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.

Photodynamic antitumor activity of Gallium(III) and Phosphorus(V) complexes of trimethoxyl A2B triaryl corrole.

Two new trimethoxyl A2B triaryl corroles 10-(2,4,6-trimethoxyphenyl)-5,15-bis(pentafluorophenyl)- corrole (1) and 10-(3,4,5-trimethoxyphenyl)-5,15-bis(pentafluorophenyl)-corrole (2) and their gallium(III) and phosphorus(V) (1-Ga, 1-P, 2-Ga and 2-P) complexes had been prepared and well characterized by UV-vis, NMR and HR-MS. Among all compounds, 2-Ga, 1-P and 2-P showed excellent in vivo photodynamic activity against the MDA-MB-231, A549, Hela and HepG2 cell lines upon light irradiation at 625 nm. And 2-P even exhibited higher phototoxicity than the clinical photosensitizer temoporfin. Also, 2-P exhibited the highest singlet oxygen quantum yield and photostability. The preliminary investigation revealed that 2-P could be rapidly absorbed by tumor cells and mainly located in the cytoplasm. After photodynamic therapy (PDT) treatment with 2-P, mitochondrial membrane potential destruction, intracellular ROS level increasing and nuclear fragmentation of cancer cells could be observed. Cell cycle analysis demonstrated that the 2-P PDT may cause tumor cell arrest at sub-G1 stage and induce early and late apoptosis of cells. These results suggest that 2-P is a promising candidate as a photosensitizer for photodynamic therapy.

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.

The photodynamic activity and toxicity evaluation of 5,10,15-tris(ethoxylcarbonyl)corrole phosphorus(V) in vivo and in vitro.

The development of novel, efficient and nontoxic photosensitizers (PSs) is a challenging task for photodynamic therapy (PDT). In our previous study, corrole had been demonstrated to be a promising PS in PDT for cancer cells. In this paper, a novel electron-deficient flat phosphorus tris(ethoxycarbonyl) corrole (1-P) was synthesized and characterized. In vitro photodynamic activities and toxicity of 1-P in HepG2 xenograft tumours was evaluated by standard assay. The results shown 1-P displayed a potential efficient and low-toxic PS, which suggesting this kind of corrole is a powerful and promising antitumor PS for PDT. In addition, the potential anti-tumour mechanism study of 1-P was also investigated by the apoptosis antibody array, immunohistochemical and western blotting assay (WB) experiments, we found that the PDT activity of 1-P can degrade SIRT1 (an important deacetylase), and activate the Fas signal pathway to inhibit the growth of liver cancer cells.

Corrole-BODIPY Dyad as Small-Molecule Donor for Bulk Heterojunction Solar Cells.

Dyes based on charge-transfer (CT) characteristics are attractive candidates for organic photovoltaics due to their intense and broad absorption window. In these molecular frameworks, electron-rich donors and electron-deficient acceptors are covalently linked to achieve an effective CT process. Corrole, a tetrapyrrolic congener of porphyrin, is an excellent example of an electron-rich molecule with a large molar extinction coefficient. BODIPY, on the other hand, is a well-known electron-deficient bypyrrolic boron difluoride complex with intense absorption complementary to the corrole. A combination of these two structural motifs should result in a dyad having a wide absorption window, which will be suitable for organic photovoltaics. Herein, a corrole derivative has been envisaged as an efficient donor for solution-processed bulk heterojunction solar cells with PC71BM as an acceptor for the first time. The current molecule exhibits broad absorption in the visible range in solution as well as in thin films, with a high molar extinction coefficient and a low band gap of 1.79 eV. Frontier molecular orbital energy levels were found to be complementary to those of the well-known acceptor PC71BM. The optimized devices based on Cor-BODIPY:PC71BM showed a high power conversion efficiency (PCE) of 6.6% with Jsc = 11.46 mA/cm2, Voc = 0.90 V, and FF = 0.61. A remarkable value of incident photon-to-current conversion efficiency (IPCE) of 61% has also been observed.

Selective nitration and bromination of surprisingly ruffled phosphorus corroles.

Phosphorus complexes of corrole have recently attracted increasing interest since these compounds can be easily prepared in good yields, are stable, and show unusual optical properties. For these reasons, phosphorus corroles represent a class of interesting compounds to be exploited in the field of material science or for biomedical investigations and the definition of synthetic pathways for their functionalization is an important step to optimize their properties for various applications. We report here the reactivity of the phosphorus complex of 5,10,15-tritolylcorrole in the nitration or bromination reaction. Both these attempts were successful, allowing the preparation of substituted phosphorus corroles, which can be used as intermediates of more complex architectures endowed with useful properties. Furthermore, the crystallographic characterization of both complexes shows that they have an unusual ruffled geometry of the corrole core, a conformation that has not been considered possible for such a macrocycle.