
PDT: photodynamic therapy; PDI: photodynamic inactivation; PTT: photothermal therapy; Elements with green backgrounds mean those corrole complexes have been obtained but have not yet been used in biological applications.
Corrole, whose first introduction can be traced back to the early 1960s, is a representative porphyrin branch. The name was derived from its hydrogenated form, corrin, which is the main skeleton of vitamin B12 without the cobalt center[1] (Fig. 1). Soon after, the first X-ray structure of corrole was reported in 1974[2]. However, the continued advancement of corrole assays encountered significant challenges over the following decades, primarily stemming from the intricate and inefficient synthetic methods required for corroles.
PDT: photodynamic therapy; PDI: photodynamic inactivation; PTT: photothermal therapy; Elements with green backgrounds mean those corrole complexes have been obtained but have not yet been used in biological applications.
A significant turning point emerged in 1999 with the introduction of a groundbreaking and highly efficient synthesis method for triarylcorroles. This innovative approach opened up a plethora of possibilities for modification, sparking a new era of exploration and advancement in the field[3-4]. The subsequent surge of interest and investment in corrole studies has yielded a rich tapestry of literature and propelled the scientific community towards more advanced and comprehensive research into corroles and their intricate complexes. The development and implementation of enhanced preparatory techniques have played a significant role in driving the study of corrole-based transition metal chemistry, enabling researchers to delve deeper into the properties and potential applications of these fascinating molecules. Over several decades, scientists from around the globe have collaborated tirelessly to compile the "Periodic Table of Metallocorroles", a comprehensive visual representation illustrated in Fig. 1. Element symbols with a background signify the existence of reported corrole complexes, while those highlighted in red denote corrole complexes that have undergone thorough characterization via X-ray crystallography.
Corroles exhibit similar chemical and physical properties compared to porphyrin and its derivatives, particularly in terms of their high light-induced singlet oxygen (1O2) quantum yields. Meanwhile, a notable difference is that corroles have enabled the successful isolation of high-valent, multiply bonded compounds, highlighting the versatility and potential of corrole complexes in synthetic chemistry. However, the precise synthesis of corroles remains a challenge and has not yet reached the same level of mastery as that available for the prototypical porphyrins and their derivatives[5-7]. To address these challenges, scientists are working to explore large-scale synthesis strategies and the industrial production of corroles. However, the low yield in corrole synthesis continues to be a barrier to their commercialization. Currently, the one-step synthesis method for corroles achieves a maximum yield of only 32% after optimization[8]. In contrast, the two-step method, which uses dipyrromethanes as intermediates, offers a better yield of around 50% in the latter step but still results in a low overall yield[9]. Therefore, from both industrial and synthetic perspectives, it′s still urgent to develop precise synthesis strategies for corroles.
The typical coordination configuration of metal corroles results in unique optical and magnetic properties, leading to various applications in the fields of catalysts[10-12], solar cells[13-15], chemical sensors[16-18], in vivo imaging[19-21], phototherapy[22], anticancer, and antimicrobial therapy[23]. Up to now, several corroles have been reported for in vivo imaging technologies, including manganese corroles for magnetic resonance imaging (MRI)[19], phosphorus corroles for fluorescence imaging (FI)[20], and nickel corroles for photoacoustic imaging (PAI)[21]. Additionally, a range of corrole complexes, such as gallium, gold, and iridium corroles, serve as excellent photosensitizers (PS) for phototherapy. Currently, research on the biological applications of corroles remains in the experimental stage, leaving significant opportunities for further industrial production and clinical translation.
In this review, we commence with a brief discussion of the remarkable properties of corroles complexes, focusing on their various structures and chelation properties. Special attention is given to the unique optical, thermal, electrical, and magnetic properties of metallocorroles. The review then presents a summary of the biological applications of corrole complexes, highlighting their roles in in vivo imaging, cancer therapy, and potential applications in theranostic clinical translation using corrole-based radionuclide-labeling probes. Subsequently, the discussion outlines commonly used corroles complexes, addresses current research bottlenecks and challenges, and offers insights into the future potential applications in disease diagnosis and therapy. Overall, this review provides a glimpse into the world of corrole complexes, to garner significant attention and exploit further potential biological applications.
In this section, we will enumerate the remarkable properties of corroles and their complexes based on their various structures and chelation characteristics. The anchoring of different metals into the inner core of corroles can lead to quite different results. Emphasizing and expanding upon these properties can help us gain insight into corroles and their complexes in the realms of diagnosis and treatment, thereby fostering additional research endeavors in the field of corroles.
As an important branch of porphyrins, corrole can be viewed as a ring-contracted porphyrinoid containing direct pyrrole-pyrrole linkages and with the trianionic characteristics of the macrocyclic ligand. The syntheses and electronic structures of corroles have been reviewed in previous works[24-25]. Compared with porphyrins, the inner N4 coordination core of corroles is smaller due to the lack of a meso-carbon and relevant aryl group. In addition, corroles act as trianionic rather than dianionic ligands just like porphyrins for the same reason (Fig. 1).
Interestingly, these two particular structure properties caused abnormal formal oxidation (usually valence state≥3) of central metal ions when post-transition metal ion is inserted into corrole ligand to form a complex, such as silver(Ⅲ)[26], gold(Ⅲ)[27], chromium(Ⅴ)[28], manganese(Ⅴ)[29]. This phenomenon leads to another remarkable property of corrole complexes defined as noninnocence which will be discussed in detail in the following part. On the other hand, a small inner core also results in stronger metal-nitrogen bonds which makes corrole complexes more stable and harder to demetallize[30]. The outstanding stability implies the potential prospect of corrole chelates in medical applications.
The structures of corrole complexes with different center atoms which were fully characterized by X-ray crystallography are shown in Fig. 2. Except those common patterns such as planar 4-coordination[26, 27, 31-37], 5-coordination[3, 28, 29, 38-49] and 6-coordination[33, 41, 44, 50-52] adopted by transition metal-controls, some special coordination modes are adapted when it comes to those larger atoms, especially lanthanides, and actinides, These metal atoms are away from the N4 plane since their big size don′t match the narrow inner cavity of corroles. Additional ligands are needed to stabilize the chelates such as cyclopentadiene[53-54], polydentate ligands[53], and other macrocyclic ligands which are linked directly or through a heteroatomic bridge[55-62]. The distinctive structure of free-based corrole results in a complicated coordination situation but also has brought a huge number of corrole chelates which demonstrate a coordinative versatility that can compete with the more famous porphyrin rings. Further, these complexes with various and fascinating properties will play important roles in different fields.
Noninnocence means an ambiguous oxidation state of a coordinated atom. A noninnocent system possesses oxidizing site (holes) or reducing site (electrons) both at the ligand and the coordinated atom[63]. Electron-rich corrole complexes containing a macrocyclic resonance system provide the most fertile soil for noninnocence so it is widespread in the corrole complexes.
Copper corroles are the most notable in this regard[64-65]. However, the conclusion about copper corroles was not accomplished in one move. There has been a fierce debate on the structure and oxidation state of the copper center. Initially, copper corroles were defined as macrocyclic chelates containing a Cu(Ⅱ) center with a N—H of inner core retained[1-2]. Then, an electronic structure consisting of a fully deprotonated corrole ligand and a Cu(Ⅲ) center was proposed[64]. But that's not the end, Nocera and coworkers[66] reported that the one-electron reduction and one-electron oxidation processes are both ligand-based through spectroelectrochemistry (Fig. 3a) and proved that the Cu(Ⅱ) center is retained in these copper corroles. Much more clues thus suggested that an antiferromagnetically coupled Cu(Ⅱ) corrole radical cation would be the most reasonable explanation for copper corroles' electronic structure.
Electron density is allowed to flow into the corrole π HOMO from the Cudx2 - y2 orbital due to the significant overlap between them so that the spin states of copper corroles are determined by the d-π interaction which is the fundamental source of noninnocence. Shen and coworkers[67] further explored copper corroles' spin states through introducing fused benzene rings on the corrole periphery. In this study, a tetrabenzocorrole (Cu-Benzo) was formed in situ from a precursor containing four bicyclo[2.2.2]octadiene group (Cu-BCOD) by a retro-Diels-Alder reaction (Fig. 3b) when the molecule was adsorbed onto an Au(111) substrate in a scanning tunneling microscopy (STM). Its STM topographic image and scanning tunneling spectroscopy (STS) spectrum reveal that there is a delocalized electron over the ligand and lead to the conclusion that the ground state of Cu-Benzo is a ferromagnetically coupled Cu(Ⅱ) corrole radical cation as well as noninnocent.
Compared to the noninnocence conformed in copper corroles, describing silver corroles as innocent or noninnocent is very challenging[68-72]. Shen and coworkers[73] extended their work to silver corrole. In this assay, the first free-base fused-ring-expansion silver corrole (Ag-1) was reported. In the same way, they explored the electronic state of Ag-1 by detecting the Kondo effect when it is adsorbed on the Ag(111) substrate through a retro-Diels-Alder reaction from a precursor. Interestingly, an unprecedented "dome-like" configuration with different directions (Fig. 3c) is observed rather than the usual "saddle-like" configuration of other silver corroles. In addition, this is the first direct spectroscopic observation of the existence of Ag(Ⅱ) corrole radical as obvious Kondo resonances were observed by STM both at the corrole ligand and the Ag center.
Another benzo-fused nickel corrole (Ni-1) acting as a neutral radical with remarkable stability for air, water, light irradiation, and high temperature was reported by Shen's group[21]. The process of research on nickel corroles is very tortuous. At first, nickel ion can just be chelated by a corrole ligand without meso-aryl group which can be easily oxidized[64, 74], or a triarylcorrole ligand which must be recharge-balanced by suitable counterions[33, 75]. Ni-1 is the first case as a neutral radical because most of the spin population (95%) is delocalized around the inner carbons, which are well protected by the fused benzene rings (Fig. 3d). In addition, stable aromatic and antiaromatic ions are easily obtained by one-electron reduction and one-electron oxidation, respectively.
Corroles acting as famous noninnocent ligands in various corrole complexes provide a useful platform to learn more about these metal-ligand interactions and have earned their places in different fields, such as catalyzing, clinical applications, and molecular spintronics.
Excellent photophysical property is another essential feature of corroles and corrole complexes. Overall, free-base corroles present better photophysical properties than corresponding porphyrins and phthalocyanines including stronger fluorescence and higher quantum yields[76]. Moreover, stronger fluorescence is observed when free-based corroles chelate light elements like Ga[46], Al[52], and P[77]. By the way, the aluminum complex of tris-(pentafluorophenyl) corrole owns the highest fluorescence quantum yields (0.76) thus far. However, heavy post-transition metal coordination like Sb[78] and Sn[79] or heavy atom substitution like Br and I[34, 80-82] will reduce their fluorescence quantum yields while increasing their phosphorescence quantum yields.
Another equally important aspect of corroles' photophysical properties is the ability to form 1O2 via irradiation[83]. Table 1 lists the maximal wavelengths of fluorescence (λmax), the corresponding quantum yields (ΦFl), and the 1O2 quantum yields (ΦΔ) of corroles and metallocorroles owning fairly high 1O2 quantum yields of typical corroles and their relevant complexes[84-87] whose structures are shown in Fig. 4. The data in the Table implies that corroles and their complexes can be perfectly qualified for the job as excellent photosensitizers (PSs).
Nowadays, a variety of imaging methods have been widely used to diagnose and examine diseases including positron imaging tomography (PET), single-photon emission computed tomography (SPECT), PAI, photothermal imaging (PTI), MRI, and optical imaging.
Among the technologies mentioned above, molecular optical imaging enables early visualization and detection of subtle molecular abnormalities with high sensitivity and specificity[88]. The most promising corrole complex for clinical diagnosis by optical imaging is gallium corroles which present the highest fluorescence quantum yields. Agadjanian and coworkers[89] reported an amphiphilic sulfonated gallium(Ⅲ) corrole as an optical imaging probe as well as a therapeutic agent by PDT. In this study, they combine the gallium corrole with the human epidermal growth factor receptor (HER) through a noncovalent method to obtain a tumor-targeting protein-corrole complex (HerGa). Compared to the control group probe (S2Ga) without HER, it is obvious that HerGa has a better accumulation in vivo over time bringing good imaging effect as a consequence (Fig. 5a). It is also declared that a lower dose is needed for protein-corrole complex compared with standard chemotherapeutic agents to achieve the same treatment effect.
Another field where corrole fluorescence has been successfully used is fluorescent heme proteins. Lemon and coworkers[20] introduced a new kind of fluorescent heme protein which consists of carboxyl-modified phosphorus corroles inserted in the heme pocket of certain stable heme proteins which includes H-NOX from Caldanaerobacter subterraneus (Cs H-NOX) and heme acquisition system protein A (HasA) from Pseudomonas aeruginosa (Pa HasA). Obvious changes in the emission and absorption spectra successfully demonstrated the assembly of phosphorus corroles and heme proteins. In addition, these novel heme proteins exhibit more intense fluorescence in a narrower spectral profile than traditional fluorescent proteins that emit in the same spectral window (Fig. 5b). The researchers are now working to utilize corroles complexes possessing more intense fluorescence such as six-coordination phosphorus corroles[90], aluminum corroles or gallium corroles to improve the optical properties of such corrole-protein conjugate.
Each imaging method has its own inherent advantages and disadvantages, so the concept of combining two or more imaging methods in the same subject and making full use of their complementarity to ultimately achieve a win-win consequence is increasingly recognized by scientists around the world. A bimodal probe based on MRI and PET was introduced[91]. Gadolinium chelated by 1, 4, 7, 10-tetraazacyclododecane-N, N′, N, N′-tetraacetic acid (DOTA) as a contrast agent for MRI application, copper corrole as a contrast agent for PET and folate as a tumor-targeting group were combined through an efficient sequential route. In addition, they declared a higher relaxivity of the folic heterobimetallic derivative rather than the clinically used Gd-DOTA MRI contrast agent (Fig. 5c). Although they did not implement PET experiments, the idea of combining these two imaging methods was refreshing as early as in 2015.
Tian and coworkers[92] exhibited a typical example as a multimodal probe for tumor diagnosis and treatment. They demonstrated a photoactive agent act as supramolecular nanovesicles (NVs) formed by self-assembling of long-chain molecules which consist of hydrophobic gadolinium corroles and hydrophilic PEG5000 chains linked through cystamines (GCCP NVs). In this study, MRI, PTI and PAI technique were utilized throughout the procedure (Fig. 5d). First, in vivo MRI was performed on CT26 tumor-bearing mice because gadolinium chelates are excellent MRI contrast agents[93-94]. T1-weighted images of mice were recorded after intravenous injection of GCCP NVs, and the signal in the tumor regions gradually became stronger within 1 h of post-injection. Then, IR thermal images were recorded under continuous irradiation for 5 min on the intravenous GCCP NVs injected mice at different time intervals (2, 12, and 24 h). The results demonstrated that the value of temperature gaps decreased gradually with the extension of time, indicating that the GCCP NVs potentially dissociated and switched PTT into PDT under the trigger of GSH at the tumor site and proved that real-time temperature rise images could simultaneously serve as PTI technique to demonstrate the enrichment and disintegration of GCCP NVs at the tumor site. It is also demonstrated that there is a concentration-dependent manner (0-250 μg·mL-1) when GCCP NVs were excited by 660 nm laser irradiation implying GCCP NVs can act as photoacoustic (PA) contrast agents in vivo applications.
PDT is the main approach that corroles and their complexes are adopted in anti-cancer treatments[95-96]. During the photophysical processes involved in PDT, a ground state photosensitizer absorbs certain light to populate the singlet excited state and then is converted to the triplet excited state via intersystem crossing (ISC). This highly active triplet excited state is the key point. Photosensitizers work in two ways in PDT due to their different behaviors when they return from the triplet excited state to the ground state. One is the direct electron transfer (ET) between the PDT agents with excited state and cellular targets, which usually results in oxidation at guanine sites possessing the lowest oxidation potential of all bases and further DNA photocleavage. Another indirect way is producing highly reactive oxidation species (ROS) like 1O2 which can effectively cause damage in cells.
The method causing direct DNA damage avoids the limits on the efficacy of generating 1O2 in a hypoxic environment and is recently under ardent investigation. A water-soluble anionic gallium corrole was reported[97]. Femtosecond transient absorption spectroscopy was performed and demonstrated that the ultrafast ET between the gallium corroles and the guanine bases of ct-DNA occurred within the pulse duration (156 fs) which implied the potential applications of corroles about DNA photocleavage (Fig. 6a).
The outstanding ability to generate 1O2 of corroles is well-known. Recent efforts have been made to find better ones through targeted structural modifications. Very recently, Liu and coworkers[98] reported several dihydroxyl A2B triaryl phosphorus corroles based on their previous works about corrole complexes such as iron, manganese, copper, and gallium corroles[99-100]. The extra hydroxyl groups on meso-benzene ring and another two hydroxyl groups as the axial ligands of phosphorus corroles reduce the intermolecular π-π stacking and enhance their photodynamic effect[101], so that these two hydroxyl phosphorus corroles (1-P & 2-P) have better behavior in antitumor therapy by PDT. Photophysical and photo-chemical characterizations of phosphorus corroles showed that both of them have high photo-induced 1O2 quantum yields which are up to 0.78 and 0.75, respectively. Meanwhile, high phototoxicity towards tumor cells is proved by in vitro antitumor experiments, which would trigger the destruction of the mitochondrial membrane potential and finally lead to apoptosis (Fig. 6b)[98]. Notably, 1-P presents a higher PDT activity than clinical Foscan® against A549 (0.08 μmol·L-1 for 1-P, 0.16 μmol·L-1 for Foscan®) and MDA-MB-231 (0.12 μmol·L-1 for 1-P, and 0.27 μmol·L-1 for Foscan®) cells.
Another popular candidate among corrole complexes for PDT is gallium corroles[95, 102]. Three modulated mono-hydroxy corroles (1-3) and their gallium complexes (Ga1-3) were reported[103] (Fig. 6c). Photodynamic antitumor experiments demonstrated that all these three gallium corroles could effectively produce 1O2 by red light irradiation and the para-substituent gallium corrole (Ga3) exhibited the highest phototoxicity against breast cancer cells ((0.06±0.03) μmol·L-1) and an excellent selective index (1 338.83) between breast cancer and normal cells. Ga3 showed high intracellular uptake at mitochondria and lysosomes and disrupted the mitochondria membrane potential to induce tumor cell death via apoptosis. These results suggest that Ga3 are promising candidate for use in the PDT of breast cancer.
PTT is a treatment inducing apoptosis or increasing sensibility to radio- or chemotherapy through increasing the temperature of tissue whose cells are susceptible of heat[104-105]. PTT has become a promising cancer therapy owing to its high inherent specificity and a lower invasive burden. PTT must have a photothermal agent (PTA) as a medium. Organic PTAs are superior to inorganic PTAs because of their potential excellent biocompatibility, targeting capabilities, and photophysical properties which can be easily fine-tuned via dedicated synthesis. Recently, stable organic π-radical materials become the new darling in the field of PTT as PTAs. Shen' group[106] reported a series of nickel corroles (1-b, 2-b, 3-b) with an extended conjugation system by introducing different numbers of benzene rings to corrole ligands as new PTAs (Fig. 6d). As the number of fused benzene rings increases radially, the ability of light absorbing become stronger. Those nickel corroles have considerable absorption from the visible to NIR area and their extremely narrow gap between the singly highest occupied molecular orbital (SOMO) and singly lowest unoccupied molecular orbital (SUMO) is the just reason for the outstanding photostability and high photothermal conversion efficiency of nickel corrole radicals and their nanoparticles. They chose 3-b which was turned into nanoparticles combined with DSPE-PEG2000 (Na-NPs) as the PTA to perform in vivo PTT experiments irradiated by 808 nm light. The results of in vitro and in vivo studies proved that Na-NPs have excellent PAI ability and PTT performance (Fig. 6d).
Corroles are also active in other areas of biological applications. The principle of PDI is the same as PDT while PDI focuses on the elimination of pathogenic microbial cells rather than cancer cells. Unfortunately, little work has been done on PDI[87, 107-109]. The research is still in its infancy. Iron and manganese were used in antioxidant therapy (AT). They were employed in the prevention and treatment of oxidative stress-induced cardiovascular and neurodegenerative disorders, as well as against diabetes complications[110-113].
From the first corrole reported in the 1960s to the pivotal advancements in synthesis method nearing the millennium, and up to the enduring prosperity seen today, corrole can be likened to a youthful elder. An increasing number of corroles and their complexes, exhibiting a range of unique properties, have been synthesized and characterized over the past two decades, prompting numerous endeavors to identify suitable applications across various fields (Fig. 7). This review detailed delves into corroles and their complexes, shedding light on their properties and pertinent applications. Serving as renowned non-innocent ligands in diverse corrole complexes, corroles offer a valuable platform for studying metal-ligand interactions, securing their positions in fields such as catalysis, clinical applications, and molecular spintronics. With easily tunable exceptional photophysical and chemical properties, corroles have found successful implementation in both therapeutic and imaging interventions. Demonstrating prowess not only as a versatile imaging agent but also as one of the premier photosensitizers in antitumor treatments, corroles have solidified their standing in the realm of advanced medical applications.
Although corroles have obtained many achievements in the field of diagnosis and treatment, there remain a lot of emergencies which should be solved properly, particularly in clinical applications.
(1) The poor yield of corroles′ synthesis remains a persistent challenge throughout the developmental journey of corroles. The realization of various applications hinges on continued synthetic advancements, particularly in achieving gram-scale and even kilogram-scale syntheses. Given the significant demand for corroles across diverse fields, particularly in clinical applications, prioritizing further optimization of corrole synthesis and related complexes is imperative.
(2) It is worth noting that increasing attention is being directed towards newly developed corroles with low molecular weight (< 500 Da), as they contribute a crucial component to the drug-likeness criteria, thus enhancing their suitability for clinical applications[99, 115]. These particular corroles are poised to emerge as a key focal point in the coming years.
(3) Corrole macrocycles present themselves as up-and-coming candidates for chelating various radionuclides (64Cu, 68Ga, 32P, 99mTc, etc.), owing to their exceptional coordination properties. Particularly, the usage of 68Ga and 64Cu isotopes in PET imaging has been on the rise in recent times. Despite the emergence of numerous innovative and encouraging concepts regarding radionuclide-labeled corroles over the past decade, few have come to fruition. This discrepancy may be attributed to the limitations associated with the rigidity of current nuclide labeling methods. Therefore, enhancing the techniques for radionuclide labeling with corroles stands out as a compelling area for further exploration and development.
(4) Integrated diagnosis and treatment are poised to become significant components of anticancer therapies in the future. The excellent photophysical properties and coordination capabilities exhibited by corroles affirm their status as one of the primary contenders in the realm of integrated diagnosis and treatment, underscoring their potential significance in advancing cancer treatment strategies.
In conclusion, in the field of biological applications, the investigation of corroles is still under development. As researchers investigate further into the difficult realm of corroles, it is apparent that they will encounter increasingly complex challenges that demand innovative solutions. Despite the hurdles that lie ahead, we believe that that the collaborative and unwavering efforts of scientists worldwide will serve as the driving force propelling corroles towards unique levels of achievement and advancement in the future.
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Figure 1 Main skeleton structure of corrole (top); Elements chelated by corroles commonly used for different biological applications (down)
PDT: photodynamic therapy; PDI: photodynamic inactivation; PTT: photothermal therapy; Elements with green backgrounds mean those corrole complexes have been obtained but have not yet been used in biological applications.
Figure 3 Corroles as noninnocence ligands for stabling macrocyclic radicals: (a) typical noninnocent copper corrole whose one-electron reduction and one-electron oxidation processes are both ligand-based[66]; (b) copper tetrabenzocorrole behaviors as a ferromagnetically coupled Cu(Ⅱ) corrole radical when adsorbed onto the Au(111) substrate[67]; (c) silver dibenzocorrole adopting unprecedented "dome-like" configurations behaviors as an antiferromagnetically coupled Ag(Ⅱ) corrole radical when adsorbed onto the Ag(111) substrate[73]; (d) schematic diagram of introducing nickel tetrabenzocorrole as the first highly stable Ni(Ⅱ) corrole radical[21] (Adapted from Ref.[66], Copyright©2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim; Ref.[67], Copyright©2015, The Author(s); Ref.[73], Copyright©2021 Wiley-VCH GmbH; Ref.[21], Copyright©2022, Journal of American Chemical Society)
Figure 5 Corroles as contrast agent of in vivo imaging: (a) amphiphilic sulfonated gallium(Ⅲ) corrole combined with HER as an optical imaging probe as well as an excellent therapeutic agent by PDT[89]; (b) fluorescent heme proteins with highly intense fluorescence in the spectral window consisting of phosphorus corroles and heme proteins[20]; (c) folate-targeting (Cu)corrole-(Gd)DOTA complex as a potential bimodal contrast agent for PET and MRI[91]; (d) self-assembled (Gd)Cor-PEG conjugated nanovesicles (GCCP NVs) as MRI, PAI, and PTI imaging agents for anticancer treatment[92] (Adapted from Ref.[89] Copyright©2009 National Academy of Sciences. All rights reserved; Ref.[20], Copyright©2009 National Academy of Sciences. All rights reserved; Ref.[91] Copyright©2015 Elsevier Ltd. All rights reserved; Ref.[92] Copyright©2023 Elsevier B.V. All rights reserved)
Figure 6 Roles of corroles in antitumor therapies: (a) anionic gallium corrole with ultrafast ET (156 fs) as a potential agent for DNA photocleavage[97]; (b) dihydroxyl A2B triaryl phosphorus corroles with higher PDT activity than clinical drugs against A549 & MDA-MB-231 cells[98]; (c) mono-hydroxy gallium corroles with high phototoxicity against breast cancer cells and an excellent selective index between breast cancer and normal cells[103]; (d) nickel corroles with extended conjugation system as a PAI contrast agent as well as an outstanding PTT agent for antitumor treatment[106] (Adapted from Ref.[97], Copyright©2016, American Chemical Society; Ref.[98], Copyright©2023 Elsevier B.V. All rights reserved; Ref.[103], Copyright©2020 Elsevier Masson SAS. All rights reserved; Ref.[106], Copyright©2023 Wiley-VCH GmbH)
Table 1. λmax, ΦFl, and ΦΔ of corroles and metallocorroles