Design Principles of Chemiluminescence Chemodosimeter for Self- Signaling Detection: Luminol Protective Approach

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1 Electronic Supplementary Material (ESI) for RSC Advances. This journal is The Royal Society of Chemistry 1 Supporting Information Design Principles of Chemiluminescence Chemodosimeter for Self- Signaling Detection: Luminol Protective Approach Min Sang Kwon, Geunseok Jang, David Bily, Begoña Milián-Medina, Johannes Gierschner, Taek Seung Lee, and Jinsang Kim* Synthetic details. TBS-luminol and TIPS-luminol were synthesized according to the procedure shown in Scheme S1 and Scheme S, respectively. All chemicals purchases commercially, and used without further purification. The progress of reaction was checked on TLC plates (Merck 555 Kiesel gel 6 F5), and the spots were visualized under 5 nm UV light and/or charring after dipping the TLC plate into vanillin solution (9. g of vanillin and 1.5 ml of concentrated sulfuric acid in ml of MeH) and KMn solution ( g of KMn, g of K C, and 5 ml of 5% NaH solution in ml of water). Column chromatography was performed on silica gel (Merck 985 Kiesel gel 6). Unless otherwise specified, all reactions were conducted under a slight positive pressure of dry nitrogen. The usual work-up refers to washing the quenched reaction mixture with rine, drying the organic extracts over anhydrous MgS and evaporating under reduced pressure using a rotary evaporator. Spectroscopic Characterization. 1 H-NMR, 1 C-NMR, D NESY NMR, and D HMBC NMR spectra were recorded on a Varian, MR ( MHz) in DMS solution. Chemical shift values were recorded as parts per million relative to tetramethylsilane as an internal standard, and coupling constants in Hertz. Mass spectra were recorded on an Agilent Q-TF 65 systemusing electrospray in positive ion detection (ESI+) mode. Significant fragments are reported in the following fashion: m/z (relative intensity). Elemental analysis was carried out using a CE instruments, EA111 elemental analyzer. UV-visile asorption spectra were measured on a Varian Cary5 UV/Vis 1

2 spectrophotometer. Chemiluminescence and Time-dependent chemiluminescence were otained using PTI Quanta Master TM spectrofluorometers equipped with an integrating sphere and an laser excitation system. Calculation details. DFT calculations are used to rationalize the reaction path for the synthesis of TBS-Luminol from Luminol in aqueous media under asic condition (pyridine). Lum + Py + TBSCl IM + PyH + + TBSCl TBS-Lum + Py + HCl All possile reactants, intermediates and products were geometry optimized y density functional theory (DFT) in water, descried y the Polarizale Continuum Model (PCM) as implemented in the Gaussian9 program package. 1 Since the geometry might e a critical issue, all calculations were done without symmetry constraints using the BHandHLYP functional. For comparison, the BLYP was used which yield very similar results. The asolute geometries were confirmed y the asence of negative frequencies in the respective frequency calculations, which also yield the free Gis energies ΔG. Comparison of ΔG for reactants, intermediates (IM) and products were otained y applying Hess's law. The reaction conditions and injection sequence of TBS-luminol and luminol for CL measurements. Addition of tetrahydrofuran (THF) solution of TBS-luminol or luminol ( M, μl) to a mixed water solution of Co(N ) (5 1 - M, μl), H ( 1 - M, μl) and Na C / NaHC ( M, μl). The evaluation of the performance of TBS- and TIPS-luminol as a sensor of F -. We used 1 M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Ro, J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenerg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda,. Kitao, H. Nakai, T. Vreven, J. A. Montgomery, Jr., J. E. Peralta, F. gliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, R. Koayashi, J. Normand, K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J. M. Millam, M. Klene, J. E. Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann,. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. chterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J. Dannenerg, S. Dapprich, A. D. Daniels, Ö. Farkas, J. B. Foresman, J. V. rtiz, J. Cioslowski, and D. J. Fox, Gaussian, Inc., Wallingford, CT 9, Gaussian 9, Gaussian, Inc., Wallingford CT, 9

3 tetrautylammonium fluoride (TBAF, M, 1 μl) as a F - source and added TBAF into the THF solution of TBS-luminol (. 1 - M, 1 μl) or TIPS-luminol (. 1 - M, 1 μl). Susequent exposure of the resulting solution to the mixed water solution of Co(N ) (5 1 - M, μl), H ( 1 - M, μl) and Na C /NaHC ( M, μl) produced strong lue CL emission,

4 TBSCl Pyridine r.t. overnight N TBS Scheme S1. The synthetic scheme of TBS-luminol TBS-luminol tert-butylsilyl chloride (5.11 g,.9 mmol) was added to a solution of luminol (. g, 11. mmol) in pyridine (9. ml) at room temperature. The solution was stirred at room temperature for overnight. The reaction mixture was poured into water and extracted with ethyl acetate and washed with water and rine. The organic phase was dried over MgS and the solvent was evaporated in vacuo. Purification of the residue y column chromatography (hexanes-ethyl acetate, 1:1) provided TBS-luminol (.1 g, 6 %). 1 H NMR ( MHz, DMS-d 6 ): δ 11.5 (s, 1 H), 7.5 (t, 1 H, J = 7.8 Hz), 7.5 (r s, H), 6.89 (d, H, J = 7.5 Hz), 1. (s, 9H),. (s, 6H). 1 C NMR (1 MHz, DMS-d 6 ): δ 161.7, 15.8, 19., 1., 17.1, 116., 11.5, 18.8, 5.7, 17.8, -.6. HRMS (ESI + ) calcd. for C 1 H 1 N Si (M + +1) 9.176, found TIPSCl Pyridine r.t. overnight N TIPS Scheme S. The synthetic scheme of TIPS-luminol TIPS-luminol Triisopropyl silyl chloride (6.5 g,.9 mmol) was added to a solution of luminol (. g, 11. mmol) in pyridine (9. ml) at room temperature. The solution was stirred at room temperature for overnight. The reaction mixture was poured into water and extracted with ethyl acetate and washed with water and rine. The organic phase was dried over MgS and the solvent was evaporated in vacuo. Purification of the residue y column chromatography (hexanes-ethyl acetate, 1:1) provided TIPS-luminol (.5 g, 67 %). 1 H NMR ( MHz, DMS-d 6 ): δ 11. (s, 1 H), 7.51 (t, 1 H, J = 8. Hz), 7. (r s, H), 6.9 (d, 1H, J = 8. Hz), 6.9 (d, 1H, J = 8. Hz), (m, H), 1.8 (d, 18H, J = 8. Hz). 1 C NMR (1 MHz, DMS-d 6 ): δ 161.8, 15.9, 19., 1., 16.9, 116., 11.5, 18.8, 17.8, 1.1. HRMS (ESI + ) calcd. for C 1 H 1 N Si (M + +1).187, found.1879.

5 a 1 H 7 H 5 5 N TBS 6 7 H H, H Water DMS H 6 H H 5, H H 6 H, H H 1 TMS Chemical Shift (ppm) c C 8 C 7 C 1 C C6 C 5 C C N TBS DMS TBS d C C 8 C C 7 C6 C C 1 C Chemical Shift (ppm) Figure S1. 1 H-NMR spectra of (a) TBS-luminol and () luminol registered in DMS-d 6. 1 C-NMR spectra of (c) TBS-luminol and (d) luminol registered in DMS-d 6 5

6 a TBS-luminol + Base 5 l 1.5 l 5 l 5 l 1 l l l Luminol + Base l Base 5 l Base 1.5 l Base 5 l Base 5 l Base 1 l Base l Base l Time (sec) Wavelength (nm) Figure S. Chemiluminescence (CL) spectra of (a) TBS-luminol and () Luminol depending upon addition of ase. a TIPS-luminol + Base l Base 5 l Base 1.5 l Base 5 l Base 5 l Base 1 l Base l Base l TIPS-luminol + Base l Base 5 l Base 1.5 l Base 5 l Base 5 l Base 1 l Base l Base l Base 6 l Time (sec) Time (sec) Figure S. CL spectra of (a) TIPS-luminol and () Luminol depending upon addition of ase. 6

7 Asorance (a.u.) TBS-luminol TIPS-luminol TBS-luminol + TBAH ( sec) TIPS-luminol + TBAH ( sec) Wavelength (nm) Figure S. UV-Vis spectra of the luminol derivatives efore and after adding tetrautylammonium hydroxide (TBAH). Experimental conditions are as follows: luminol derivatives (. X 1 - M in THF,.1 ml), THF (.6 ml), DI-water (.6 ml), and TBSH (1 M,. ml). a TBS-Luminol +.57 X1-6 M TBAF 1.79 X1-6 M 7.1 X1-7 M Integrated.5x1 7 TBS-luminol Linear fit.x x1 7 1.x1 7 5.x1 6 LD = 6 nm Time (s).. 1.x1-6.x1-6.x1-6.x1-6 Concentration (M) Figure S5. (a) CL intensity curves of TBS-luminol were plotted versus time at various TBAF concentrations, () linear caliration data for F - concentration. 7

8 a CL intensity (a.u.) TIPS-luminol +.57X1-7 M TBAF 1.79 X1-7 M TBAF 7.1 X1-8 M TBAF.57 X1-8 M TBAF Time (sec) Integrated TIPS-luminol Linear Fit. 1.x1-7.x1-7.x1-7.x1-7 Concentration (M) LD = 18 nm Figure S6. (a) CL intensity curves of TIPS-luminol were plotted versus time at various TBAF concentrations, () linear caliration data for F - concentration. Asorance (a.u.) TIPS-luminol TIPS-lumino +TBAF, 1sec sec mins mins Wavelength (nm) Figure S7. UV-Vis spectra of TIPS-luminol (THF, M) and TBAF (THF, M) treated TIPS-luminol with different incuation time were plotted. 8

9 .x x1 7 Integrated CL intensity (a.u.) 1.6x1 7 1.x1 7 1.x1 7 1.x1 7 8.x1 6 6.x1 6.x1 6.x1 6. TBAF/THF KF/THF KF/DMS CsF/DMS Figure S8. Relative integrated CL intensity of TIPS-luminol (THF, M; DMS, M) after treatment of excess amount of TBAF, KF, and CsF ( M). 9