Post on 09-Aug-2020
1
DOI: 10.1002/adfm.200800947
Fluorimetric �erve Gas Sensing Based on Pyrene Imines Incorporated into Films and Sub-
micron Fibers
By Jeremy M. Rathfon, Zoha M. AL-Badri, Raja Shunmugam, Scott M. Berry, Santosh Pabba,
Robert S. Keynton, Robert W. Cohn, and Gregory #. Tew*
[*] Prof. Gregory N. Tew, Jeremy M. Rathfon, Dr. Zoha M. AL-Badri, Raja Shunmugam
Department of Polymer Science and Engineering
University of Massachusetts Amherst
120 Governors Drive
Amherst, Massachusetts 01003
E-mail: tew@mail.pse.umass.edu
Scott M. Berry, Santosh Pabba, Prof. Robert S. Keynton, Prof. Robert W. Cohn
ElectroOptics Research Institute and Nanotechnology Center
University of Louisville
Louisville, Kentucky 40292
Supporting Information
I. Characterization
II. 1H and
13C �MR
2
I. Characterization
350 400 450 500 550 600 650
0.00
0.01
0.02
0.03
0.04
0.05
0.06
0.07
Absorbance
Wavlength (nm)
No Exposure
Exposed to SAS-Cl
350 400 450 500 550 600 650
0.00
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09BA
Wavlength (nm)
Figure S1. UV-Vis spectra of 1 (A) and 2 (B) in toluene before and after exposure to a large
excess (20 µL) of SAS-Cl.
400 450 500 550 600 650
0.0
0.2
0.4
0.6
0.8
1.0BA
Norm
alized Intensity (a.u.)
Wavelength (nm)
No Exposure
Exposed to SAS-Cl
350 400 450 500 550 600 650
0.00
0.02
0.04
0.06
0.08
0.10
Absorbance
Wavelength (nm)
Figure S2. FL (A) and UV-Vis (B) spectra of 1-pyrenecarboxaldehyde in toluene before and
after exposure to a large excess (20 µL) of SAS-Cl.
3
400 450 500 550 600 650
0.0
0.2
0.4
0.6
0.8
1.0
Norm
alized Intensity (a.u.)
Wavelength (nm)
160 ppmv SAS-Cl
80 ppmv
40 ppmv
20 ppmv
10 ppmv
5 ppmv
2.5 ppmv
No Exposure
Figure S3. The sensitivity of 1, at 1 x 10
-4 wt % in CHCl3, to SAS-Cl.
400 450 500 550 600 650
0.0
0.2
0.4
0.6
0.8
1.0
Norm
alized Intensity (a.u.)
Wavelength (nm)
80 ppmv SAS-Cl
40 ppmv
20 ppmv
10 ppmv
5 ppmv
2.5 ppmv
No Exposure
Figure S4. The sensitivity of 2, at 1 x 10
-4 wt % in toluene, to SAS-Cl.
Figure S5. FOM of a PS film cross
ppmv SAS-Cl). Film formed from a solution of 15 wt % PS
Figure S6. SEM of various electrospun fibers at 1k and 10k (inset) magnification. 15 wt% PS in
DMF containing 0.1 wt% 1 at 12 (A), 16 (B), and 20 (C) kV applied voltage. 20 wt% PS in
DMF containing 0.13 wt% 1 at 12 (D), 16 (E),
4
FOM of a PS film cross-section ~ 34 µm thick with partial exposure to SAS
Film formed from a solution of 15 wt % PS and 0.1 wt % 1 in toluene.
SEM of various electrospun fibers at 1k and 10k (inset) magnification. 15 wt% PS in
at 12 (A), 16 (B), and 20 (C) kV applied voltage. 20 wt% PS in
at 12 (D), 16 (E), and 20 (F) kV applied voltage.
section ~ 34 µm thick with partial exposure to SAS-Cl (~ 5
in toluene.
SEM of various electrospun fibers at 1k and 10k (inset) magnification. 15 wt% PS in
at 12 (A), 16 (B), and 20 (C) kV applied voltage. 20 wt% PS in
5
400 450 500 550 600 650
0.0
0.2
0.4
0.6
0.8
1.0
Norm
alized Intensity (a.u.)
Wavelength (nm)
10 ppmv SAS-Cl
5 ppmv
No Exposure
Figure S7. The sensitivity of 1 to SAS-Cl in electrospun PS fibers, from a solution of 20 wt %
PS and 0.13 wt % 1 in DMF.
II. 1H and
13C �MR
Figure S8.
1H NMR of [2-(3,5-dioxo-10-oxa-4-aza-tricyclo[5.2.1.0
2,6]dec-8-en-4-yl)-ethyl]-
carbamic acid tert-butyl ester in CDCl3.
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0
Chemical Shift (ppm)
9.072.012.052.051.002.002.01
Chloroform-d
7.25
6.48
5.22
4.80 3.613.59
3.57
3.29 3.27
3.25
3.23
2.82
1.37
O
N
O
O NH
O
O
6
Figure S9.
13C NMR of [2-(3,5-dioxo-10-oxa-4-aza-tricyclo[5.2.1.0
2,6]dec-8-en-4-yl)-ethyl]-
carbamic acid tert-butyl ester in CDCl3.
180 160 140 120 100 80 60 40 20 0
Chemical Shift (ppm)
Chloroform-d
176.26
155.87
136.41
80.93
77.44
77.00
76.59 47.33
38.71
38.42
28.27
O
N
O
O NH
O
O
Figure S10. 1H NMR of 1 in CDCl
11 10 9 8
7.071.031.09
Chloroform-d7.98
8.018.03
8.06
8.09
8.15
8.18
8.21
8.43
8.458.87
8.90
9.16
180 160 140
128.58
130.53
131.14
136.38
162.10
176.12
7
in CDCl3.
7 6 5 4 3 2
Chemical Shift (ppm)
2.004.012.002.01
Chloroform-d
2.79
4.01
5.16
6.38
7.25
120 100 80 60 40
Chemical Shift (ppm)
Chloroform-d
39.62
47.35
59.14
76.56
77.00
77.41
80.75
122.82
124.86
125.58
125.79128.58
1 0
20 0
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Figure S11. 13C NMR of 1 in CDCl3.
Figure S12.
1H NMR of 2 in CDCl3.
11 10 9 8 7 6 5 4 3 2 1 0
Chemical Shift (ppm)
6.004.001.077.091.041.08
Chloroform-d
9.24
8.88
8.85
8.55 8.52
8.22
8.19
8.18
8.09
8.07
8.04
8.02
7.99 7.25
3.14 3.12
3.10
1.84
1.82
1.79
1.77
1.75
0.99
0.96
0.94
N
H
2
9
Figure S13.
13C NMR of 2 in CDCl3.
170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0
Chemical Shift (ppm)
Chloroform-d
158.08
132.54
131.26
130.62
129.13
128.46
128.29
127.45
126.02
125.70
125.47
124.92
122.73
77.44
77.00
76.59
76.10
29.03
11.22
N
H
2
10
Figure S14.
1H NMR of 2 exposed to SAS-Cl in CD2Cl2.