 7a (1.0 × 10−6 mol/L) recorded in the presence of various amounts of NB (a), 1,3-DNB (b), 1,3,5-TNB (c), 2-NP (d), 4-NP (e), 2,4-DNP (f), PA (g),
SA (h), 4-NT (i), 2,4-DNT (j), TNT (k), DNAN (l), TNAN (m), TATB (n) and DDBu (o) for which 433 nm was taken as the excitation wavelength.
General Papers Arkivoc 2017, v, S1-S15
Page S3 ©ARKAT USA, Inc
(a)
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(d)
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(e)
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(f)
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(i)
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(j)
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(n)
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(o)
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Figure S3. Fluorescence quenching studies of 7b (1.0 × 10−6 mol/L) recorded in the presence of various amounts of NB (a), 1,3-DNB (b), 1,3,5-TNB (c), 2-NP (d), 4-NP (e), 2,4-DNP (f), PA (g),
SA (h), 4-NT (i), 2,4-DNT (j), TNT (k), DNAN (l), TNAN (m), TATB (n) and DDBu (o) for which 412 nm was taken as the excitation wavelength.
General Papers Arkivoc 2017, v, S1-S15
Page S4 ©ARKAT USA, Inc
Figure S4. Photographs of solution 7a (c = 1.0×10-6 M) with the presence of solution TNT (c = 1.0×10-6 M) in acetonitrile (1), solution 7a with the presence of solution 4-NT (c = 1.0×10-6 M) in acetonitrile (2), solution 7a with the presence of solution 2-NP (c = 1.0×10-6 M) in acetonitrile (3), solution 7a with the presence of solution NB (c = 1.0×10-6 M) in acetonitrile (4), solution 7a with the presence of solution PA (c = 1.0×10-6 M) in acetonitrile (5), solution 7a with the presence of solution DDBu (c = 1.0×10-6 M) in acetonitrile (6), solution 7a with the presence of solution DNAN (c = 1.0×10-6 M) in acetonitrile (7), solution 7a with the presence of solution 1,3-DNB (c = 1.0×10-6 M) in acetonitrile (8), solution 7a with the presence of solution TATB (c = 1.0×10-6 M) in acetonitrile (9), solution 7a with the presence of solution 4-NP (c = 1.0×10-6 M) in acetonitrile (10), solution 7a with the presence of solution TNAN (c = 1.0×10-6 M) in acetonitrile (11), solution 7a with the presence of solution 1,3,5-TNB (c = 1.0×10-6 M) in acetonitrile (12), solution 7a with the presence of solution 2,4-DNP (c = 1.0×10-6 M) in acetonitrile (13), solution 7a with the presence of solution 2,4-DNT (c = 1.0×10-6 M) in acetonitrile (14), solution 7a with the presence of solution SA (c = 1.0×10-6 M) in acetonitrile (15): before radiation (a – no emission) and during radiation (b – emission, λex= 400 nm) at room temperature.
General Papers Arkivoc 2017, v, S1-S15
Page S5 ©ARKAT USA, Inc
Figure S5. Photographs of solution 7b (c = 1.0×10-6 M) with the presence of solution TNT (c = 1.0×10-6 M) in acetonitrile (1), solution 7b with the presence of solution 4-NT (c = 1.0×10-6 M) in acetonitrile (2), solution 7b with the presence of solution 2-NP (c = 1.0×10-6 M) in acetonitrile (3), solution 7b with the presence of solution NB (c = 1.0×10-6 M) in acetonitrile (4), solution 7b with the presence of solution PA (c = 1.0×10-6 M) in acetonitrile (5), solution 7b with the presence of solution DDBu (c = 1.0×10-6 M) in acetonitrile (6), solution 7b with the presence of solution DNAN (c = 1.0×10-6 M) in acetonitrile (7), solution 7b with the presence of solution 1,3-DNB (c = 1.0×10-6 M) in acetonitrile (8), solution 7b with the presence of solution TATB (c = 1.0×10-6 M) in acetonitrile (9), solution 7b with the presence of solution 4-NP (c = 1.0×10-6 M) in acetonitrile (10), solution 7b with the presence of solution TNAN (c = 1.0×10-6 M) in acetonitrile (11), solution 7b with the presence of solution 1,3,5-TNB (c = 1.0×10-6 M) in acetonitrile (12), solution 7b with the presence of solution 2,4-DNP (c = 1.0×10-6 M) in acetonitrile (13), solution 7b with the presence of solution 2,4-DNT (c = 1.0×10-6 M) in acetonitrile (14), solution 7b with the presence of solution SA (c = 1.0×10-6 M) in acetonitrile (15): before radiation (a – no emission) and during radiation (b – emission, λex= 400 nm) at room temperature.
General Papers Arkivoc 2017, v, S1-S15
Page S6 ©ARKAT USA, Inc
Details for the determination and calculation of the detection limits of the fluorophore to nitro compounds in acetonitrile solution.
Detection limit of the fluorophore to the analyte in acetonitrile solution was determined and
calculated according to the following functions:
1
)(1
2
−
−=∑=
n
xxs
n
ii
b (1)
cIS
∆∆
= (2)
SsDL b3
= (3)
Firstly, the standard deviation (Sb) was calculated by measuring the intensity of the fluorophore
in blank solution for more than 10 times and then got the average intensity ( x ). By fitting the data
into Function 1, the value of standard deviation (Sb) was obtained. Secondly, a certain amount of
analyte such as NB, 1,3-DNB, 1,3,5-TNB, 2-NP, 4-NP, 2,4-DNP, PA, SA, 4-NT, DNT, TNT,
DNAN, TNAN, TATB or DDBu was added into the blank solution and the resulting variation of the
intensity ( c∆ ) was recorded. By fitting the data into Function 2, where I∆ is the variation of
intensity, and c∆ is the variation of quencher concentration, the value of precision S was
calculated. Finally the detection limit, DL, was calculated according to Function 3.
General Papers Arkivoc 2017, v, S1-S15
Page S7 ©ARKAT USA, Inc
0,0000000 0,0000005 0,0000010 0,0000015 0,00000200,000
0,002
0,004
0,006
0,008
0,010
0,012
0,014
0,016
0,018
0,020
(I0/I)
-1
Concentrations (mM)
PA TNT DNT SA NB DNAN TATB TETNB
y = 239,23xR2 = 0,971
y = 416,11xR2 = 0,9663
y = 1361,7xR2 = 0,6916
0,0000000 0,0000005 0,0000010 0,0000015 0,00000200,000
0,002
0,004
0,006
0,008
0,010
0,012
0,014
0,016
0,018
0,020
(I0/I)
-1
Concentrations (mM)
PA TNT DNT SA NB DNAN TATB TETNB
y = 239,23xR2 = 0,971
y = 416,11xR2 = 0,9663
y = 1361,7xR2 = 0,6916
Figure S6. The Stern–Volmer plots as function of NB, 1,3-DNB, 1,3,5-TNB, 2-NP, 4-NP, 2,4-
DNP, PA, SA, 4-NT, 2,4-DNT, TNT, DNAN, TNAN, TATB and DDBu concentration in CH3CN, with an excitation wavelength of 433 nm for 7a solution.
0,0000000 0,0000005 0,0000010 0,0000015 0,00000200,000
0,002
0,004
0,006
0,008
0,010
0,012
0,014
0,016
0,018
0,020
(I0/I)
-1
Concentrations (mM)
PA TNT DNT SA NB DNAN TATB TETNB
y = 239,23xR2 = 0,971
y = 416,11xR2 = 0,9663
y = 1361,7xR2 = 0,6916
0,0000000 0,0000005 0,0000010 0,0000015 0,00000200,000
0,002
0,004
0,006
0,008
0,010
0,012
0,014
0,016
0,018
0,020
(I0/I)
-1
Concentrations (mM)
PA TNT DNT SA NB DNAN TATB TETNB
y = 239,23xR2 = 0,971
y = 416,11xR2 = 0,9663
y = 1361,7xR2 = 0,6916
Figure S7. The Stern–Volmer plots as function of NB, 1,3-DNB, 1,3,5-TNB, 2-NP, 4-NP, 2,4-
DNP, PA, SA, 4-NT, 2,4-DNT, TNT, DNAN, TNAN, TATB and DDBu concentration in CH3CN, with an excitation wavelength of 412 nm for 7b solution.
General Papers Arkivoc 2017, v, S1-S15
Page S8 ©ARKAT USA, Inc
Figure S8. Photograph (from the website http://nitroscan.pro.) of the portable sniffer «Nitroscan» for detecting of nitroaromatic explosives in vapor phase (Plant «Promautomatika», Ekaterinburg,
Russia).
General Papers Arkivoc 2017, v, S1-S15
Page S9 ©ARKAT USA, Inc
1H NMR (500 MHz, CDCl3) spectrum of 5.
General Papers Arkivoc 2017, v, S1-S15
Page S10 ©ARKAT USA, Inc
0102030405060708090100110120130140150160170180ppm
-500
0
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1000
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4500
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5500
6000
6500HEM467cmik: A*14433; ~11 mg
31.4
4
34.9
9
76.7
577
.00
77.2
5
118.
98
125.
0712
7.40
129.
1413
0.95
131.
3713
2.25
144.
08
153.
6315
6.63
156.
97
13C NMR (126 MHz, CDCl3) spectrum of 5.
General Papers Arkivoc 2017, v, S1-S15
Page S11 ©ARKAT USA, Inc
1H NMR (500 MHz, CDCl3) spectrum of 7a.
General Papers Arkivoc 2017, v, S1-S15
Page S12 ©ARKAT USA, Inc
0102030405060708090100110120130140150160170180ppm
-2000
-1000
0
1000
2000
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9000
10000
11000
12000
13000
14000
15000
16000
17000
18000
19000
20000
21000
22000
23000HEM474ema: A*15706; 7 mg
31.5
1
34.9
6
76.7
477
.00
77.2
5
123.
0312
3.07
123.
3712
4.79
126.
6212
7.21
127.
4412
8.44
128.
5312
9.35
131.
9013
1.93
132.
0513
2.13
132.
2713
3.47
140.
87
147.
2714
7.97
148.
62
156.
6415
7.45
13C NMR (126 MHz, CDCl3) spectrum of 7a.
General Papers Arkivoc 2017, v, S1-S15
Page S13 ©ARKAT USA, Inc
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0ppm
0
5000
10000
15000
20000
25000
30000
HEM4682bema: A*14009
6.03
9.06
4.00
2.02
2.01
2.11
4.01
2.03
2.03
3.03
1.01
2.01
2.01
1.00
-0.0
0
1.42
1.44
1.45
1.52
4.34
4.35
4.37
4.38
6.44
6.45
7.09
7.10
7.25
7.36
7.38
7.41
7.48
7.68
7.70
7.70
8.06
8.08
8.32
8.32
9.10
1H NMR (500 MHz, CDCl3) spectrum of 7b.
General Papers Arkivoc 2017, v, S1-S15
Page S14 ©ARKAT USA, Inc
0102030405060708090100110120130140150160170ppm
-5000
0
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15000
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35000
40000
45000
50000
55000
60000
65000HEM4682bema: A*14010
-0.0
2
13.8
1
31.6
135
.03
37.6
9
76.7
577
.00
77.2
077
.25
108.
7210
8.78
118.
0011
9.28
120.
5312
2.88
122.
8912
3.42
124.
0112
6.12
127.
2512
9.56
132.
40
139.
9314
0.46
140.
57
150.
3715
3.02
156.
7115
7.58
13C NMR (126 MHz, CDCl3) spectrum of 7b.
General Papers Arkivoc 2017, v, S1-S15
Page S15 ©ARKAT USA, Inc
1H NMR (500 MHz, CDCl3) spectrum of 7c.