Supporting Information. Nanoparticles with Embedded Porphyrin Photosensitizers. for Photooxidation Reactions and Continuous Oxygen.

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1 Supporting Information Nanoparticles with Embedded Porphyrin Photosensitizers for Photooxidation Reactions and Continuous Oxygen Sensing Pavel Kubát, Petr Henke, Veronika erzediová, Miroslav Štěpánek, Kamil Lang $ and Jiří Mosinger $ * J. Heyrovský Institute of Physical Chemistry of the Czech cademy of Sciences, v.v.i., Dolejškova 3, 18 3 Prague 8, Czech Republic Faculty of Science, Charles University, 3 Hlavova, Prague, Czech Republic $ Institute of Inorganic Chemistry of the Czech cademy of Sciences, v.v.i., 5 68 Řež, Czech Republic Corresponding uthor * address: mosinger@natur.cuni.cz S-1

2 Content Experimental details S-3 Figure S1 Light scattering measurements S-5 Figure S Normalized UV-Vis spectra of TPP-NPs S-5 Figure S3 Normalized UV-Vis spectra of TMPyP-NPs S-6 Figure S4 Fluorescence emission spectra of TPP-NPs S-6 Figure S5 Fluorescence emission spectra of TMPyP-NPs S-7 Figure S6 Photostability test S-7 Figure S7 Kinetics of O ( 1 Δ g ) photogenerated by TPP-NPs and TMPyP-NPs S-8 Figure S8 Kinetics of the triplet states of TMPyP dissolved in H O S-8 Figure S9 Kinetics of the triplet states of TPP-NPs in H O S-8 Figure S1 Kinetics of the triplet states of TMPyP-NPs in H O S-9 Figure S11 Kinetics of O ( 1 Δ g ), TPP triplet states and SODF of TPP-NPs S-9 Figure S1 SODF of TMPyP-NPs and TPP-NPs in the presence of NaN 3 S-1 Figure S13 Temperature dependence of O ( 1 Δ g ) and TPP triplet state kinetics in the polystyrene nanofiber material S-1 Figure S14 Dependence of SODF on oxygen concentration S-11 Figure S15 Photooxidation of uric acid by the TPP-NPs or TMPyP-NPs dispersions containing the same number of NPs S-1 Figure S16 Photooxidation of uric acid by the TPP-NPs or TMPyP-NPs dispersions containing the same content of TPP S-1 Table S1 Parameters of prepared sulfonated NPs S-13 Table S Parameters of prepared photoactive NPs S-14 Table S3 Oxygen properties S-15 S-

3 Experimental details Photophysical measurements. The measurements were performed in a 1 mm quartz cell placed inside a thermostatically-controlled holder that was heated or cooled using the Peltier effect to maintain temperature stability to within.1 C. piece of the nanofiber material was placed on a quartz plate and inserted in a quartz cell with H O. The samples were saturated by argon for the measurement in oxygen-free conditions. ll samples were excited by a Lambda Physik FL 3 dye laser (45 nm, pulse width 8 ns). The triplet state kinetics were recorded by transient absorption spectroscopy at 46-5 nm using a 15 W Xe lamp (Phillips) equipped with a pulse unit and a R98 photomultiplier (Hamamatsu) using a laser kinetic spectrometer LKS (pplied Photophysics, UK). Time-resolved near-infrared phosphorescence of O ( 1 Δ g ) at 17 nm was observed at a right angle to the excitation pulse using a homemade detector unit (interference filter, Ge diode Judson J16-8SP-R5M-HS). ll measurements were performed in air atmosphere or in air-saturated solutions. Singlet oxygen-sensitized delayed fluorescence (SODF) was monitored at 65 nm (i.e., at the maximum of the fluorescence emission band) on the laser kinetic spectrometer LKS (pplied Photophysics). The signals of both SODF and O ( 1 Δ g ) were averaged and were calculated as the differences between signals in air-saturated solutions and detector responses in argon-saturated solutions. The initial part of the signals fails due to light scattering and strong prompt porphyrin fluorescence, and they were omitted in all figures. Light scattering measurements. The scattering intensities I(t,q), were acquired for the scattering vector magnitudes, q=(4 n / )sin( /) (n is the solvent refractive index), from 1.1 m 1 to 5.5 m 1 corresponding to the scattering angles from 45 to 15. Each measurement took 1 s and provided the time-averaged scattering intensities, I(q)= I(t,q), and the normalized autocorrelation functions of the scattered light intensity, g () (,q)= I(t,q)I(t+,q) /I (q). The I(q) values were recalculated to the absolute scale using calibration by the toluene standard. The static scattering data (Figure S1, curve 1) were fitted by the Guinier formula, I(q)=I()exp( R g q /3), to obtain the gyration radius of NPs, R g = 4 nm, and the forward scattering intensity, I(). The latter value provided the molar mass of the NPs as M w 4 N 4π n (dn / dc) I () I c g mol, (S1) S-3

4 where N is the vogadro constant, I is the scattering from the solvent and (dn/dc) =.7 ml g -1 is the refractive index increment for polystyrene in water. The autocorrelation functions were fitted using the second-order cumulant expansion, () ( q) (, q) 1 exp 1 ( q) g, (S) where 1 (q) and (q) are the 1-st and -nd order cumulants and β is the coherence factor. The hydrodynamic radius, R H, was calculated using the Stokes-Einstein formula from the z-averaged translation diffusion coefficient, D, obtained from 1 (q)/q values extrapolated to q (Fig. S1, curve ) as q) D(1 R Cq g q ( ), (S3) where C is the parameter dependent on the shape, dispersity and internal dynamics of the NPs. S-4

5 ln(i(q) / m 1 ) q ( m ) /q ( m s 1 ) Figure S1. (a) Logarithm of the scattering intensity, ln(i(q)) (curve 1), and the apparent diffusion coefficient, 1 (q)/q (curve ) as functions of q, from the SLS and DLS measurement of.15 mg ml -1 NPs dispersion. Normalized absorbance TPP-NPs (NPs/mL) 1 wt% ( ) 5 wt% ( ).5 wt% (3 1 1 ).5 wt% ( ).5 wt% ( ) Figure S. Normalized UV-Vis spectra of TPP-NPs. The dispersions have the same overall amount of TPP which was achieved by a different number of NPs. S-5

6 Normalized absorbance TMPyP/IES (NPs/mL).1 ( ).1 (3 1 1 ).1 ( ) TMPyP in water () Figure S3. Normalized UV-Vis spectra of TMPyP and TMPyP-NPs. The dispersions have the same overall amount of TMPyP which was achieved by a different number of NPs. Normalized fluorescence wt%.5 wt%.5 wt% 5 wt% 1 wt% Fluorescence intensity (a.u.) 3x1 4 x1 4 1x1 4.5 wt%.5 wt% 5 wt% 1 wt% Figure S4. Normalized fluorescence emission spectra () and the same spectra in original intensities () of TPP-NPs dispersions. The samples have the same overall content of TPP ( 1-7 mol l -1 ) which was achieved by a different number of NPs ( NPs ml -1 ). Excitation at exc = 516 nm. S-6

7 Normalized fluorescence TMPyP/IES Fluorescence (a.u.) 1.x1 5 1.x1 5 8.x1 4 6.x1 4 4.x1 4.x1 4 TMPyP/IES Figure S5. Normalized fluorescence emission spectra () and the same spectra in original intensities () of TMPyP-NPs dispersions. The samples have the same overall content of TMPyP (1 1-6 mol l -1 ) which was achieved by a different number of NPs ( NPs ml -1 ). Excitation at exc = 43 nm. bsorbance bsorbance min 3 min 6 min 9 min 1 min 15 min Figure S6. Photostability test: Photodegradation of TPP-NPs (.5 wt%; panel ) and TMPyP- NPs (.1 TMPyP/IEC; panel ) dispersions ( NPs ml -1 ) during the irradiation by a 5 W xenon lamp equipped with a 4 nm long pass filter. S-7

8 Luminescence at 17 nm (a.u.) 4 TMPyP TPP-NPs TMPyP-NPs Figure S7. Kinetics of O ( 1 Δ g ) photogenerated by TMPyP in H O (τ Δ ~ 3-4 μs) (), TPP-NPs () and TMPyP-NPs (C). The kinetics of O ( 1 Δ g ) deactivation in TPP-NPs is controlled by the polymer (i.e., oxygen diffusion coefficient, number of quenching groups and the size of NPs) (). The kinetics of O ( 1 Δ g ) produced by TMPyP-NPs is evidently affected by partial diffusion of O ( 1 Δ g ) through the polymer matrix having higher τ Δ than water (C). C bsorbance oxygen.3 T =.44 s. air.3 T =. s..4 argon T = 155 s Figure S8. Kinetics of the triplet states of TMPyP in H O bsorbance oxygen T = 3.4 s air T = 13.8 s.1 argon.8.6 T = 157 s Figure S9. Kinetics of the triplet states of.5 wt% TPP-NPs in H O S-8

9 bsorbance oxygen T = 1.7 s air T = 7.8 s argon double exponential T1 = 175 s (63 %) T = 936 s (37 %) Figure S1. Kinetics of triplet states of TMPyP-NPs in oxygen-, air-, or argon-saturated H O. The traces were recorded at 46 nm upon excitation by a 45 nm laser pulse; red lines represent corresponding exponential fits. Normalized signal (a.u.) SODF TPP triplet states Singlet oxygen Figure S11. Kinetics of O ( 1 Δ g ), porphyrin triplet states and SODF in air-saturated.5 wt% TPP-NPs water dispersion. S-9

10 1 3 % H O+7 % D O without NaN % H O+7 % D O without NaN 3 Fluorescence (a.u.) 5 with NaN 3 saturated with argon Fluorescence (a.u.) 3 1 with NaN Figure S1. SODF of TMPyP-NPs (.1 TMPyP/IES) () and.5 wt% TPP-NPs () in the presence and absence of a singlet oxygen quencher, NaN 3, in air-saturated D O/H O. The absence of SODF is documented by the measurement of TMPyP-NPs in oxygen-free D O/H O. Phosporescence of singlet oxygen(a.u.) 6 4 C, =.4 s 5 C, =9.6 s bsorbance at 46 nm C, T =16.7 s 5 C, T =1.3 s Figure S13. Temperature dependence of O ( 1 Δ g ) phosphorescence () and TPP triplet state () kinetics in the polystyrene nanofiber material containing 1 wt% TPP. S-1

11 SODF (a.u.).1 1E-3 ORIGINL DT SODF (a.u.).1 SINGLE EXPONENTIL FITS 1E-3 1E-4 1E-5 1E mplitudes (a.u.) MPLITUDES 1/ (s -1 ) x1 5 1x1 5 RTE CONSTNTS Intensity (a.u.) 1.5x1-7 SODF INTENSITY FTER s 1.x1-7 5.x Concentration of O (mg l -1 ) Concentration of O (mg l -1 ) Concentration of O (mg l -1 ) Figure S14. Dependence of SODF on dissolved oxygen concentration: amplitudes of exponential fits vs. oxygen concentration (left), the Stern-Volmer plot, i.e., 1/τ SODF vs. oxygen concentration (middle), and overall SODF intensity after μs vs. oxygen concentration (right). S-11

12 bsorbance at 91 nm TPP-NPs.5 wt%.5 wt% 5% wt% 1% wt% TMPyP/IEC Time (s) Figure S15. Photooxidation of uric acid by the TPP-NPs () or TMPyP-NPs () dispersions containing the same number of NPs ( NPs ml -1 ) during continuous irradiation at 5 C. Irradiated by a 5 W Xe-lamp equipped with a long pass filter (λ 4 nm), absorption of 3 ml of air-saturated 1-4 M uric acid was recorded at 91 nm. bsorbance at 91 nm TPP-NPs (NPs/ml).5 wt% ( ).5 wt% (3 1 1 ).5 wt% ( ) 5 wt% (3 1 1 ) 1 wt% ( ) TMPyP/IEC (NPs/ml).96.1 ( ).9.1 ( ).1 ( ) Time (min) Figure S16. Photooxidation of uric acid by the TPP-NPs () or TMPyP-NPs () dispersions containing the same content of TPP ( mol l -1 ) or TMPyP ( mol l -1 ) achieved by the varying number of NPs. The experimental conditions are described above. S-1

13 Table S1. Parameters of prepared sulfonated NPs, the case analysis. Parameter Description Calculation / Note P1 Mass of NPs per ml (mg ml -1 ) From the gravimetric measurement 3.±. P Mass of sulfonated nanofiber membrane (mg) From the gravimetric measurement 154 P3 Volume of the stock dispersion (ml) - 45 P4 Yield of NPs preparation P4 = (P1 P3)/P 94 % P5 Molar mass of the NPs (g mol -1 ) See Equation S P6 vogadro s number (mol -1 ) P7 verage radius of NPs (cm) From TEM measuring P8 Surface of 1 NP (cm ) P8 = 4 (P7) P9 Volume of 1 NP (cm 3 ) P9 = 4/3 (P7) P1 Number of NPs per ml (in the stock dispersion) P1 = (P1/(P5 1)) P P11 P11 =P1 4/3 (r ef ) 3 Theoretical effective r volume reached by O ( 1 ef = P7 + lr Δ g ) Effective radius (r ef ) = average radius in 1 ml of the stock of NPs (P7) + effective range of dispersion (ml) O ( 1 Δ g ) (l r = cm) 1.3 verage IEC of NPs P (mol ml -1 ) Determined by titration verage IEC of NPs P (mol g -1 ) S-13

14 Table S. Parameters of prepared photoactive NPs: PE is the relative photo-oxidation efficacy of NPs towards uric acid (U), calculated as the slope of (U)/ΣI (1-1 -i ) vs. irradiation time plot (Figure 11), where ΣI (1-1 -i ) is the sum of absorbed light intensities at wavelengths i (4-7 nm) and (U) is the absorbance of U at 91 nm; F is the fluorescence quantum yields at indicated wavelength in parentheses. Continuous irradiation was performed with a 5 W Xe-lamp equipped with a long pass filter (λ 4 nm). NPs TPP-NPs (wt %) TMPyP-NPs (TMPyP/IES) verage number of TPP Slope PE molecules per (U)/ΣI (1-1 -i ) NP (443 nm) (443 nm) (443 nm).1 (41 nm) (41, 516 nm) (41, 516 nm) (48 nm) (48, 516 nm) (48, 516 nm) F S-14

15 Table S3. Oxygen properties: D(O ) are the diffusion coefficients, c are the oxygen solubility in H O and τ Δ are the O ( 1 Δ g ) lifetimes at indicated temperatures. Temperature D(O ) (1 5 cm s -1 ) c (mg l -1 ) c τ Δ (μs) ( C) H O a Polystyrene b H O d Polystyrene e a Han, P.; artels, D. M. Temperature Dependence of Oxygen Diffusion in H O and D O. J. Phys. Chem. 1996, 1, b Gao, Y.; aca,. M.; Wang,.; Ogilby, P. R., ctivation arriers for Oxygen Diffusion in Polystyrene and Polycarbonate Glasses: Effects of Low Molecular Weight dditives. Macromolecules 1994, 7, c Measured by InPro 688i oxygen sensor (Mettler Toledo). d Jensen, R. L.; rnbjerg, J.; Ogilby, P. R. Temperature Effects on the Solvent-Dependent Deactivation of Singlet Oxygen. J. m. Chem. Soc. 1, 13, e Calculated using data in Suchánek, J.; Henke, P.; Mosinger, J.; Zelinger, Z.; Kubát, P., Effect of Temperature on Photophysical Properties of Polymeric Nanofiber Materials with Porphyrin Photosensitizers. J. Phys. Chem. 14, 118, S-15