Synthesis and characterization of a calix[4]pyrrole functional polystyrene via
“click chemistry” and its use in the extraction of halide anion salts
Abdullah Aydogan
Department of Chemistry, Istanbul Technical University, Istanbul, Turkey
Corresponding author email: aydoganab@itu.edu.tr
Supporting Information
NMR, Mass and FTIR Spectra
Figure S1.
1
H NMR spectrum of 3 recorded in CDCl3. * = Residual solvent.
S2
Figure S2.
13
C NMR spectrum of 3 recorded in CDCl3.
S3
Figure S3.
1
H NMR spectrum of 1 recorded in CD2Cl2.
S4
Figure S4.
1
H NMR spectrum of 1 recorded in CD2Cl2 after exposing to TBAF.
S5
Figure S5.
1
H NMR spectrum of 1 recorded in CD2Cl2 after exposing to TBACl.
S6
Figure S6.
1
H NMR spectrum of P(S-co-CMS) recorded in CD2Cl2 after exposing to TBAF.
S7
Figure S7.
1
H NMR spectrum of P(S-co-CMS) recorded in CD2Cl2 after exposing to TBACl.
S8
Figure S8.
1
H NMR spectrum of P(S-co-CPS) recorded in CD2Cl2 after exposing to TBAF.
S9
Figure S9.
1
H NMR spectrum of P(S-co-CPS) recorded in CD2Cl2 after exposing to TBACl.
S10
090923-AA-ITU-MONOALKIN-1-ESI
Kutle Lab. Sira No:
CH2Cl2 0.2 ml/dakMeOH
9/23/2009 1:58:33 PM
I.U.Ileri Analizler Lab Kayit No:
090923-AA-ITU-MONOALKIN-1-ESI #1344-1430 RT: 23.22-23.58 AV: 69 NL: 2.83E6
F: - c ESI Full ms2 537.00@20.00 [ 145.00-1000.00]
467.35
100
90
80
70
537.29
60
50
40
30
20
10
438.47 485.42
0
200
300
400
500
596.90 632.23
600
m/z
700
800
090923-AA-ITU-MONOALKIN-1-ESI#1362-1430 RT: 23.22-23.58 AV: 69
F: - c ESI Full ms2 537.00@20.00 [ 145.00-1000.00]
m/z= 160.00-1000.00
Figure
S10.
ESI Mass spectrum of 3.
m/z
Intensity Relative
438.47
448.1
0.02
466.70
2376.8
0.08
467.35 2831162.7
100.00
468.39
1693.3
0.06
485.42
20698.0
0.73
486.05
0.4
0.00
527.01
448.5
0.02
536.54
5195.2
0.18
537.29 1798127.3
63.51
538.36
747.7
0.03
561.27
631.5
0.02
595.90
302.5
0.01
596.90
1440.8
0.05
628.67
486.7
0.02
632.23
1096.9
0.04
# 1344 Status Log Time: 23.09
API SOURCE
Source Voltage (kV):
Source Current (uA):
Vaporizer Thermocouple OK:
Vaporizer Temp (C):
Sheath Gas Flow Rate ():
Aux/Sweep Gas Flow Rate():
Figure
S11. FTIR spectrum of
Capillary RTD OK:
Capillary Voltage (V):
Capillary Temp (C):
Tube Lens Voltage (V, set po
4.03
0.34
No
1.60
39.45
3. 19.71
Yes
-39.89
300.40
-15.00
S11
900
1000
GPC Chromatogram
P(S-co-CMS)
P(S-co-CPS)
10
15
20
25
30
35
Elution time (min.)
Figure S12.
GPC traces of P(S-co-CMS) and P(S-co-CPS).
S12
Quantification of 4 Using UV/Vis Spectroscopy
Quantification of the dye 4 extracted from the aqueous phase was determined by measuring the
amount of the dye remain using UV/Vis spectroscopy. Calibration curve was generated using
standardized solutions of 4, independently, in water. The results are summarized in tables and
figures below. Using this procedure, the error in the concentrations of 4 measured after extraction
described is estimated to be less than 0.02 M.
Table S1. Absorbance values (left) and UV/Vis spectra (right) of standardized dye solution.
0.6
4
Absorbance
(630 nm)
0.000
1.667
0.037
3.330
0.075
6.670
0.174
13.33
0.372
20.00
1.543
0.5
0.4
Absorbance
Concentration
(M)
0.000
20 um
13.33um
6.67um
3.33um
1.667 um
0.3
0.2
0.1
0.0
500
600
700
800
Wavelenghth (nm)
0.6
0.5
Absorbance
0.4
y = a + b*x
Equation
No Weighting
Weight
Residual Sum 3.01772E4
of Squares
0.99934
Pearson's r
0.99836
Adj. R-Square
Value Standard Err
Intercept
-0.0079
0.00518
Absorbance
Slope
0.0277 5.02657E-4
0.3
0.2
0.1
0.0
0
10
20
Conc. (mM)
Figure S13.
Calibration curve generated by measuring the absorbance values at 630 nm
produced by standardized solutions of 4.
S13
Table S2. Summary of extraction data.
4
Absorbance Concentration Remaining
Extracted
Extracted
(630 nm)
(M)
(M)
(M)
(%)
CH2Cl2
0.044
1.9
9.5
10.5
52.5
1
0.041
1.77
8.86
11.14
55.7
P(S-co-CMS)
0.054
2.25
11.26
8.74
43.7
1 + P(S-co-CMS)
0.039
1.71
8.59
11.41
57.1
P(S-co-CPS)
0.002
0.36
1.82
18.18
90.9
S14
Thermogravimetric Analyses
The thermal properties of P(S-co-CMS) and P(S-co-CPS) were compared pre- and postextraction. Extractions were performed in a manner analogous to the NMR experiments. Prior to
analysis, the extractant solutions were evaporated to dryness, dissolved in CH2Cl2, filtered (using
0.45 m PTFE filters), and then dried under high vacuum.
100
Mass (%)
80
60
40
20
0
0
100
200
300
400
500
600
700
800
Temp (C)
Figure S14.
Thermogravigram of P(S-co-CMS) taken under an atmosphere of nitrogen at a
scan rate = 20 °C/min.
100
Mass (%)
80
60
40
20
0
0
100
200
300
400
500
600
700
800
Temp. (C)
Figure S15.
Thermogravigram of P(S-co-CMS) taken under an atmosphere of nitrogen at a
scan rate = 20 °C/min after exposing to TBAF.
S15
100
Mass (%)
80
60
40
20
0
0
100
200
300
400
500
600
700
800
Temp. (C)
Figure S16.
Thermogravigram of P(S-co-CMS) taken under an atmosphere of nitrogen at a
scan rate = 20 °C/min after exposing to TBACl.
100
Mass (%)
80
60
40
20
0
100
200
300
400
500
600
700
800
Temp. (C)
Figure S17.
Thermogravigram of P(S-co-CPS) taken under an atmosphere of nitrogen at a scan
rate = 20 °C/min
S16
100
Mass (%)
80
60
40
20
0
100
200
300
400
500
600
700
800
Temp. (C)
Figure S18.
Thermogravigram of P(S-co-CPS) taken under an atmosphere of nitrogen at a scan
rate = 20 °C/min after exposing to TBAF.
100
Mass (%)
80
60
40
20
0
0
100
200
300
400
500
600
700
800
Temp. (C)
Figure S19.
Thermogravigram of P(S-co-CPS) taken under an atmosphere of nitrogen at a scan
rate = 20 °C/min after exposing to TBACl.
S17