Array-Based Sensing of Explosives by Water- Soluble Poly(para-phenyleneethynylene)s

Transcription

1 Supporting Information Array-Based Sensing of Explosives by Water- Soluble Poly(para-phenyleneethynylene)s Benhua Wang,,# Jinsong Han,,# Markus Bender, Kai Seehafer, and Uwe H. F. Bunz,, * Organisch-Chemisches Institut, Ruprecht-Karls-Universität Heidelberg, Im Neuenheimer Feld 270, Heidelberg, Germany CAM, Centre for Advanced Materials, Ruprecht-Karls-Universität Heidelberg, Im Neuenheimer Feld 225, Heidelberg, Germany Corresponding Author: *(U.H.F.B.) uwe.bunz@oci.uni-heidelberg.de 1

2 Contents 1. General Information Synthetic Details and Analytical Data Synthesis of P Synthesis of P Synthesis of P Lifetime Measurements Fluorescence Response Pattern and Linear Discriminant Analysis NMR-Spectra Supplemental References

3 1. General Information Chemicals were either purchased from the chemical store at the Organisch-Chemisches Institut of the University of Heidelberg or from commercial laboratory suppliers. Reagents were used without further purification unless otherwise noted. Solvents were purchased from the store of the chemical store at the Organisch-Chemisches Institut of the University of Heidelberg and if necessary distilled prior use. All of the other absolute solvents were dried by a MB SPS-800 using drying columns. Analytical thin layer chromatography (TLC) was performed on Macherey & Nagel Polygram SIL G/UV254 precoated plastic sheets. Components were visualized by observation under UV light (254 nm or 365 nm) or in the case of UV-inactive substances by using the suitably colouring solutions. The following colouring solutions were used for the visualization of UV-inactive substances: KMnO4 solution: 2.0 g KMnO4, 10.0 g K2CO3, 0.3 g NaOH, 200 ml distilled water. Cer solution: 10.0 g Ce(SO)4, 25 g phosphomolybdic acid hydrate, 1 L distilled water, 50 ml conc. H2SO4. Flash column chromatography was carried out using silica gel S (0.032 mm mm), purchased from Sigma Aldrich, according to G. Nill, unless otherwise stated. 1 1 H NMR spectra were recorded at room temperature on the following spectrometers: Bruker Avance III 300 (300 MHz), Bruker Avance III 400 (400 MHz) and Bruker Avance III 600 (600 MHz). The data were interpreted in first order spectra. The spectra were recorded in CDCl3 or D2O as indicated in each case. Chemical shifts are reported in δ units relative to the solvent residual peak (CHCl3 in CDCl3 at δh = 7.27 ppm, HDO in D2O at δh = 4.79 ppm) or TMS (δh = 0.00 ppm). 2 The following abbreviations are used to indicate the signal multiplicity: s (singlet), d (doublet), t (triplet), q (quartet), quin (quintet), sext (sextet), dd (doublet of doublet), dt (doublet of triplet), ddd (doublet of doublet of doublet), etc., bs (broad 3

4 signal), m (multiplet). All NMR spectra were integrated and processed using ACD/Spectrus Processor. 13 C NMR spectra were recorded at room temperature on the following spectrometers: Bruker Avance III 300 (75 MHz), Bruker Avance III 400 (100 MHz) and Bruker Avance III 600 (150 MHz). The spectra were recorded in CDCl3 or D2O as indicated in each case. Chemical shifts are reported in δ units relative to the solvent signal: CDCl3 [δc = ppm (central line of the triplet)] or TMS (δc = 0.00 ppm). High resolution mass spectra (HR-MS) were either recorded on a Bruker ApexQehybrid 9.4 T FT-ICR-MS (ESI + ) or a Finni-gan LCQ (ESI + ) mass spectrometer at the Organisch- Chemisches Institut der Universität Heidelberg. Absorption and emission spectra were recorded using a Jasco V660 and Jasco FP6500 spectrometer. IR spectra were recorded on a JASCO FT/IR Substances were applied as a film, solid or in solution. The obtained data was processed with the software JASCO Spectra anager II. Elemental analyses were carried out at the Organisch-Chemisches Institut der Universität Heidelberg. Gel Permeation Chromatography (GPC): Number- (Mn) and weight-average (Mw) molecular weights and polydispersities (PDI, Mw/Mn) were determined by GPC versus polystyrene standards. Measurements were carried out at room temperature in chloroform with PSS-SDV columns (8.0 mm x 30.0 mm, 5 μm particles, , and Å pore size) on a Jasco PU-2050 GPC unit equipped with a Jasco UV-2075 UV- and a Jasco RI-2031 RIdetector. Dialysis was realized with regenerated cellulose tubular membranes (ZelluTrans, Carl Roth ) with a molecular weight cut-off of 3500 Da against deionized (DI) water. 4

5 Photographs for PPEs were taken with a Canon EOS 7D camera equipped with an EF-S 60mm F/2.8 Macro lens. Quantum yields Φ were obtained by the absolute method described in ref. 3 using an Ulbricht sphere. Given Φ for each sample are average values of at least three independent measurements. Fluorescence lifetimes τ were acquired by an exponential fit according to the least mean square with commercially available software HORIBA Scientific Decay Data Analyses 6 (DAS6) version The luminescence decays were recorded with a HORIBA Scientific Fluorocube single photon counting system operated with HORIBA Scientific DataStationversion 2.2. Fluorescence response patterns (I-I 0 )/I 0 were recorded using a CLARIOstar (firmware version 1.13) platereader from BMG Labtech using the corresponding software (software version 5.20 R5). Data were analysed with CLARIOstar MARS Data Analysis Software (software version 3.10 R5) from BMG Labtech. The specific response for each anaylte was measured five times. These acquired data was used as the observables for the subsequent linear discriminant analysis. Linear discriminant analysis was carried out using using classical linear discriminant analysis (LDA) in SYSTAT (version 13.0). In LDA, all variables were used in the model (complete mode) and the tolerance was set as The fluorescence response patterns were transformed to canonical patterns. The Mahalanobis distances of each individual pattern to the centroid of each group in a multidimensional space were calculated and the assignment of the case was based on the shortest Mahalanobis distance. 5

6 2. Synthetic Details and Analytical Data Synthesis of have been reported previously. 1, Synthesis of P2 Scheme 1. Synthesis of P2. Synthesis of P2. 1,4-Diiodobenzene (80 mg, µmol) and monomer 5 ( mg, µmol) were dissolved in degassed THF/piperidine (1.3 ml/1.3 ml). Pd(PPh3)2Cl2 (0.51 mg, 0.73 µmol) and CuI (0.28 mg, 1.45 µmol) were added and the mixture was stirred under nitrogen at 60 C for 2 days. CHCl3 were added to the mixture, and then washed with water, NaCl saturated solution and NH4Cl saturated solution. The combined organic layers were dried over MgSO4, filtered and concentrated under vacuum. The crude product was dissolved in CHCl3 and slowly added to an excess of n-hexane to gave P2 as as sticky orange oil (130 mg, 56 %). The Mn was estimated to be 1.1 x 10 4 with a PDI of H NMR (300 MHz, CDCl3): δ = (m, 2 H), (m, 4 H), (m, 2 H), (m, 56 H), (m, 12 H) ppm. Due to low solubility, 13 C NMR spectrum could not be obtained. IR (cm -1 ): ν 2867, 2361, 2328, 1508, 1489, 1460, 1406, 1350, 1280, 1245, 1200, 1100, 950, 845,

7 2.2 Synthesis of P3 Scheme 2. Synthesis of P3. Compound 1a was purchased by Sigma-Aldrich. Compund 3 was synthesized according to the literature. 3 Compund 5 was synthesized according to the literature. 4, 5 Synthesis of 2a. Ethyl 4-methylbenzoate 1a (10 g, mmol) and N-Bromosuccinimide (11.38 g, mmol) were dissolved in 100 ml HPLC-grade acetonitrile. The mixture was stirred under strong light for 12 h. After the solvent was removed, water and CH2Cl2 were added, the aqueous layer was separated and extracted with CH2Cl2. The combined organic layers were dried over MgSO4, filtered and concentrated under reduced pressure. The crude product was recrystallized from ethanol to afford 2a as a colorless solid (9.54 g, 64.4 %). 1 H NMR (300 MHz, CDCl3): δ = 8.02 (d, J = 8.4 Hz, 2 H), 7.45 (d, J = 8.4 Hz, 2 H), 4.50 (s, 2 H), 4.38 (q, J = 7.1 Hz, 2 H), 1.39 (t, J = 7.1 Hz, 3 H) ppm. 13 C NMR (75 MHz, CDCl3): δ = , , , , , 61.10, 32.26, ppm. Synthesis of 4a. Compound 2a (3.99 g, mmol), 3 (2.89 g, 8.00 mmol) and K2CO3 (11.06 g, mmol) were dissolved in degassed butanone (160 ml). The mixture was stirred at ambient temperature for 2 days. Removed the salts by filtration and the filtrate was 7

8 concentrated under reduced pressure. Then water and CH2Cl2 were added, the aqueous layer was extracted with CH2Cl2. The combined organic layers were dried over MgSO4, filtered and concentrated under vacuum. The crude product was purified by recrystallization two times from toluene to afford 4a (5.20 g, 90 %) as a white solid. 1 H NMR (300 MHz, CDCl3): δ = 8.08 (d, J = 8.3 Hz, 4 H), 7.56 (d, J = 8.3 Hz, 4 H), 7.25 (d, J = 1.5 Hz, 2 H), 5.11 (s, 4 H), 4.38 (q, J = 7.1 Hz, 4 H), 1.40 (t, J = 7.1 Hz, 6 H) ppm. 13 C NMR (75 MHz, CDCl3): δ = , , , , , , , 86.36, 71.33, 61.03, ppm. IR (cm -1 ): ν 2978, 2901, 1713, 1613, 1481, 1439, 1354, 1267, 1221, 1105, 1065, 1029, 844, 750, 688, 473. HR-MS (DART + ): m/z calcd. for C26H24I2O [M+NH4] + ; found C26H24I2O6: calcd. C 45.50, H 3.53; found C 45.60, H Synthesis of 6a. Monomer 4a (150 mg, µmol) and monomer 5 ( mg, µmol) were dissolved in degassed THF/piperidine (1.8 ml/1.3 ml). Pd(PPh3)2Cl2 (0.47 mg, 0.67 µmol) and CuI (0.26 mg, 1.36 µmol) were added and the mixture was stirred under nitrogen at room temperature for 2 days. CHCl3 were added to the mixture, and then washed with water, NaCl saturated solution and NH4Cl saturated solution. The combined organic layers were dried over MgSO4, filtered and concentrated under vacuum. The crude product was dissolved in CHCl3 and slowly added to an excess of n-hexane to gave 6a as as sticky, dark orange oil (280 mg, 96 %). The Mn was estimated to be 1.3 x 10 4 with a PDI of H NMR (600 MHz, CDCl3): δ = (m, 4 H), (m, 4 H), (m, 4 H), (m, 4 H), (m, 2 H), (m, 4 H), (m, 56 H), (m, 12 H), (m, 6 H) ppm. 13 C NMR (150 MHz, CDCl3): δ = , , , , , , , , , , , 78.73, 70.84, 70.05, 69.50, 69.46, 69.43, 69.42, 59.96, 57.96, ppm. IR (cm -1 ): ν 2916, 2869, 2361, 2342, 1715, 1508, 1489, 1460, 1413, 1364, 1274, 1200, 1100, 1019, 851,

9 Synthesis of P3. NaOH (60.54 mg, 1.51 mmol) was added to a solution of polymer 6a (200 mg, 0.15 mmol) in THF/H2O (10 ml/10 ml) and the mixture was stirred at 70 C for 2 days. After reducing the solvent in vacuo, the residue was dissolved in H2O and adjusted the ph to 7 by HCl solution, and then dialyzed against DI H2O for 3 d. After freezy-drying, a spongy, yellow solid (156 mg, 78 %) was obtained. The Mn and PDI result from polymer 6a. 1 H NMR (600 MHz, D2O): δ = (m, 4 H), (m, 4 H), (m, 4 H), (m, 4 H), (m, 58 H), (m, 12 H) ppm. Due to low solubility, 13 C NMR spectrum could not be obtained. IR (cm -1 ): ν 2868, 2361, 1715, 1508, 1489, 1460, 1412, 1270, 1198, 1091, 1034, 948, 847, 756, 635, Synthesis of P4 Scheme 3. Synthesis of P4 Compounds 1b 6, 7 and 2b 8 were synthesized according to the literature. Synthesis of 4b. 2b (2.00 g, 7.32 mmol), 3 (1.29 g, 3.57 mmol) and K2CO3 (4.94 g, mmol) were dissolved in degassed butanone (50 ml). The mixture was stirred at ambient temperature for 2 days. Removed the salts by filtration and the filtrate was concentrated under 9

10 reduced pressure. Then water and CH2Cl2 were added, the aqueous layer was extracted with CH2Cl2. The combined organic layers were dried over MgSO4, filtered and concentrated under vacuum. The crude product was purified by recrystallization from toluene to afford 4b (2.0 g, 75%) as a white solid. 1 H NMR (300 MHz, CDCl3): δ = 7.40 (d, J = 8.7 Hz, 4 H), 7.26 (s, 2 H), 6.93 (d, J = 8.7 Hz, 4 H), 4.98 (s, 4 H), 4.63 (s, 4 H), 4.28 (q, J = 7.1 Hz, 4 H), 1.30 (t, J = 7.1 Hz, 6 H) ppm. 13 C NMR (100 MHz, CDCl3): δ = , , , , , , , 86.65, 71.81, 65.33, 61.42, ppm. IR (cm -1 ): ν 2989, 2897, 1753, 1514, 1488, 1456, 1425, 1384, 1353, 1258, 1197, 1178, 1081, 1063, 1026, 849, 817, 781, 592, 514, 439. HR-MS (DART + ): m/z calcd. for C28H28I2O [M+NH4] + ; found Synthesis of 6b. Monomer 4b (150 mg, µmol) and monomer 5 ( mg, µmol) were dissolved in degassed THF/N,N-Diisopropylethylamine (1.8 ml/1.3 ml). Pd(PPh3)2Cl2 (0.42 mg, 0.60 µmol) and CuI (0.23 mg, 1.21 µmol) were added and the mixture was stirred under nitrogen at room temperature for 2 days. CHCl3 were added to the mixture, and then washed with water, NaCl saturated solution and NH4Cl saturated solution. The combined organic layers were dried over MgSO4, filtered and concentrated under vacuum. The crude product was dissolved in CHCl3 and slowly added to an excess of n-hexane to gave 6b as as sticky, dark orange oil (230 mg, 83 %). The Mn was estimated to be 8.3 x 10 3 with a PDI of H NMR (600 MHz, CDCl3): δ = (m, 4 H), (m, 2 H), (m, 2 H), (m, 4 H), (m, 4 H), (m, 4 H), (m, 2 H), (m, 4 H), (m, 56 H), (m, 12 H), (m, 6 H) ppm. 13 C NMR (150 MHz, CDCl3): δ = , , , , , , , , , , , 72.20, 72.16, 71.36, 70.88, 70.82, 70.77, 70.33, 65.67, 61.60, 59.31, 59.27, ppm. IR (cm -1 ): ν 2869, 2361, 1755, 1509, 1489, 1460, 1417, 1385, 1352, 1197, 1101, 1028, 950, 850, 820,

11 Synthesis of P4. NaOH (46.36 mg, 1.16 mmol) was added to a solution of polymer 6b (180 mg, µmol) in THF/H2O (10 ml/10 ml) and the mixture was stirred at 70 C for 2 days. After reducing the solvent in vacuo, the residue was dissolved in H2O and adjusted the ph to 7 by HCl solution, and then dialyzed against DI H2O for 3 d. After freezy-drying, a spongy, yellow solid (170 mg, 95 %) was obtained. The Mn and PDI result from polymer 6b. 1 H NMR (600 MHz, D2O): δ = (m, 4 H), (m, 8 H), (m, 4 H), (m, 6 H), (m, 68 H) ppm. 13 C NMR spectrum could not be obtained. IR (cm -1 ): ν 3441, 3355, 2872, 1611, 1512, 1487, 1456, 1415, 1351, 1200, 1075, 1028, 951, 848, 821,

12 Normalized Photon Count (a.u.) Normalized Photon Count (a.u.) 3. Lifetime Measurements (A) P2 P3 P4 (B) P2 P3 P Times (ns) Figure S1. Fluorescence decay profiles of -P4 at 465nm (A) and 515nm (B) in ph 7 buffer solution Times (ns) 12

13 4. Fluorescence Response Pattern and Linear Discriminant Analysis Table S1. Training matrix of fluorescence response pattern from water-soluble PPEs -P4 (1 µm, at ph 7, buffered) against 9 nitroaromaitc analytes at a concentration of 0.5 mm. LDA was carried out as described above resulting in the four factors of the canonical scores and group generation. The jackknifed classification matrix with cross-validation reveals an accuracy of 100 %. Analytes Fluorescence Response Pattern Results LDA Nitroaromaitc P2 P3 P4 Factor 1 Factor 2 Factor 3 Factor 4 Group A A A A A A NA NA NA NA NA NA NA NA NA NA NA NA DNB DNB DNB DNB DNB DNB DNT DNT DNT DNT DNT DNT NB NB NB NB NB NB NP NP NP NP

14 NP NP PA PA PA PA PA PA TNT TNT TNT TNT TNT TNT Table S2. Detection and identification of 36 unknown samples using LDA training matrix from PPEs -P4 (1 µm, at ph 7, buffered). All unknown samples could be assigned to the corresponding group defined by the training matrix according to their shortest Mahalanobis distance. All of the 36 unknown explosive samples were correctly identified, reveals a 100 % accuracy. Sample Fluorescence Response Pattern Results LDA Analyte Identi Verifi # P2 P3 P4 Factor 1 Factor 2 Factor 3 Factor 4 Group fication cation DNB DNB DNT DNT PA PA TNT TNT NP NP PA PA NA 2-NA NA 3-NA NB NB A A TNT TNT NA 3-NA NB NB DNB DNB NP NP NA 2-NA NP NP A A NA 2-NA TNT TNT DNT DNT NB NB NA 3-NA PA PA DNT DNT 14

15 A A DNB DNB NA 3-NA PA PA TNT TNT DNB DNB NB NB A A DNT DNT NP NP NA 2-NA Jackknifed Classification Matrix 2-NA 3-NA A DNB DNT NB NP PA TNT %correct 2-NA NA A DNB DNT NB NP PA TNT Total Figure S2. Jackknifed Classification Matrix from water-soluble PPEs sensor array -P4 (1 µm, at ph 7, buffered) against 9 nitroaromaitc analytes at a concentration of 0.5 Mm. Figure S3. Correlations of canonical fluroescence response patterns from PPEs sensor array -P4 (1 µm, at ph 7, buffered) against 8 aromatic analytes.the 95% confidence ellipses for the individual acids are also shown. 15

16 Table S3. Training matrix of fluorescence response pattern from water-soluble PPEs P3-P4 (1 µm, at ph 7, buffered) against 9 nitroaromaitc analytes at a concentration of 0.5 mm. LDA was carried out as described above resulting in the two factors of the canonical scores and group generation. The jackknifed classification matrix with cross-validation reveals an accuracy of 98 %. Analytes Fluorescence Response Pattern Results LDA Nitroaromaitc P3 P4 Factor 1 Factor 2 Group A A A A A A NA NA NA NA NA NA NA NA NA NA NA NA DNB DNB DNB DNB DNB DNB DNT DNT DNT DNT DNT DNT NB NB NB NB NB NB NP NP NP NP NP

17 NP PA PA PA PA PA PA TNT TNT TNT TNT TNT TNT Classification: 53/54 = 98% Table S4. Detection and identification of 36 unknown samples using LDA training matrix from PPEs sensor array P3-P4 (1 µm, at ph 7, buffered). All unknown samples could be assigned to the corresponding group defined by the training matrix according to their shortest Mahalanobis distance. All of the 36 unknown explosive samples were correctly identified, reveals a 100 % accuracy. Sample Fluorescence Response Pattern Results LDA Analyte # P3 P4 Factor 1 Factor 2 Group Identification Verification NA 2-NA NA 3-NA DNT DNT NB NB NP NP A A NA 2-NA PA PA TNT TNT NP NP NP NP PA PA DNB DNB NB NB TNT TNT DNB DNB DNT DNT NA 3-NA NA 2-NA A A TNT TNT DNT DNT NP NP PA PA DNB DNB 17

18 DNT DNT NB NB NB NB A A NA 2-NA NA 3-NA PA PA TNT TNT DNB DNB NA 3-NA A A Jackknifed Classification Matrix 2-NA 3-NA A DNB DNT NB NP PA TNT %correct 2-NA NA A DNB DNT NB NP PA TNT Total Figure S4. Jackknifed Classification Matrix from water-soluble PPEs sensor array P3-P4 (1 µm, at ph 7, buffered) against 9 nitroaromaitc analytes at a concentration of 0.5 Mm. 18

19 Factor SCORE(2) 2 (19.7%) 15 TNT 10 NB 5 DNT 0 3-NA A 2-NA NP PA -5 DNB Factor 1 (80.3%) SCORE(1) Figure S5. 2-D canonical score plot of fluorescence response patterns obtained with an array of the PPEs P3-P4 (1 µm, ph 7, buffered) with 95% confidence ellipses. Each point represents the response pattern for a single analyte in the array. (A) 0.0 (B) (I-I 0 )/I (I-I 0 )/I ph7 ph10 ph P2 ph7 P2 ph10 P2 ph13 A 2NA 3NA DNB DNT NB NP PA A 2NA 3NA DNB DNT NB NP PA (C) 0.0 (D) (I-I 0 )/I (I-I 0 )/I P3 ph7 P3 ph10 P3 ph P4 ph7 P4 ph10 P4 ph13 A 2NA 3NA DNB DNT NB NP PA A 2NA 3NA DNB DNT NB NP PA Figure S6. Fluorescence response pattern ((I I0)/I0) obtained by (A), P2 (B), P3(C) and P4 (D) (1 µm) treated with analytes (0.5 mm) at different buffered solution. 19

20 Fluorescence Intensity (a.u.) Fluorescence Intensity (a.u.) (A) 600 (B) A +NB NA +PA +NP 100 +DNT +TNT +DNB +2-NA x x x x x x10-4 Concentration (M) P2+A 200 P2+NB P2+3-NA P2+PA P2+NP 100 P2+DNT P2+TNT P2+DNB P2+2-NA x x x x x x10-4 Concentration (M) Figure S7. Fluorescence intensity change of (0.5 µm) (A) and P2 (0.5 µm) (B) treated with different concentrations of the analytes at ph 7 (buffered). 20

21 NMR-Spectra NAME a161018ubbw89 EXPNO 1 PROCNO 1 Date_ Time h INSTRUM spect PROBHD Z104275_0201 ( PULPROG zg30 TD SOLVENT CDCl3 NS 128 DS 2 SWH Hz FIDRES Hz AQ sec RG 724 DW usec DE 6.50 usec TE K D sec TD0 16 SFO MHz NUC1 1H usec SI SF MHz WDW EM SSB 0 LB 0.30 Hz GB 0 PC ppm NAME a160518ubbw23 EXPNO 1 PROCNO 1 Date_ Time h INSTRUM spect PROBHD Z104275_0201 ( PULPROG zg30 TD SOLVENT CDCl3 NS 128 DS 2 SWH Hz FIDRES Hz AQ sec RG 724 DW usec DE 6.50 usec TE K D sec TD0 16 SFO MHz NUC1 1H usec SI SF MHz WDW EM SSB 0 LB 0.30 Hz GB 0 PC ppm 21

22 NAME a160518ubbw23 EXPNO 2 PROCNO 1 Date_ Time h INSTRUM spect PROBHD Z104275_0201 ( PULPROG zgpg30 TD SOLVENT CDCl3 NS 64 DS 4 SWH Hz FIDRES Hz AQ sec RG 2050 DW usec DE usec TE K D sec D sec TD0 8 SFO MHz NUC1 13C 8.00 usec SI SF MHz WDW EM SSB 0 LB 0.70 Hz GB 0 PC ppm NAME a160525ubbw25 EXPNO 1 PROCNO 1 Date_ Time h INSTRUM spect PROBHD Z104275_0201 ( PULPROG zg30 TD SOLVENT CDCl3 NS 128 DS 2 SWH Hz FIDRES Hz AQ sec RG 812 DW usec DE 6.50 usec TE K D sec TD0 16 SFO MHz NUC1 1H usec SI SF MHz WDW EM SSB 0 LB 0.30 Hz GB 0 PC ppm 22

23 NAME a160525ubbw25 EXPNO 3 PROCNO 1 Date_ Time h INSTRUM spect PROBHD Z104275_0201 ( PULPROG zgpg30 TD SOLVENT CDCl3 NS 64 DS 4 SWH Hz FIDRES Hz AQ sec RG 2050 DW usec DE usec TE K D sec D sec TD0 8 SFO MHz NUC1 13C 8.00 usec SI SF MHz WDW EM SSB 0 LB 0.70 Hz GB 0 PC ppm ppm NAME e160627ubbw.37 EXPNO 2 PROCNO 1 Date_ Time h INSTRUM spect PROBHD Z132808_0001 ( PULPROG zg30 TD SOLVENT CDCl3 NS 128 DS 2 SWH Hz FIDRES Hz AQ sec RG 7.02 DW usec DE usec TE K D sec TD0 16 SFO MHz NUC1 1H 7.63 usec SI SF MHz WDW EM SSB 0 LB 0.30 Hz GB 0 PC ppm 23

24 NAME e160627ubbw.37 EXPNO 1 PROCNO 1 Date_ Time h INSTRUM spect PROBHD Z132808_0001 ( PULPROG zgpg30 TD SOLVENT CDCl3 NS DS 4 SWH Hz FIDRES Hz AQ sec RG 2050 DW usec DE usec TE K D sec D sec TD SFO MHz NUC1 13C usec SI SF MHz WDW EM SSB 0 LB 1.00 Hz GB 0 PC ppm ppm NAME e160704ubbw.39 EXPNO 2 PROCNO 1 Date_ Time h INSTRUM spect PROBHD Z132808_0001 ( PULPROG zg30 TD SOLVENT D2O NS 128 DS 2 SWH Hz FIDRES Hz AQ sec RG DW usec DE usec TE K D sec TD0 16 SFO MHz NUC1 1H 7.63 usec SI SF MHz WDW EM SSB 0 LB 0.30 Hz GB 0 PC ppm 24

25 NAME a160915ubbw67 EXPNO 1 PROCNO 1 Date_ Time h INSTRUM spect PROBHD Z104275_0201 ( PULPROG zg30 TD SOLVENT CDCl3 NS 128 DS 2 SWH Hz FIDRES Hz AQ sec RG 812 DW usec DE 6.50 usec TE K D sec TD0 16 SFO MHz NUC1 1H usec SI SF MHz WDW EM SSB 0 LB 0.30 Hz GB 0 PC ppm NAME a160915ubbw67 EXPNO 1 PROCNO 1 Date_ Time h INSTRUM spect PROBHD Z104275_0201 ( PULPROG zg30 TD SOLVENT CDCl3 NS 128 DS 2 SWH Hz FIDRES Hz AQ sec RG 812 DW usec DE 6.50 usec TE K D sec TD0 16 SFO MHz NUC1 1H usec SI SF MHz WDW EM SSB 0 LB 0.30 Hz GB 0 PC ppm 25

26 ppm ppm ppm 5.10 ppm ppm NAME e161010ubbw.74 EXPNO 2 PROCNO 1 Date_ Time 5.36 h INSTRUM spect PROBHD Z132808_0001 ( PULPROG zg30 TD SOLVENT CDCl3 NS 128 DS 2 SWH Hz FIDRES Hz AQ sec RG DW usec DE usec TE K D sec TD0 16 SFO MHz NUC1 1H 7.63 usec SI SF MHz WDW EM SSB 0 LB 0.30 Hz GB 0 PC ppm NAME e161010ubbw.74 EXPNO 1 PROCNO 1 Date_ Time 5.27 h INSTRUM spect PROBHD Z132808_0001 ( PULPROG zgpg30 TD SOLVENT CDCl3 NS DS 4 SWH Hz FIDRES Hz AQ sec RG 2050 DW usec DE usec TE K D sec D sec TD SFO MHz NUC1 13C usec SI SF MHz WDW EM SSB 0 LB 1.00 Hz GB 0 PC ppm 26

27 ppm ppm NAME e161021ubbw.88 EXPNO 2 PROCNO 1 Date_ Time h INSTRUM spect PROBHD Z132808_0001 ( PULPROG zg30 TD SOLVENT D2O NS 256 DS 2 SWH Hz FIDRES Hz AQ sec RG DW usec DE usec TE K D sec TD0 32 SFO MHz NUC1 1H 7.63 usec SI SF MHz WDW EM SSB 0 LB 0.30 Hz GB 0 PC ppm 27

28 6. Supplemental References 1. Han, J.; Wang, B.; Bender, M.; Kushida, S.; Seehafer, K.; Bunz, U. H. Poly(aryleneethynylene) Tongue That Identifies Nonsteroidal Anti-Inflammatory Drugs in Water: A Test Case for Combating Counterfeit Drugs. ACS Appl. Mater. Interfaces 2017, 9, Khan, A.; Muller, S.; Hecht, S. Practical synthesis of an amphiphilic, non-ionic poly(paraphenyleneethynylene) derivative with a remarkable quantum yield in water. Chem. Commun. 2005, Gan, H.; Li, Y.; Liu, H.; Wang, S.; Li, C.; Yuan, M.; Liu, X.; Wang, C.; Jiang, L.; Zhu, D. Self-Assembly of Conjugated Polymers and ds-oligonucleotides Directed Fractal-like Aggregates. Biomacromolecules 2007, 8, Khan, A.; Muller, S.; Hecht, S. Practical synthesis of an amphiphilic, non-ionic poly(paraphenyleneethynylene) derivative with a remarkable quantum yield in water. Chem. Commun. 2005, Kim, I.-B.; Phillips, R.; Bunz, U. H. F. Carboxylate Group Side-Chain Density Modulates the ph-dependent Optical Properties of PPEs. Macromolecules 2007, 40, Leung, J. C. T.; Chatalova-Sazepin, C.; West, J. G.; Rueda-Becerril, M.; Paquin, J.-F.; Sammis, G. M. Photo-fluorodecarboxylation of 2-Aryloxy and 2-Aryl Carboxylic Acids. Angew. Chem., Int. Ed. 2012, 51, Ozcan, S.; Kazi, A.; Marsilio, F.; Fang, B.; Guida, W. C.; Koomen, J.; Lawrence, H. R.; Sebti, S. M. Oxadiazole-isopropylamides as Potent and Noncovalent Proteasome Inhibitors. J. Med. Chem. 2013, 56, Mizuno, C. S.; Chittiboyina, A. G.; Shah, F. H.; Patny, A.; Kurtz, T. W.; Pershadsingh, H. A.; Speth, R. C.; Karamyan, V. T.; Carvalho, P. B.; Avery, M. A. Design, Synthesis, and Docking Studies of Novel Benzimidazoles for the Treatment of Metabolic Syndrome. J. Med. Chem. 2010, 53,