Efficient green-colored electrochemiluminescence from cyclometalated iridium(III) complex

The spectroscopy, electrochemistry, and electrochemiluminescence (ECL) of cyclometalated iridium(III) bis(2-(p-tolyl)pyridinato-N, C^2′) (picolinate) [(tpy)₂Ir(pico)] was investigated. (tpy)₂Ir(pico) shows high photoluminescence efficiency (Φ_PL = ∼0.31) and quasi-reversible redox behaviors in acetonitrile solution. Intense green ECL was observed from all three modes of ECL generation (annihilation, oxidative-reduction, and reductive-oxidation). Relative ECL efficiencies with or without coreactants from (tpy)₂Ir(pico) were estimated using Ru(bpy)₃²⁺ (bpy, 2,2′-bipyridine) as a relative standard. Typically, in the reductive-oxidation process with peroxodisulfate (S₂O₈²⁻), (tpy)₂Ir(pico) produces 8-fold more efficient ECL at approximately 531 nm than Ru(bpy)₃². This efficient green ECL indicates potential for the development of multicolored ECL analysis in addition to standard Ru(bpy)₃²⁺ systems.     

Ru(III)-catalyzed oxidation of N-acetyl-L-cysteine by methylene blue in absence and in presence of Cu(II) in acidic medium: influence of solvent and morphology

N-acetyl l-cysteine (NAC), the substrate used presently has got diverse medicinal applications and is widely used as a mucolytic agent. The oxidation of bioactive molecules, in general, involves metal ion catalysis facilitated by the participation of metal nanoparticles. In view of this, the oxidation of NAC by a phenothiazine dye methylene blue (MB), a model electron receptor, catalyzed by Ru(III) in the absence and in the presence of Cu(II) has been investigated in acidic medium. The concentration order in MB is zero, while the order in NAC is one and two in Ru(III)-catalyzed and Ru(III)-Cu(II)-catalyzed reactions, respectively. Hydrogen ions retard the rate in Ru(III)-Cu(II)-catalyzed reaction, whereas the rate increases linearly with increasing [Ru(III)] in both the systems. The rate increases with increasing [Cu(II)] and attains a limiting value. The addition of the reaction products does not affect the rate of reaction. The reaction is characterized by a large negative entropy of activation. The kinetic deviations of the reaction, explained by presuming the participation of a reactive form of the NAC molecule or its new conformational polymorph reported recently, indicate the regulatory influence of the morphology of nanoparticles.     

Rational Design of Phosphorescent Iridium(III) Complexes for Selective Glutathione Sensing and Amplified Photodynamic Therapy

It is a huge challenge to avoid irreversible damage to normal tissues during irradiation in photodynamic therapy (PDT) for cancer. An effective strategy is to develop smart photosensitizers, which exhibit amplified generation of reactive oxygen species (ROS) through triggering specific reaction in the tumor microenvironment. In this work, we designed a class of glutathione (GSH)-activatable photosensitizers ( Ir1 and Ir4 ) based on an effective strategy of GSH-induced nucleophilic substitution reaction. The addition of GSH, induced changes in both phosphorescence intensity and lifetime of photosensitizers with high sensitivity. Importantly, the amount of singlet oxygen generated was increased significantly by GSH-induced activation reaction. Hence, the photosensitizers can selectively distinguish cancer cells from normal cells through luminescence and lifetime imaging, and can amplify PDT effects in cancer cells, owing to the evidently higher level of GSH compared to normal cells. This work presents a novel paradigm for GSH-amplified PDT against cancer cells and provides a new avenue for smart-responsive theranostic systems that can avoid nonspecific damage to normal cells.     

Polypyridyl Ruthenium(II) Complexes with Red-Shifted Absorption: New Promises in Photodynamic Therapy

In the field of cancer photodynamic therapy (PDT) research, development of metal-based PDT drugs that can be used under red light exposure is the “holy grail” to achieve. This highlight highlighted few current literatures on polypyridyl-based Ru(II) complexes with significantly red-shifted absorption to achieve in-vitro and in-vivo PDT effect in 540–600 nm light. The enormous potential of judicial ligand choice and in-silico optimization to achieve the red light, metal-based PDT drugs are discussed.     

Towards Selective Delivery of a Ruthenium(II) Polypyridyl Complex-Containing Bombesin Conjugate into Cancer Cells

An increasing number of novel Ru(II) polypyridyl complexes have been successfully applied as photosensitizers (PSs) for photodynamic therapy (PDT). Despite recent advances in optimized PSs with refined photophysical properties, the lack of tumoral selectivity is often a major hurdle for their clinical development. Here, classical maleimide and versatile NHS-activated acrylamide strategies were employed to site-selectively conjugate a promising Ru(II) polypyridyl complex to the N-terminally Cys-modified Bombesin (BBN) targeting unit. Surprisingly, the decreased cell uptake of these novel Ru-BBN conjugates in cancer cells did not hamper the high phototoxic activity of the Ru-containing bioconjugates and even decreased the toxicity of the constructs in the absence of light irradiation. Overall, although deceiving in terms of selectivity, our new bioconjugates could still be useful for advanced cancer treatment due to their nontoxicity in the dark.     

Homogeneous Catalytic Isomerization of Allylbenzene and Phenylbutenes by Some Platinum-Metal Oomplexes

The isomerization of Allylbenzene, p-allylanisole, 4-phenylbut-1-ene and trans-1-phenylbut-2-ene catalyzed by various ruthenium, rhodium and iridium complexes has been investigated. At the boiling point of the olefins the reaction does not require co-catalysts. The activity of the complexes studied decreases in the order Ru > Ir > Rh. PPh₃ and AsPh₃ increase the initial rates of the Rh (III), catalyzed reactions, decrease the activities of Rh (I)- and Ir (I)-complexes and do not affect the Ru (II)-compound. Different mechanisms for the rhodium- and ruthenium-catalyzed isomerizations are suggested.     

Properties and application of poly(acrylphenylamidrazone‐phenylhydrazide) chelating fiber for enrichment–separation of trace gold and ruthenium from solution samples

An ICP‐OES method using a new poly(acrylphenylamidrazone‐phenylhydrazide) chelating fiber to enrich and separate trace Au(III) and Ru(III) ions from solution samples is established. The results show that 50–500 ng/mL of Au or Ru ions can be enriched quantitatively by 0.1 g of the fiber at pH 4, with recoveries > 96%. The ions can be desorbed quantitatively with 10 mL of 4 M HCl and 3.0% CS(NH₂)₂ solution from the fiber column, with recoveries > 97%, and 200–1000‐fold excesses of Cu(II), Zn(II), Ca(II), Mg(II), Mn(II), Cr(III), Fe(III), Ba(II), and Al(III) caused little interference in the determination of these ions by ICP–OES. The chelating fiber can be reused eight times, and the recoveries are all > 95%. The relative standard deviations for enrichment and determination of 50 ng/mL of Au and Ru are in the range 1.8–1.9% (1.9% for Au and 1.8% for Ru). The recoveries of trace Au and Ru ions added to real waste water and alloy samples are 96–98%. The concentration of each ion found in the alloy samples was in good agreement with that provided by the plant. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2656–2660, 2001     

Adsorption Behaviors of Platinum Group Metals in Simulated High Level Liquid Waste Using Macroporous (MOTDGA-TOA)/SiO2-P Silica-based Absorbent

As fundamental research for separation of platinum group metals (PGMs) from high level liquid waste (HLLW) by macroporous silica-based adsorbent, (MOTDGA-TOA)/SiO₂-P adsorbent was prepared by impregnation of N,N′-dimethyl-N,N′-di-n-octyl-thiodiglycolamide (MOTDGA) and Tri-n-octylamine (TOA) into silica/polymer composite support (SiO₂-P). The adsorption behavior of Ru(III), Rh(III), and Pd(II) in simulated HLLW onto the adsorbent were investigated by the batch method to obtain their corresponding equilibrium and kinetic data. The adsorbent showed strong adsorption for Pd(II) and the adsorption reached equilibrium within 2 hr. High distribution coefficient (K _d) values for Pd(II) were obtained in 0.1–1 M HNO₃ concentration. In addition, the use of both MOTDGA and TOA improved adsorption of Ru(III) and Rh(III) better than individual use of them. Especially, the K _d value for Ru(III) towards (MOTDGA-TOA)/SiO₂-P adsorbent was three times larger than that in the adsorption using only with MOTDGA or TOA as extractant. The adsorptions of Ru(III), Rh(III), and Pd(II) followed the Langmuir adsorption model, and were found to be controlled by the chemisorption mechanism.     

Investigating Alkylated Prodigiosenes and Their Cu(II)-Dependent Biological Activity: Interactions with DNA,Antimicrobial and Photoinduced Anticancer Activity

Prodigiosenes are a family of red pigments with versatile biological activity. Their tripyrrolic core structure has been modified many times in order to manipulate the spectrum of activity. We have been looking systematically at prodigiosenes substituted at the C ring with alkyl chains of different lengths, in order to assess the relevance of this substituent in a context that has not been investigated before for these derivatives: Cu(II) complexation, DNA binding, self-activated DNA cleavage, photoinduced cytotoxicity and antimicrobial activity. Our results indicate that the hydrophobic substituent has a clear influence on the different aspects of their biological activity. The cytotoxicity study of the Cu(II) complexes of these prodigiosenes shows that they exhibit a strong cytotoxic effect towards the tested tumor cell lines. The Cu(II) complex of a prodigiosene lacking any alkyl chain excelled in its photoinduced anticancer activity, thus demonstrating the potential of prodigiosenes and their metal complexes for an application in photodynamic therapy (PDT). Two derivatives along with their Cu(II) complexes showed also antimicrobial activity against Staphylococcus aureus strains.     

Liquid-Liquid Extraction of Ruthenium from Chloride Media by N,N'-Dimethyl- N,N'-Dicyclohexylmalonamide

Abstract

Research on the solvent extraction of ruthenium from hydrochloric acid media has been carried out using N,N'-dimethyl-N,N'-dicyclohexylmalonamide (DMDCHMA) dissolved in 1,2-dichloroethane. Ruthenium extraction percentages (%E) ranging from 50% to 80% have been achieved for HCl concentrations between 5 M and 7 M. Extraction curves exhibiting the dependence of the %E ruthenium on HCl concentration in the aqueous phases are presented, the latter solutions being obtained by dissolution of either Ru(III) or Ru(IV) salts. The influence of some experimental parameters on the %E Ru, such as the equilibration time, extractant concentrations, and hydrogen-ion activities, has been thoroughly investigated. Additionally, DMDCHMA is also adequate for extracting Pd(II) from 5 M to 7 M HCl solutions and under similar experimental conditions, %E Rh(III) is below 5%, and Pt(IV), Ir(III), and Ir(IV) cause the formation of third phases. Both Ru and Pd(II) can be successfully stripped from the loaded organic phases with water. A partition scheme to isolate Ru from a number of some associated elements has also been attempted.     

Radical carbon-carbon bond formations enabled by visible light active photocatalysts

This mini-review highlights the Stephenson group's contribution to the field of photoredox catalysis with emphasis on carbon-carbon bond formation. The realization of photoredox mediated reductive dehalogenation initiated investigations toward both intra- and intermolecular coupling reactions. These reactions commenced via visible light-mediated reduction of activated halogens to give carbon-centered radicals that were subsequently involved in carbon-carbon bond forming transformations. The developed protocols using Ru and Ir based polypyridyl complexes as photoredox catalysts were further tuned to efficiently catalyze overall redox neutral atom transfer radical addition reactions. Most recently, a simplistic flow reactor technique has been utilized to affect a broad scope of photocatalytic transformations with significant enhancement in reaction efficiency.     

Hydrogen evolution on porous Ni cathodes modified by spontaneous deposition of Ru or Ir

Porous Ni deposits, prepared by cathodic deposition, were modified by immersing them in acid deaerated solutions containing Ru(III) or Ir(IV) chloride complexes with which they readily reacted, without any activation procedure, giving rise to spontaneous deposition of either Ru or Ir. The obtained electrodes were investigated by cyclic voltammetry, impedance spectroscopy and scanning electron microscopy. All data showed that the initial large area of the Ni deposits further increased upon immersion in solutions of noble metal complexes. EDX analyses proved that the deposition of Ru reached a limiting situation in some hours, while that of Ir was slower and continued for a longer time. The persistence of intense peaks due to the Ni(II)/Ni(III) redox system showed that Ru and Ir did not form a continuous layer able to prevent the contact between Ni and electrolyte. Hydrogen evolution was studied in 1 M NaOH solutions. Spontaneous deposition of both noble metals markedly improved the performance of porous Ni. The best results were achieved with Ir-modified electrodes, after immersion in Ir(IV) solution for 6 h. Tafel slopes and overpotentials of Ru-modified electrodes were not as low as those of Ir-modified electrodes.     

Effect of composition and ageing of chloride solutions on extraction of Rh(III) and Ru(III) with phosphonium ionic liquids Cyphos IL 101 and IL 104

ABSTRACT

Rhodium(III) and ruthenium(III) were extracted from chloride solutions with phosphonium ionic liquids trihexyl(tetradecyl)phosphonium chloride or trihexyl(tetradecyl)phosphonium bis(2,4,4-trimethylpentyl)phosphinate in toluene. Influence of HCl and NaCl presence in the feed and IL concentration in the organic phase were determined. Rh(III) transport appeared to be inefficient, while over 70% of Ru(III) was extracted from 3 M HCl. Ru(III) extraction was affected by the feed acidity and the type of extractant used. The spectra of the extracts indicated some changes in the structure of Rh(III) and Ru(III) complexes in the organic phase. Also, ageing of feed solutions on the extraction of Ru(III) and Rh(III) was studied.     

Characterization of multi-walled carbon nanotube electrodes functionalized by electropolymerized tris(pyrrole-ether bipyridine) ruthenium (II)

We synthesized new electropolymerizable [Ru(bpy)_nL_m](PF₆)₂ (L = 4,4 bis(3-pyrrol-1-ylpropyloxy)bipyridyl) derivatives. The introduction of electron donating ether groups in the bipyridine ligand induced a negative shift of the Ru(III)/(II) redox couple. The electrochemical behavior of complex Ru1 (n = 2, m = 1) and complex Ru2 (n = 0, m = 3) were compared using platinum and Multi-Walled Carbon Nanotube (MWCNT) electrode. Higher polymerization yields and surface concentrations were obtained at MWCNT electrodes. Furthermore, MWCNT electrodes increase polymer permeability and decrease the charge trapping phenomenon involved in the oxidation and reduction of the polypyrrolic skeleton of the Ru(II) functionalized polymers.     

Catalytic destruction of paraoxon by metallomicelle layers of Co(II) and Cr(III)

Two micellized ion complexes, Co(II) and Cr(III), were synthesized and found to possess good catalytic activity in cleaving the paraoxon/cobalt (chromate) complex phosphate ester. The complexes orm metallomicelles, which bind the substrate by coordinating with the phosphorus in the paraoxon (which is chemically similar to the nerve agents sarin and soman). Possible reasons for the acceleration include enhanced electrophilicity of the micellized metals, enhanced surface activity, and the recognized ability of cationic micelles to accelerate the cleavage of phosphate ester. The results of kinetic data (half-lives) for paraoxon degradation were 16.5 and 28.9 min in the presence of Co(II) and Cr(III) metallomicelle layers, respectively. The higher the value of the stability constant, the more stable the Co(II) and Cr(III) complexes.     

Towards Ruthenium(II)-Rhenium(I) Binuclear Complexes as Photosensitizers for Photodynamic Therapy

The search for new metal-based photosensitizers (PSs) for anticancer photodynamic therapy (PDT) is a fast-developing field of research. Knowing that polymetallic complexes bear a high potential as PDT PSs, in this study, we aimed at combining the known photophysical properties of a rhenium(I) tricarbonyl complex and a ruthenium(II) polypyridyl complex to prepare a ruthenium-rhenium binuclear complex that could act as a PS for anticancer PDT. Herein, we present the synthesis and characterization of such a system and discuss its stability in aqueous solution. In addition, one of our complexes prepared, which localized in mitochondria, was found to have some degree of selectivity towards two types of cancerous cells: human lung carcinoma A549 and human colon colorectal adenocarcinoma HT29, with interesting photo-index (PI) values of 135.1 and 256.4, respectively, compared to noncancerous retinal pigment epithelium RPE1 cells (22.4).     

A Rapid and Efficient Synthesis of Quinone Derivatives: Ru(II)‐ or Ir(I)‐Catalyzed Hydrogen Peroxide Oxidation of Phenols and Methoxyarenes

Hydroquinone and methoxybenzene derivatives were catalytically oxidized promptly to the corresponding quinones in up to 99% yield. With a catalyst loading of 0.01 mol %, a maximum TON of 8.4×10³ was attained in the case of Ru(II)‐complex. Ru(II)(pybox‐dh)(pydic) is able to enhance the hydrogen peroxide oxidation of substituted hydroquinones as well as methoxybenzenes, but Ir[(coe)₂Cl]₂ and Ir[(cod)Cl]₂ were found to be effective catalysts only for the former substrates under similar oxidation conditions.     

Hydrolysis,polycondensation, and catalytic properties of Ru(II) complex of 3‐4,5‐dihydroimidazol‐1‐yl‐propyltriethoxysilane

The preparation and measurements of some properties of organic–inorganic hybrid materials derived from Ru(II)‐3‐4,5‐dihyroimidazol‐1‐yl‐propyltriethoxysilane inside a polysiloxane network have been achieved. The hydrolysis and polycondensation of Ru(II)‐3‐4,5‐dihyroimidazol‐1‐yl‐propyltriethoxysilane were performed in different experimental conditions, producing a new organic–inorganic silica. The alkoxysilyl groups available were used for the construction of inorganic backbone by the sol‐gel process, and the imidazole group was found suitable for incorporating Ru(II) by coordination. The coordination of metal complex is retained because there is no leaching from the metal complex containing gels. To ensure sufficient catalytic properties, a series of hybrid materials from tetraethoxysilane was prepared. These materials were identified and catalytic activities were tested for cyclization of (Z)‐3‐methylpent‐2‐en‐4‐yn‐1‐ol to 2,3‐dimethylfuran. Heterogeneous Ru(II) catalyst can also be recycled and reused without significant loss of selectivity or activity. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1329–1334, 2001     

Zeolite-encapsulated Ru(III) tetrahydro-Schiff base complex: An efficient heterogeneous catalyst for the hydrogenation of benzene under mild conditions

A series of Ru(III) tetrahydro-Schiff base complexes (denoted as Ru[H₄]-Schiff base with Schiff base = salen, salpn and salcn, see Scheme 1) were encapsulated in the supercages of zeolite Y by flexible ligand method. The prepared catalysts were characterized by X-ray diffraction, diffuse reflectance UV–Vis spectroscopy, Infrared spectroscopy, elemental analysis, as well as N₂ adsorption techniques. It was shown that upon encapsulation in zeolite Y, Ru(III) tetrahydro-Schiff base complexes exhibited higher activity for the hydrogenation of benzene than the corresponding Ru(III)-Schiff base complexes. This indicates that hydrogenation of the CN bond of the Schiff base ligands led to a modification of the coordination environment of the central Ru(III) cations. The stability of the prepared catalysts has also been confirmed against leaching of the complex molecule from the zeolite cavities, as revealed by the result that no loss of catalytic activity was observed within three successive runs with regeneration.     

Biosorption Equilibrium and Kinetics of Au（Ⅲ） and Cu（Ⅱ） on Magnetotactic Bacteria

Magnetotactic bacteria （MTB） as biosorbents for the adsorption of Au（Ⅲ） and Cu（Ⅱ） ions from aqueous solution have been investigated. The optimum adsorption conditions for both metal ions were the initial pH scope of 1-5.5 for Au（Ⅲ） and 2.0-4.5 for Cu（Ⅱ）, room temperature, biomass concentration of 10.0g.L^-1 and sorotion du-ration more than 10 min. When the initial metal concentration were within 500mg.L^-1, the maximum biosorption capacity of 1.0g of MTB （dry mass basis） for Au（Ⅲ） and Cu（Ⅱ） were calculated as 505.2mg of Au（Ⅲ） and 493.1mg of.Cu（Ⅱ） by Langmuir model in single system, respectively. The isotherm equilibrium of Au（Ⅲ） and Cu（Ⅱ） ions in the Au-Cu binary system reflected a unique phenomenon that the adsorption of Au（Ⅲ） was rein-forced and that of Cu（Ⅱ） prohibited, compared respectively-with their performances in the single metal system.When the,concentration of-Au（Ⅲ） and Cu（Ⅱ）. were below 80mg.L^-1, the waste waterafter MTB treating, wasbelow 1.0mg.L^-1, which is in conformity with Environmental Performance Standards （EPS） of Canada. Besides, all the kinetic data were fitted well to the pseudo second-order kinetic model with a high correlation coefficient （R^2〉0.999）.