Conjugated Polymer Nanoparticles for the. Amplified Detection of Nitro-explosive Picric Acid

Transcription

1 Supporting Information Conjugated Polymer Nanoparticles for the Amplified Detection of Nitro-explosive Picric Acid on Multiple Platforms Akhtar Hussain Malik a, Sameer Hussain a, Anamika Kalita b, and Parameswar Krishnan Iyer a,b * a Department of Chemistry, Indian Institute of Technology Guwahati, Guwahati India b Centre for Nanotechnology, Indian Institute of Technology Guwahati, Guwahati, , India AUTHOR ADDRESS: pki@iitg.ernet.in AUTHOR FAX: S-1

2 Figure S1. Synthesis of the polymer-pfmi. (a) 1,6-dibromohexane, 50% aq. NaOH, TBAI, 70 ºC, 4h. (b) Tetrakistriphenylphosphine palladium(0), benzene-1,4-diboronic acid, 2M K 2 CO 3 (aq.), THF, reflux, 24 h. (c) 1-methyl imidazole, reflux, 24 hr Figure S2. 1 H-NMR spectra of PF. S-2

3 Figure S3. 13 C-NMR spectra of PF. Figure S4. 1 H-NMR spectra of polymer PFMI. S-3

4 Figure S5. 13 C-NMR spectra of polymer PFMI. Figure S6. GPC chromatogram of polymer PF. S-4

5 Figure S7. Comparison of absorption maxima of PFMI and in solution.. Figure S8. Fluorescence intensity of in aqueous medium as a function of concentration. LOD=3 S.D./k LOD = / ( ) = pm or 7.07 ppt S-5

6 Table S1: A comparative study of recently reported probes for with our results. Publication Current Manuscript Chem. Commun., 2014, 50, ACS Appl. Mater. Interfaces, 2014, 6, Chem. Eur. J. 2014, 20, Chem. Comm., 2014, 50, Chem. Mater., 2014, 26, Chem. Eur. J., 2014, 20, Chem. Commun., 2014, 50, J. Mater. Chem. A, 2014, 2, Polym. Chem., 2014, 5, J. Mater. Chem. A, 2014, 2, Macromolecules 2014, 47, J. Mater. Chem. A, 2015, 3, Chem. Eur. J. 2015, DOI: /chem ACS Appl. Mater. Interfaces, 2015, DOI: /acsami.5b01102 Material used Conjugated polymer nanoparticles Stern- Volmer Constant (M -1 ) Detection Limit (LOD) M (7.07 ppt) Metal complex Medium Used Water Water/Acetone (v/v=9:1) Graphene oxide (GO) ppb Buffer Tetraphenylethelene Nanosphere Bimetallic Schiff-base Al 3+ complexes M M M Derivative of graphene ppb Derivative of α- cyanostilbene M Water/THF (v/v=9:1) MeOH/DMSO Water/THF (v/v=9:1) Water/THF (v/v=7:3) Cage compound ppb DCM PDA microtube ( M) 0.11 ppm Water Poly(acrylate) derivative Polymeric ionic liquid ppm Water/THF (v/v=9:1) DMSO Conjugated polymers µM Conjugated polymer Polyfunctional lewis acid Curcumin derivatives - Water/THF (v/v=9:1) ~1 ppm Methanol ppb DMF M M Water S-6

7 J. Org. Chem., 2015, 80, Chem. Commun., 2015, 51, Chem. Commun., 2015,51, Triphenylamine derivative Conjugated polyelectrolyte MOFs ppb M 128 ppt DMA, CHCl 3 Water DMA Figure S9. Change in emission spectra of ( M) on the addition of ( M) in the presence of various nitroexplosives ( M). S-7

8 Intensity (a.u.) x10 6 2,4-DNT Figure S10. Change in photoluminescence spectra of ( M) with 2,4-DNT ( M) followed by addition of ( M) in aqueous medium. Intensity (a.u.) x10 6 2,6-DNT Figure S11. Change in photoluminescence spectra of ( M) with 2,6-DNT ( M) followed by addition of ( M) in aqueous medium. S-8

9 Intensity (a.u.) x NT Figure S12. Change in photoluminescence spectra of ( M) with 4-NT ( M) followed by addition of ( M) in aqueous medium. Intensity (a.u.) x10 6 1,3-DNB Figure S13. Change in photoluminescence spectra of ( M) with 1,3-DNB ( M) followed by addition of ( M) in aqueous medium. S-9

10 Intensity (a.u.) x10 6 NB Figure S14. Change in photoluminescence spectra of ( M) with NB ( M) followed by addition of ( M) in aqueous medium. Intensity (a.u.)x10 6 NM Figure S15. Change in photoluminescence spectra of ( M) with NM ( M) followed by addition of ( M) in aqueous medium. S-10

11 Intensity (a.u.) x10 6 Phenol Figure S16. Change in photoluminescence spectra of ( M) with phenol ( M) followed by addition of ( M) in aqueous medium. Intensity (a.u.) x10 6 TNT Figure S17. Change in photoluminescence spectra of ( M) with TNT ( M) followed by addition of ( M) in aqueous medium. S-11

12 Intensity (a.u.) x10 6 RDX Figure S18. Change in photoluminescence spectra of ( M) with RDX ( M) followed by addition of ( M) in aqueous medium. Figure S19. Change in emission spectra of ( M) on the addition of ( M) in the presence of various common metal ions ( M). S-12

13 Figure S20. Change in emission spectra of ( M) on the addition of ( M) in the presence of various common anions ( M). Table S2. Overlap integral J (λ) values calculated for various nitroexplosives used in the study. Nitro aromatic analytes J (λ) values (M 1 cm 1 nm 4 ) TNT RDX NM NB NT ,6-DNT ,4-DNT Phenol ,3-DNB S-13

14 Figure S21. (a) PL spectra depicting the change in emission of ( M) after adding ( M) in the solution containing various concentrations of salt. (b) The effect of ionic strength on the quenching efficiency. Quenching Percentage (%) ,4-DNP 4-NP Figure S22. Comparative fluorescence quenching by, 2, 4-DNP and 4-NP in aqueous media. Concentration of and other analytes were M and M, respectively. S-14

15 Intensity (a.u. ) x10 6 Wavelength (nm) TFA Figure S23. Change in photoluminescence spectra of ( M) before and after the addition of TFA ( M) in aqueous medium. Figure S24. Optical microscope image of device showing channel and interface between PFMI- NPs film and bare aluminium surface. S-15

16 Figure S25. The response and recovery time of sensor device exposed to 1 ppb of. Figure S26. The response of the device on repeatedly exposing (0.3 ppb) vapors after certain time intervals. S-16