High Photocytotoxicity Iridium(III) Complex Photosensitizer for Photodynamic Therapy Induces Antitumor Effect Through GPX4-Dependent Ferroptosis.

The development of small molecule photosensitizers based on iridium complex is limited by the mismatch between therapeutic effect and systemic toxicity, as well as the incomplete understanding of the molecular mechanism underlying cell death induction. Herein, a small molecule iridium complex IrC with high photocytotoxicity is synthesized, with half maximal inhibitory concentration as low as 91 nm, demonstrating excellent anti-tumor, relief of splenomegaly, and negligible side effects. Starting from the factors of effective photosensitizers, the in-depth theoretical analysis on photon absorption efficiency, energy transfer level matching, and properties of the triplet excited state of IrC is conducted. This also elucidates the feasibility of generating the high singlet oxygen quantum yield. In addition, the death mechanism induced by IrC is focused, innovatively utilizing GPX4-overexpression and GPX4-knockout cells via CRISPR/Cas9 technique to comprehensively verify ferroptosis and its further molecular mechanism. The generation of ROS mediated by IrC, along with the direct inhibition of GPX4 and glutathione, synergistically increased cellular oxidative stress and the level of lipid peroxidation. This study provides an effective approach for small molecule complexes to induce GPX4-dependent ferroptosis at low-dose photodynamic therapy.

Synthesis, Photophysics and Tunable Reverse Saturable Absorption of Bis-Tridentate Iridium(III) Complexes via Modification on Diimine Ligand.

Five novel bis-tridentate Ir(III) complexes (Ir-1−Ir-5) incorporating versatile N^N^C ligands and a N^C^N ligand (1,3-di(2-pyridyl)-4,6-dimethylbenzene) were synthesized. With the combination of experimental and theoretical methods, their steady and transient state characteristics were researched scientifically. The UV-visible absorption spectra show that the broadband charge transfer absorbance of those bis-tridentate Ir(III) complexes can reach 550 nm, all of these complexes reveal the long-lasting phosphorescent emission. Because the excited-state absorption is more powerful than the ground-state absorption, a sturdy reverse saturable absorption (RSA) process can ensue in the visible and near-infrared regions when the complexes are exposed to a 532 nm laser. Therefore, the optical power limiting (OPL) effect follows the trend: Ir-5 > Ir-4 ≈ Ir-3 > Ir-2 > Ir-1. Generally speaking, the expansion of π-conjugation and the introduction of electron donating/withdrawing groups on the N^N^C ligand could effectively elevate the OPL effect. Therefore, these octahedral bis-tridentate Ir(III) complexes might be exploited as potential OPL materials.

Self-Assembled BODIPY Nanoparticles for Near-Infrared Fluorescence Bioimaging.

In vivo optical imaging is an important application value in disease diagnosis. However, near-infrared nanoprobes with excellent luminescent properties are still scarce. Herein, two boron-dipyrromethene (BODIPY) molecules (BDP-A and BDP-B) were designed and synthesized. The BODIPY emission was tuned to the near-infrared (NIR) region by regulating the electron-donating ability of the substituents on its core structure. In addition, the introduction of polyethylene glycol (PEG) chains on BODIPY enabled the formation of self-assembled nanoparticles (NPs) to form optical nanoprobes. The self-assembled BODIPY NPs present several advantages, including NIR emission, large Stokes shifts, and high fluorescence quantum efficiency, which can increase water dispersibility and signal-to-noise ratio to decrease the interference by the biological background fluorescence. The in vitro studies revealed that these NPs can enter tumor cells and illuminate the cytoplasm through fluorescence imaging. Then, BDP-B NPs were selected for use in vivo imaging due to their unique NIR emission. BDP-B was enriched in the tumor and effectively illuminated it via an enhanced penetrability and retention effect (EPR) after being injected into the tail vein of mice. The organic nanoparticles were metabolized through the liver and kidney. Thus, the BODIPY-based nanomicelles with NIR fluorescence emission provide an effective research basis for the development of optical nanoprobes in vivo.

Tailored Design of π-Extended Multi-Resonance Organoboron using Indolo[3,2-b]Indole as a Multi-Nitrogen Bridge.

Extending the π-skeletons of multi-resonance (MR) organoboron emitters can feasibly modulate their optoelectronic properties. Here, we first adopt the indolo[3,2-b]indole (32bID) segment as a multi-nitrogen bridge and develop a high-efficiency π-extended narrowband green emitter. This moiety establishes not only a high-yield one-shot multiple Bora-Friedel-Crafts reaction towards a π-extended MR skeleton, but a compact N-ethylene-N motif for a red-shifted narrowband emission. An emission peak at 524 nm, a small full width at half maximum of 25 nm and a high photoluminescence quantum yield of 96 % are concurrently obtained in dilute toluene. The extended molecular plane also results in a large horizontal emitting dipole orientation ratio of 87 %. A maximum external quantum efficiency (EQE) of 36.6 % and a maximum power efficiency of 135.2 lm/W are thereafter recorded for the corresponding device, also allowing a low efficiency roll-off with EQEs of 34.5 % and 28.1 % at luminance of 1,000 cd/m2 and 10,000 cd/m2 , respectively.

Synthesis, luminescence, and excited-state absorption properties of disubstituted perylene diimide derivatives modified at bay region.

Three A-π-A or D-π-D perylene diimide (PDI) derivatives with varied groups on π-conjugate were synthesized and characterized. The photophysical properties of these compounds were systematically studied by spectral experiments and density functional theory calculations. All compounds displayed intense absorption bands at 300-800 nm wavelengths. However, diverse groups on the π-conjugate influenced the UV-vis absorption. Electron-withdrawing groups on PDI-2 caused a slight red shift at the 350-400 nm wavelength and a blue shift after 400 nm wavelength. At the same time, the electron-donating substituents on PDI-3 caused an obvious red shift of this band. These PDI derivatives exhibited emission in solution at room temperature (λem = 500-850 nm). The quantum yield of PDI-3 decreased, while the electron-donating substituents were introduced to the π-conjugated motifs. However, the quantum yield of PDI-2 increased when electron-withdrawing substituents were introduced to the π-conjugated motifs. In addition, PDI-1 and PDI-2 exhibited broad triplet transient absorption in the visible region. These photophysical properties could help us to understand the relationship between structure and photophysical properties of perylene diimide derivatives and exploit more original perylene diimide-based optical functional materials.

Ligand-Mediated Photophysics Adjustability in Bis-tridentate Ir(III) Complexes and Their Application in Efficient Optical Limiting Materials.

A family of novel bis-tridentate Ir(III) complexes (Ir1-Ir5) incorporating both functional N∧C∧N-type ligands (L1-L5) and N∧N∧C-type ligand (L0) were synthesized attentively and characterized scientifically. The crystalline structures of Ir1, Ir3 and Ir4 were resoundingly confirmed by XRD. With the aid of experimental and theoretical methods, their photophysical properties at transient and steady states were scientifically investigated. The broadband charge-transfer absorption for these aforementioned Ir(III) complexes is up to 600 nm as shown in the UV-visible absorption spectrum. The emission lifetimes of their excited states are good. Between the visible and near-infrared regions, Ir1-Ir5 possessed powerful excited-state absorption. Hence, a remarkably robust reverse saturable absorption (RSA) process can occur once the complexes are irradiated by a 532 nm laser. The RSA effect follows the descending order: Ir3 > Ir5 > Ir4 ≈ Ir1 > Ir2. To sum up, modifying electron-donating units (-OCH3) and large π-conjugated units to the pyridyl N∧C∧N-type ligands is a systematic way to markedly raise the RSA effect. Therefore, these octahedral bis-tridentate Ir(III) complexes are potentially state-of-the-art optical limiting (OPL) materials.

Meso-substituted boron-dipyrromethene compounds: synthesis, tunable solid-state emission, and application in blue-driven LEDs.

In this work, we depict the synthesis and characterization of a series of meso-substituted boron-dipyrromethene (BODIPY) compounds. Their optical and electrochemical properties were investigated systematically. All these compounds exhibited intense absorption bands in the ultraviolet (UV) and visible regions, which arise from the π-π* transitions based on their BODIPY core segments. By comparing electron-withdrawing substituents and electron-donating substituents, we found that these compounds exhibited some similar photophysical properties but exhibited different fluorescence in the solid state. All compounds were highly emissive in dichloromethane at room temperature (λem = 512-523 nm, ΦPL > 0.9). When these compounds were applied in blue-driven light-emitting diodes (LEDs) as light-emitting materials, the devices showed luminescence efficiency ranging from 1.09 to 34.13 lm/W. Their luminescence and electrochemical properties could be used for understanding the structure-property relationship of BODIPY compounds and developing functional fluorescent materials.

New bis-photochromic compounds based on diarylimidazoles: Synthesis and multistimuli-responsive optical properties.

Three new bis-photochromic molecules containing two 4,5-diarylimidazole units were synthesized and characterized. We investigated their photophysical properties and pH response characteristics in acetonitrile solutions and polymethylmethacrylate (PMMA) membranes. All compounds displayed significant pH responses for the imidazole ring in the molecular structure, which could be potentially used as pH probes. Under ultraviolet light, these compounds show photochromism and 'turn-off' fluorescence properties either in solution or in PMMA film. The mechanism of this phenomenon may be due to photoisomerization, that is the conversion of the 4,5-diarylimidazole units open-ring form to the closed-ring form. Moreover, such systems as logic gates, high density (3D) data storage systems and optical equivalents of field-effect transistors are considered necessary for optical computing.

Synthesis, Aggregation Induced Emission and Mechanochromic Luminescence of New ß-Diketone Derivatives Bearing Tetraphenylene Moieties.

A series of ß-diketone derivatives bearing tetraphenylene (TPE) moieties were synthesized and characterized. Their photophysical properties were investigated systematically via spectroscopic and theoretical methods. All compounds exhibit broad absorption bands between 300 and 450 nm, which are assigned to the 1π-π* transition of the conjugated system mixed intramolecular charge-transfer (ICT) transitions. Meanwhile, the emission of these compounds in solution at room temperature (λ em = 458 ~ 509 nm) can be attributed to the 1π,π*/1ICT state. Introduction of freely rotatable TPE to conventional ß-diketone luminophors quenches their light emissions in the solutions, but endows these molecules with aggregation-induced emission (AIE) characteristics in the condensed phase due to the restriction of intramolecular rotation. The spectroscopic studies and theoretical calculations indicate that the photophysical properties of these ß-diketone derivatives can be tuned by the appended substituents, which would be useful for rational design of AIE compounds with high solid state luminescence performance. Furthermore, these AIE-active compounds exhibited distinct piezofluorochromic properties and switched reversibly upon grinding-fuming. Their photophysical properties have been investigated with the aim to provide a basis for elucidating the structure-property correlations and developing new multi-stimuli responsive luminescent materials.

Paratesticular metastasis arising from colonic mucinous adenocarcinoma: a rare case report.

Colonic mucinous adenocarcinoma rarely metastasizes to the paratesticular region, highlighting the importance of a correct diagnosis. We herein present a case involving a 65-year-old man with paratesticular carcinoma associated with scrotal swelling 1 year after radical resection of colon cancer. Computed tomography revealed a low-density tumor in the right scrotum and mild enhancement of the mass after administration of a contrast agent. The patient underwent radical surgery to remove the right testis. Pathology and immunohistochemistry revealed mucinous adenocarcinoma of the paratesticular tissue. The patient was discharged from the hospital 6 days after surgery. We reviewed the recent literature to summarize the clinical manifestations, treatments, and prognosis of this disease.

AIPE-Active Ir(III) complexes with tuneable photophysical properties and application in mitochondria-targeted dual-mode photodynamic therapy.

Aggregation-induced phosphorescence emission (AIPE) materials based on transition metal Ir(III) complexes have significant advantages in bioimaging and photodynamic therapy (PDT) due to the long lifetime, the reduced photobleaching and the good reactive oxygen species (ROS) generation. Herein, four cationic Ir(III) complexes (Ir1-Ir4) have been synthesized and studied. Tunable phosphorescence from green to red with the excellent properties of AIPE and long lifetimes can be achieved by varying the substituents. Moreover, these phosphorescence Ir(III) complexes exhibited dual-mode PDT potential (type I and type II). Complex Ir4 showed great prospect in bioimaging and PDT with the large Stokes shift (259 nm), the long lifetime (9.85 µs) and the high ROS yield (0.73). Confocal microscopy demonstrated that Ir4 accumulated in the mitochondria selectively and possessed remarkable photostability (reduced photobleaching up to 600 s). The results indicate that Ir4 may be used in dual-mode PDT guided by mitochondria-targeted imaging. This work provides an in-depth understanding of the relationship between structure and photophysical properties and facilitates the study in PDT applications.

Fluorene-decorated Ir(III) complexes: synthesis, photophysics and tunable triplet excited state properties in aggregation.

Two new heteroleptic cationic Ir(III) complexes bearing benzothiazole and pyridine motifs on fluorene groups were synthesized and characterized. Complexes Ir1 and Ir2 exhibit 1π,π* transitions below 430 nm, with broad but weak metal-to-ligand and ligand-to-ligand charge transfer absorption bands above 430 nm. Both complexes possess long-lived emissions (τem = 0.37 µs for Ir1, τem = 5.41 µs for Ir2) and triplet excited states (τTA = 0.14 µs for Ir1, τTA = 6.06 µs for Ir2). Their optical properties in solution and aggregated states were also investigated. Both Ir(III) complexes exhibit aggregation-induced phosphorescence emission behavior in an acetonitrile-water mixture. As the water content increased to 90%, the emission intensities of complexes Ir1 and Ir2 increased nearly 3 times and 2.8 times, respectively. Moreover, nonlinear transmittance experiments were performed in CH3CN and a CH3CN-H2O mixture (fw = 90%), and the strength of the reverse saturable absorption (RSA) at 532 nm followed the trend: Ir2 (CH3CN) ≥ Ir1 (CH3CN) > Ir2 (CH3CN-H2O) > Ir1 (CH3CN-H2O). Abundant triplet state excitons participated in the radiative transition progress, which inhibited the RSA process. These results indicate that the fluorene-decorated Ir(III) complexes are suitable for aggregation emission and optical power limiting applications.

Heteroleptic Ir(iii) complexes with varied π-conjugated diimine ligands: synthesis, tunable triplet states and nonlinear absorption properties.

Four heteroleptic Ir(iii) complexes (Ir-1-Ir-4) with varied π-conjugated diimine ligands were synthesized. Their optical properties were investigated systematically via spectroscopic methods, in order to elucidate the influence of the extended π-conjugation on the singlet and triplet states of the molecules. All these Ir(iii) complexes exhibit ligand localized 1π,π* transitions below 370 nm, and broad metal-to-ligand and ligand-to-ligand charge transfer (MLCT/LLCT) absorption bands in the visible region. Extending the π-conjugation in diimine ligands influences the electron distribution of the triplet state. The 3π,π* dominated Ir(iii) complexes (Ir-3 and Ir-4) exhibit long-lived triplet states and low phosphorescence quantum yields, compared with the charge transfer dominated Ir(iii) complexes (Ir-1 and Ir-2). Complexes Ir-3 and Ir-4 exhibit broadband transient absorption spectra from 420 to 750 nm, between which the nonlinear absorption could be observed by virtue of reverse saturable absorption. The results of nonlinear transmission measurements using 532 nm laser pulses further elucidate that selected complexes Ir-3 and Ir-4 are promising candidates for optical limiting applications.

The effects of extended π-conjugation in bipyridyl ligands on the tunable photophysics, triplet excited state and optical limiting properties of Pt(ii) naphthalimidyl acetylide complexes.

Pt(ii) complexes that exhibit long-lived triplet excited state lifetimes are promising for optical power limiting materials. The introduction of large π-conjugated substituents can switch the triplet excited state to a long-lived 3π,π* state. Herein, we report four Pt(ii) diimine complexes with high π-conjugation via inserting an aryl group on the diimine ligand. Their photophysical properties were investigated using spectroscopic techniques. All the complexes exhibit strong ground absorption bands in their UV-Vis absorption spectra (maximum peaks ranging from 370 to 530 nm) and long-lived emission and triplet excited states. The insertion of π-conjugated substituents induces a pronounced red-shift in the ground state absorption and longer emission lifetime. Broadband transient absorption spectra in the visible-NIR region and Z-scan properties under 532 nm were carried out on the Pt(ii) diimine complexes, resulting in a remarkably strong reverse saturable absorption at 532 nm for nanosecond laser pulses. Otherwise, the high π-conjugation in the bipyridyl ligand increases the reverse saturable absorption. Therefore, these Pt(ii) diimine complexes with high π-conjugation are excellent candidates for devices that require strong reverse saturable absorption.

Synergistically Enhanced Optical Limiting Property of Graphene Oxide Hybrid Materials Functionalized with Pt Complexes.

Recently, graphene-based materials have become well-known nonlinear optical materials for the potential application of laser protection. Two new graphene oxide-platinum  complex (GO-Pt) hybrid materials (GO-Pt-1, GO-Pt-2) have been fabricated through covalent modification and electrostatic adsorption of different Pt complexes with GO. The structural and photophysical properties of the resultant hybrid materials were studied. The nonlinear optical properties and optical power limiting (OPL) performance of Pt complexes, GO, and GO-Pt hybrid materials were investigated by using Z-scan measurements at 532 nm. At the same transmittance, the results illustrate that functionalization of GO makes GO-Pt hybrid materials possess better nonlinear optical properties and OPL performance than individual Pt complexes and GO due to a combination of nonlinear scattering, nonlinear absorption, and photoinduced electron and energy transfer between GO and Pt complex moieties. Furthermore, the nonlinear optics and OPL performance of GO-Pt-2 are better than those of GO-Pt-1, due to not only the excellent optical limiting of Pt-2 and more molecules per area of GO but also the way of combination of Pt-2 and GO.