Supporting Information (SI) for Highly sensitive and selective fluorescent probe for ascorbic acid with a broad detection range through dual-quenching and bimodal action of nitronyl-nitroxide Haerim Nam, a Ji Eon Kwon, a Min-Woo Choi, a Jangwon Seo, a, Seunghoon Shin, a,b Sehoon Kim, b and Soo Young Park *a a Center for Supramolecular Optoelectronic Materials, Department of Materials Science and Engineering, Seoul National University, 1 Gwanak-ro, Gwanak-gu, Seoul 151-744 Korea. *E-mail: parksy@snu.ac.kr. b Center for Theragnosis, Korea Institute of Science and Technology, 39-1 Hawolgok-dong, Seongbuk-gu, Seoul 136-791 Korea. Current address: Division of Advanced Materials, Korea Research Institute of Chemical Technology, 141 Gajeong-Ro, Yuseong-Gu, Daejeon 35-6, Republic of Korea. These authors contributed equally to this work. Contents Table S1. Calculated absorption transition energies of...s-2 Figure S1. Calculated absorption spectra of in MeOH...S-3 Figure S2. Absorption and photoluminescence spectra changes of 2 M in MeOH...S-4 Figure S3. Plot of fluorescence intensity vs. AA concentration...s-5 Figure S4. Linear relationship between the relative fluorescence intensity (F/F ) and AA concentration...s-6 Figure S5. Linear relationship between the relative double integratged ESR intensity (DI/DI ) and AA concentration...s-7 Figure S6. (a) Photoluminescence and (b) ESR spectra of with addition of various antioxidants...s-8 Figure S7. (a) Photoluminescence and (b) ESR spectra of with addition of 2 mm of CA...S-9 Figure S8. (a) Photoluminescence and (b) ESR spectra of with addition of Vitamin drink samples. (c) Photoluminescence and (d) ESR spectra of with addition of orange juice samples...s-1 Figure S9. HPLC analysis results of the Vitamin drink sample...s-11 Figure S1. HPLC analysis results of the orange juice sample...s-12 Figure S11. (a) Photoluminescence and (b-d) ESR spectra of with addition of various antioxidants and acids...s-13 Figure S12. (a) ESR spectra of in MeOH solution and nanoparticles (2 μm in water/thf = 7:3 in vol%). (b) ESR spectrum and (c,d) SEM images of nanoparticles (2 μm in water/thf = 8:2 in vol%)....s-14 Figure S13. (a) Photoluminescence and (b) ESR spectra of nanoparticles (2 μm in water/thf = 7:3 in vol%) at various ph...s-15 S-1
Table S1. Calculated energies, oscillator strength, orbitals, and character of absorption transition of in MeOH. Name Transition Energy Oscillator Strength (f) Excited-State 1 1.93 ev (643.68 nm) (doublet, neutral) Reduced (singlet, neutral) Reduced & Protonated (singlet, cationic) Excited-State 5 Excited-State 7 Excited-State 1 Excited-state 2 Excited-State 1 2.94 ev (421.48 nm) 3.11 ev (398.38 nm) 2.57 ev (482.14 nm) 3.31 ev (374.4 nm) 3.7 ev (44.45 nm) Orbitals (Expansion Coefficient).4 HOMOa LUMOa (.86268) HOMOa LUMOa+1 (.14148) HOMOa LUMOa+2 (-.1965).5821 HOMOa-2 LUMOa (.27517) HOMOa-1 LUMOa (-.47586) HOMOa-1 LUMOa+1 (.2451).676 HOMOa-8 LUMOa+2 (.1269) HOMOa-2 LUMOa (-.32292) HOMOa-2 LUMOa+1 (.12434) HOMOa-1 LUMOa (-.42893) HOMOa-1 LUMOa+1 (-.29574) Character n- * - * - *.5598 HOMO LUMO (.7348) - *.9422 HOMO-1 LUMO (.69987) - * 1.2189 HOMO LUMO (.749) - * S-2
Calculated Molar Extinction Coefficient ( ) 6 5 4 3 2 1 3 4 5 6 7 Reduced Reduced & Protonated Figure S1. Calculated absorption spectra of in MeOH. S-3
(a) Absorbance.8.6.4.2 Absorbance.28.245 eq.1eq.2eq.3eq.5eq.8eq 1eq 2eq.21 385 39 395 (b) 2.x1 4 1.5x1 4 1.x1 4 5.x1 3.1eq.2eq.3eq.5eq.8eq 1eq 2eq. 3 4 5 6 7. 35 4 45 5 55 6 Figure S2. (a) Absorption and (b) photoluminescence spectra changes of 2 M in MeOH solution upon addition of 4 M AA. S-4
4x1 7 Integrated Intensity 3x1 7 2x1 7 1x1 7 Model Equation Adj. R-Square bindingconstant1 (User) y = (A+B*K*x)/(1+K*x).98943 Value Standard Err D A 547653.7586 -- B 5.16365E7 2.38748E6 D K 199.8785 231.336..5.1.15.2 AA Concentration (M) Figure S3. Plot of fluorescence intensity vs. AA concentration. The red line is the non-linear regression fit to the experimental data points using 1:1 model (eq. S1). F F F K 1 KM [ ] [M] lim (S1) S-5
(a) 12 1 8 Equation y = a + b*x Adj. R-Squ.9827 Value Standard Error Intercept -4.79643 2.48651 F/Fo Slope 547448.3299 2612.6289 (b) 3 25 2 Equation y = a + b*x Adj. R-Squ.99145 Value Standard Error Intercept 676.76218 17.511 F/Fo Slope 154.47693 4.77928 F/Fo 6 F/Fo 15 4 1 2 5. 5.x1-5 1.x1-4 1.5x1-4 2.x1-4 AA concentration (M) -6. -5.5-5. -4.5-4. -3.5-3. -2.5 log [AA] Figure S4. Linear relationship between the relative fluorescence intensity (F/F) and AA concentration (a) from 1 M to.2 mm and (b) from.1 mm to 2 mm. S-6
1..8 Equatio y = a + b*x Adj. R-S.98886 Value Standard Error Intercept.9914.2634 DI/DIo Slope -84365.7124 3652.71285 DI/DIo.6.4.2.. 5.x1-6 1.x1-5 1.5x1-5 2.x1-5 AA concentration (M) Figure S5. Linear relationship between the relative double integratged ESR intensity (DI/DI) and AA concentration. S-7
(a) 4 2 w/ BHT w/ HQ w/ Cys w/ Tyr w/ GSH w/ AA (b) 22 11 w/ BHT w/ HQ w/ Cys w/ Tyr w/ GSH -11 4 45 5 55 6 65 7 Emission -22 333.5 335.8 338.1 Magnetic Field (mt) Figure S6. (a) Photoluminescence and (b) ESR spectra of with addition of various antioxidants. S-8
(a) 35 3 Citric Acid (b) 2 Citric Acid 25 2 15 1-1 1 5 4 45 5 55 6 65-2 Magnetic Field (mt) Figure S7. (a) Photoluminescence and (b) ESR spectra of with addition of 2 mm of citric acid (CA). S-9
(a) 35 3 25 2 15 1 Blank Unspiked Spiked (b) 2 1-1 Blank Unspiked Spiked 5 4 45 5 55 6-2 Magnetic Field (mt) (c) 1 8 Blank Unspiked Spiked (d) 2 1 Blank Unspiked Spiked 6 4-1 2 4 45 5 55 6-2 Magnetic Field (mt) Figure S8. (a) Photoluminescence and (b) ESR spectra of with addition of Vitamin drink samples. (c) Photoluminescence and (d) ESR spectra of with addition of orange juice samples. S-1
Sample Name: 1 Injection Volume: 1. Vial Number: RA6 Channel: UV_VIS_1 Sample Type: unknown Wavelength: 265. Control Program: Vit C_GREDIENT Bandwidth: 8 Quantif. Method: VitaminC Dilution Factor: 5. Recording Time: 215-5-19 18:55 Sample Weight: 1. Run Time (min): 2. Sample Amount: 1. 8 519_ 권지언VitC #8 [modified by NICEM_1] 1 UV_VIS_1 mau WVL:265 nm 1 - Vitamin C - 4.823 625 5 375 25 125-1 min. 2.5 5. 7.5 1. 12.5 15. 17.5 2. No. Ret.Time Peak Name Height Area Rel.Area Amount Type min mau mau*min % mg/l 1 4.82 Vitamin C 76.114 76.721 1. 5418.562 BM * Total: 76.114 76.721 1. 5418.562 Figure S9. HPLC analysis results of the Vitamin drink sample. S-11
Sample Name: 3 Injection Volume: 1. Vial Number: RA7 Channel: UV_VIS_1 Sample Type: unknown Wavelength: 265. Control Program: Vit C_GREDIENT Bandwidth: 8 Quantif. Method: VitaminC Dilution Factor: 5. Recording Time: 215-5-19 19:16 Sample Weight: 1. Run Time (min): 2. Sample Amount: 1. 14 519_ 권지언VitC #9 [modified by NICEM_1] 3 UV_VIS_1 mau WVL:265 nm 1 - Vitamin C - 4.76 1 75 5 25-2 min. 2.5 5. 7.5 1. 12.5 15. 17.5 2. No. Ret.Time Peak Name Height Area Rel.Area Amount Type min mau mau*min % mg/l 1 4.76 Vitamin C 118.355 1.169 1. 718.186 BM * Total: 118.355 1.169 1. 718.186 Figure S1. HPLC analysis results of the orange juice sample. S-12
(a) 6 5 4 3 2 Dopamine Fructose Glucose NADH NAD+ UA AA (b) 2 1 Dopamine Fructose Glucose -1 1 (c) 2 1 4 45 5 55 6 NADH NAD+ (d) -2 2 1 Magnetic field (mt) UA -1-1 -2 Magnetic Field (mt) -2 Magnetic Field (mt) Figure S11. (a) Photoluminescence and (b-d) ESR spectra of with addition of various antioxidants and acids. S-13
Figure S12. (a) ESR spectra of in MeOH solution (black solid line) and nanoparticles (red solid line; 2 μm in water/thf = 7:3 in vol%). (b) ESR spectrum and (c,d) SEM images of nanoparticles (2 μm in water/thf = 8:2 in vol%). S-14
(a) 2 15 1 ph4 ph7 ph1 ph4 + AA ph7 + AA ph1 + AA (b) 15 1 5-5 ph4 ph7 ph1 ph4 + AA ph7 + AA ph1 + AA 5-1 4 45 5 55 6-15 Magnetic Field (mt) Figure S13. (a) Photoluminescence and (b) ESR spectra of nanoparticles (2 μm in water/thf = 7:3 in vol%) at various ph in the absence (solid lines) and the presence of 2 mm of AA (dotted lines). S-15