## 2 Materials and Methods  
TPPS (Tokyo Chemical Industry Co., Tokyo, Japan) aqueous solution was prepared by dissolving TPPS in deionized water. The TPPS monomer in aqueous solution becomes a free-base monomer (F-monomer) under low acidity conditions (pH = 11), and diacid monomer (D-monomer) with protons coordinated to the two N\({}_{2}\) atoms in the center of the porphyrin ring under high acidity conditions (pH = 4) [37]. D-monomers in aqueous solution form J-aggregates under higher acidity conditions (pH = 0.8). NaOH (Wako Pure Chemical Industries, Ltd. (currently known as FUJIFILM Wako Pure Chemical Corporation), Tokyo, Japan) aqueous solution was mixed with the TPPS aqueous solution in order to prepare a sample in which absorption of F-monomer is dominant. In addition, by mixing MeOH (Kanto Chemical Co., Tokyo, Japan) with the F-monomer aqueous solution, the water-MeOH mixed solution of F-monomer was prepared. The prepared solution samples are summarized in Table 1.  
F-monomer sample incorporated in polyvinyl alcohol (PVA) (Wako Pure Chemical Industries, Ltd. (currently known as FUJIFILM Wako Pure Chemical Corporation), Tokyo, Japan) matrix was prepared by dissolving 2 mg TPPS and 80 mg PVA in 2 mL of deionized water. This aqueous solution was dropped on a slide glass and spin-coated to make a TPPS-doped PVA thin film. The absorption spectra were observed at room temperature \begin{table}
\begin{tabular}{c c c} \hline
**[TPPS]** & **[NaOH]** & **Mole Fraction of MeOH** \\ \hline
20 \(\mu\)M & 1 mM & 0.00 \(\sim\) 0.96 \\
20 \(\mu\)M & 10 mM & 0.00 \(\sim\) 0.95 \\ \hline \end{tabular}
\end{table} 
Table 1: Concentration of each component in TPPS aqueous solutions mixed with MeOH and NaOH. using a spectrophotometer (SolidSpec-3700 DUV, Shimadzu, Kyoto, Japan). In the case of solution samples, a 1 mm path length quartz cell with a screw cap was used. Figure 1 shows the experimental set-up for the measurement of the DAS of samples induced by laser irradiation. White light from a Xe lamp (L14286, Hamamatsu, Japan) as the probe was focused on a sample, and the transmitted light was observed through a spectrometer (Acton SpectraPro 300i, Acton Research Co., Acton, MA, USA) with a 128-channel lock-in detector (7210, Signal Recovery, Edinburgh, UK) [38]. A CW laser light as the pump, which was chopper-modulated at 226 Hz, was irradiated to the focal point of the probe light on the sample and the pump-induced change in the transmitted probe light spectrum was measured. However, the signal observed with a 128-channel lock-in detector also includes a signal of the fluorescence of the sample if the sample emits fluorescence by laser irradiation. Therefore, to obtain a DAS, it is needed to subtract the fluorescence signal from the observed signal. By irradiating only with the pump light, only the fluorescence signal was detected, so that the DAS was able to be obtained from the observed signal. CW laser at 532 nm (MGL-FN-532-1W, Changchun New Industries Optoelectronics Tech. Co., Changchun, China) and CW laser at 808 nm (MLL-III-808-500 mW, Changchun New Industries Optoelectronics Tech. Co., Changchun, China) were used as the pump. The 532 nm laser was not focused by a lens. The 808 nm laser was focused by a lens with a focal length of 50 mm. The intensity of the 532 nm and 808 nm lasers at the sample location was approximately 100 W/cm\({}^{2}\) and 1.3 kW/cm\({}^{2}\), respectively. A 532 nm excitation is accompanied by the effect of real excitation of F-monomer, while 808 nm excitation is not. Therefore, it is possible to observe effects caused by other than real excitation using 808 nm laser. When using the 532 nm laser, a notch filter at 532 nm was used as shown in Figure 1, because the scattering of the laser light from the sample overlaps with the DAS. When using the 808 nm laser, the notch filter was removed. In addition to DAS of F-monomer aqueous solution equilibrated with ambient oxygen, those immediately after N\({}_{2}\) bubbling were also observed to confirm the triplet quenching effect on DAS.