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The use of non–precious metals for electrocatalytic hydrogen reaction (HER) is particularly important for energy conservation and environmental protection. In this work, three new cobalt corroles containing o−, m−, and p−nitrobenzyl (1, 2, 3) at the meso 10−position of the corrole macrocycle were synthesized, and their electrocatalytic hydrogen evolution reaction in organic and neutral aqueous systems was also investigated. The results show that these three cobalt corroles have significant catalytic HER activity in both systems, and the catalytic efficiency follows 1 > 3 > 2, which indicates that the position of the nitro group can affect the catalytic property of the complexes. In the organic phase, when using trifluoroacetic acid or p−toluenesulfonic acid as the proton source, the electrocatalytic HER may undergo an EECC (E: electron transfer, C: proton coupling) pathway. In a neutral aqueous system, the HER turnover frequency value of 1 is up to 137.4 h−1 at 938 mV overpotential. [ABSTRACT FROM AUTHOR]

In this study, we have successfully synthesized two non‐metallic‐based silicon corrole complexes (F10C−Si, F10C−CN−Si) and used them as HER electrocatalysts for the first time. Electrochemical studies indicate the electrocatalytic HER may go via EE‐CEEC (E: electron transfer step, C: chemical step) pathway. Notably, it can be seen that the introduction of electron‐withdrawing cyano group on the meso‐phenyl of the corrole macrocycle may enhance the catalytic activity of silicon corrole complexes. In DMF with TsOH as the proton source, F10C−CN−Si exhibits a turnover frequency (TOF) of 331.48 s−1 and a high catalytic efficiency (C.E) of 1.29. Furthermore, the catalytic prowess of the silicon corrole complexes extends to neutral aqueous solution, with F10C−CN−Si achieving a TOF of 52.72 h−1 at an overpotential of 1188 mV. This study extends the application of non‐metallic‐based silicon corrole molecular catalysts in the electrocatalytic HER field. [ABSTRACT FROM AUTHOR]

The study of the hydrogen evolution reaction (HER) by non-noble transition metals is of great significance for the production of hydrogen energy. In this work, a new 5,15-bis-(pentafluorophenyl)-10-[4-(1H-imidazole) phenyl]-corrole and its metal complexes (metal = Co, Cu, Fe) were synthesized and used for electrocatalyzed HER in DMF organic solvent and aqueous media. The prepared cobalt corrole showed the best catalytic performance in both media. Its turnover frequency (TOF) and catalytic efficiency (C.E) could reach 265 s−1 and 1.04 when TsOH was used as the proton source in a DMF solvent. In aqueous media, its TOF could also reach 405 h−1. The catalytic HER may go through an EECEC or ECEC (E: electron transfer, C: chemical step) pathway for these catalysts, depending on the acidity and concentration of the proton source. The present work successfully demonstrates that imidazole at a meso-phenyl group may improve the electrocatalytic HER activity of transition metal corroles. [ABSTRACT FROM AUTHOR]

Four A2B cobalt corrole complexes 1–4 appending two methoxy or hydroxyl groups on the 10‐meso phenyl group had been synthesized. Four cobalt corroles showed high electrocatalytic activity for hydrogen evolution reaction (HER) in the organic phase and in the aqueous phase. The hydrogen evolution pathway was EECEC when using acetic acid as proton source. When trifluoroacetic acid was used as proton source, the hydrogen evolution route via EECEC or EECC depending on the concentration of trifluoroacetic acid. Cobalt corrole 4 showed the best HER performance with the kobs of 122.68 s−1 in organic phase and the TOF of 832.2 h−1 in aqueous phase respectively. The results suggested the phenyl hydroxyl group at the cobalt corrole peripheral may act as the proton relay group in HER and the o‐hydroxyl of phenyl was better than m‐ hydroxyl for proton relay. [ABSTRACT FROM AUTHOR]

This work reports the preparation and characterization of an A2B 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. [ABSTRACT FROM AUTHOR]

Phosphorus corrole has been explored as a promising photosensiter for photodynamic therapy (PDT) treatment in decade. A new trans‐bishydroxyl axial ligated phosphorus(V) 5, 15‐bis(pentafluorophenyl)‐10(p‐hydroxylphenyl) corrole (1‐P) was synthesized and well characterized by X‐ray structure determination. Complex 1‐P could bind ct‐DNA via an outside binding mode and displayed good photonuclease activity. After illumination, it might significantly generate singlet oxygen, hydroxyl radical and superoxide anion radical. 1‐P exhibited low dark toxicity but high photocytotoxicity against HepG2, CNE‐2, A549 and MDA‐MB‐231 tumor cell lines. Preliminary results show 1‐P is a promising candidate of PDT photosensitizer. [ABSTRACT FROM AUTHOR]

Two A2B cobalt triaryl corroles bearing ester (1) or carboxylic acid group (2) at the 10-para-phenyl group were prepared and used as homogeneous electrocatalysts for hydrogen evolution reaction (HER) with acetic acid and water as proton sources. CV results revealed the HER underwent two routes with [CoIII–H]– (EECC pathway) and [CoII–H]2– (ECEC pathway) as the intermediates at low acetic acid concentration. While the HER mainly went through the ECEC route at high acetic acid concentration. The HER turnover frequencies of 1 and 2 in neutral aqueous media were 291.8 and 190.6 h−1, respectively, at an overpotential of 838 mV. Unexpectedly, 1 exhibited significantly better HER activity than 2, showing the factors controlling electrocatalytic HER activity of cobalt corrole are complicated. [ABSTRACT FROM AUTHOR]

Three cobalt triaryl corroles bearing an electron‐withdrawing or electron‐donating group at 10‐meso‐phenyl were synthesized and characterized. Two of them are new cobalt corroles prepared in this study. These cobalt corroles were characterized using high‐resolution mass spectrometry, UV–Vis., nuclear magnetic resonance, X‐ray photoelectron spectroscopy, and single‐crystal X‐ray structure determination. All synthesized cobalt corroles efficiently catalyzed the hydrogen evolution reaction (HER) in neutral aqueous media at an overpotential of 838 mV. The HER activity of these cobalt corroles significantly depended on the virtue of peripheral substituents. [ABSTRACT FROM AUTHOR]

Study of photodynamic therapy (PDT) based on corroles has become one of the most important topics in corrole chemistry. Advances in synthetic methodology have made it possible for the preparation of structurally diverse corrole photosensitizers. This review covers the recent progress in the study of corrole as a photosensitizer in the photodynamic antitumor therapy. The content is organized in three sections: cellular uptaking and localization of corrole in tumor cells; morphological changes and cytotoxicity after corrole PDT treatment; and the animal level corrole PDT test. The possible mechanism of corrole‐based PDT antitumor activity is also summarized. [ABSTRACT FROM AUTHOR]

Catalytic activities for hydrogen (H2) evolution of cobalt 5,10,15-tris(phenyl)corrole (1) and 5,10,15-tris(4-nitrophenyl)corrole (2) (in homogeneous system was examined from acetic acid and water. In phosphate buffer solution (pH 7.0), the hydrogen evolution turnover frequency (TOF) for 1 and 2 were 62 and 150 h−1 at the overpotential of −1.53 V versus Ag/AgCl. In acetic acid media, hydrogen evolution TOF for 1 and 2 were 56 and 127 h−1, respectively, at an overpotential of 961 mV versus Ag/AgNO3. In the practical electrocatalytic hydrogen evolution experiment at −1.45 V (vs. Ag/AgCl) overpotential for 1 h, the TOF were 76 and 188 h−1 for 1 and 2, respectively. No observable decomposition of the catalyst could be observed after electrolysis for 72 h with a glassy carbon electrode. [ABSTRACT FROM AUTHOR]

An electron-deficient flat 5,10,15-tris(ethoxycarbonyl)corrole (TECC) cobalt complex, [Co(TECC)(Py)2] ( 1; py = pyridine), was prepared and employed as a catalyst for homogeneous hydrogen evolution. It turns out that water can be successfully used as a proton source in acetonitrile-water (2:3 v/v) solvent system for electrocatalytic hydrogen evolution. Complex 1 is also an efficient photocatalyst for hydrogen generation from aqueous solution, an example of the first application of metal corrole as photocatalyst for hydrogen production. [ABSTRACT FROM AUTHOR]

Two new gallium corrole complexes, 10-(4-Methoxycarbonylphenyl) -5, 15-bis(pentafluorophenyl)corrolatogallium(III)( 1-Ga) and 5,15-bis(4-Methoxycarbonylphenyl)-10-(pentafluorophenyl)corrolatogallium(III)( 2-Ga), were synthesized and characterized. The interaction of these gallium corrole complexes with CT-DNA was studied by fluorescence methods, UV-visible, viscosity measurements, molecular docking as well as agarose gel electrophoresis. The results revealed that both 1-Ga and 2-Ga interact with DNA via major groove binding and could cleavage the supercoiled plasmid DNA efficiently under irradiation. The inhibitor and singlet oxygen test indicated that singlet oxygen was the reactive oxygen species involved in the photocleavage DNA initiated by 1-Ga or 2-Ga. Cell viability experiments indicated that 1-Ga and 2-Ga show high photocytotoxicity and low dark toxicity towards tested QGY-7701 and MHCC-H/L tumor cell lines. Fluorescence probe tests showed the absorbed 1-Ga and 2-Ga in tumor cells are mainly localized in mitochondria, and the mitochondria membrane potential disruption was observed after irradiation. [ABSTRACT FROM AUTHOR]

A water-soluble cationic gallium corrole, 5,10,15-tris( N-methyl-4-pyridyl)corrolatogallium(III) ( 3), was prepared and characterized. The photocytotoxicity of 3 was investigated using Hep G2 cancer cell line. Upon treatment with corrole 3 and irradiation, of tumor cell nuclei was observed, which led to apoptosis. Flow cytometric analysis clearly showed the efficient induction of apoptotic cell death, and corrole 3 exhibited high photocytotoxicity towards Hep G2 cancer cells (IC50 = 60 nM). Furthermore, the binding behavior of corrole 3 with c-MYC G-quadruplex DNA, a potent target for antitumor drugs, was investigated using spectroscopic methods and molecular docking simulation. Copyright © 2015 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

The DNA binding of amphiphilic iron(III) 2,17-bis(sulfonato)-5,10,15-tris(pentafluorophenyl)corrole complex (Fe-SC) was studied using spectroscopic methods and viscosity measurements. Its nuclease-like activity was examined by using pBR322 DNA as a target. The interaction of Fe-SC with human serum albumin (HSA) in vitro was also examined using multispectroscopic techniques. Experimental results revealed that Fe-SC binds to ct-DNA via an outside binding mode with a binding constant of 1.25 × 104 M-1. This iron corrole also displays good activity during oxidative DNA cleavage by hydrogen peroxide or tert-butyl hydroperoxide oxidants, and high-valent (oxo)iron(V,VI) corrole intermediates may play an important role in DNA cleavage. Fe-SC exhibits much stronger binding affinity to site II than site I of HSA, indicating a selective binding tendency to HSA site II. The HSA conformational change induced by Fe-SC was confirmed by UV/Vis and CD spectroscopy. Copyright © 2015 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

Based on Ga-corrole dye C0, three new Ga-corrole-based dyes C1-3 were designed as solar cell dyes and investigated by DFT and TD-DFT calculations. The optical and electronic features showed that the dye molecules C2 has better charge separation and more favorable intramolecular charge transfer, showing that it is more helpful to improve the intermolecular charge transfer of gallium corrole dyes when the electron donor and acceptor are linked at the parallel meso-positions of the corrole macrocycle. [Display omitted] • Three new Ga-corrole-based dyes C1-3 were designed as solar cell dyes and investigated by DFT and TD-DFT calculations. • The dye molecules C2 has better charge separation and more favorable intramolecular charge transfer. • Gallium corrole dyes with the electron donor and acceptor linked at the parallel meso-positions exhibits the best performance. In order to investigate the effect of spatial arrangement of donor-acceptor group on gallium corroles for dye-sensitized solar cells (DSSCs), this work had designed three new gallium corrole dye isomers C1-3 based on Ga-corrole dye C0. Their geometric structures, electronic structures, optical properties, intramolecular charge transfer (ICT) characteristics and the interactions with TiO 2 clusters had been examined by using density functional theory (DFT) and time-dependent density functional theory (TD-DFT) calculations. The results showed that the C1-3 dye molecules have good planarity, suitable HOMO-LUMO energy gap and strong UV–visible light absorption. Moreover, the dye molecule C2 has better charge separation and more favorable intramolecular charge transfer, showing that it is more helpful to improve the intermolecular charge transfer of gallium corrole dyes when the electron donor and acceptor are linked at the parallel meso-positions of the corrole macrocycle. [ABSTRACT FROM AUTHOR]

Cationic meso(4- N-methylpyridyl)-based metallocorroles, μ-oxo iron corrole dimer ( 1b) and manganese corrole monomer ( 2b), were synthesized and characterized. The interactions of these two metal corrole complexes with CT-DNA were studied by UV-visible, fluorescence and circular dichroism spectroscopic methods, as well as by viscosity measurements. The results revealed that 1b interacts with CT-DNA in a difunctional binding mode, i.e. non-classical intercalation and outside groove binding with H-aggregation, while 2b can interact with CT-DNA via an outside groove binding mode only. The binding constants Kb of 1b and 2b were 4.71 × 105 m−1 and 2.17 × 105 m−1, respectively, indicating that 1b can bind more tightly to CT-DNA than 2b. Furthermore, both complexes may cleave the supercoiled plasmid DNA efficiently in the presence of or tert-butyl hydroperoxide (TBHP), albeit 1b exhibited a little higher efficiency. The inhibitor tests suggested that singlet oxygen and high-valent (oxo)iron(VI) corrole or (oxo)manganese(V) corrole might be the active intermediates responsible for the oxidative DNA scission. Copyright © 2014 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

Abstract: The first direct synthesis of A3-type unsymmetrical porphyrin is achieved via conventional pyrrole–aldehyde condensation in a one-pot procedure in an appreciable yield. Generalization of this approach to a variety of other aldehydes revealed that it is advantageous for highly electron-rich aldehydes giving unsymmetrical porphyrin, while electron-poor aldehydes even failed to cyclize under the same experimental conditions. [Copyright &y& Elsevier]

Abstract: Among metallocorroles, manganese corrole chemistry is one that has flourished prominently in recent years. Numerous manganese corroles have been reported in which the oxidation state of the central manganese ranges from +3 to +6. Manganese(III) corroles are the most common form of stable Mn-corrole complexes. High-valent manganese corroles exhibit quite different spectroscopic and electrochemical properties compared with manganese(III) corroles. (Imido)manganese(V) and (nitrido)manganese(V) corroles are stable enough to be well characterized by spectroscopy. (Oxo)manganese(V) corroles may be prepared by chemical or laser flash photolysis methods, and are important mechanistic probes for oxygen atom transfer reactions in the catalytic oxidation of alkenes. While various (oxo)manganese complexes have been synthesized and extensively studied, the factors controlling their reactivity are not completely understood, suggesting that manganese corrole-mediated oxidation reactions have room for further exploration. In this review, recent advances in the field of manganese corroles are summarized. [Copyright &y& Elsevier]

A series of manganese corroles bearing different substituents had been prepared and characterized by UV–vis, 1H NMR, 19F NMR, HRMS and XPS. These manganese corrole complexes were applied to electrocatalytic hydrogen evolution reaction (HER) for the first time. The results showed that manganese corroles are effective catalysts for HER in DMF solvent by using acetic acid (AcOH), trifluoroacetic Acid (TFA) and p-toluenesulfonic acid (TsOH) proton sources, and strong acid leads to higher electrocatalytic activity. When using TsOH as proton source, protonation of corroles ligand may be involved in HER. The electrocatalytic HER activity can be improved by increasing the electron-withdrawing substituent of the corrole macrocycle in both organic and aqueous media. [Display omitted] • Manganese corrole was firstly used as HER electrocatalyst. • Manganese corrole exhibits good electrocatalytic HER activity in aqueous solution. • Electron-withdrawing substituent benefits the HER activity. [ABSTRACT FROM AUTHOR]

A new cobalt 5,15-bis(perfluorophenyl)-10-(4-N-(triphenylphosphoranylidene)-2,3,5,6-tetrafluorophenyl) corrole complex (Co-BPNC-PPh 3) containing –N=PPh 3 group has been prepared by Staudinger reaction and characterized by the single-crystal X-ray structure determination. The electrocatalytic hydrogen evolution reaction (HER) of Co-BPNC-PPh 3 by using acetic acid (AcOH), trifluoroacetic acid (TFA) and p -toluenesulfonic acid (TsOH) as proton sources in N, N-dimethylformamide (DMF) solvent had been investigated. The turn-over frequency (TOF) value of Co-BPNC-PPh 3 was observed 450 h−1 at an overpotential of 838 mV in neutral aqueous solution, showing excellent electrocatalytic HER activity. This Co-BPNC-PPh 3 exhibited excellent durability and stability in the 5-hours electrolysis. Its activity is also better than cobalt 5, 10, 15-(tris-pentatfulorophenyl) corrole (Co-TPFC-PPh 3), which may be ascribed to the –N=PPh 3 proton relay effect in the electrocatalytic HER. [Display omitted] • A novel cobalt corrole containing –N=PPh 3 group (Co-BPNC-PPh 3) had been prepared for the first time. • The complex Co-BPNC-PPh 3 showed excellent electrocatalytic HER activity in aqueous solution. • The –N=PPh 3 group of Co-BPNC-PPh 3 is stable in aqueous solution. [ABSTRACT FROM AUTHOR]

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 (Φ Δ = 0.75). This renders it remarkable PDT activity at a very low dosage (IC 50 = 23 nM) towards HepG2 tumor cell line while ablating solid tumors in vivo with excellent biosecurity. Furthermore, 2-P exhibits intense red fluorescence (Φ F = 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. A new kind of azide-modified corrole gallium (III) and phosphorus(V) complexes were synthesized and used as PDT photosensitizers. The prepared corrole phosphorus complex (2-P) can precisely target the endoplasmic reticulum (ER) and in situ generate massive reactive oxygen species (ROS) under irradiation to induce tumor regression at a very low dosage. [Display omitted] • Novel azide-modified corrole complexes for PDT were synthesized and evaluated. • 2-P could specifically target to endoplasmic reticulum. • 2-P could generate ROS and evoke mitochondria dysfunction upon PDT. • 2-P -mediated PDT could effectively eliminate tumor in vitro and in vivo. • 2-P -mediated PDT caused cell apoptosis in the caspase pathway. [ABSTRACT FROM AUTHOR]

• Dihydroxyl A 2 B triaryl corroles and their gallium and phosphorus complexes were synthesized. • 10-(2,4-dihydroxyphenyl)-5,15-bis(pentafluorophenyl)corrole phosphorus(V) (1-P) exhibited high singlet oxygen quantum yield. • 1-P exhibited excellent photodynamic activity against MDA-MB-231 and A549 cells. • 1-P photodynamic therapy arrested MDA-MB-231 cells in the sub-G1 phase. • 1-P induced apoptosis by increasing intracellular ROS under illumination at 620–625 nm. Two new dihydroxyl A 2 B triaryl corroles 10-(2,4-dihydroxyphenyl)-5,15-bis(pentafluorophenyl)corrole (1) and 10-(3,4-dihydroxyphenyl)-5,15-bis(pentafluorophenyl)corrole (2) and their gallium(III) and phosphorus(V) complexes (1-Ga, 2-Ga, 1-P and 2-P) were synthesized and investigated as photodynamic antitumor agents. All synthesized corrole derivatives could generate singlet oxygen smoothly under illumination at 620–625 nm and showed remarkable in vitro photodynamic antitumor activity. Excited, phosphorus(V) corrole 1-P even exhibited better phototoxicity towards A549 and MDA-MB-231 tumor cell line (IC 50 , 0.08 and 0.12 µM) than clinical drug Foscan® (IC 50 , 0.27 µM). The laser confocal microscopy results showed that the cellular absorbed 1-P was located in the cytoplasm. Under illumination, intracellular reactive oxygen species (ROS) could be detected, which would triger the destruction of the mitochondrial membrane potential and finally lead to apoptosis. Furthermore, the 1-P photodynamic treatment would cause the cancer cells arrested at sub-G1 stage. 10-(2,4-dihydroxyphenyl)-5,15-bis(pentafluorophenyl)corrole phosphorus(V) (1-P) exhibited remarkable in vitro photodynamic antitumor activity under illumination of red light at 620–625 nm. [Display omitted] [ABSTRACT FROM AUTHOR]

Tin corrole complexes were firstly used as electrocatalyst in hydrogen evolution reaction (HER) and found excellent electrocatalytic HER activity in both organic and aqueous phase. [Display omitted] • This work presents the first example of using tin corrole complexes as the electrocatalyst in HER. • Four tin corrole complexes showed excellent electrocatalytic HER activity and complex (3) exhibit the best HER performance in organic media. • Electrochemical testing showed that the HER may undergo E-ECEC pathway whether using strong acid or weak acid as proton source in organic media. In this paper, four post-transition metal tin corrole complexes bearing different numbers of cyano-substituents (1, 2, 3, 4) had been synthesized and characterized. In which tin corroles Sn-CDPC (1) and Sn-PBCC (2) are new compounds. Among four prepared tin corroles, Sn-TCPC complex (3) exhibits the best electrocatalytic HER performance in organic phase. Its i cat /i p and the turnover frequency (TOF) reaches 13.12 and 25.6 h−1 in DMF when using trifluoroacetic acid (TFA) as the proton source. The TOF of Sn-CDPC complex (1) in acetonitrile/water (V/V = 2/3) neutral water system is the highest (474.3 h−1) and may produce 4.7 mL H 2 with in 1 h of electrolysis. Electrochemical testing showed that the HER undergoes E-ECEC pathway whether using strong acid or weak acid as a proton source in organic media. This work presents the first example of using tin corroles as the electrocatalyst in HER. [ABSTRACT FROM AUTHOR]

10-(3-Bromo-4-Hydroxyphenyl)-5,15-bis(pentafluorophenyl)corrole phosphorus(V) (1-P) exhibited excellent photodynamic antitumor activity in vivo and in vitro. Edible bird's nest (EBN) might have a positive effect on the elimination of tumor in mice treated with PDT by enhancing the expression of immune T cells. [Display omitted] • Several new Ga(III) and P(V) corrole complexes were synthesized. • P(V) corrole complex 1-P exhibited high singlet oxygen quantum yield and photostability. • P(V) corrole complex 1-P showed excellent photodynamic antitumor activity in vivo and vitro. • PDT treatment may enhance antitumor immune responses (eg, CD3+, CD4+ and CD8+) of tumor grafted mice. • Edible bird's nest (EBN) administration might help to eliminate tumors by enhancing T cell expression. Four new phosphorus(V) and gallium(III) corrole complexes were prepared and evaluated as antitumor agents in photodynamic therapy (PDT) in vivo and vitro. All complexes showed low dark toxicity and good photocytotoxicity under light illumination (625 ± 2 nm, 3 W/m2). Especially, phosphorus(V) corrole (1-P) exhibited quite excellent photocytotoxicity with IC 50 of 0.03 (±0.003) μM with phototoxic indices (p.i.) of >3333.33 against MDA-MB-231 tumor cells. Under light irradiation, 1-P could produce reactive oxygen species (ROS) in cells and destroy mitochondrial membrane potential, leading to apoptosis. The PDT treatment with 1-P arrested the cell at sub-G1 phase. Animal test showed 1-P could effectively inhibit the growth of MDA-MB-231 tumor cell grafted BALB/c nude mice. The PDT generated ROS might boost the anti-tumor immune response (e.g., CD3+, CD4+ and CD8+). It is well known that edible bird's nest (EBN) helps to improve the immune system and thus is beneficial to health. Photodynamic therapy combined with EBN (100 mg/kg) treatment was conducted for the first time to evaluate the possible antitumor synergistic effect in mice. It turned that EBN may do significant positive help in eliminating the tumors in PDT-treated mice by enhancing T cell expression as indicated by the detection of remarkable higher CD3+ expression in tumor and spleen tissue. [ABSTRACT FROM AUTHOR]

Two novel donor-acceptor dyads, in which phenothiazine (PTZ) connected at β-pyrrolic position of either freebase corrole (TPC) or freebase porphyrin (TPP) via vinylic spacer have been synthesized. Both the dyads were characterized by ESI-MS, IR, 1 H NMR (1D and 2D 1 H- 1 H COSY and J-Resolved), UV–Vis, Study state Fluorescence, Time-resolved fluorescence (Time-correlated single photon counting (TCSPC), Streak Camera) as well as electrochemical methods. In the absorption spectra of the dyads, both Soret and Q-bands were red shifted by 8–20 nm indicating weak electronic communication between the two chromophores. However, the fluorescence emission from the PTZ of the dyad was efficiently quenched (96–99%) as compared to pristine PTZ where the dyad was excited at 310 nm, which is attributed to singlet-singlet excited energy transfer. Fluorescence emission from porphyrin part of the TPP-PTZ dyad also quenched when excite the dyad at 420 nm, which is ascribed to photoinduced electron transfer from ground state of PTZ to excited state of porphyrin. In contrast, when excite the corrole at 420 nm in TPC-PTZ dyad, we found there are no significant changes in photophysical properties. In both the cases the solvent dependence of the rate of energy and electron transfer was observed. [ABSTRACT FROM AUTHOR]

Four cobalt (III) corroles bearing different number of pentafluorophenyl and phenyl groups were synthesized and characterized by elemental analysis, HR-MS, UV–vis, NMR, XPS as well as cyclic voltammetry. The first investigation of cobalt corrole catalyzed oxidation of alkene was conducted by using styrene as substrate. The best yield was obtained in acetonitrile solvent in the air with TBHP oxidant (96% yield based on oxidant, up to 96 TON). Benzaldehyde was detected as the main product by using PhI(OAc) 2 , TBHP, KHSO 5 , PhIO as oxidants. In contrast, styrene oxide was found to be the major product when using m -CPBA oxidant. Nearly no products could be found by using H 2 O 2 oxidant. Possible catalytic oxidation pathway was also discussed based on the obsewrvations of UV–vis changes of the ctatalytic system in the absence of substrate and in-situ HR-MS. [ABSTRACT FROM AUTHOR]

Phosphorus(V) trimethoxyl A 2 B triaryl corrole (2-P) with excellent optical characteristics induced cancer cells apoptosis upon light irradiation at 625 nm. [Display omitted] • Ga(III) and P(V) trimethoxyl A 2 B triaryl corrole were synthesized and characterized. • P(V) m , m' , p -trimethoxyl A 2 B triaryl corrole exhibited high singlet oxygen quantum yield, photostability, and excellent photodynamic activity against cancer cells. • P(V) m , mʼ , p -trimethoxyl A 2 B triaryl corrole photodynamic therapy treatment might cause tumor cells arrest at the sub-G1 phase and induced apoptosis triggered by ROS increasing upon light irradiation. Two new trimethoxyl A 2 B 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. [ABSTRACT FROM AUTHOR]

A new phosphorus(V) corrole, 10-(4-hydroxylphenyl)-5,15-bis(pentafluorophenyl)corrolato ( trans -dihydroxo)phosphorus(V) 1 -P, was synthesized and characterized. The interaction of 1 -P with calf thymus DNA (CT-DNA) was studied by multi-spectroscopic methods. The photonuclease activity of this complex was examined by agarose gel electrophoresis. 1 -P may bind to CT-DNA via an outside binding mode and display good photonuclease activity. 1 -P displayed low dark toxicity but high photocytotoxic activity against H460 and A549 tumor cell lines. [ABSTRACT FROM AUTHOR]

[Display omitted] • New A 2 B metallocorroles (metal = Ga, Co, Fe) bearing ethoxycarbonyl and pentafluorophenyl groups had been synthesized and characterized. • Gallium corrole was used in hydrogen evolution reaction for the first time. • Central metal ion and proton source play an important role in adjusting HER catalytic activity of metal corroles. 5,15-bis(pentalfluorophenyl)-10-ethoxycarbonylcorrole and their metal complexes (metal = Ga, Co, Fe) had been synthesized and characterized (new complexes). These metal complexes had been used as electrocatalysts for hydrogen evolution reaction (HER) in organic acid and aqueous medium, in which the gallium corrole was firstly used for HER. The results showed that the redox potential of central metal atom for metal-centered metal (eg. Co and Fe) corroles plays a significant role in adjusting catalytic HER activity. Gallium corrole is a ligand-centered HER catalyst, the electronic structure of corrole ligand may play a key role in controlling the electrocatalytic activity. [ABSTRACT FROM AUTHOR]

Three mono-hydroxy corroles 1 – 3 and their gallium(III) complexes Ga1 - 3 were synthesized, and their photodynamic antitumour activities towards breast cancer cells were investigated. All corroles showed excellent cytotoxicity against the MDA-MB-231 and 4T1 cell lines upon light irradiation at 625 nm. Ga3 exhibited excellent phototoxicity and selectivity against MDA-MB-231 cells, with an IC 50 of 0.06 ± 0.03 μM and a selective index value of 1338.83 (relative to human normal Huvec cells). The performance of Ga3 was even better than that of the clinical photodynamic therapy drug m -THPC. A preliminary mechanistic investigation revealed that corrole 3 and Ga3 were mainly located in the cytoplasm. Upon irradiation, they could generate intracellular reactive oxygen to destroy the mitochondrial membrane potential and arrest the cell cycle at the sub-G1 phase. Flow cytometry revealed that corrole 3 and Ga3 induced cancer cell apoptosis after photodynamic treatment. Corrole 3 and Ga3 displayed negligible cytotoxicity in the dark. These results suggest that corrole 3 and Ga3 are promising candidates for use in the photodynamic therapy of breast cancer. Hydroxy-corrole and its gallium(III) complex induced breast cancer cells apoptosis with red light irradiation. Image 1 • The photophysical and photochemical properties of hydroxy-corroles were studied. • Corrole 3 and Ga3 exhibited excellent PDT efficacy against breast cancer cells. • Corrole 3 and Ga3 induced breast cancer cells apoptosis upon 625 nm LED irradiation. [ABSTRACT FROM AUTHOR]

• The excited-state dynamics of a series of pyridyl corroles were reported. • A very fast ISC rate in tin corrole yielded a high triplet population. • The photostability and singlet oxygen generation were evaluated. • The interaction of corroles with ct-DNA was investigated. The photophysical properties of a series of pyridyl corroles were reported. Their excited-state dynamics were investigated by femtosecond transient absorption, which revealed a very fast intersystem crossing in the tin complex (3.9 × 109 s−1) with a high triplet yield of 0.91. An accelerated vibrational cooling of free-base corrole in DMF was observed due to deprotonation. The ability of these corroles to generate singlet oxygen was also quantitatively measured, which demonstrated the tin complex as a promising photosensitizer. The photo-induced reactive oxygen species (ROS) were detected by EPR. Additionally, the DNA binding affinity of these corroles was evaluated to inspect their potential biological use. [ABSTRACT FROM AUTHOR]

A series of transition metal corroles were synthesized and evaluated for photodynamic therapy (PDT). Complex Fe-2c exhibited significant photocytotoxicity and low dark cytotoxicity to A549 tumor cells and could induce apoptosis of A549 cells after PDT treatment. • Transition metal mono-hydroxyl corrole bind to CT-DNA via external binding mode. • Transition metal mono-hydroxyl corrole have no dark or photo- cytotoxicity to human normal cells. • Iron para -mono-hydroxyl corrole has significant photodynamic activity to A549 lung cancer cell. • Transition metal mono-hydroxyl corrole may be used as potential photodynamic anticancer drugs. A series of iron(III), manganese(III) and copper(III) mono-hydroxyl corrole complexes had been prepared and well characterized by UV–vis, 1H NMR, 19F NMR and HR-MS. These metallocorroles may bind to CT-DNA through external binding mode. Metallocorrole Fe-2c exhibited significant phototoxicity and low toxicity toward A549 tumor cells. While manganese (III) and copper (III) corroles showed hypotoxicity to A549, MCF-7 and HepG-2 tumor cells, whether under dark or illumination conditions. All tested metallocorroles exhibited non-toxicity to human normal cells (GES-1) with or without irradiation at 625 nm. Cell cycle analysis indicated that metallocorrole Fe-2c arrested the cell cycle at G2/M phase and increased the Sub-G1 phase in A549 cell lines. It was mainly localized at mitochondria and could significantly reduce mitochondrial membrane potential after photodynamic treatment, which would further induce tumor cell apoptosis. [ABSTRACT FROM AUTHOR]