Singlet Oxygen Generation in Ferriporphyrin-Polymer Dots Catalyzed Chemiluminescence System for Cancer Therapy

Abstract

Chemiluminescence (CL) systems have been used as excitation sources through chemiluminescence resonance energy transfer (CRET) between CL substrates and photosensitizers for photodynamic therapy (PDT). However, it is still a tremendous challenge to construct a highly effective CL system that has a strong emission intensity and long duration time for PDT. Here, we constructed a Fe­(III) deuteroporphyrin IX chloride-polymer dots (FeDP-Pdots) catalyzed CL system for cancer therapy, where the CL system was used as the generation of singlet oxygen for inhibiting and killing tumor cells with the use of FeDP-Pdots as both the catalysts and the photosensitizers. We prepared metalloporphyrin-polymer dots (M-Pdots) by nanoprecipitation and systematically investigated the relationship between the catalytic CL activities of M-Pdots and the structures of metalloporphyrins. It is found that FeDP-Pdots have the highest catalytic activity among 11 M-Pdots. Their CL intensity is almost 200-fold higher than the hemin-Pdots catalyzed system. The strong catalytic activity of FeDP is derived from its center ion Fe­(III), carboxyl groups, conjugated system, and smaller steric hindrance. Importantly, our results demonstrated that the higher the chemiluminescence intensity is, the more reactive oxygen species are produced during the Pdots catalyzed CL reaction. The FeDP-Pdots catalyzed luminol analogue L012-H2O2 CL system was used successfully for in vitro and in vivo cancer therapy. Our proposed method is characterized by the mass production of singlet oxygen through CRET and no requirement of light source. It is simple, selective, and effective, which develops a strong emission intensity and long-duration CL system for PDT and can be applied for the therapy of deep cancer tissues.

Direct and Indirect Chemiluminescence: Reactions, Mechanisms and Challenges

“…The same luminol analogue L012 and H2O2 were recently studied in the presen Fe(III) deuteroporphyrin IX chloride-polymer dots (FeDP-Pdots) as CL catalysts tow cancer therapy, providing high concentrations of ROS due to high CRET efficiency (F 17) [118]. CL has been also used in polymerization reactions.…”

“…LuminolChlorine6 Containing QDs Polymeric NPs, Fe(III) Deuteroporphyrin IX Chloride NPs, H2O2 Imaging and Therapy[116][117][118] …”

Disordered Assembly of Donors and Acceptors on Layered Double Hydroxides for High-Efficiency Chemiluminescence Resonance Energy Transfer

“…To confirm that the CL enhancement was attributed to the highly efficient CRET, ESR and CL spectra were used to investigate the CL emitter. Singlet oxygen ( 1 O 2 ) as the ONOO – CL emitter can be captured by TEMP to form a stable nitroxide radical, that is, 2,2,6,6-tetramethyl-4-piperidine- N -oxide (TEMPO). − Figure a shows the ESR signals of the ONOO – CL system in the presence of TEMP. A typical 1:1:1 triplet signal corresponding to the TEMPO nitroxide radical was observed as a result of the generation of 1 O 2 . − Moreover, the CL spectrum of the ONOO – CL system in the presence of LDH-supported Na 4 TCBPE was measured by using a fluorescence spectrophotometer with the xenon lamp off.…”

“…Singlet oxygen ( 1 O 2 ) as the ONOO – CL emitter can be captured by TEMP to form a stable nitroxide radical, that is, 2,2,6,6-tetramethyl-4-piperidine- N -oxide (TEMPO). − Figure a shows the ESR signals of the ONOO – CL system in the presence of TEMP. A typical 1:1:1 triplet signal corresponding to the TEMPO nitroxide radical was observed as a result of the generation of 1 O 2 . − Moreover, the CL spectrum of the ONOO – CL system in the presence of LDH-supported Na 4 TCBPE was measured by using a fluorescence spectrophotometer with the xenon lamp off. As shown in Figure b, the CL emission peak is located at around 520 nm, coinciding with the fluorescence emission peak of LDH-supported Na 4 TCBPE (Figure c).…”

Multicolor Chemiluminescent Resonance Energy-Transfer System for In Vivo High-Contrast and Targeted Imaging

“…As reported recently, FeDP has the highest catalytic activity to the L012-H 2 O 2 CL reaction among 11 metalloporphyrins because of its center ion Fe(III), carboxyl groups, conjugated system, and smaller steric hindrance. 48 Since the catalytic activity of FeDP is much higher than that of hemin, the CRET efficiency is much better for the FeDP-catalyzed CL system. To further confirm this point, we synthesized 20 kinds of Feporphyrin-Pdots to study their CL catalytic activity and CRET properties.…”