Scheme S1. - Royal Society of Chemistry · Mariia Pushina, Pavel Anzenbacher,Jr.*_____ Department...
Transcript of Scheme S1. - Royal Society of Chemistry · Mariia Pushina, Pavel Anzenbacher,Jr.*_____ Department...
Supporting information
Biguanides, anion receptors and sensors
Mariia Pushina, Pavel Anzenbacher,Jr.*___________________________________
Department of Chemistry, Bowling Green State University Bowling Green, OH 43403, USA E-mail: [email protected]
Table of Contents 1 General 2 2 Sensors Synthesis 3 Synthesis Schemes 3 Procedures 6 The synthesis of all sensors was based on general method of preparation of biscyanoguanidines. 6 3 Photophysical Properties 14 4 UV-vis absorption Titrations 16 5 Fluorescence Titrations 26 6 Proton NMR titrations 37 7 Stoichiometry determination: Job’s plot 40 8 Paper microzone plates study 43 Qualitative Assay for S1-S6 with different analytes 44 Semi-Quantitative Paper-Based Assay 45 Quantitative Assays 51 9 Competitive titrations of acetate anion in chloride rich solutions 55 Supplemental References 57
Electronic Supplementary Material (ESI) for ChemComm.This journal is © The Royal Society of Chemistry 2017
Supporting information
1 General
Materials and Methods. All chemicals were analytical grade and they were used without purification. NMR. Proton NMR (1H-NMR) and carbon-13 NMR (13C-NMR) spectra were recorded on Bruker Avance III spectrometer at 500 MHz at 348 K. Proton and carbon NMR chemical shifts (δ) are reported in parts per million (ppm) relative to residual solvent signals in DMSO-d6 (δ = 2.50, 39.52). Coupling constants (J) are reported in hertz (Hz) and refer to apparent multiplicities. The following abbreviations are used for the multiplicities: s (singlet), d (doublet), t (triplet), q (quartet), p (pentet), m (multiplet), br (broad). High-Resolution Mass Spectra. High-resolution mass spectra (HRMS) were obtained on Shimadzu AXIMA Performance MALDI TOF mass spectrometer in reflectron mode using Dithranol (CAS 1143-38-0) as a matrix. Absorbance. The absorption spectra were recorded between 250 nm and 550 nm for S1, 250 nm and 500 nm for S2, 250 nm and 450 nm for S3, 250 nm and 500 nm for S4, 250 nm and 500 nm for S5, and 250 nm and 500 nm for S6, respectively. The absorbance from probes was scanned in 2 nm step. Scans were taken under laboratory temperature. The titrations were performed in mixture dimethyl sulfoxide (DMSO):CHCl3 (3:7) with addition of Triton X-100 at laboratory temperature. Titration isotherms were constructed from changes in the absorbance maximum at 420 nm for S1, 317 nm for S2, 280 nm for S3, 400 nm for S4, 315 nm for S5, and 280 nm for S6, respectively. Fluorescence. The emission spectra were recorded between 420 nm and 620 nm for S1, 320 nm and 500 nm for S2, 320 nm and 500 nm for S3, 400 nm and 650 nm for S4, and 320 nm and 500 nm for S6, respectively. The emission from probes was scanned in 2 nm step with appropriate excitation and emission monochromators band pass settings with dwell time 0.20 sec. Scans were taken under laboratory temperature. Fluorescence guest and competitive titrations were performed in mixture DMSO:CHCl3 (3:7) with addition of Triton X-100 at laboratory temperature. Titration isotherms were constructed from changes in the fluorescence maximum at 451 nm for S1, 358 nm for S2, 352 nm for S3, 448 nm for S4, and 351 nm for S6, respectively. Data analysis and curve fitting were performed according to previously published methods1.
2
Supporting information
2 Sensors Synthesis
Synthesis Schemes Scheme S1. Synthesis of intermediate 1: butanol, reflux, 18 h, 82%.
Scheme S2. Synthesis of sensor S1: 1) 2-ethoxyethanol, reflux, 5 h, 43%; 2) H2O, r.t., 34%. Scheme S3. Synthesis of sensor S2: 1) 2-ethoxyethanol, reflux, 5 h, 44%; 2) H2O, r.t., 80%.
+N
H
H 2-ethoxyethanol, refuxed
N N
N N
NH
H
H
H
H
N N
N
H H
H
N
N
H
HMix 1:2
2HCl1
2, 44 %3, 44 %
+
2-ethoxyethanol, refuxed
N H
H
HClN N
N N
NH
H
H
H
H
N N
N
H H
H
N
N
H
H
2HClMix 1:21
3, 43 %2, 44 %
N N
N NH
NH
H
H H
N N
NH
H HN
N
H
H
FB-
F FFNa+
2
BF4
BF4
+
H
H
3
S2, 34 %S1, 34 %
2
N N
N NH
NH
H
H H
N N
NH
H HN
N
H
H
FB-
F FFNa+
2
BF4
BF4
+
H
H
2
S1, 80 %S2, 80 %
3
3
Na+
N-
N NN
NH
HH
H+
butanol, refluxed
NN
H
H
N-
NNC
H
Na+
N-
NCN
H
Na+
2HClMix 1:2
1, 82 %
Supporting information
Scheme S4. Synthesis of sensor S3: 1) 2-ethoxyethanol, reflux, 5 h, 43%; 2) H2O, r.t., 66%.
Scheme S5. Synthesis of intermediate 5: butanol, reflux, 18 h, 62%.
Scheme S6. Synthesis of sensor S4: 1) 2-ethoxyethanol, reflux, 5 h, 37%; 2) H2O, r.t., 63%.
+
2-ethoxyethanol, refuxed
N H
H
HClN N
N
H H
H
N
N
H
H
HCl5
S5, 37 %6, 37 %
N N
NH
H HN
N
H
H
FB-
F FFNa+
2
BF4
+
H
6
S4, 63 %
4
+
2-ethoxyethanol, refuxed
N H
H
HCl N N
N N
NH
H
H
H
H
N N
N
H H
H
N
N
H
H2HCl1
Mix 1:2
4, 43 %
N N
N NH
NH
H
H H
N N
NH
H HN
N
H
H
FB-
F FFNa+
2
BF4
BF4
+
H
H
4
S3, 66 %
Na+
N-
N NN
H
H+
butanol, refluxedNH
N-
NCN
H
Na+
HCl
5, 62 %
Supporting information
Scheme S7. Synthesis of sensor S5: 1) 2-ethoxyethanol, reflux, 3 h, 24%; 2) H2O, r.t., 31%. Scheme S8. Synthesis of sensor S6: 1) 2-ethoxyethanol, reflux, 3 h, 29%; 2) H2O, r.t., 32%.
+N
H
H 2-ethoxyethanol, refuxed
HClN N
N N
NH
H
H
H
H
HCl5
6, 24 %7, 24 %
N N
N NH
NH
H
H H
FB-
F FFNa+
BF4
+
H
6
S4, 31 %
7
S5, 31 %
+ NH
H2-ethoxyethanol, refuxed
HCl N N
N N
NH
H
H
H
H
HCl5
7, 29 %8, 29 %
N N
N NH
NH
H
H H
FB-
F FFNa+
BF4
+H
7
S6, 32 %
8
5
Supporting information
Procedures
The synthesis of all sensors was based on general method of preparation of biscyanoguanidines.2
6-Di-(N3-cyano-N1-guanidino)hexane (1). Commercially available Hexane-1,6-diamine dihydrochloride (2.00 g, 10.6 mmol) and sodium dicyanimide (1.88 g, 21.2 mmol) were powdered together and refluxed in butanol (50 mL) for 18 h. The solvent was removed under reduced pressure and obtained white powder was recrystallized from water. 1,14-Bis(anthracen-1-ylamino)-3,12-diimino-2,4,11,13-tetraazatetradecane-1,14-diiminium tetrafluoroborate (S1). Compound 1 (0.25 g, 1 mmol) was mixed with 2-aminoanthracene hydrochloride (0.46 g, 2 mmol). The mixture was refluxed in 2-ethoxyethanol (5 mL) for 5 h. The solvent was then evaporated on a rotary evaporator. The powder was recrystallized from water. The obtained compound was dissolved in water:DMSO (8:2) and added into saturated solution of NaBF4 in water. The pale yellow precipitate was filtered and dried in vacuum. Spectral data for S1: 1H-NMR (DMSO-d6, 500 MHz): δ = 9.20 (s, 2H), 8.48 (s, 2H), 8.38 (s, 2H), 8.08 – 7.96 (m, 8H), 7.71 – 7.42 (m, 8H), 7.29 (s, 2H), 6.78 (s, 2H), 2.54 (s, 4H), 1.48 (m, 4H), 1.29 (m, 4H). 13C-CPD (DMSO-d6, 125 MHz): δ = 159.52, 154.44, 135.12, 131.42, 131.22, 130.31, 128.37, 127.73, 127.26, 125.54, 125.45, 125.36, 124.68, 124.46, 233.31, 115.84, 41.14, 28.24, 25.68 ppm. HRMS (MALDI) m/z found 637.3444 [M+H]+; calc 637.3499 for C38H41N10+. 1H-NMR spectrum in DMSO-d6 at 500 MHz (Figure S1), and 13C-CPD-NMR spectrum in DMSO-d6 at 125 MHz (Figure S2) for S1 are shown below. 3,12-Diimino-1,14-bis(naphthalen-1-ylamino)-2,4,11,13-tetraazatetradecane-1,14-diiminium tetrafluoroborate (S2). Compound 1 (1.00 g, 4 mmol) was mixed with naphthylamine hydrochloride (1.44 g, 8 mmol). The mixture was refluxed in 2-ethoxyethanol (20 mL) for 5 h. The solvent was then evaporated on a rotary evaporator. The powder was recrystallized from water and 3,12-diimino-1,14-bis(naphthalen-1-ylamino)-2,4,11,13-tetraazatetradecane-1,14-diiminium dihydrochloride was obtained. The compound was dissolved in water and added into saturated solution of NaBF4 in water. The light purple precipitate was filtered and dried in vacuum. Spectral data for S2: 1H-NMR (DMSO-d6, 500 MHz): δ = 9.05 (s, 2H), 8.07 (d, J = 8.0 Hz, 2H), 7.98 – 7.89 (m, 2H), 7.79 (d, J = 8.1 Hz, 2H), 7.62 – 7.48 (m, 8H), 7.33 (s, 2H), 7.04 (s, 3H), 6.84 (s, 3H), 2.98 (d, J = 6.0 Hz, 4H), 1.33 (s, 4H), 1.14 (s, 4H). 13C-CPD (DMSO-d6, 125 MHz): δ = 159.11, 156.26, 133.58, 133.03, 128.44, 127.85, 125.82, 125.79, 125.59, 125.18, 122.63, 122.12, 40.97, 28.12, 25.54 ppm. HRMS (MALDI) m/z found 537.3292 [M+H]+; calc 537.3188 for C30H37N10+. 1H-NMR spectrum in DMSO-d6 at 500 MHz (Figure S3), and 13C-CPD-NMR spectrum in DMSO-d6 at 125 MHz (Figure S4) for S2 are shown below. 3,12-Diimino-1,14-bis(phenylamino)-2,4,11,13-tetraazatetradecane-1,14-diiminium tetrafluoroborate (S3). Compound 1 (1.00 g, 4 mmol) was mixed with aniline hydrochloride (1.04 g, 8 mmol). The mixture was refluxed in 2-ethoxyethanol (5 mL) for 5 h. The solvent was then evaporated on a rotary evaporator. The powder was recrystallized from water. The obtained compound was dissolved in water and added into saturated solution of NaBF4 in water. The precipitate was filtered and dried in vacuum. Spectral data for S3: 1H-NMR (DMSO-d6, 500 MHz): δ = 9.26 (s, 2H), 7.65 (s, 2H), 7.39 – 7.35 (m, 4H), 7.32 – 7.27 (m, 4H), 7.21 (s, 3H), 7.06 (t, J = 7.3 Hz, 3H), 6.76 (s, 3H), 3.08 (s, 4H), 1.51 – 1.44 (m, 4H), 1.30 (m, 4H). 13C-CPD (DMSO-d6, 125 MHz): δ = 159.52, 154.55, 138.22, 128.28, 123.12, 120.74, 41.03, 28.25, 25.60 ppm. HRMS (MALDI) m/z found 437.2706 [M+H]+; calcd 437.2877 for C22H33N10+. 1H-NMR spectrum in DMSO-d6 at 500 MHz (Figure S5), and 13C-CPD-NMR spectrum in DMSO-d6 at 125 MHz (Figure S6) for S3 are shown below. N3-cyano-N1-guanidinohexane (5). Hexylamine hydrochloride (the hexylamine hydrochloride was prepared by bubbling gaseous hydrogen chloride through a dichloromethane solution of hexylamine) (3.14 g, 22.4 mmol) and sodium dicyanimide (2.00 g, 24.4 mmol) were powdered together and refluxed in butanol (60 mL) for 18 h. The solvent was removed under reduced pressure and obtained white powder was recrystallized from water.
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Supporting information
(3-(Anthracen-2-yl)guanidino)(hexylamino)methaniminium hydrochloride (S4). Compound 5 (0.22 g, 1.3 mmol) was mixed with 2-aminoanthracene hydrochloride (0.30 g, 1.3 mmol). The mixture was refluxed in 2-ethoxyethanol (4 mL) for 5 h. The solvent was then evaporated on a rotary evaporator. The pale green powder was recrystallized from water. Spectral data for S4: 1H-NMR (DMSO-d6, 500 MHz): δ = 9.18 (s, 1H), 8.50 (s, 1H), 8.41 (s, 1H), 8.08 – 8.00 (m, 4H), 7.68 – 7.24 (m, 5H), 6.76 (s, 2H), 3.10 (m, 2H) 1.54 – 1.46 (m, 2H), 1.29 (m, 2H), 1.25 (m, 4H), 0.83 (m, 3H). 13C-CPD (DMSO-d6, 125 MHz): δ = 159.31, 154.22, 135.08, 131.15, 130.90, 130.06, 128.09, 127.49, 127.45, 126.99, 125.26, 125.08, 124.41, 124.23, 121.91, 115.58, 40.95, 30.22, 27.90, 25.27, 21.27, 13.09 ppm. HRMS (MALDI) m/z found 362.2452 [M+H]+; calcd 362.2335 for C22H28N5+. 1H-NMR spectrum in DMSO-d6 at 500 MHz (Figure S7), and 13C-CPD-NMR spectrum in DMSO-d6 at 125 MHz (Figure S8) for S4 are shown below. (3-Hexylguanidino)(naphthalen-1-ylamino)methaniminium tetrafluoroborate (S5). Compound 5 (1.00 g, 5.96 mmol) was mixed with naphthylamine hydrochloride (1.07 g, 5.96 mmol). The mixture was refluxed in 2-ethoxyethanol (5 mL) for 3 h. The solvent was then evaporated on a rotary evaporator. The powder was recrystallized from water. The obtained compound was dissolved in water and added into saturated solution of NaBF4 in water. The light purple precipitate was filtered and dried in vacuum. Spectral data for S5: 1H-NMR (DMSO-d6, 500 MHz): δ = 9.04 (s, 1H), 8.06 (d, J = 8.0 Hz, 1H), 8.00 – 7.92 (m, 1H), 7.79 (d, J = 8.1 Hz, 1H), 7.68 – 7.44 (m, 4H), 7.34 (s, 1H), 7.04 (s, 1H), 6.83 (s, 2H), 2.99 (dd, J = 13.1, 6.7 Hz, 2H), 1.48 – 1.06 (m, 8H), 0.85 (t, J = 7.0 Hz, 3H). 13C-CPD (DMSO-d6, 125 MHz): δ = 159.16, 156.24, 133.61, 133.07, 128.46, 127.88, 125.83, 125.79, 125.60, 125.21, 122.64, 122.15, 41.04, 30.50, 28.17, 25.50, 21.58, 13.43 ppm. HRMS (MALDI) m/z found 312.2279 [M+H]+; calcd 312.2179 for C18H26N5+. 1H-NMR spectrum in DMSO-d6 at 500 MHz (Figure S9), and 13C-CPD-NMR spectrum in DMSO-d6 at 125 MHz (Figure S10) for S5 are shown below. (3-Hexylguanidino)(phenylamino)methaniminium tetrafluoroborate (S6). Compound 5 (1.50 g, 8.9 mmol) was mixed with aniline hydrochloride (1.15 g, 8.9 mmol). The mixture was refluxed in 2-ethoxyethanol (10 mL) for 5 h. The solvent was then evaporated on a rotary evaporator. The powder was recrystallized from water. The obtained compound was dissolved in water and added into saturated solution of NaBF4 in water. The precipitate was filtered and dried in vacuum. Spectral data for S6: 1H-NMR (DMSO-d6, 500 MHz): δ = 8.94 (s, 1H), 7.60 – 7.05 (m, 7H), 6.64 (s, 1H), 3.09 (dd, J = 7.1, 5.8 Hz, 2H), 1.47 (dd, J = 14.0, 7.0 Hz, 2H), 1.38 – 1.22 (m, 6H), 0.87 (m, 3H). 13C-CPD (DMSO-d6, 125 MHz): δ = 159.52, 154.41, 138.18, 128.38, 123.32, 121.01, 41.17, 30.53, 28.22, 25.55, 21.60, 13.44 ppm. HRMS (MALDI) m/z found 262.2077 [M+H]+; calcd 262.2024 for C14H24N5+. 1H-NMR spectrum in DMSO-d6 at 500 MHz (Figure S11), and 13C-CPD-NMR spectrum in DMSO-d6 at 125 MHz (Figure S12) for S6 are shown below.
7
Supporting information
Figure S1. Spectral data for S1: 1H-NMR (DMSO-d6, 500 MHz, 348 K).
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8.02
8.04
8.38
8.48
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Figure S2. Spectral data for S1: 13C-NMR (DMSO-d6, 125 MHz, 348 K).
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52
δ ppm
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Supporting information
Figure S3. Spectral data for S2: 1H-NMR (DMSO-d6, 500 MHz, 348 K).
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Figure S4. Spectral data for S2: 13C-NMR (DMSO-d6, 125 MHz, 348 K).
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9.11
δ ppm
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Supporting information
Figure S5. Spectral data for S3: 1H-NMR (DMSO-d6, 500 MHz, 348 K).
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Figure S6. Spectral data for S3: 13C-NMR (DMSO-d6, 125 MHz, 348 K).
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δ ppm
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Supporting information
Figure S7. Spectral data for S4: 1H-NMR (DMSO-d6, 500 MHz, 348 K).
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Figure S8. Spectral data for S4: 13C-NMR (DMSO-d6, 125 MHz, 348 K).
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Supporting information
Figure S9. Spectral data for S5: 1H-NMR (DMSO-d6, 500 MHz, 348 K).
Figure S10. Spectral data for S5: 13C-NMR (DMSO-d6, 125 MHz, 348 K).
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Supporting information
Figure S11. Spectral data for S6: 1H-NMR (DMSO-d6, 500 MHz, 348 K).
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Figure S12. Spectral data for S6: 13C-NMR (DMSO-d6, 125 MHz, 348 K).
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Supporting information
3 Photophysical Properties
The photophysical properties of sensors S1-S6 (Table S1) were measured in mixture DMSO:CHCl3 at room temperature. Absorption spectra were obtained using Hitachi U-3010 double beam UV-visible spectrophotometer (Tokyo, Japan). Fluorescence spectra were acquired at laboratory temperature using a quartz cuvette with 1 cm path length at right angle detection. Emission spectra and fluorescence lifetime measurements were carried out with Edinburgh FLS920-stm combined steady state and lifetime spectrofluorimeter (Edinburgh Instruments Ltd., Livingston, UK). Laser radiation (λ = 355 nm) was used as an excitation source for fluorescence lifetime determination experiments. Absolute quantum yields were obtained upon excitation at absorption maxima using Hamamatsu Quantaurus-QY C11347-11 Absolute PLQY Spectrometer equipped with 150 W xenon lamp and multichannel detector/CCD sensor (Hamamatsu, Japan).
Table S1. Photophysical properties of sensors S1-S6. Absorption and emission maxima (λABS,max, λEM,max, repectively), absolute fluorescence quantum yields ΦFL, fluorescence lifetimes τFL, and molar extinction coefficients εM were acquired in DMSO:CHCl3 (3:7 v/v).
Sensor λABS,maxa λEM,maxb ΦFL (λEXC)c τFL τFL with addition of
Triton X-100 (0.1 mM) [nm] [nm] [%] [ns] [ns]
S1 397 441 47.03 (395 nm) 5.00 (42.90 %) 10.38 (57.10 %)
4.59 (20.65 %) 9.42 (79.35 %)
S2 295 350 37.54 (296 nm) 2.11 (68.24 %) 11.05 (31.76 %)
2.32 (80.14 %) 11.27 (19.86 %)
S3 275 344 1.11 (300 nm) 3.75 (85.42 %) 20.08 (14.58 %)
2.77 (88.93 %) 20.57 (11.07 %)
S4 397 442 41.06 (395 nm) 8.33 (45.15 %) 13.08 (54.85 %)
6.94 (29.71 %) 12.16 (70.29 %)
S5 295 352 6.54 (296 nm) 2.66 (70.40 %) 11.03 (29.60 %)
2.84 (73.75 %) 11.20 (26.25 %)
S6 275 348 1.01 (300 nm) 3.10 (83.10 %) 19.24 (16.90 %)
2.50 (87.16 %) 20.52 (12.84 %)
a Only the lowest energy maxima are listed. b Only the highest energy maxima are listed. c Absolute quantum yields were determined upon excitation at wavelength indicated for solutions with optical density A = 0.2 (all errors < 4%).
14
Supporting information
Figure S13. UV-vis absorption spectra of S1-S6 in DMSO:CHCl3 (3:7) with addition of Triton X-100.
250 300 350 4000
1x104
2x104
3x104 [S2] = 20 µM in DMSO_CHCl3
Wavelength, nm
ε, M
-1 c
m-1
N N
N N
NH
H
H H
N N
N
H HN
N
H
H
H
H
H
H
250 300 350 400 450 500 5500
2x104
4x104
6x104
8x104
1x105
Wavelength, nm
ε, M
-1 c
m-1
[S1] = 20 µM in DMSO_CHCl3
N N
N N
NH
H
H H
N N
N
H HN
N
H
H
HH
HH
250 275 300 325 350 375 4000
1x104
2x104
3x104
Wavelength, nm
ε, M
-1 c
m-1
[S3] = 8.0 µM in DMSO_CHCl3
N N
N NH
N
H
H H
N N
HN
H HN
N
H
HHH
H
250 300 350 400 450 5000
1x104
2x104
3x104
4x104
5x104
6x104
7x104
Wavelength, nm
ε, M
-1 c
m-1
[S4] = 20 µM in DMSO_CHCl3N N
N
H HN
N
H
HH
H
250 300 350 400
5.0x103
1.0x104
1.5x104
2.0x104
2.5x104
Wavelength, nm
ε, M
-1 c
m-1
[S6] = 8 µM in DMSO_CHCl3
N N
N N
NH
H
H H
HH
250 300 350 4000.0
5.0x103
1.0x104
1.5x104
2.0x104
Wavelength, nm
ε, M
-1 c
m-1
[S5] = 20 µM in DMSO_CHCl3
N N
N N
NH
H
H H
HH
15
Supporting information
4 UV-vis absorption Titrations
All UV-vis absorbtion titrations were measured in DMSO:CHCl3 (3:7 v/v) with addition of Triton X-100 (0.36 mM) at room temperature. The absorbance spectra were recorded using a Hitachi U-3010 spectrophotometer. The bathochromic shifts of spectra of sensors S1-S6 upon the titration with anions were used to calculate the binding constants. Titration isotherms were obtained by plotting the change in optical density at a certain wavelength, usually in their absorption maximum against the concentration of the anion. Table S2. Binding affinities Ka (M-2) for sensors S1-S6 to various anions obtained from UV-vis absorption titration in DMSO:CHCl3 (3:7 v/v) at room temperature. NR – no response. ND – Binding constants could not be determined due to more complex equilibria.
Analyte Affinity constant (Ka, M-2 × 104)
S1 S2 S3 S4 S5 S6 Fluoride 2.90 1.70 0.99 1.90 1.40 0.83 Chloride NR NR NR NR NR NR Acetate 37.0 5.80 1.80 12.0 5.20 1.20 Oxalate 49.0 6.80 1.60 19.0 6.70 1.40
Malonate 5.60 2.90 1.10 5.60 2.00 2.90 Glutamate 0.51 0.39 0.27 0.44 0.29 0.54 Benzoate 4.90 0.92 ND 4.30 ND ND Phthalate 0.10 0.74 ND 0.86 ND ND
H2Phosphate 15.0 NR 1.20 8.80 NR NR
Figure S14. Left: Absorption titration spectra and isotherm of S1 (20μM) upon addition of Fluoride anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM). Right: Absorption titration spectra and isotherm of S1 (20μM) upon addition of Acetate anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM).
250 300 350 400 450 500 5500.0
0.5
1.0
1.5
2.0
Wavelength, nm
Abso
rban
ce
Ka = (2.9 ± 0.5)×104 M-2
0 200 400 600 800
0.0
0.2
0.4
0.6
0.8
1.0
[Fluoride], µM
(A -
A 0) / (
A i - A
0)
420 nm
250 300 350 400 450 500 5500.0
0.5
1.0
1.5
2.0
Wavelength, nm
Abso
rban
ce
Ka = (3.7 ± 0.8)×105 M-2
0 100 200 300 400 500
0.0
0.2
0.4
0.6
0.8
1.0
[Acetate], µM
(A -
A 0) / (
A i - A
0)
420 nm
16
Supporting information
Figure S15. Left: Absorption titration spectra and isotherm of S1 (20μM) upon addition of Oxalate anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM). Right: Absorption titration spectra and isotherm of S1 (20μM) upon addition of Malonate anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM).
Figure S16. Left: Absorption titration spectra and isotherm of S1 (20μM) upon addition of Glutamate anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM). Right: Absorption titration spectra and isotherm of S1 (20μM) upon addition of Benzoate anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM).
250 300 350 400 450 500 5500.0
0.5
1.0
1.5
2.0
Wavelength, nm
Abso
rban
ceKa = (4.9 ± 0.4)×105 M-2
0 100 200 300 400 500 600
0.0
0.2
0.4
0.6
0.8
1.0
[Oxalate], µM
(A -
A 0) / (
A i - A
0)
420 nm
250 300 350 400 450 5000.00.20.40.60.81.01.21.41.61.8
Wavelength, nm
Abso
rban
ce
Ka = (5.6 ± 1.1)×104 M-2
0 100 200 300 400 500
0.0
0.2
0.4
0.6
0.8
1.0
[Malonate], µM
(A -
A 0) / (
A i - A
0)
420 nm
250 300 350 400 450 5000.00.20.40.60.81.01.21.41.61.8
Wavelength, nm
Abso
rban
ce
Ka = (5.1 ± 0.5)×103 M-2
0 300 600 900 1200 1500 1800
0.0
0.2
0.4
0.6
0.8
1.0
[Glutamate], µM
(A -
A 0) / (
A i - A
0)
420 nm
250 300 350 400 450 500 5500.0
0.5
1.0
1.5
2.0
Wavelength, nm
Abso
rban
ce
Ka = (4.9 ± 0.6)×104 M-2
0 100 200 300 400 500
0.0
0.2
0.4
0.6
0.8
1.0
[Benzoate], µM
(A -
A 0) / (
A i - A
0)420 nm
17
Supporting information
Figure S17. Left: Absorption titration spectra and isotherm of S1 (20μM) upon addition of Phthalate anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM). Right: Absorption titration spectra and isotherm of S1 (20μM) upon addition of Dihydrogen phosphate anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM).
Figure S18. Left: Absorption titration spectra and isotherm of S1 (20μM) upon addition of Fluoride anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM). Right: Absorption titration spectra and isotherm of S1 (20μM) upon addition of Acetate anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM).
250 300 350 400 450 500 5500.0
0.5
1.0
1.5
2.0
Wavelength, nm
Abso
rban
ceKa = (1.0 ± 0.1)×103 M-2
0 100 200 300 400 500
0.0
0.2
0.4
0.6
0.8
1.0
[Phthalate], µM
(A -
A 0) / (
A i - A
0)
420 nm
250 300 350 400 450 500 5500.0
0.5
1.0
1.5
2.0
Wavelength, nm
Abso
rban
ce
Ka = (1.5 ± 0.2)×105 M-2
0 100 200 300 400 500
0.0
0.2
0.4
0.6
0.8
1.0
[Dihydrogen phosphate], µM
(A -
A 0) / (
A i - A
0)
420 nm
250 300 350 400 450 5000.0
0.2
0.4
0.6
0.8
1.0
Ka = (1.7 ± 0.1)×104 M-1
Wavelength, nm
Abso
rban
ce
0 50 100 150 200 250 300
0.0
0.2
0.4
0.6
0.8
1.0
[Fluoride], µM
(A -
A 0) / (
A i - A
0)
317 nm
250 300 350 400 450 5000.0
0.2
0.4
0.6
0.8
Wavelength, nm
Abso
rban
ce
Ka = (5.8 ± 0.6)×104 M-2
0 50 100 150 200 250
0.0
0.2
0.4
0.6
0.8
1.0
[Acetate], µM
(A -
A 0) / (
A i - A
0)317 nm
18
Supporting information
Figure S19. Left: Absorption titration spectra and isotherm of S2 (20μM) upon addition of Oxalate anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM). Right: Absorption titration spectra and isotherm of S2 (20μM) upon addition of Malonate anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM).
Figure S20. Left: Absorption titration spectra and isotherm of S2 (20μM) upon addition of Glutamate anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM). Right: Absorption titration spectra and isotherm of S2 (20μM) upon addition of Benzoate anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM).
Figure S21. Absorption titration spectra and isotherm of S2 (20μM) upon addition of Phthalate anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM).
250 300 350 400 4500.00.10.20.30.40.50.60.70.8
Ka = (6.8 ± 0.1)×104 M-2
Wavelength, nm
Abso
rban
ce
0 20 40 60 80
0.0
0.2
0.4
0.6
0.8
1.0
325 nm
[Oxalate], µM
(A -
A 0) / (
A i - A
0)
250 300 350 400 450 5000.0
0.2
0.4
0.6
0.8
Wavelength, nm
Abso
rban
ce
Ka = (2.9 ± 0.6)×104 M-2
0 20 40 60 80 100 120
0.0
0.2
0.4
0.6
0.8
1.0
[Malonate], µM
(A -
A 0) / (
A i - A
0)
317 nm
250 300 350 400 450 5000.0
0.2
0.4
0.6
0.8
Wavelength, nm
Abso
rban
ce
Ka = (3.9 ± 0.5)×103 M-2
0 20 40 60 80 100 120 140 160 180
0.0
0.2
0.4
0.6
0.8
1.0
[Glutamate], µM
(A -
A 0) / (
A i - A
0)
317 nm
250 300 350 400 450 5000.0
0.2
0.4
0.6
Wavelength, nm
Abso
rban
ceKa = (9.2 ± 0.5)×103 M-2
0 20 40 60 80 100
0.0
0.2
0.4
0.6
0.8
1.0
[Benzoate], µM
(A -
A 0) / (
A i - A
0)
317 nm
250 300 350 400 450 5000.0
0.2
0.4
0.6
Wavelength, nm
Abso
rban
ce
Ka = (7.4 ± 1.1)×103 M-2
0 100 200 300 400
0.0
0.2
0.4
0.6
0.8
1.0
[Phthalate], µM
(A -
A 0) / (
A i - A
0)
317 nm
19
Supporting information
Figure S22. Left: Absorption titration spectra and isotherm of S3 (8μM) upon addition of Fluoride anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM). Right: Absorption titration spectra and isotherm of S3 (8μM) upon addition of Acetate anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM).
Figure S23. Left: Absorption titration spectra and isotherm of S3 (8μM) upon addition of Oxalate anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM). Right: Absorption titration spectra and isotherm of S3 (8μM) upon addition of Malonate anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM).
250 300 350 400 4500.0
0.1
0.2
0.3
Wavelength, nm
Abso
rban
ceKa = (9.9 ± 1.1)×103 M-2
0 100 200 300 400
0.0
0.2
0.4
0.6
0.8
1.0
(A
- A 0)
/ (A i -
A0)
[Fluoride], µM
280 nm
250 300 350 400 4500.0
0.1
0.2
0.3
0.4
Wavelength, nm
Abso
rban
ce
Ka = (1.8 ± 0.2)×104 M-2
0 100 200 300 400 500
0.0
0.2
0.4
0.6
0.8
1.0
[Acetate], µM
(A -
A 0) / (
A i - A
0)
280 nm
250 300 350 400 4500.0
0.1
0.2
0.3
0.4
Wavelength, nm
Abso
rban
ce
Ka = (1.6 ± 0.2)×104 M-2
0 100 200 300 400 500 600
0.0
0.2
0.4
0.6
0.8
1.0
[Oxalate], µM
(A -
A 0) / (
A i - A
0)
280 nm
250 300 350 400 4500.0
0.1
0.2
0.3
0.4
Wavelength, nm
Abso
rban
ce
Ka = (1.1 ± 0.2)×104 M-2
0 100 200 300 400 500
0.0
0.2
0.4
0.6
0.8
1.0
[Malonate], µM
(A -
A 0) / (
A i - A
0)
280 nm
20
Supporting information
Figure S24. Left: Absorption titration spectra and isotherm of S3 (8μM) upon addition of Glutamate anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM). Right: Absorption titration spectra and isotherm of S3 (8μM) upon addition of Dihydrogen phosphate anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM).
250 300 350 400 4500.0
0.1
0.2
0.3
0.4
Wavelength, nm
Abso
rban
ceKa = (2.7 ± 0.2)×103 M-2
0 100 200 300 400 500 600 700 800
0.0
0.2
0.4
0.6
0.8
1.0
[Glutamate], µM
(A -
A 0) / (
A i - A
0)
280 nm
250 300 350 400 4500.0
0.1
0.2
0.3
Wavelength, nm
Abso
rban
ce
Ka = (1.2 ± 0.1)×104 M-2
0 100 200 300 400 500
0.0
0.2
0.4
0.6
0.8
1.0
[Dihydrogen phosphate], µM
(A -
A 0) / (
A i - A
0)
280 nm
21
Supporting information
Figure S25. Left: Absorption titration spectra and isotherm of S4 (20μM) upon addition of Fluoride anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM). Right: Absorption titration spectra and isotherm of S4 (20μM) upon addition of Acetate anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM).
Figure S26. Left: Absorption titration spectra and isotherm of S4 (20μM) upon addition of Oxalate anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM). Right: Absorption titration spectra and isotherm of S4 (20μM) upon addition of Malonate anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM).
250 300 350 400 450 5000.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
Wavelength, nm
Abso
rban
ceKa = (1.9 ± 0.2)×104 M-2
0 100 200 300 400 500 600 700
0.0
0.2
0.4
0.6
0.8
1.0
[Fluoride], µM
(A -
A 0) / (
A i - A
0)
400 nm
250 300 350 400 450 5000.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
Wavelength, nm
Abso
rban
ce
Ka = (1.2 ± 0.3)×105 M-2
0 100 200 300 400 500
0.0
0.2
0.4
0.6
0.8
1.0
[Acetate], µM
(A -
A 0) / (
A i - A
0)
400 nm
250 300 350 400 450 5000.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
Wavelength, nm
Abso
rban
ce
Ka = (1.9 ± 0.4)×105 M-2
0 100 200 300 400 500
0.0
0.2
0.4
0.6
0.8
1.0
[Oxalate], µM
(A -
A 0) / (
A i - A
0)
400 nm
250 300 350 400 450 500 5500.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
Wavelength, nm
Abso
rban
ce
Ka = (4.8 ± 0.1)×104 M-2
0 100 200 300 400 500
0.0
0.2
0.4
0.6
0.8
1.0
[Malonate], µM
(A -
A 0) / (
A i - A
0)
400 nm
22
Supporting information
Figure S27. Left: Absorption titration spectra and isotherm of S4 (20μM) upon addition of Glutamate anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM). Right: Absorption titration spectra and isotherm of S4 (20μM) upon addition of Benzoate anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM).
Figure S28. Left: Absorption titration spectra and isotherm of S4 (20μM) upon addition of Phthalate anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM). Right: Absorption titration spectra and isotherm of S4 (20μM) upon addition of Dihydrogen phosphate anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM).
250 300 350 400 450 500 5500.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
Wavelength, nm
Abso
rban
ceKa = (1.5 ± 0.2)×105 M-2
0 100 200 300 400 500
0.0
0.2
0.4
0.6
0.8
1.0
[Glutamate], µM
(A -
A 0) / (
A i - A
0)
400 nm
250 300 350 400 450 500 5500.00.20.40.60.81.01.21.41.6
Wavelength, nm
Abso
rban
ce
Ka = (4.3 ± 0.7)×104 M-2
0 100 200 300 400 500
0.0
0.2
0.4
0.6
0.8
1.0
[Benzoate], µM
(A -
A 0) / (
A i - A
0)
400 nm
250 300 350 400 450 500 5500.00.20.40.60.81.01.21.41.61.8
Wavelength, nm
Abso
rban
ce
Ka = (8.6 ± 0.3)×103 M-2
0 100 200 300 400 500
0.0
0.2
0.4
0.6
0.8
1.0
[Phthalate], µM
(A -
A 0) / (
A i - A
0)
400 nm
250 300 350 400 450 500 5500.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
Wavelength, nm
Abso
rban
ce
Ka = (8.8 ± 0.4)×104 M-2
0 100 200 300 400 500 600
0.0
0.2
0.4
0.6
0.8
1.0
[Dihydrogen phosphate], µM
(A -
A 0) / (
A i - A
0)
400 nm
23
Supporting information
Figure S29. Left: Absorption titration spectra and isotherm of S5 (20μM) upon addition of Fluoride anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM). Right: Absorption titration spectra and isotherm of S5 (20μM) upon addition of Acetate anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM).
Figure S30. Left: Absorption titration spectra and isotherm of S5 (20μM) upon addition of Oxalate anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM). Right: Absorption titration spectra and isotherm of S5 (20μM) upon addition of Malonate anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM).
Figure S31. Absorption titration spectra and isotherm of S5 (20μM) upon addition of Glutamate anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM).
250 300 350 400 450 5000.0
0.1
0.2
0.3
0.4
0.5
0.6
Wavelength, nm
Abso
rban
ceKa = (1.4 ± 0.1)×104 M-2
0 200 400 600 800 1000 1200
0.0
0.2
0.4
0.6
0.8
1.0
[Fluoride], µM
(A -
A 0) / (
A i - A
0)
315 nm
250 300 350 400 450 5000.0
0.1
0.2
0.3
0.4
0.5
Wavelength, nm
Abso
rban
ce
Ka = (5.2 ± 0.2)×104 M-2
0 200 400 600 800 1000 1200
0.0
0.2
0.4
0.6
0.8
1.0
[Acetate], µM
(A -
A 0) / (
A i - A
0)
315 nm
250 300 350 400 450 5000.0
0.1
0.2
0.3
0.4
0.5
Wavelength, nm
Abso
rban
ce
Ka = (6.7 ± 0.6)×104 M-2
0 100 200 300 400 500 600 700 800
0.0
0.2
0.4
0.6
0.8
1.0
[Oxalate], µM
(A -
A 0) / (
A i - A
0)
315 nm
250 300 350 400 450 5000.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
Wavelength, nm
Abso
rban
ce
Ka = (2.0 ± 0.1)×104 M-2
0 200 400 600 800 1000 1200 1400
0.0
0.2
0.4
0.6
0.8
1.0
[Malonate], µM
(A -
A 0) / (
A i - A
0)
315 nm
250 300 350 400 4500.0
0.1
0.2
0.3
0.4
0.5
0.6
Wavelength, nm
Abso
rban
ce
Ka = (2.9 ± 0.9)×103 M-2
0 200 400 600 800 1000
0.0
0.2
0.4
0.6
0.8
1.0
[Glutamate], µM
(A -
A 0) / (
A i - A
0)
315 nm
24
Supporting information
Figure S32. Left: Absorption titration spectra and isotherm of S6 (8μM) upon addition of Fluoride anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM). Right: Absorption titration spectra and isotherm of S6 (8μM) upon addition of Acetate anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM).
Figure S33. Left: Absorption titration spectra and isotherm of S6 (8μM) upon addition of Oxalate anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM). Right: Absorption titration spectra and isotherm of S6 (8μM) upon addition of Malonate anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM)
Figure S34. Absorption titration spectra and isotherm of S6 (8μM) upon addition of Glutamate anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM).
250 300 350 400 450 5000.00
0.05
0.10
0.15
0.20
Wavelength, nm
Abso
rban
ceKa = (8.3 ± 1.0)×103 M-2
0 100 200 300 400 500 600 700 800
0.0
0.2
0.4
0.6
0.8
1.0
[Fluoride], µM
(A -
A 0) / (
A i - A
0)
280 nm
250 300 350 400 450 500
0.05
0.10
0.15
0.20
0.25
Wavelength, nm
Abso
rban
ce
Ka = (1.2 ± 0.2)×104 M-2
0 20 40 60 80 100 120 140 160
0.0
0.2
0.4
0.6
0.8
1.0
[Acetate], µM
(A -
A 0) / (
A i - A
0)
280 nm
250 300 350 400 450 500
0.05
0.10
0.15
0.20
Wavelength, nm
Abso
rban
ce
Ka = (1.4 ± 0.2)×104 M-2
0 10 20 30 40 50 60 70 80
0.0
0.2
0.4
0.6
0.8
1.0
[Oxalate], µM
(A -
A 0) / (
A i - A
0)
280 nm
250 300 350 400 450 500
0.05
0.10
0.15
0.20
0.25
Wavelength, nm
Abso
rban
ceKa = (2.9 ± 0.1)×104 M-2
0 20 40 60 80 100 120 140 160
0.0
0.2
0.4
0.6
0.8
1.0
[Malonate], µM
(A -
A 0) / (
A i - A
0)
280 nm
250 300 350 400 450 500
0.05
0.10
0.15
0.20
0.25
Wavelength, nm
Abso
rban
ce
Ka = (2.7 ± 0.2)×105 M-2
0 20 40 60 80 100 120 140 160
0.0
0.2
0.4
0.6
0.8
1.0
[Glutamate], µM
(A -
A 0) / (
A i - A
0)
280 nm
25
Supporting information
5 Fluorescence Titrations
All fluorescence titrations were measured in DMSO:CHCl3 (3:7 v/v) with addition of Triton X-100 (0.36 mM) at room temperature using a quartz fluorescence cuvette (Starna Cells) with 1 cm path length at right angle detection on Edinburgh FLS920-stm steady state spectrofluorimeter (Edinburgh Instruments Ltd., Livingston, UK). The titrations were carried as follows. The sensor solutions (2.5 mL) in DMSO:CHCl3 (3:7 v/v) with Triton X-100 (0.36 mM) in cuvette were titrated with stock solution of various anions (62.5 mM in DMSO:CHCl3 (3:7 v/v)) and the change in fluorescence intensity was recorded. Table S3. Binding affinities Ka (M-2) for sensors S1-S6 to various anions obtained from fluorescence titration in DMSO:CHCl3 (3:7 v/v) with addition of Triton X-100 (0.36 mM) at room temperature.
Analyte Affinity constant (Ka, M-2 × 104)
S1 S2 S3 S4 S5 S6 Fluoride 10.0 6.90 1.40 6.30 ND 1.00 Chloride 5.80 0.12 NR NR NR NR Acetate 51.0 11.0 3.30 12.0 ND 3.30 Oxalate 41.0 12.0 4.10 19.0 ND 1.70
Malonate 14.0 5.50 2.60 4.80 ND 3.00 Glutamate 1.30 0.87 0.57 4.40 ND 0.28 Benzoate 7.80 5.00 0.66 4.30 ND 3.10 Phthalate 0.48 3.80 0.30 0.86 ND 1.70
H2Phosphate 35.0 ND 0.48 8.80 ND 2.20
Figure S35. Left: Fluorescence titration spectra (λex=375 nm) and isotherm of S1 (0.2 μM) upon addition of Fluoride anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM). Right: Fluorescence titration spectra (λex=375 nm) and isotherm of S1 (0.2 μM) upon addition of Acetate anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM).
450 500 550 6001x105
2x105
3x105
4x105
5x105
Fl. I
nten
sity
, a.u
.
Wavelength, nm
Ka = (1.0 ± 0.1)×105 M-2
0 2 4 6 8 10 12
0.0
0.2
0.4
0.6
0.8
1.0
[Fluoride], µM
(I 0 - I)
/ (I 0 -
I i)
451 nm
450 500 550 600
1x105
2x105
3x105
4x105
5x105
6x105
Wavelength, nm
Fl. I
nten
sity
, a.u
.
Ka = (5.1 ± 1.0)×105 M-2
0 20 40 60 80 100 120 140 160
0.0
0.2
0.4
0.6
0.8
1.0
[Acetate], µM
(I 0 - I)
/ (I 0 -
I i)
451 nm
26
Supporting information
Figure S36. Left: Fluorescence titration spectra (λex=375 nm) and isotherm of S1 (0.2 μM) upon addition of Oxalate anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM). Right: Fluorescence titration spectra (λex=375 nm) and isotherm of S1 (0.2 μM) upon addition of Malonate anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM).
Figure S37. Left: Fluorescence titration spectra (λex=375 nm) and isotherm of S1 (0.2 μM) upon addition of Glutamate anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM). Right: Fluorescence titration spectra (λex=375 nm) and isotherm of S1 (0.2 μM) upon addition of Benzoate anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM).
450 500 550 600
1x105
2x105
3x105
4x105
5x105
6x105
7x105Fl
. Int
ensi
ty, a
.u.
Wavelength, nm
Ka = (4.1 ± 0.2)×105 M-2
0 5 10 15 20 25 30 35 40
0.0
0.2
0.4
0.6
0.8
1.0
[Oxalate], µM
(I 0 - I)
/ (I 0 -
I i)
451 nm
450 500 550 600
1x105
2x105
3x105
4x105
5x105
Fl. I
nten
sity
, a.u
.
Wavelength, nm
Ka = (1.4 ± 0.2)×105 M-2
0 10 20 30 40 50 60 70 80
0.0
0.2
0.4
0.6
0.8
1.0
[Malonate], µM
(I 0 - I)
/ (I 0 -
I i)
451 nm
0 5 10 15 20 25 30 35
0.0
0.2
0.4
0.6
0.8
1.0
[Glutamate], µM
(I 0 - I)
/ (I 0 -
I i)
451 nm
450 500 550 600
1x105
2x105
3x105
4x105
5x105
Fl. I
nten
sity
, a.u
.
Wavelength, nm
Ka = (1.3 ± 0.2)×104 M-2
450 500 550 600
1x105
2x105
3x105
4x105
5x105
Fl. I
nten
sity
, a.u
.
Wavelength, nm
Ka = (7.8 ± 0.9)×104 M-2
0 10 20 30 40 50 60 70 80
0.0
0.2
0.4
0.6
0.8
1.0
[Benzoate], µM
(I 0 - I)
/ (I 0 -
I i)
451 nm
27
Supporting information
Figure S38. Left: Fluorescence titration spectra (λex=375 nm) and isotherm of S1 (0.2 μM) upon addition of Phthalate anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM). Right: Fluorescence titration spectra (λex=375 nm) and isotherm of S1 (0.2 μM) upon addition of Dihydrogen phosphate anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM).
Figure S39. Left: Fluorescence titration spectra (λex=305 nm) and isotherm of S2 (20μM) upon addition of Fluoride anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM). Right: Fluorescence titration spectra (λex=305 nm) and isotherm of S2 (20μM) upon addition of Acetate anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM).
450 500 550 600
1x105
2x105
3x105
4x105
5x105
6x105Fl
. Int
ensi
ty, a
.u.
Wavelength, nm
Ka = (4.8 ± 0.9)×103 M-2
0 5 10 15 20 25 30 35 40 45
0.0
0.2
0.4
0.6
0.8
1.0
[Phthalate], µM
(I 0 - I)
/ (I 0 -
I i)
451 nm
450 500 550 600
1x105
2x105
3x105
4x105
5x105
6x105
Fl. I
nten
sity
, a.u
.
Wavelength, nm
Ka = (3.5 ± 0.9)×105 M-2
0 2 4 6 8 10 12 14 16
0.0
0.2
0.4
0.6
0.8
1.0
[Dihydrogen phosphate], µM
(I 0 - I)
/ (I 0 -
I i)
451 nm
320 340 360 380 400 420 440 460 480 500
5.0x104
1.0x105
1.5x105
2.0x105
2.5x105
3.0x105
3.5x105
Fl. I
nten
sity
, a.u
.
Wavelength, nm
Ka = (6.9 ± 0.5)×104 M-2
0 20 40 60 80 100
0.0
0.2
0.4
0.6
0.8
1.0
[Fluoride], µM
(I 0 - I)
/ (I 0 -
I i)
358 nm
325 350 375 400 425 450 475 500
5.0x104
1.0x105
1.5x105
2.0x105
2.5x105
3.0x105
3.5x105
Fl. I
nten
sity
, a.u
.
Wavelength, nm
Ka = (1.1 ± 0.1)×105 M-2
10 20 30 40 50 60 70 80 90 100
0.0
0.2
0.4
0.6
0.8
1.0
[Acetate], µM
(I 0 - I)
/ (I 0 -
I i)
40 60 80 100
-0.00016
-0.00012
-0.00008
[Acetate], µM
[Ace
tate
] / (I
/I 0 - 1
)
28
Supporting information
Figure S40. Left: Fluorescence titration spectra (λex=305 nm) and isotherm of S2 (20μM) upon addition of Oxalate anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM). Right: Fluorescence titration spectra (λex=305 nm) and isotherm of S2 (20μM) upon addition of Malonate anion in DMSO:CHCl3 (3:7,
v/v) with Triton X-100 (0.36mM).
Figure S41. Left: Fluorescence titration spectra (λex=305 nm) and isotherm of S2 (20μM) upon addition of Glutamate anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM). Right: Fluorescence titration spectra (λex=305 nm) and isotherm of S2 (20μM) upon addition of Benzoate anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM).
325 350 375 400 425 450 475 500
1x105
2x105
3x105
4x105
5x105
Fl. I
nten
sity
, a.u
.
Wavelength, nm
Ka = (1.2 ± 0.1)×105 M-2
0 50 100 150 200 250
0.0
0.2
0.4
0.6
0.8
1.0
[Oxalate], µM
(I 0 - I)
/ (I 0 -
I i)
358 nm
325 350 375 400 425 450 475 500
1x105
2x105
3x105
4x105
5x105
Ka = (5.5 ± 0.8)×104 M-2
Fl. I
nten
sity
, a.u
.
Wavelength, nm
0 20 40 60 80 100 120 140
0.0
0.2
0.4
0.6
0.8
1.0
[Malonate], µM
(I 0 - I)
/ (I 0 -
I i)
358 nm
325 350 375 400 425 450 475 500
1x105
2x105
3x105
4x105
5x105
Fl. I
nten
sity
, a.u
.
Wavelength, nm
Ka = (8.7 ± 0.8)×103 M-2
0 20 40 60 80 100 120 140 160
0.0
0.2
0.4
0.6
0.8
1.0
[Glutamate], µM
(I 0 - I)
/ (I 0 -
I i)
358 nm
325 350 375 400 425 450 475 500
1x105
2x105
3x105
4x105
5x105
Fl. I
nten
sity
, a.u
.
Wavelength, nm
Ka = (5.0 ± 0.1)×104 M-2
0 20 40 60 80 100 120 140 160
0.0
0.2
0.4
0.6
0.8
1.0
[Benzoate], µM
(I 0 - I)
/ (I 0 -
I i)
358 nm
29
Supporting information
Figure S42. Left: Fluorescence titration spectra (λex=305 nm) and isotherm of S2 (20μM) upon addition of Phthalate anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM). Right: Fluorescence titration spectra (λex=305 nm) and isotherm of S2 (20μM) upon addition of Dihydrogen phosphate anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM).
Figure S43. Left: Fluorescence titration spectra (λex=315 nm) and isotherm of S3 (8 μM) upon addition of Fluoride anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM). Right: Fluorescence titration spectra (λex=315 nm) and isotherm of S3 (8 μM) upon addition of Acetate anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM).
325 350 375 400 425 450 475 500
1x105
2x105
3x105
4x105
5x105Fl
. Int
ensi
ty, a
.u.
Wavelength, nm
Ka = (3.8 ± 0.2)×104 M-1
0 50 100 150 200 250 300 350 400
0.0
0.2
0.4
0.6
0.8
1.0
[Phthalate], µM
(I 0 - I)
/ (I 0 -
I i)
0.00018 0.00024 0.00030 0.00036-0.0005
-0.0004
-0.0003
[Phthalate], M
[Pht
hala
te] /
(I/I 0 -
1)
325 350 375 400 425 450 475 500
1x105
2x105
3x105
4x105
5x105
Fl. I
nten
sity
, a.u
.
Wavelength, nm
Ka = ND
0 20 40 60 80 100 120 140 160 180
0.0
0.2
0.4
0.6
0.8
1.0
[Dihydrogen phosphate], µM
(I 0 - I)
/ (I 0 -
I i)
358 nm
350 400 450 5002x105
4x105
6x105
8x105
1x106
Fl. I
nten
sity
, a.u
.
Wavelength, nm
Ka = (1.4 ± 0.1)×104 M-2
0 200 400 600 800 100012001400
0.0
0.2
0.4
0.6
0.8
1.0
[Fluoride], µM
(I 0 - I)
/ (I 0 -
I i)
352 nm
350 400 450 5002.0x105
4.0x105
6.0x105
8.0x105
1.0x106
1.2x106
1.4x106
Fl. I
nten
sity
, a.u
.
Wavelength, nm
Ka = (3.3 ± 0.7)×104 M-2
0 200 400 600 800 1000
0.0
0.2
0.4
0.6
0.8
1.0
352 nm
[Acetate], µM
(I 0 - I)
/ (I 0 -
I i)
30
Supporting information
Figure S44. Left: Fluorescence titration spectra (λex=315 nm) and isotherm of S3 (8 μM) upon addition of Oxalate anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM). Right: Fluorescence titration spectra (λex=315 nm) and isotherm of S3 (8 μM) upon addition of Malonate anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM).
Figure S45. Left: Fluorescence titration spectra (λex=315 nm) and isotherm of S3 (8 μM) upon addition of Glutamate anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM). Right: Fluorescence titration spectra (λex=315 nm) and isotherm of S3 (8 μM) upon addition of Benzoate anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM).
350 400 450 5002x105
4x105
6x105
8x105
1x106
Fl. I
nten
sity
, a.u
.
Wavelength, nm
Ka = (4.1 ± 1.0)×104 M-2
0 100 200 300 400 500
0.0
0.2
0.4
0.6
0.8
1.0
352 nm
[Oxalate], µM
(I 0 - I)
/ (I 0 -
I i)
350 400 450 500
2x105
3x105
4x105
5x105
6x105
7x105
8x105
Fl. I
nten
sity
, a.u
.
Wavelength, nm
Ka = (2.6 ± 0.2)×104 M-2
0 200 400 600 800 1000
0.0
0.2
0.4
0.6
0.8
1.0
352 nm
[Malonate], µM
(I 0 - I)
/ (I 0 -
I i)
350 400 450 5002x105
3x105
4x105
5x105
6x105
7x105
8x105
Fl. I
nten
sity
, a.u
.
Wavelength, nm
Ka = (5.7 ± 1.0)×103 M-2
0 200 400 600 800 1000 1200
0.0
0.2
0.4
0.6
0.8
1.0
352 nm
[Glutamate], µM
(I 0 - I)
/ (I 0 -
I i)
350 400 450 500
4x105
6x105
8x105
1x106
Fl. I
nten
sity
, a.u
.
Wavelength, nm
Ka = (6.6 ± 0.4)×103 M-2
0 200 400 600 800 1000
0.0
0.2
0.4
0.6
0.8
1.0
352 nm
[Benzoate], µM
(I 0 - I)
/ (I 0 -
I i)
31
Supporting information
Figure S46. Left: Fluorescence titration spectra (λex=315 nm) and isotherm of S3 (8 μM) upon addition of Phthalate anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM). Right: Fluorescence titration spectra (λex=315 nm) and isotherm of S3 (8 μM) upon addition of Dihydrogen phosphate anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM).
Figure S47. Left: Fluorescence titration spectra (λex=375 nm) and isotherm of S4 (0.2 μM) upon addition of Fluoride anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM). Right: Fluorescence titration spectra (λex=375 nm) and isotherm of S4 (0.2 μM) upon addition of Acetate anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM).
350 400 450 5002x105
4x105
6x105
8x105
1x106
Fl. I
nten
sity
, a.u
.
Wavelength, nm
Ka = (3.0 ± 0.2)×103 M-2
0 200 400 600 800 100012001400
0.0
0.2
0.4
0.6
0.8
1.0
352 nm
[Phthalate], µM
(I 0 - I)
/ (I 0 -
I i)
350 400 450 5002x105
3x105
4x105
5x105
6x105
7x105
8x105
Fl. I
nten
sity
, a.u
.
Wavelength, nm
Ka = (4.8 ± 0.4)×103 M-2
0 200 400 600 800 1000 1200
0.0
0.2
0.4
0.6
0.8
1.0
352 nm
[Dihydrogen phosphate], µM
(I 0 - I)
/ (I 0 -
I i)
400 450 500 550 600 650
1x105
2x105
3x105
4x105
5x105
Fl. I
nten
sity
, a.u
.
Wavelength, nm
Ka = (6.3 ± 0.8)×104 M-2
0 20 40 60 80 100 120 140 160
0.0
0.2
0.4
0.6
0.8
1.0
[Fluoride], µM
(I 0 - I)
/ (I 0 -
I i)
448 nm
400 450 500 550 600 650
1x105
2x105
3x105
4x105
5x105
6x105
Fl. I
nten
sity
, a.u
.
Wavelength, nm
Ka = (2.7 ± 0.6)×105 M-2
0 50 100 150 200
0.0
0.2
0.4
0.6
0.8
1.0
448 nm
[Acetate], µM
(I 0 - I)
/ (I 0 -
I i)
32
Supporting information
Figure S48. Left: Fluorescence titration spectra (λex=375 nm) and isotherm of S4 (0.2 μM) upon addition of Oxalate anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM). Right: Fluorescence titration spectra (λex=375 nm) and isotherm of S4 (0.2 μM) upon addition of Malonate anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM).
Figure S49. Left: Fluorescence titration spectra (λex=375 nm) and isotherm of S4 (0.2 μM) upon addition of Glutamate anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM). Right: Fluorescence titration spectra (λex=375 nm) and isotherm of S4 (0.2 μM) upon addition of Benzoate anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM).
400 450 500 550 600 650
1x105
2x105
3x105
4x105
5x105
Fl. I
nten
sity
, a.u
.
Wavelength, nm
Ka = (3.1 ± 0.1)×105 M-2
0 20 40 60 80 100 120 140 160
0.0
0.2
0.4
0.6
0.8
1.0
448 nm
[Oxalate], µM
(I 0 - I)
/ (I 0 -
I i)
400 450 500 550 600 650
1x105
2x105
3x105
4x105
5x105
Fl. I
nten
sity
, a.u
.
Wavelength, nm
Ka = (7.7 ± 0.4)×104 M-2
0 20 40 60 80 100 120 140
0.0
0.2
0.4
0.6
0.8
1.0
448 nm
[Malonate], µM
(I 0 - I)
/ (I 0 -
I i)
400 450 500 550 600 650
1x105
2x105
3x105
4x105
5x105
6x105
Fl. I
nten
sity
, a.u
.
Wavelength, nm
Ka = (1.3 ± 0.2)×104 M-2
0 50 100 150 200
0.0
0.2
0.4
0.6
0.8
1.0
448 nm
[Glutamate], µM
(I 0 - I)
/ (I 0 -
I i)
400 450 500 550 600 650
1x105
2x105
3x105
4x105
Fl. I
nten
sity
, a.u
.
Wavelength, nm
Ka = (6.1 ± 0.4)×104 M-2
0 50 100 150 200 250
0.0
0.2
0.4
0.6
0.8
1.0
448 nm
[Benzoate], µM
(I 0 - I)
/ (I 0 -
I i)
33
Supporting information
Figure S50. Left: Fluorescence titration spectra (λex=375 nm) and isotherm of S4 (0.2 μM) upon addition of Phthalate anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM). Right: Fluorescence titration spectra (λex=375 nm) and isotherm of S4 (0.2 μM) upon addition of Dihydrogen phosphate anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM).
Figure S51. Left: Fluorescence titration spectra (λex=315 nm) and isotherm of S6 (8 μM) upon addition of Fluoride anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM). Right: Fluorescence titration spectra (λex=315 nm) and isotherm of S6 (8 μM) upon addition of Acetate anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM).
400 450 500 550 600 650
2x105
4x105
6x105
8x105Fl
. Int
ensi
ty, a
.u.
Wavelength, nm
Ka = (1.1 ± 0.1)×104 M-2
0 50 100 150 200 250 300
0.0
0.2
0.4
0.6
0.8
1.0
448 nm
[Phthalate], µM
(I 0 - I)
/ (I 0 -
I i)
400 450 500 550 600 650
1x105
2x105
3x105
4x105
5x105
6x105
Fl. I
nten
sity
, a.u
.
Wavelength, nm
Ka = (1.9 ± 0.2)×105 M-2
0 50 100 150 200 250 300
0.0
0.2
0.4
0.6
0.8
1.0
448 nm
[Dihydrogen phosphate], µM
(I 0 - I)
/ (I 0 -
I i)
350 400 450 500
4x105
6x105
8x105
1x106
Fl. I
nten
sity
, a.u
.
Wavelength, nm
Ka = (1.0 ± 0.2)×104 M-2
0 200 400 600 800 1000
0.0
0.2
0.4
0.6
0.8
1.0
[Fluoride], µM
(I 0 - I)
/ (I 0 -
I i)
351 nm
350 400 450
4x105
6x105
8x105
1x106
Fl. I
nten
sity
, a.u
.
Wavelength, nm
Ka = (3.3 ± 0.2)×104 M-2
0 200 400 600 800 1000
0.0
0.2
0.4
0.6
0.8
1.0
351 nm
[Acetate], µM(I 0 -
I) /
(I 0 - I i)
34
Supporting information
Figure S52. Left: Fluorescence titration spectra (λex=315 nm) and isotherm of S6 (8 μM) upon addition of Oxalate anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM). Right: Fluorescence titration spectra (λex=315 nm) and isotherm of S6 (8 μM) upon addition of Malonate anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM).
Figure S53. Left: Fluorescence titration spectra (λex=315 nm) and isotherm of S6 (8 μM) upon addition of Glutamate anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM). Right: Fluorescence titration spectra (λex=315 nm) and isotherm of S6 (8 μM) upon addition of Benzoate anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM).
340 360 380 400 420 440 460 480 500
2x105
4x105
6x105
8x105
1x106Fl
. Int
ensi
ty, a
.u.
Wavelength, nm
Ka = (1.7 ± 0.3)×104 M-2
0 200 400 600 800
0.0
0.2
0.4
0.6
0.8
1.0
351 nm
[Oxalate], µM
(I 0 - I)
/ (I 0 -
I i)
350 400 450 500
2x105
4x105
6x105
8x105
1x106
Fl. I
nten
sity
, a.u
.
Wavelength, nm
Ka = (3.0 ± 1.0)×104 M-2
0 200 400 600 800 1000
0.0
0.2
0.4
0.6
0.8
1.0
351 nm
[Malonate], µM
(I 0 - I)
/ (I 0 -
I i)
350 400 450 500
2x105
4x105
6x105
8x105
Fl. I
nten
sity
, a.u
.
Wavelength, nm
Ka = (2.8 ± 0.4)×103 M-2
0 200 400 600 800 1000
0.0
0.2
0.4
0.6
0.8
1.0
351 nm
[Glutamate], µM
(I 0 - I)
/ (I 0 -
I i)
350 400 450 500
2x105
4x105
6x105
8x105
Fl. I
nten
sity
, a.u
.
Wavelength, nm
Ka = (3.0 ± 0.2)×103 M-2
0 200 400 600 800 1000
0.0
0.2
0.4
0.6
0.8
1.0
351 nm
[Benzoate], µM
(I 0 - I)
/ (I 0 -
I i)
35
Supporting information
Figure S54. Left: Fluorescence titration spectra (λex=315 nm) and isotherm of S6 (8 μM) upon addition of Phthalate anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM). Right: Fluorescence titration spectra (λex=315 nm) and isotherm of S6 (8 μM) upon addition of Dihydrogen phosphate anion in DMSO:CHCl3 (3:7, v/v) with Triton X-100 (0.36mM).
350 400 450 500
2x105
4x105
6x105
8x105
1x106Fl
. Int
ensi
ty, a
.u.
Wavelength, nm
Ka = (1.7 ± 0.3)×103 M-2
0 200 400 600 800 1000
0.0
0.2
0.4
0.6
0.8
1.0
351 nm
[Phthalate], µM
(I 0 - I)
/ (I 0 -
I i)
350 400 450 500
2x105
4x105
6x105
8x105
1x106
Fl. I
nten
sity
, a.u
.
Wavelength, nm
Ka = (2.2 ± 0.1)×104 M-2
0 200 400 600 800 1000 1200
0.0
0.2
0.4
0.6
0.8
1.0
351 nm
[Dihydrogen phosphate], µM
(I 0 - I)
/ (I 0 -
I i)
36
Supporting information
6 Proton NMR titrations
The anion binding properties of S1-S6 in DMSO solution were studied with 1H NMR titration method. 1H NMR spectra were recorded on a Bruker Avance III (500 MHz) spectrometer at 348 K in DMSO-d6.
Figure S55. Panel A: 1H NMR titration (selected region) of a solution of S1 (16 mM) with tetrabutylammonium chloride (0-10.0 mol. eq.) in DMSO (500 MHz) at 348K. Panel B: 1H NMR titration isotherm for selected NH signal (●).
Figure S56. Panel A: 1H NMR titration (selected region) of a solution of S2 (16 mM) with tetrabutylammonium chloride (0-8.5 mol. eq.) in DMSO (500 MHz) at 348K. Panel B: 1H NMR titration isotherm for selected NH signal (●).
0 25 50 75 100 125 150 175
0.0
0.2
0.4
0.6
0.8
1.0
[Chloride], mM∆δ
NH
Ka = (8.6 ± 1.0)×101 M-1
[S1] = 16 mM in DMSO
0 mol equiv.
0.5 mol equiv.
1.0 mol equiv.
2.0 mol equiv.
5.0 mol equiv.
7.0 mol equiv.
10.0 mol equiv.
N N
N N
NH
H
H H
N N
N
H HN
N
H
H
HH
HH
A
0 20 40 60 80 100 120 140
0.0
0.2
0.4
0.6
0.8
1.0
[Chloride], mM
∆δNH
Ka = (6.8 ± 0.9)×101 M-1
[S2] = 16 mM in DMSO
B0 mol equiv.
0.5 mol equiv.
1.0 mol equiv.
2.0 mol equiv.
5.5 mol equiv.
6.5 mol equiv.
8.5 mol equiv.
N N
N N
NH
H
H H
N N
N
H HN
N
H
H
H
H
H
H
A
37
Supporting information
Figure S57. Panel A: 1H NMR titration (selected region) of a solution of S3 (16 mM) with tetrabutylammonium chloride (0-10.0 mol. eq.) in DMSO (500 MHz) at 348K. Panel B: 1H NMR titration isotherm for selected NH signal (●).
Figure S58. Panel A: 1H NMR titration (selected region) of a solution of S4 (12 mM) with tetrabutylammonium chloride (0-10.0 mol. eq.) in DMSO (500 MHz) at 348K. Panel B: 1H NMR titration isotherm for selected NH signal (●).
0 mol equiv.
0.5 mol equiv.
1.0 mol equiv.
2.0 mol equiv.
5.0 mol equiv.
7.0 mol equiv.
10.0 mol equiv.
A
0 20 40 60 80 100 120 140 160 180
0.0
0.2
0.4
0.6
0.8
1.0
[Chloride], mM
∆δNH
Ka = (6.4 ± 0.7)×101 M-1
[S3] = 16 mM in DMSO
B
N N
N N
N
H
H
H
H
N N
N
H H
H
N
N
H
HHH
H
6.57.07.58.08.59.09.510.010.511.011.512.012.5f1 (ppm)
1
2
3
4
5
6
70 mol equiv.
0.5 mol equiv.
1.0 mol equiv.
2.0 mol equiv.
5.0 mol equiv.
7.0 mol equiv.
10.0 mol equiv.
A
0 20 40 60 80 100 120 140 160
0.0
0.2
0.4
0.6
0.8
1.0
[Chloride], mM
∆δNH
Ka = (3.0 ± 0.1)×101 M-1
[S4] = 16 mM in DMSO
B
N N
N
H HN
N
H
HH
H
38
Supporting information
Figure S59. Panel A: 1H NMR titration (selected region) of a solution of S5 (12 mM) with tetrabutylammonium chloride (0-10.0 mol. eq.) in DMSO (500 MHz) at 348K. Panel B: 1H NMR titration isotherm for selected NH signal (●).
Figure S60. Panel A: 1H NMR titration (selected region) of a solution of S6 (16 mM) with tetrabutylammonium chloride (0-10.0 mol. eq.) in DMSO (500 MHz) at 348K. Panel B: 1H NMR titration isotherm for selected NH signal (●).
0 mol equiv.
0.5 mol equiv.
1.0 mol equiv.
2.0 mol equiv.
5.0 mol equiv.
7.0 mol equiv.
10.0 mol equiv.
A
0 20 40 60 80 100 120 140 160 180
0.0
0.2
0.4
0.6
0.8
1.0
[Chloride], mM
∆δNH
Ka = (5.6 ± 0.7)×101 M-1
[S5] = 12 mM in DMSO
B
N N
N N
NH
H
H H
HH
0 50 100 150 200
0.0
0.2
0.4
0.6
0.8
1.0
[Chloride], mM
∆δNH
[S6] = 16 mM in DMSOKa = (4.8 ± 0.5)×101 M-1
B0 mol equiv.
0.5 mol equiv.
1.0 mol equiv.
2.0 mol equiv.
5.0 mol equiv.
7.0 mol equiv.
10.0 mol equiv.
A
N N
N N
NH
H
H H
HH
39
Supporting information
7 Stoichiometry determination: Job’s plot
The anion binding properties, namely the ratio between sensors S1-S6 and an anion, were studied with Job’s plot fluorescence method, using tetrabutylammonium fluoride and tetrabutylammonium acetate as the anion sources in mix DMSO:CHCl3 (3:7) with addition of surfactant Triton X-100. The obtained results show 1:2 ratio for all complexes of fluoride and acetate anions.
Figure S61. Left: Job’s plot for the determination of the stoichiometry of S1 and F– in the complex in DMSO:CHCl3 (3:7) with addition of surfactant Triton X-100 (0.36mM). Right: Job’s plot for the determination of the stoichiometry of S1 and OAc– in the complex in DMSO:CHCl3 (3:7) with addition of surfactant Triton X-100 (0.36mM).
Figure S62. Left: Job’s plot for the determination of the stoichiometry of S2 and F– in the complex in DMSO:CHCl3 (3:7) with addition of surfactant Triton X-100 (0.36mM). Right: Job’s plot for the determination of the stoichiometry of S2 and OAc– in the complex in DMSO:CHCl3 (3:7) with addition of surfactant Triton X-100 (0.36mM).
0.0 0.2 0.4 0.6 0.8 1.0
0.0
2.0x104
4.0x104
6.0x104
8.0x104
1.0x105
1.2x105
1.4x105
χ Fluoride
Inte
nsity
x χ
Flu
orid
e ʎEx=400 nmʎEm=445 nm
Sensor S1: Fluoride= 1:2
0.0 0.2 0.4 0.6 0.8 1.0
0.0
2.0x104
4.0x104
6.0x104
8.0x104
1.0x105
1.2x105
1.4x105
χ Acetate
Inte
nsity
x χ
Ace
tate
ʎEx=400 nmʎEm=445 nm
Sensor S1: Acetate= 1:2
0.0 0.2 0.4 0.6 0.8 1.0
0.0
5.0x104
1.0x105
1.5x105
2.0x105
χ Fluoride
Inte
nsity
x χ
Flu
orid
e ʎEx=320 nmʎEm=358 nm
Sensor S2: Fluoride= 1:2
0.0 0.2 0.4 0.6 0.8 1.0
0.0
5.0x104
1.0x105
1.5x105
2.0x105
2.5x105
χ Acetate
Inte
nsity
x χ
Ace
tate
ʎEx=320 nmʎEm=358 nm
Sensor S2: Acetate= 1:2
40
Supporting information
Figure S63. Left: Job’s plot for the determination of the stoichiometry of S3 and F– in the complex in DMSO:CHCl3 (3:7) with addition of surfactant Triton X-100 (0.36mM). Right: Job’s plot for the determination of the stoichiometry of S3 and OAc– in the complex in DMSO:CHCl3 (3:7) with addition of surfactant Triton X-100 (0.36mM).
Figure S64. Left: Job’s plot for the determination of the stoichiometry of S4 and F– in the complex in DMSO:CHCl3 (3:7) with addition of surfactant Triton X-100 (0.36mM). Right: Job’s plot for the determination of the stoichiometry of S4 and OAc– in the complex in DMSO:CHCl3 (3:7) with addition of surfactant Triton X-100 (0.36mM).
0.0 0.2 0.4 0.6 0.8 1.00.0
5.0x104
1.0x105
1.5x105
2.0x105
2.5x105
3.0x105
3.5x105
4.0x105
χ Fluoride
Inte
nsity
x χ
Flu
orid
e ʎEx=320 nmʎEm=345 nm
Sensor S3: Fluoride= 1:2
0.0 0.2 0.4 0.6 0.8 1.0
0.0
5.0x104
1.0x105
1.5x105
2.0x105
2.5x105
3.0x105
χ Acetate
Inte
nsity
x χ
Ace
tate
ʎEx=320 nmʎEm=345 nm
Sensor S3: Acetate= 1:2
0.0 0.2 0.4 0.6 0.8 1.0
0.0
2.0x104
4.0x104
6.0x104
8.0x104
1.0x105
1.2x105
χ Fluoride
Inte
nsity
x χ
Flu
orid
e ʎEx=365 nmʎEm=442 nm
Sensor S4: Fluoride= 1:2
0.0 0.2 0.4 0.6 0.8 1.0
0.0
2.0x104
4.0x104
6.0x104
8.0x104
1.0x105
1.2x105
χ Acetate
Inte
nsity
x χ
Ace
tate
ʎEx=365 nmʎEm=442 nm
Sensor S4: Acetate= 1:2
41
Supporting information
Figure S65. Left: Job’s plot for the determination of the stoichiometry of S6 and F– in the complex in DMSO:CHCl3 (3:7) with addition of surfactant Triton X-100 (0.36mM). Right: Job’s plot for the determination of the stoichiometry of S6 and OAc– in the complex in DMSO:CHCl3 (3:7) with addition of surfactant Triton X-100 (0.36mM).
0.0 0.2 0.4 0.6 0.8 1.0
0
1x105
2x105
3x105
4x105
5x105
χ Fluoride
Inte
nsity
x χ
Flu
orid
e ʎEx=303 nmʎEm=348 nm
Sensor S6: Fluoride= 1:20.0 0.2 0.4 0.6 0.8 1.0
0
1x105
2x105
3x105
4x105
χ Acetate
Inte
nsity
x χ
Ace
tate
ʎEx=303 nmʎEm=348 nm
Sensor S6: Acetate= 1:2
42
Supporting information
8 Paper microzone plates study
The plates were printed on chromatography paper (Whatman) with a Xerox ColorQube model 8570 wax printer. After printing, it was baked in an oven for 4 minutes at 110 oC allowing for the penetration of wax into the paper. These plates were used for qualitative classification of analytes and quantitative analysis of various anions in water. Qualitative analysis was made by reacting 5 mM solution of sensors S1-S6 (1 µL) in DMSO with 5 mM solution of different analytes (1 µL) in water. The responses were recorded by Kodak Image Station 440CF and Kodak Image Station 4000MM. Fluorescence intensities were classified by using Linear Discriminant Analysis (LDA). In quantitative analysis the responses from sensor arrays were evaluated by LDA classification for semi-quantitative analysis and Support Vector Machine (SVM) regression. Cross-validation results confirms 100% classification.
Figure S66. Top: Fluorescence photograph of sensor S1 (0.4mM) with different anions (2.5mM) in DMSO:CHCl3 (3:7). Middle: Fluorescence image from the paper microzone array of sensor S1 (5mM) with four analytes (10mM), obtained as a sum of the RGB channels collected in the measurements. Bottom: Fluorescence spectrum of S1 (0.2 μM) (DMSO:CHCl3, 3:7, v/v) (black). Fluorescence spectrum of S1 (0.2 μM) in a presence of Dihydrogen phosphate anion (DMSO:CHCl3, 3:7, v/v) (red). Fluorescence spectrum of S1 (0.2 μM) in a presence of Fluoride anion (DMSO:CHCl3, 3:7, v/v) (blue)
S1 Ctrl
Fluoride
Chloride
Acetate
Ctrl F Cl OAc Ox Mal Glu OBz Pht Pi
43
Supporting information
Qualitative Assay for S1-S6 with different analytes
Table S4. Table of cumulative proportion of total dispersion for the qualitative assay of S1-S6 (5mM) with various anions (5mM) in water (and one control).
F1 F2 F3 F4 F5 F6 F7 F8 F9 F10 F11 F12 0.799 0.912 0.957 0.976 0.989 0.995 0.998 0.999 0.999 1 1 1
Figure S67. Graphical output of the qualitative LDA for a competitive assay of S1-S6 (5mM) with various anions (5mM) in water. Achieved with 10 excitation/emission channels for each sensor, 13 repetitions, 100 % correct classification.
-60 -40 -20 0 20 40 60
-40
-20
0
20
40
Control Fluoride Chloride Bromide Acetate Oxalate Malonate Glutamate Benzoate Phthalate Pi PPi
F2
(11.
3%)
F1(79.9%)
44
Supporting information
Semi-Quantitative Paper-Based Assay
Figure S68. Canonical scores plot for LDA for the semi-quantitative assay for S1-S6 and Oxalate, Chloride and Hydrogen pyrophosphate anions and a control.
45
Supporting information
Figure S69. 2 D graphical output of Linear Discriminant Analysis for paper-based assay for sensors S1-S6 (5mM) with chloride, hydrogen pyrophosphate and oxalate anions. Achieved with 6 excitation/emission channels for each sensor, 15 repetitions, 100 % correct classification.
-60 -40 -20 0 20 40 60-40
-20
0
20
40
10.0 mM5.0 mM
4.0 mM
3.0 mM
2.0 mM
1.0 mM
0.5 mM
F2 (2
8.9%
)
F1(45.3%)
Control
10.0 mM
1.0 mM
2.0 mM
3.0 mM
4.0 mM
5.0 mM
5.0 mM
4.0 mM
3.0 mM
2.0 mM
1.0 mM
0.5 mMOP-O O-O
OP
OHO- O-
OO
O-
Cl-
46
Supporting information
Figure S70. Canonical scores plot for LDA for the semi-quantitative assay for S1-S6 Chloride, Dihydrogen phosphate and Hydrogen pyrophosphate anions and a control.
47
Supporting information
Figure S71. 3 D graphical output of Linear Discriminant Analysis for paper-based assay for sensors S1 -S6 (5mM) with chloride, hydrogen pyrophosphate and dihydrogen phosphate anions. Achieved with 6 excitation/emission channels for each sensor, 15 repetitions, 100 % correct classification.
-30 0 30
-20
0
20
-10010
1.0 mM
0.5 mM
F3 (5.9%)F1 (69.3%)
F2 (16.4%)
1.0 mM2.0 mM
3.0 mM
4.0 mM
5.0 mM
10.0 mM
10.0 mM
5.0 mM
4.0 mM
3.0 mM
2.0 mM
0.5 mM
Control
0.5 mM1.0 mM
2.0 mM3.0 mM
4.0 mM5.0 mM
10.0 mM
OP-O O-O
OP
OHO-
OP
HO O-OH
Cl-
48
Supporting information
Figure S72. Canonical scores plot for LDA for the semi-quantitative assay for S1-S6 Chloride, Oxalate, Dihydrogen phosphate and Hydrogen pyrophosphate anions and a control.
Table S5. Table of cumulative proportion of total dispersion for the qualitative assay of S1-S6 (5mM) with Chloride, Oxalate, Dihydrogen phosphate and Hydrogen pyrophosphate anions (5mM) in water (and one control).
F1 F2 F3 F4 F5 F6 F7 F8 F9 F10 F11 F12 F13 F14 0.359 0.695 0.957 0.925 0.980 0.991 0.995 0.998 0.998 0.999 0.999 0.999 0.999 1
49
Supporting information
Figure S73. 3 D graphical output of Linear Discriminant Analysis for paper-based assay for sensors S1- S6 (5mM) with Chloride, Hydrogen pyrophosphate, Dihydrogen phosphate and Oxalate anions and a control. Achieved with 6 excitation/emission channels for each sensor, 15 repetitions, 100 % correct classification.
-30
0
30
-30
0
30-20
0
20
F1 (35.9%)
F3 (2
3.0%
)
F3 (33.6%)
OP-O O-O
OP
OHO-
OP
HO O-OH
O-
OO
O-
Cl-
10.0 mM 5.0 mM
10.0 mM
10.0 mM
50
Supporting information
Quantitative Assays The plot of the actual vs. predicted concentration shows high accuracy of prediction for multiple Chloride concentration values. The root-mean-square errors (RMSE) of calibration (RMSEC), cross-validation (RMSECV), and prediction (RMSEP) attest to the quality of the model and prediction. Two unknown samples (red circle ●) were simultaneously correctly analyzed for Chloride (1mM and 4mM).
Figure S74. Results of linear regression by Support Vector Machine (SVM) for Chloride anion. Red circles (●) represent two unknown samples (1.0mM and 4.0mM), which were correctly analyzed using the model.
0 2 4 6 8 100
2
4
6
8
10
X-block Preprocessing: Group ScaleX-block Compression: PCA
RMSEC: 0.0429 RMSECV: 0.2025 RMSEP: 0.1454
Actual [Chloride]/mM
Pre
dict
ed [C
hlor
ide]
/mM
Calibration Data Set Validation Data Set
Cl-
51
Supporting information
The plot of the actual vs. predicted concentration shows high accuracy of prediction for multiple Oxalate concentration values. The root-mean-square errors (RMSE) of calibration (RMSEC), cross-validation (RMSECV), and prediction (RMSEP) attest to the quality of the model and prediction. Two unknown samples (red circle ●) were simultaneously correctly analyzed for Oxalate (0.5mM and 3mM).
Figure S75. Results of linear regression by Support Vector Machine (SVM) for Oxalate anion. Red circles (●) represent two unknown samples (0.5mM and 3.0mM), which were correctly analyzed using the model.
0 1 2 3 4 50
1
2
3
4
5
X-block Preprocessing: Log10X-block Compression: PLS
RMSEC: 0.026RMSECV: 0.137 RMSEP: 0.122
Actual [Oxalate]/mM
Pre
dict
ed [O
xala
te]/m
M
Calibration Data Set Validation Data Set
O-
OO
O-
52
Supporting information
The plot of the actual vs. predicted concentration shows high accuracy of prediction for multiple Hydrogen pyrophosphate concentration values. The root-mean-square errors (RMSE) of calibration (RMSEC), cross-validation (RMSECV), and prediction (RMSEP) attest to the quality of the model and prediction. Two unknown samples (red circle ●) were simultaneously correctly analyzed for Hydrogen pyrophosphate (1mM and 4mM).
Figure S76. Results of linear regression by Support Vector Machine (SVM) for Hydrogen pyrophosphate anion. Red circles (●) represent two unknown samples (1.0mM and 4.0mM), which were correctly analyzed using the model.
0 2 4 6 8 100
2
4
6
8
10
X-block Preprocessing: Log10X-block Compression: PCA
RMSEC: 0.0634 RMSECV: 0.2655 RMSEP: 0.2327
Actual [Hydrogen pyrophosphate]/mM
Pre
dict
ed [H
ydro
gen
pyro
phos
phat
e]/m
M
Calibration Data Set Validation Data Set
OOPP--OO OO--
OO
OOPP
OOHHOO--
53
Supporting information
The plot of the actual vs. predicted concentration shows high accuracy of prediction for multiple Dihydrogen phosphate concentration values. The root-mean-square errors (RMSE) of calibration (RMSEC), cross-validation (RMSECV), and prediction (RMSEP) attest to the quality of the model and prediction. Two unknown samples (red circle ●) were simultaneously correctly analyzed for Dihydrogen phosphate (1mM and 4mM).
Figure S77. Results of linear regression by Support Vector Machine (SVM) for Dihydrogen phosphate anion. Red circles (●) represent two unknown samples (1.0mM and 4.0mM), which were correctly analyzed using the model.
0 2 4 6 8 100
2
4
6
8
10
X-block Preprocessing: Log 10X-block Compression: PLS
RMSEC: 0.0311RMSECV: 0.2682 RMSEP: 0.2046
Actual [Dihydrogen phosphate]/mM Pre
dict
ed [D
ihyd
roge
n ph
osph
ate]
/mM
Calibration Data Set Validation Data Set
OP
HO O-OH
54
Supporting information
9 Competitive titrations of acetate anion in chloride rich solutions
Figure S78. Left: Fluorescence titration spectra and isotherm of S1 (0.2 μM) upon addition of acetate anion. Right: Fluorescence titration spectra and isotherm of S1 (0.2 μM) upon addition of acetate anion in a presence of chloride anion (500 μM). Both titrations were acquired in DMSO:CHCl3 (3:7, v/v).
Figure S79. Results of linear regression by Support Vector Machine (SVM) based on fluorescence titrations for Acetate anion in a presence of Chloride anion (500μM). Red circles (●) represent two unknown samples (8.0μM and 32μM), which were correctly analyzed using the model.
450 500 550 600
1x105
2x105
3x105
4x105
5x105
6x105
Wavelength, nm
Fl. I
nten
sity
, a.u
.
Ka = (5.1 ± 1.0)×105 M-2
0 20 40 60 80 100 120 140 160
0.0
0.2
0.4
0.6
0.8
1.0
[Acetate], µM
(I 0 - I)
/ (I 0 -
I i)451 nm
450 500 550 600
1x105
2x105
3x105
4x105
5x105
6x105
7x105
Wavelength, nmFl
. Int
ensi
ty, a
.u.
Ka = (1.5 ± 0.1)×105 M-2
0 50 100 150 200 250
0.0
0.2
0.4
0.6
0.8
1.0
451 nm
[Acetate], µM
(I 0 - I)
/ (I 0 -
I i)
0.0 2.0x10-5 4.0x10-5 6.0x10-5 8.0x10-50.0
1.0x10-5
2.0x10-5
3.0x10-5
4.0x10-5
5.0x10-5
6.0x10-5
7.0x10-5
8.0x10-5
X-block Preprocessing: Log10X-block Compression: PCA
RMSEC: 1.968x10-8 RMSECV: 2.499x10-7 RMSEP: 1.475x10-6
Actual [Acetate]/M
Pre
dict
ed [A
ceta
te]/M
Calibration Data Set Validation Data Set
55
Supporting information
Figure S80. Left: Canonical scores plot for LDA for the semi-quantitative assay for S1 and Acetate and a control in a presence of Chloride anion (10mM). Right: 2 D graphical output of Linear Discriminant Analysis for paper-based assay for sensors S1 (5mM) with acetate anion in a presence of chloride anion (10mM). Achieved with 9 excitation/emission channels, 15 repetitions, 100 % correct classification.
Figure S81. Results of linear regression by Support Vector Machine (SVM) for Acetate anion in a presence of Chloride anion (10mM). Red circle (●) represents one unknown sample (3mM), which was correctly analyzed using the model.
-30 -15 0 15 30-50
-25
0
25
50
10.0 mM
5.0 mM
4.0 mM
3.0 mM
2.0 mM
1.0 mM
F2 (0
.6%
)
F1(99.3%)
Control
0 2 4 6 8 100
2
4
6
8
10
X-block Preprocessing: Group ScaleX-block Compression: PCA
RMSEC: 0.1830RMSECV: 0.3627 RMSEP: 0.0421
Actual [Acetate]/mM
Pre
dict
ed [A
ceta
te]/m
M
Calibration Data Set Validation Data Set
56
Supporting information
Supplemental References
1 A. K. Connors. Binding Constants: the Measurement of Molecular Complex Stability; Wiley: New York, 1987. 2 Rose, F.L.; Swain, G. J. Chem. Soc. 1956, 4422–4425.
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