Catalytic Enantioselective Friedel-Crafts Allenylation.

The first enantioselective Friedel-Crafts (FC) allenylation reaction for the creation of central chirality is developed under cooperative Ir(I)/(phosphoramidite,olefin) and Lewis acid catalysis. This enantioconvergent reaction utilizes racemic allenylic alcohol as the electrophile and shows compatibility with a variety of electron-rich arenes and heteroarenes. The resulting highly enantioenriched (up to >99.5:0.5 e.r.) 1,1-disubstituted allenylic methanes, bearing a benzylic carbon stereocenter, are obtained with complete regiocontrol - both on (hetero)arenes as well as on the allenylic fragment. This protocol allows for the enantioselective formal introduction of a 4-carbon alkyl chain into (hetero)arenes, along with the creation of a benzylic stereocenter. Judicious synthetic elaborations not only lead to formal enantioselective FC alkylation products of less electron-rich arenes but also of substituted arenes in ortho- and even meta-selective fashion. An intramolecular version of this FC allenylation is shown to proceed with promising enantioselectivity under the same catalytic conditions. Mechanistic studies revealed the involvement of dynamic kinetic asymmetric transformation (DyKAT) of racemic allenylic alcohols in this reaction.

Supported IrO2 Nanocatalyst with Multilayered Structure for Proton Exchange Membrane Water Electrolysis.

The design of a low-iridium-loading anode catalyst layer with high activity and durability is a key challenge for a proton exchange membrane water electrolyzer (PEMWE). Here, the synthesis of a novel supported IrO2 nanocatalyst with a tri-layered structure, dubbed IrO2@TaOx@TaB that is composed of ultrasmall IrO2 nanoparticles anchored on amorphous TaOx overlayer of TaB nanorods is reported. The composite electrocatalyst shows great activity and stability toward the oxygen evolution reaction (OER) in acid, thanks to its dual-interface structural feature. The electronic interaction in IrO2/TaOx interface can regulate the coverage of surface hydroxyl groups, the Ir3+/ Ir4+ ratio, and the redox peak potential of IrO2 for enhancing OER activity, while the dense TaOx overlayer can prevent further oxidation of TaB substrate and stabilize the IrO2 catalytic layers for improving structural stability during OER. The IrO2@TaOx@TaB can be used to fabricate an anode catalyst layer of PEMWE with an iridium-loading as low as 0.26 mg cm-2. The low-iridium-loading PEMWE delivers high current densities at low cell voltages (e.g., 3.9 A cm-2@2.0 V), and gives excellent activity retention for more than 1500 h at 2.0 A cm-2 current density.

Effect of model-based dose-calculation algorithms in high dose rate brachytherapy of cervical carcinoma.

Background: Task Group 43 (TG-43) formalism does not consider the tissue and applicator heterogeneities. This study is to compare the effect of model-based dose calculation algorithms, like Advanced Collapsed Cone Engine (ACE), on dose calculation with the TG-43 dose calculation formalism in patients with cervical carcinoma. Materials and methods: 20 patients of cervical carcinoma treated with a high dose rate of intracavitary brachytherapy were prospectively studied. The target volume and organs at risk (OARs) were contoured in the Oncentra treatment planning system (Elekta, Veenendaal, The Netherlands). All patients were planned with cobalt-60 (Co-60) and iridium-192 (Ir-192) sources with doses of 21 Gy in 3 fractions. These plans were calculated with TG-43 formalism and a model-based dose calculation algorithm ACE. The dosimetric parameters of TG-43 and ACE-based plans were compared in terms of target coverage and OAR doses. Results: For Co-60-based plans, the percentage differences in the D90 and V100 values for high-risk clinical target volume (HR-CTV) were 0.36 ± 0.43% and 0.17 ± 0.31%, respectively. For the bladder, rectum and sigmoid, the percentage differences for D2cc volumes were -0.50 ± 0.51%, -0.16 ± 0.53% and -0.37 ± 1.21%, respectively. For Ir-192-based plans, the percentage difference in the D90 for HR-CTV was 0.54 ± 0.79%, while V100 was 0.24 ± 0.29%. For the bladder, rectum and sigmoid, the doses to 2cc volume were 0.35 ± 1.06%, 0.99 ± 0.74% and 0.74 ± 1.92%, respectively. No significant differences were found in the dosimetric parameters calculated with ACE and TG-43. Conclusion: The ACE algorithm reduced doses to OARs and targets. However, ACE and TG-43 did not show significant differences in the dosimetric parameters of the target and OARs with both sources.

Development and application of bisphenol S electrochemical immunosensor and iridium oxide nanoparticle-based lateral flow immunoassay.

Bisphenol S (BPS) is a common pollutant in the environment and has posed a potential threat to aquatic animals and human health. To accurately assess the pollution level and ecological risk of BPS, there is an urgent need to establish simple and sensitive detection methods for BPS. In this study, BPS complete antigen was successfully prepared by introducing methyl 4-bromobutyrate and coupling bovine serum albumin (BSA). The monoclonal antibody against BPS (anti-BPS mAb) with high affinity (1: 256,000) was developed based on the BPS complete antigen, which showed low cross-reactivity with BPS structural analogues. Then, an electrochemical immunosensor was constructed to detect BPS using multi-walled carbon nanotubes and gold nanoflower composites as signal amplification elements and using anti-BPS mAb as the probe. The electrochemical immunosensor had a linear range from 1 to 250 ng⋅mL-1 and a limit of detection (LOD) down to 0.6 ng⋅mL-1. Additionally, a more stable and sensitive lateral flow immunoassay (LFIA) for BPS was developed based on iridium oxide nanoparticles, with a visual detection limit of 1 ng⋅mL-1, which was 10 times lower than that of classical Au-NPs LFIA. After evaluation of their stability and specificity, the reliability of these two methods were further validated by measuring BPS concentrations in the water and fish tissues. Thus, this study provides sensitive, robust and rapid methods for the detection of BPS in the environment and organisms, which can provide a methodological reference for monitoring environmental contaminants.

Direct Reductive Amination of HMF to 5-(Aminomethyl)-2-furanmethanol Using Supported Iridium-based Catalysts.

In this work, partial reductive amination of 5-hydroxymethylfurfural (HMF) with gaseous ammonia over iridium supported on γ-Al2O3, TiO2, SiO2 and carbon has been studied. The influence of the support and pressure was investigated in the valorization under mild conditions of HMF to 5-(aminomethyl)-2-furanmethanol (AMFM). The catalysts were characterized by TEM, SEM-EDS, N2 sorption Isotherms, TGA, CO-Chemisorption, TPR, XRD, NH3-TPD, ICP-AES and XPS. The maximum activity and high rates were obtained for all catalytic systems. At 50 minutes of the reaction the Ir/C catalyst achieved 93% of conversion and exhibited the highest yield and selectivity of 92% and 99% respectively, to the desired product 5-(aminomethyl)-2-furanmethanol. The main properties that influence activity and selectivity are related to the amount of iridium on the surface and catalyst acidity. After the third cycle, 63% and 59% of selectivity and yield to AMFM respectively at 93% of conversion were obtained.

Enhanced Emitting Dipole Orientation Based on Asymmetric Iridium(III) Complexes for Efficient Saturated-Blue Phosphorescent OLEDs.

Three novel asymmetric Ir(III) complexes have been rationally designed to optimize their emitting dipole orientations (EDO) and enhance light outcoupling in blue phosphorescent organic light-emitting diodes (OLEDs), thereby boosting their external quantum efficiency (EQE). Bulky electron-donating groups (EDGs), namely: carbazole (Cz), di-tert-butyl carbazole (tBuCz), and phenoxazine (Pxz) are incorporated into the tridentate dicarbene pincer chelate to induce high degree of packing anisotropy, simultaneously enhancing their photophysical properties. Angle-dependent photoluminescence (ADPL) measurements indicate increased horizontal transition dipole ratios of 0.89 and 0.90 for the Ir(III) complexes Cz-dfppy-CN and tBuCz-dfppy-CN, respectively. Analysis of the single crystal structure and density functional theory (DFT) calculation results revealed an inherent correlation between molecular aspect ratio and EDO. Utilizing the newly obtained emitters, the blue OLED devices demonstrated exceptional performance, achieving a maximum EQE of 30.7% at a Commission International de l'Eclairage (CIE) coordinate of (0.140, 0.148). Optical transfer matrix-based simulations confirmed a maximum outcoupling efficiency of 35% due to improved EDO. Finally, the tandem OLED and hyper-OLED devices exhibited a maximum EQE of 44.2% and 31.6%, respectively, together with good device stability. This rational molecular design provides straightforward guidelines to reach highly efficient and stable saturated blue emission.

High-Performance Low-Iridium Catalyst for Water Oxidation: Breaking Long-Ranged Order of IrO2 by Neodymium Doping.

Exploring efficacious low-Ir electrocatalysts for oxygen evolution reaction (OER) is crucial for large-scale application of proton exchange membrane water electrolysis (PEMWE). Herein, an efficient non-precious lanthanide-metal-doped IrO2 electrocatalyst is presented for OER catalysis by doping large-ionic-radius Nd into IrO2 crystal. The doped Nd breaks the long-ranged order structure by triggering the strain effect and thus inducing an atomic rearrangement of Nd─IrO2 involving the forming of Nd─O─Ir bonds along with an increased amount of oxygen vacancies (Ov), giving rise of a long-ranged disorder but a short-ranged order structure. The formed Nd─O─Ir bonds tailor the electronic structure of Ir, leading to a lowered d-band center that weakens intermediates absorption on Ir sites. Moreover, doping Nd triggers Nd─IrO2 to catalyze OER mainly through lattice oxygen mechanism (LOM) by activating lattice oxygen owing to abundant Ov. The optimal catalyst only requires a relatively low overpotential of 263 mV@10 mA cm-2 with a high mass activity of 216.98 A gIr -1 (at 1.53 V) (eightfold of commercial IrO2), and also shows a superior durability at 50 mA cm-2 (20 h) than commercial IrO2 (3 h) due to the oxidation-suppressing effect induced by Nd doping. This work offers insights into designing high-performance low-Ir electrocatalysts for PEMWE application.

Atomically Dispersed Iridium on Polyimide Support for Acidic Oxygen Evolution.

Designing a high-performing iridium (Ir) single-atom catalyst is desired for acidic water electrolysis, which shows enormous potential given its high catalytic activity toward acidic oxygen evolution reaction (OER) with minimum usage of precious Ir metal. However, it still remains a substantial challenge to stabilize the Ir single atoms during the OER operation without sacrificing the activity. Here, we report a high-performing OER catalyst by immobilizing Ir single atoms on a polyimide support, which exhibits a high mass activity on a carbon paper electrode while simultaneously achieving outstanding stability with negligible decay for 360 h. The resulting electrode (denoted as Ir1-PI@CP) reaches a 49.7-fold improvement in mass activity compared to the counterpart electrode prepared without polyimide support. Both our experimental and theoretical results suggest that, owing to the strong metal-support interactions, the polyimide support can enhance the Ir 5d states of Ir single atoms in Ir1-PI@CP, which can tailor the adsorption energies of intermediates and decrease the thermodynamic barrier at the rate-determining step of the OER, but also facilitate the proton-electron-transfer process and improve the reaction kinetics. This work offers an alternative avenue for developing single-atom catalysts with superior activity and durability toward various catalytic systems and beyond.

Ruthenium Single-Atom Modulated Protonated Iridium Oxide for Acidic Water Oxidation in Proton Exchange Membrane Electrolysers.

Proton exchange membrane water electrolysers promise to usher in a new era of clean energy, but they remain a formidable obstacle in designing active and durable electrocatalysts for the acidic oxygen evolution reaction (OER). In this study, a protonated iridium oxide embedded with single-atom dispersed ruthenium atoms (H3.8Ir1- xRuxO4) that demonstrates exceptional activity and stability in acidic water oxidation is introduced. The single Ru dopants favorably induce localized oxygen vacancies in the Ir─O lattice, synergistically strengthening the adsorption of OOH* intermediates and enhancing the intrinsic OER activity. In addition, the preferential oxidation of Ru and the electronegativity of the oxygen vacancies significantly stabilize the Ir─O active sites, improving the OER stability. Consequently, the H3.8Ir1─ xRuxO4 catalyst shows an overpotential of 255 mV at 10 mA cm-2 and displays exceptional catalytic endurance in acidic electrolytes, surpassing 1100 h, representing a remarkable one-order-of-magnitude increase in stability compared to that of pristine H3.8IrO4. A proton exchange membrane electrolyser utilizing the H3.8Ir1- xRuxO4 catalyst as an anode exhibits stable performance for more than 1280 h under a high current density of 2 A cm-2.

Endoplasmic reticulum-targeted iridium(III) photosensitizer induces pyroptosis for augmented tumor immunotherapy.

An ideal tumor treatment strategy involves therapeutic approaches that can enhance the immunogenicity of the tumor microenvironment while simultaneously eliminating the primary tumor. A cholic acid-modified iridium(III) (Ir3) photosensitizer, targeted to the endoplasmic reticulum (ER), has been reported to exhibit potent type I and type II photodynamic therapeutic effects against triple-negative breast cancer (MDA-MB-231). This photosensitizer induces pyroptotic cell death mediated by gasdermin E (GSDME) through photodynamic means and enhances tumor immunotherapy. Mechanistic studies have revealed that complex Ir3 induces characteristics of damage-related molecular patterns (DAMPs) in MDA-MB-231 breast cancer cells under light conditions. These include cell-surface calreticulin (CRT) eversion, extracellular high mobility group box 1 (HMGB1) and ATP release, accompanied by ER stress and increased reactive oxygen species (ROS). Consequently, complex Ir3 promotes dendritic cell maturation and antigen presentation under light conditions, fully activates T cell-dependent immune response in vivo, and ultimately eliminates distant tumors while destroying primary tumors. In conclusion, immune regulation and targeted intervention mediated by metal complexes represent a new and promising approach to tumor therapy. This provides an effective strategy for the development of combined targeted therapy and immunotherapy.

New cyclometalated iridium(III) complexes bearing substituted 2-(1H-benzimidazol-2-yl)quinoline: Synthesis, characterization, electrochemical and anticancer studies.

New iridium(III) compounds (C1-C3) bearing 2-(1H-benzimidazol-2-yl)quinoline ligands with different side groups (benzyl, 2,3,4,5,6-pentamethylbenzyl and 2,3,4,5,6-pentafluorobenzyl) were synthesized and characterized by using spectroscopic analyses. The effects of different side groups of iridium compounds on the photophysical and electrochemical properties have been investigated. The cytotoxicity and apoptosis of the compounds have been evaluated on breast cancer cell lines using various methods including MTT assay, flow cytometry, qRT-PCR, and colony formation. The cytotoxicity of C1, expressed as IC50 values, was found to be 11.76 µM for MDA-MB-231 and 5.35 µM for MCF-7 cells. For C3, the IC50 value was 16.22 µM for MDA-MB-231 and 8.85 µM for MCF-7 cells. In both cell lines, increased levels of Bax and caspase 3, along with downregulation of BCL-2 and positive annexin V staining, were observed, confirming apoptosis. Moreover, the colony-forming abilities in both cell lines decreased after C1 and C3 complex treatment. All these results suggest that the compounds C1 and C3 may have potential in the treatment of breast cancer, though further research is needed to confirm their efficacy.

Sustained Area-Selectivity in Atomic Layer Deposition of Ir Films: Utilization of Dual Effects of O3 in Deposition and Etching.

Area-selective deposition (ASD) based on self-aligned technology has emerged as a promising solution for resolving misalignment issues during ultrafine patterning processes. Despite its potential, the problems of area-selectivity losing beyond a certain thickness remain critical in ASD applications. This study reports a novel approach to sustain the area-selectivity of Ir films as the thickness increases. Ir films are deposited on Al2O3 as the growth area and SiO2 as the non-growth area using atomic-layer-deposition with tricarbonyl-(1,2,3-η)-1,2,3-tri(tert-butyl)-cyclopropenyl-iridium and O3. O3 exhibits a dual effect, facilitating both deposition and etching. In the steady-state growth regime, O3 solely contributes to deposition, whereas in the initial growth stages, longer exposure to O3 etches the initially formed isolated Ir nuclei through the formation of volatile IrO3. Importantly, longer O3 exposure is required for the initial etching on the growth area(Al2O3) compared to the non-growth area(SiO2). By controlling the O3 injection time, the area selectivity is sustained even above a thickness of 25 nm by suppressing nucleation on the non-growth area. These findings shed light on the fundamental mechanisms of ASD using O3 and offer a promising avenue for advancing thin-film technologies. Furthermore, this approach holds promise for extending ASD to other metals susceptible to forming volatile species.

Near Infrared-Fluorescent Dinuclear Iridium(III) Nanoparticles for Immunogenic Sonodynamic Therapy.

Dinuclear iridium(III) complexes activated by light-inducible spatiotemporal control are emerging as promising candidates for cancer therapy. However, broader applications of current light-activated dinuclear iridium(III) complexes are limited by the ineffective tissue penetration and undesirable feedback on guidance activation. Here, an ultrasound (US) triggered near infrared-fluorescent dinuclear iridium(III) nanoparticle, NanoIr, is first reported to precisely and spatiotemporally inhibit tumor growth. It is demonstrated that reactive oxygen species can be generated by NanoIr upon exposure to US irradiation (NanoIr + US), thereby inducing immunogenic cell death. When combined with cisplatin, NanoIr + US elicits synergistic effects in patient-derived tumor xenograft mice models of ovarian cancer. This work first provides a design of dinuclear iridium(III) nanoparticles for immunogenic sonodynamic therapy.

Iridium(III)-Incorporating Self-Healing Polysiloxanes as Materials for Light-Emitting Oxygen Sensors.

Polymer-metal complexes (PMCs) based on poly(2,2'-bipyridine-4,4'-dicarboxamide-co-polydimethylsiloxanes) with cyclometalated di(2-phenylpyridinato-C2,N')iridium(III) fragments and cross-linked by Zn2+ (Zn[Ir]-BipyPDMSs) or Ir3+ (Ir[Ir]-BipyPDMSs) represent flexible, stretchable, phosphorescent, and self-healing molecular oxygen sensors. PMCs provide strong phosphorescence at λem = 595-605 nm. Zn[Ir]-BipyPDMS with PDMS chain length of Mn = 5000 has the highest quantum yield of 9.3% and is a molecular oxygen sensor at different O2 concentrations (0-100 vol%) compared to Ir[Ir]-BipyPDMSs. A Stern-Volmer constant is determined for Zn[Ir]-BipyPDMS as KSV = 0.014%-1, which is similar to the reported oxygen-sensitive iridium(III) complexes. All synthesized PMCs exhibit high elongation at break (up to 1100%) and self-healing efficiency (up to 99%).

Performance Enhancement of Ti/IrO2-Ta2O5 Anode through Introduction of Tantalum-Titanium Interlayer via Double-Glow Plasma Surface Alloying Technology.

Ti/IrO2-Ta2O5 electrodes are extensively utilized in the electrochemical industries such as copper foil production, cathodic protection, and wastewater treatment. However, their performance degrades rapidly under high current densities and severe oxygen evolution conditions. To address this issue, we have developed a composite anode of Ti/Ta-Ti/IrO2-Ta2O5 with a Ta-Ti alloy interlayer deposited on a Ti substrate by double-glow plasma surface alloying, and the IrO2-Ta2O5 surface coating prepared by the traditional thermal decomposition method. This investigation indicates that the electrode with Ta-Ti alloy interlayer reduces the agglomerates of precipitated IrO2 nanoparticles and refines the grain size of IrO2, thereby increasing the number of active sites and enhancing the electrocatalytic activity. Accelerated lifetime tests demonstrate that the Ti/Ta-Ti/IrO2-Ta2O5 electrode exhibits a much higher stability than the Ti/IrO2-Ta2O5 electrode. The significant improvement in electrochemical stability is attributed to the Ta-Ti interlayer, which offers high corrosion resistance and effective protection for the titanium substrate.

Modification of Silica with Sucrose and Ammonium Fluoride Agents: A Facile Route to Prepare Supports of Iridium Catalysts for Hydrogenation Reaction.

Mesoporous silica materials were synthesized using inexpensive and environmentally friendly sucrose as a porogeneous agent. It was found that the presence of sucrose and the products of its chemical transformation during synthesis (e.g., furfural polymer) significantly affected the structure of the obtained porous silica. The influence of synthesis conditions (pH, temperature, time) on the textural properties of the final materials was determined. Samples obtained in an acidic medium, at pH = 1, and treated at room temperature, yielded products with a large surface area and a narrow pore size distribution in the range of 2-5 nm, while the synthesis at pH = 8 allowed for the formation of mesoporous systems with pores in the range of 14-20 nm. To generate acidity, the silicas were modified with an ammonium fluoride solution and then used as supports for iridium catalysts in a hydrogenation reaction, with toluene as a model hydrocarbon. The influence of parameters such as specific surface area, support acidity, and iridium dispersion on catalytic activity was determined. It was shown that modification with sucrose improved the porous structure, and NH4F modification generated acidity. These parameters favored better reducibility and dispersion of the active phase, resulting in higher activity of the catalysts in the studied hydrogenation reaction.

A Nanoencapsulated Ir(III)-Phthalocyanine Conjugate as a Promising Photodynamic Therapy Anticancer Agent.

Despite the potential of photodynamic therapy (PDT) in cancer treatment, the development of efficient and photostable photosensitizing molecules that operate at long wavelengths of light has become a major hurdle. Here, we report for the first time an Ir(III)-phthalocyanine conjugate (Ir-ZnPc) as a novel photosensitizer for high-efficiency synergistic PDT treatment that takes advantage of the long-wavelength excitation and near infrared (NIR) emission of the phthalocyanine scaffold and the known photostability and high phototoxicity of cyclometalated Ir(III) complexes. In order to increase water solubility and cell membrane permeability, the conjugate and parent zinc phthalocyanine (ZnPc) were encapsulated in amphoteric redox-responsive polyurethane-polyurea hybrid nanocapsules (Ir-ZnPc-NCs and ZnPc-NCs, respectively). Photobiological evaluations revealed that the encapsulated Ir-ZnPc conjugate achieved high photocytotoxicity in both normoxic and hypoxic conditions under 630 nm light irradiation, which can be attributed to dual Type I and Type II reactive oxygen species (ROS) photogeneration. Interestingly, PDT treatments with Ir-ZnPc-NCs and ZnPc-NCs significantly inhibited the growth of three-dimensional (3D) multicellular tumor spheroids. Overall, the nanoencapsulation of Zn phthalocyanines conjugated to cyclometalated Ir(III) complexes provides a new strategy for obtaining photostable and biocompatible red-light-activated nano-PDT agents with efficient performance under challenging hypoxic environments, thus offering new therapeutic opportunities for cancer treatment.

Post-Synthetic Modification of Calix[4]arene Framework by Iridium-Mediated Alkyne Insertion into an Inert C-C Bond: A Novel Strategy for Unsymmetrical Macrocycles.

As a novel synthetic method for unsymmetrical macrocycles, we herein developed a post-synthetic modification of calix[4]arenes by insertion of a terminal alkyne into an inert C(methylene)-C(aryl) bond of the macrocyclic framework. In this transformation, C-iridated calix[4]arenes, readily synthesized through C-H bond activation of the parent calix[4]arene, undergoes C(methylene)-C(aryl) bond cleavage followed by insertion of an alkyne to provide a ring-expanded calix[4]arene complex. Removal of the iridium metal from the resulting complex was readily accomplished by a simple treatment with an acid. The developed sequential method affords novel unsymmetrical, monofunctionalized macrocyclic compounds via 3 steps from the parent calix[4]arene in good yield. The unique unsymmetrical structures of the alkyne-inserted macrocycles were evaluated by X-ray single crystal analyses. On the basis of theoretical calculations, we propose a reaction mechanism involving an uncommon C-C bond cleavage step through δ-carbon elimination for the ring enlargement process.

The molecular design and electroluminescent performance of near-infrared (NIR) iridium(â ¢) complexes bearing isoquinoline-, phenazine- and phthalazine-based ligands.

Near-infrared (NIR) light has characteristics of invisibility to human eyes, less background interference, low light scattering, and strong cell penetration. Therefore, NIR luminescent materials have significant applications in imaging, sensing, energy, information storage and display. The development of NIR luminescent materials thus has emerged as a highly dynamic area of research in the realm of contemporary materials. To date, NIR luminescent materials are roughly divided into inorganic materials and organic materials. Compared with inorganic materials, organic NIR luminescent materials have become a hot research topic in recent years due to their rich sources, easy control of structure, simple preparation process, low cost, and good film-forming properties. Among them, iridium(III) [Ir(III)] complexes exhibit excellent properties such as thermal stability, simple synthesis, easy color modulation, short excited state lifetimes, and high brightness, thus becoming one of the ideal luminescent material systems for preparing high-quality organic light-emitting diodes. Therefore, how to obtain Ir(III) complexes with NIR emission and high efficiency through molecular design is a necessary and promising research topic. This work reviews the research progress of representative NIR Ir(III) complexes bearing isoquinoline-, phenazine-, and phthalazine-based ligands reported in recent years and introduces the design strategies and electroluminescent performances of NIR Ir(III) complexes.

Electro-oxidation of ammonia nitrogen using W, Ti-doped IrO2 DSA as a treatment method for mariculture and livestock wastewater.

Animal farming wastewater is one of the most important sources of ammonia nitrogen (NH4+-N) emissions. Electro-oxidation can be a viable solution for removing NH4+-N in wastewater. Compared with other treatment methods, electro-oxidation has the advantages of i) high removal efficiency, ii) smaller size of treatment facilities, and iii) complete removal of contaminant. In this study, a previously prepared DSA (W, Ti-doped IrO2) was used for electro-oxidation of synthetic mariculture and livestock wastewater. The DSA was tested for chlorine evolution reaction (CER) activity, and the reaction kinetics was investigated. CER current efficiency reaches 60-80% in mariculture wastewater and less than 20% in livestock wastewater. In the absence of NH4+-N, the generation of active chlorine follows zero-order kinetics and its consumption follows first-order kinetics, with cathodic reduction being its main consumption pathway, rather than escape or conversion to ClO3-. Cyclic voltammetry experiments show that NH4+-N in the form of NH3 can be oxidized directly on the anode surface. In addition, the generated active chlorine combines with NH4+-N at a fast rate near the anode, rather than in the bulk solution. In electrolysis experiments, the NH4+-N removal rate in synthetic mariculture wastewater (30-40 mg/L NH4+-N) and livestock wastewater (~ 450 mg/L NH4+-N) is 112.9 g NH4+-N/(m2·d) and 186.5 g NH4+-N/(m2·d), respectively, which is much more efficient than biological treatment. The specific energy consumption (SEC) in synthetic mariculture wastewater is 31.5 kWh/kg NH4+-N, comparable to other modified electro-catalysts reported in the literature. However, in synthetic livestock wastewater, the SEC is as high as 260 kWh/kg NH4+-N, mainly due to the suppression of active chlorine generation by HCO3- and the generation of NO3- as a by-product. Therefore, we conclude that electro-oxidation is suitable for mariculture wastewater treatment, but is not recommended for livestock wastewater. Electrolysis prior to urea hydrolysis may enhance the treatment efficiency in livestock wastewater.