Azide-modified corrole phosphorus complexes for endoplasmic reticulum-targeted fluorescence bioimaging and effective cancer photodynamic therapy.

Study on corrole photosensitizers (PSs) for photodynamic therapy (PDT) has made remarkable progress. Targeted delivery of PSs is of great significance for enhancing therapeutic efficiency, decreasing the dosage, and reducing systemic toxicity during PDT. The development of PSs that can be specifically delivered to the subcellular organelle is still an attractive and challenging work. Herein, we synthesize a series of azide-modified corrole phosphorus and gallium complex PSs, in which phosphorus corrole 2-P could not only precisely target the endoplasmic reticulum (ER) with a Pearson correlation coefficient (PCC) up to 0.92 but also possesses the highest singlet oxygen quantum yields (ΦΔ = 0.75). This renders it remarkable PDT activity at a very low dosage (IC50 = 23 nM) towards HepG2 tumor cell line while ablating solid tumors in vivo with excellent biosecurity. Furthermore, 2-P exhibits intense red fluorescence (ΦF = 0.25), outstanding photostability, and a large Stokes shift (190 nm), making it a promising fluorescent probe for ER. This study provides a clinically potential photosensitizer for cancer photodynamic therapy and a promising ER fluorescent probe for bioimaging.

Non-Metallic Phosphorus Corrole as Efficient Electrocatalyst in Hydrogen Evolution Reaction.

The economical consideration of using an electrocatalyst in energy-related field, composed of non-precious/sustainable elements is quite noteworthy. In this work, the phosphorus(V) complex of tris-(pentafluorophenyl)corrole [(TPFC)PV (OH)2 ] was reported as electrocatalyst for the hydrogen evolution reaction (HER). The electrochemical studies revealed that the HER experienced a ECEC pathway (E: electron transfer step, C: chemical step), and the possible intermediate [PV ]-H species was suggested. (TPFC)PV (OH)2 displayed excellent HER activity in dimethylformamide (DMF) with trifluoroacetic acid (TFA) as the proton source, and the turnover frequency (TOF) reached 31.75 s-1 at an overpotential of 900 mV. Interestingly, the HER electrocatalytic performance remained extraordinary even applying water as a proton source in acetonitrile/water (v/v=2 : 3), with a TOF of 18.40 mol H 2 ${{_{{\rm H}{_{2}}}}}$ molcat -1 h-1 at an overpotential of 900 mV.

Photodynamic Antitumor Activity of 5,15-Bis(perfluorophenyl)-10-(4-carboxyphenyl)corrole and its Gallium(III) and Phosphorus(V) Complexes.

This work reports the preparation and characterization of an A2 B corrole 5,15-bis(perfluorophenyl)-10-(4-carboxyphenyl)corrole and its gallium(III) and phosphorus(V) complexes. Their in-vitro photodynamic anticancer activities against A549, MDA-MB-231, B16, HepG2, and Hela cell lines were also investigated. Among three compounds, phosphorus(V) complexexhibits the best photostability, highest fluorescence quantum yields (ΦF =0.138), and the highest singlet-oxygen quantum yields (ΦΔ =0.87). Also, the phosphorus(V) complex exhibits the best photodynamic antitumor activity against MDA-MB-231 cells with a low IC50 (0.08 µM) upon light irradiation at 625±2 nm, which is much lower than commercial PDT drug Temoporfin (0.1 µM) at the same conditions. The cellular localization assay confirmed that the phosphorus(V) complexis mainly distributed in the cytoplasm and have a good ability to produce reactive oxygen species (ROS) under light illumination, which would further cause oxidative damage to tumor cells and finally result in the apoptosis. After PDT treatment, phosphorus(V) complex may cause tumor cell arrest at the G2/M stage. The preliminary results showed phosphorus(V) corrole complex is a good candidate for photodynamic therapy (PDT) of tumors.