Inner Filter Effect Based Selective Detection of. Nitroexplosive-Picric Acid in Aqueous Solution and. Solid Support Using Conjugated Polymer

Transcription

1 Supporting Information Inner Filter Effect Based Selective Detection of Nitroexplosive-Picric Acid in Aqueous Solution and Solid Support Using Conjugated Polymer Arvin Sain Tanwar, a Sameer Hussain, a Akhtar H. Malik, a Mohammad Adil Afroz a and Parameswar Krishnan Iyer* a,b a Department of Chemistry, Indian Institute of Technology Guwahati, Guwahati-789. India b Centre for Nanotechnology, Indian Institute of Technology Guwahati, Guwahati, 789, India AUTHOR ADDRESS: pki@iitg.ernet.in AUTHOR FAX: S

2 Table of Contents Description Page Scheme S. Chemical structures of various nitroexplosives used in the study. S Figure S-S6 NMR spectra of various synthesized compound. S-S6 Figure S7. GPC chromatogram of polymer P. S-6 Figure S8. Image of under UV-light before and after addition of PA. S-7 Figure S9. Detection limit plot for PA. S-7 Table S: Fluorescence lifetime decay of each component and their fractions. S-7 Table S: A comparative study of some conjugated polymer based reports for picric acid detection S-8 Figure S. PL spectra showing the effect of various nitro analytes on the emission of. S-9 Figure S. Bar diagram depicting effect of various metal ions on the fluorescence intensity of. S-9 Figure S. Bar diagram depicting effect of various anions on the emission of. S- Figure S-S. Change in emission spectra of with various nitroexplosives followed by addition of PA. Figure S. Overlap between excitation/emission spectra of and absorbance spectra of various nitrophenols. S-5 Figure S4. Change in emission spectra of before and after adding TFA. S-6 Figure S5. Emission spectra of /TFA with different concentrations of PA salt solution. S-6 Figure S6. Change in emission spectra of with TFA followed by the addition of TNT. S-7 Figure S7. Calibration plot for the estimation of PA. S-7 S-S5 Figure S8. Recyclability test of coated paper strips. S-8 Figure S9. Colour of coated paper strips under UV light after addition of various analytes. S-8 S

3 O N OH NO O N NO NO N NO PA OH NO OH N N O N NO NO, 4, 6 - TNT RDX NO NO, 4 - DNP 4 - NP NO O N NO NO NO NO NO, 4 - DNT 4 - NT, 6 - DNT, - DNB COOH NO OH H C NO BA NB NM Phenol Scheme S: Chemical structures of various nitroexplosives used in the study. Figure S. H-NMR spectra of M. S

4 Figure S. C-NMR spectra of monomer M. Figure S. High resolution mass spectrum of monomer M. S4

5 Figure S4. H-NMR spectra of polymer P. Figure S5. C NMR of polymer P. S5

6 Figure S6. H-NMR spectra of polymer. Figure S7. GPC chromatogram of polymer P. S6

7 Figure S8. Image of under UV-light before and after addition of PA. PL Intensity (a.u. ).. y = -6x + E+6 R² = [Picric acid] -6 M Figure S9. Fluorescence intensity of in 4:/THF:HEPES buffer (ph=7, mm) vs PA concentration. LOD= S.D./k LOD = 48.88/ (6 6 ) = 57.8 nm or. ppb Table S: Fluorescence lifetime decay of each component and their fractions. Sample τ (ns) % τ (ns) % χ² PA τ avg (ns) S7

8 Table S: A comparative study of some conjugated polymers based reports for picric acid detection. Publication K sv (M - Sensing ) Detection Limit Selectivity Mechanism Present Manuscript M Inner Filter Selective (.4 ppb) Effect J. Am. Chem. Soc., In the range Electrontransfer 5, Not reported Not selective Macromolecules 9, 4, ppm - Not studied (.7 µm) Macromol. Rapid Commun ,, Upto ppm Not studied Macromolecules, 44, Macromol. Rapid Commun., 4, RSC Adv.,,, Macromolecules, 46, Macromolecules 4, 47, Polym. Chem., 4, 5, J. Mater. Chem. A, 4,, J. Mater. Chem. A, 4,, Chem. Commun., 5, 5, 77 7 J. Mater. Chem. A, 5,, Upto ppm Not studied M Not studied. 5 ppm Not studied Upto µg/ml Not studied.7 5 µm Not selective ppm Not selective ppm Selective (.48µM) Not reported Not selective 7.8 ppb Selective About ppm Selective Electron and/or energy transfer Energy transfer - - Energy transfer Electron transfer Electron transfer π π interactions Electron and/or energy transfer Electron transfer S8

9 Intensity(a.u.).5.5 +,-DNB +,6DNT +4NT +,4DNT +NM +NB +BA +Phenol +TNT +RDX +PA Wavelength(nm) Figure S. Photoluminescence spectra showing the effect of various nitro analytes (5-5 M) on the emission of ( -6 M) in 4:/THF:HEPES buffer (ph=7., mm). PL Intensity (a.u. ).5.5 Figure S. Bar diagram depicting effect of various metal ions (5-5 M) on the fluorescence intensity of ( -6 M). S9

10 PL Intensity (a.u. ).5.5 Figure S. Bar diagram showing effect of various anions (5-5 M) on the fluorescence intensity of ( -6 M) in 4:/THF:HEPES buffer (ph=7., mm). PL Intensity (a.u.).5.5 +,4-DNT -,4-DNT+PA Figure S. Emission spectra of ( -6 M) with,4-dnt (5-5 M) followed by addition of PA (5-5 M) in 4:/THF:HEPES buffer (ph=7., mm). S

11 PL Intensity (a.u.).5.5 +,6-DNT -,6-DNT+PA Figure S4. Emission spectra of ( -6 M) with,6-dnt (5-5 M) followed by addition of PA (5-5 M) in 4:/THF:HEPES buffer (ph=7., mm). PL Intensity (a.u.) NT +4-NT+PA Figure S5. Emission spectra of ( -6 M) with 4-NT (5-5 M) followed by addition of PA (5-5 M) in 4:/THF:HEPES buffer (ph=7., mm). S

12 PL Intensity (a.u.).5.5 +,-DNB +,-DNB+PA Figure S6. Emission spectra of ( -6 M) with,-dnb (5-5 M) followed by addition of PA (5-5 M) in 4:/THF:HEPES buffer (ph=7., mm). PL Intensity (a.u.).5.5 +NB +NB+PA Figure S7. Emission spectra of ( -6 M) with NB (5-5 M) followed by addition of PA (5-5 M) in 4:/THF:HEPES buffer (ph=7., mm). S

13 PL Intensity (a.u.).5.5 +NM +NM+PA Figure S8. Emission spectra of ( -6 M) with NM (5-5 M) followed by addition of PA (5-5 M) in 4:/THF:HEPES buffer (ph=7., mm). PL Intensity (a.u.).5.5 +BA +BA+PA Figure S9. Emission spectra of ( -6 M) with BA (5-5 M) followed by addition of PA (5-5 M) in 4:/THF:HEPES buffer (ph=7., mm). S

14 PL Intensity (a.u.).5.5 +Phenol +Phenol+PA Figure S. Emission spectra of ( -6 M) with Phenol (5-5 M) followed by addition of PA (5-5 M) in 4:/THF:HEPES buffer (ph=7., mm). PL Intensity (a.u.).5.5 +TNT +TNT+PA Figure S. Emission spectra of ( -6 M) with TNT (5-5 M) followed by addition of PA (5-5 M) in 4:/THF:HEPES buffer (ph=7., mm). S4

15 PL Intensity (a.u.).5.5 +RDX +RDX+PA Figure S. Emission spectra of ( -6 M) with RDX (5-5 M) followed by addition of PA (5-5 M) in 4:/THF:HEPES buffer (ph=7., mm).. Normalised Absorbance Absorbance of PA Absorbance of,4-dnp Absorbance of 4-NP Emission of Excitation of Normalised PL Intensity Figure S. Overlap between excitation/emission spectra of and absorbance spectra of various nitrophenols. S5

16 PL Inetensity(a.u.) TFA Figure S4. Emission spectra of ( -6 M) before and after adding TFA ( -4 M) in 4:/THF:HEPES buffer (ph=7., mm). PL Intensity (a.u) µM TFA + 5µM TFA + µm PA + 5µM TFA + µm PA + 5µM TFA + µm PA + 5µM TFA + 4 µm PA Figure S5. Emission spectra of /TFA ( µm/5 µm) with different concentrations of PA salt solution in 4:/THF:HEPES buffer (ph=7., mm). S6

17 PL Intensity (a. u.).5.5 +TFA +TFA+TNT Figure S6. Change in emission spectra of ( -6 M) with TFA ( -4 M) followed by the addition of TNT (5-5 M) in 4:/THF:HEPES buffer (ph=7., mm). Figure S7. Calibration plot obtained for the estimation of PA. S7

18 Fresh Dipped in PA Washed Dipped in PA Washed Dipped in PA Washed Figure S8. Recyclability test of coated paper strip. NB 4-NT TNT RDX Phenol BA,4-DNT,6-DNT,-DNB PA Figure S9. Colour of coated paper strips under UV light (lamp excitation-65 nm) after addition ( μl) of - M solution of various analytes. S8