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Ru(II) complexes with polypyridyl ligands (2,2′-bipyridine = bpy, 1,10-phenanthroline = phen) play a central role in the development of photocatalytic organic reactions. In this work, we synthesized four mixed-ligand [Ru(phen)(bpy)2]2+-type complexes (Ru-Pcat-A) bearing two phosphonate substituents P(O)(OH)(OR) (R = H, Et) attached to the phen core at positions 3,8 (Ru-3,8PH and Ru-3,8PHEt) and 4,7 (Ru-4,7PH and Ru-4,7PHEt) of the heterocycle in high yields (87–99%) and characterized them using spectral methods. Single crystal X-ray diffraction was employed to determine the coordination mode of the ditopic phen ligand in Ru-4,7PH. This complex exists as the neutral species and forms a 1D hydrogen-bonded framework in the crystals. The light absorption characteristics were found to be similar for all complexes prepared in this work. However, the emission maxima in aqueous solutions were significantly affected by the substitution of the heterocycle, ranging from 629 nm for Ru-4,7PH to 661 nm for Ru-3,8PHEt. The emission quantum yields in Ar-saturated deionized water showed a strong dependence on the substitution pattern of the phen ligand, with maximal values reaching approximately 0.11 for Ru-4,7PHEt and Ru-4,7PH, which is twice as high as that of the classical [Ru(bpy)3]2+ complex (Ru-bpy). The photocatalytic performance of Ru-Pcat-A was investigated using visible light photoredox catalytic transformations of tertiary amines. With Ru-Pcat-A, we achieved the phosphonylation of N-aryl-1,2,3,4-tetrahydroisoquinolines (THIQs) and cyanation of THIQs and N,N-dimethylaniline in methanol, while a mixture of nitromethane/methanol (1 : 1 v/v) proved to be the optimal solvent for conducting the nitromethylation of THIQs. In the majority of the studied reactions, Ru-4,7PHEt exhibited greater efficiency compared to Ru-bpy, and it could be easily separated from the products using water extraction and reused in the next catalytic cycle. We successfully performed seven consecutive nitromethylation and phosphonylation of N-phenyl-1,2,3,4-tetrahydroisoquinoline using the recycled homogeneous photoredox catalyst. [ABSTRACT FROM AUTHOR]

The state-of-the-art alkaline hydrogen evolution catalyst of united ruthenium single atoms and small ruthenium nanoparticles has sparked considerable research interest. However, it remains a serious problem that hydrogen evolution primarily proceeds on the less active ruthenium single atoms instead of the more efficient small ruthenium nanoparticles in the catalyst, hence largely falling short of its full activity potential. Here, we report that by combining highly oxophilic cerium single atoms and fully-exposed ruthenium nanoclusters on a nitrogen functionalized carbon support, the alkaline hydrogen evolution centers are facilely reversed to the more active ruthenium nanoclusters driven by the strong oxophilicity of cerium, which significantly improves the hydrogen evolution activity of the catalyst with its mass activity up to −10.1 A mg−1 at −0.05 V. This finding is expected to shed new light on developing more efficient alkaline hydrogen evolution catalyst by rational regulation of the active centers for hydrogen evolution. The Ru single atom-nanocluster alkaline hydrogen evolution catalyst suffers from that hydrogen forms on its less active single atom side. Here, the authors report that oxophilic Ce single atom can reverse the hydrogen formation site to more active Ru nanocluster, enabling enhanced hydrogen evolution capabilities. [ABSTRACT FROM AUTHOR]

Systematic optimization of the ruthenium‐catalyzed oxidation of alcohols with tert‐butyl hydroperoxide (TBHP) as the oxidizing agent was carried out. This resulted in the development of a sustainable protocol with a water/tert‐butanol mixture as the solvent and an optimum use of the oxidizing agent by continuous addition with a syringe pump. The protocol is applicable for a broad variety of substrates. High yields of ketones and aldehydes are accessible. [ABSTRACT FROM AUTHOR]

Complexes PyrDPE-RuCl and PyrDPE-Ruacac with a π-extended 2,7-di(4-phenylethynyl)pyrene linker undergo simultaneous one-electron oxidations of their {Ru}-styryl entities. The absence of an intervalence charge-transfer (IVCT) band at intermediate stages, where the mixed-valent, singly oxidized radical cation is present, and spin density confinement to the terminal styryl ruthenium site(s) are tokens of a lack of electronic coupling between the {Ru} entities across the π-conjugated linker. The close similarity of the linker-based π → π* bands in the complexes and the free ligand and their insensitivity towards oxidations at the terminal sites indicate that the central pyrenyl fluorophore is electronically decoupled from the electron-rich {Ru}-styryl termini. As a consequence, the complexes offer stable pyrene-based fluorescence emissions at 77 K, which are red-shifted from that of the linker. [ABSTRACT FROM AUTHOR]

The three typical oxygen-containing functional groups on C-dots have been selectively deactivated to elucidate their impact on the co-reactant behavior of C-dots, and the carboxyl groups on C-dots are revealed for the first time as co-reactant sites for Ru(bpy) 3 2+-ECL. [Display omitted] Carbon nanodots (C-dots) with good biocompatibility have been extensively utilized as co-reactants for electrochemiluminescence (ECL) of the tris(2,2′-bipyridine)ruthenium(II) (Ru(bpy) 3 2+) system. However, the ECL intensity of this system is still relatively low and the mechanism of C-dots as co-reactants remains unclear, which greatly limits its further application in bio-analysis. In this work, we revealed that the carboxyl groups on C-dots are co-reactant sites for Ru(bpy) 3 2+ ECL by systematically investigating the contribution of carboxyl, hydroxyl and carbonyl groups on the surface of C-dots to the ECL intensity. Further treatment with hydrogen peroxide to increase the carboxyl-group content on C-dots resulted in a 10-fold increase in ECL intensity over the original Ru(bpy) 3 2+/C-dots system. This work provides new insights for the rational design of ECL systems with C-dots as co-reactants and offers new chances for further applications of C-dots in the field of ECL. [ABSTRACT FROM AUTHOR]

The creation of affordable, long-lasting, and effective electrocatalysts is a significant research issue in the area of water splitting. In this work, Ru-modified CoP x spearhead on nickel foam (Ru-CoP x /NF) is fabricated by simple hydrothermal, impregnation and subsequent low-temperature phosphorization process. The incorporation of Ru into the Co-P structure enables the effective reconstruction of the electronic coordination environment. The Ru-CoP x /NF catalyst performs well for hydrogen evolution reaction (HER), achieving a current density of 10 mA cm−2 with low overpotentials of 41 mV and outstanding stability in 1 M KOH. Furthermore, the produced CoP x /NF has low overpotential of 280 mV, allowing 10 mA cm−2 for the oxygen evolution reaction (OER) in 1 M KOH. In addition, the developed asymmetric Ru-CoP x /NF||CoP x /NF electrolyzer could drive 10 mA cm−2 in alkaline electrolyte with a low cell voltage of 1.51 V. Surprisingly, water-splitting may be efficiently by renewable energy sources, presenting a viable strategy for lowering the cost of creating hydrogen energy. The synthesized Ru-CoP x /NF exhibits excellent electrocatalytic performance for HER, with low overpotentials of 41, 73 and 168 mV, driving 10 mA cm−2 in alkaline, acidic and neutral media, respectively. The synthesized CoP x /NF without Ru has excellent OER performance, with an overpotential of only 280 mV@10 mA cm−2. The Ru-CoP x /NF||CoP x /NF electrolyzer can be powered by sustainable energies. [Display omitted] • The spearhead-like nanostructures provide abundant active sites. • The introduction of Ru optimized the reaction kinetics for HER. • The prepared catalysts exhibit excellent catalytic performance for HER and OER. [ABSTRACT FROM AUTHOR]

Chiral hybrid organic–inorganic metal halides have attracted wide attention owing to their superior chiroptoelectronic and chirospintronic properties. Here, a new class of chiral lead‐free metal halides, (R/S‐MBA)3Ru2Br9 (MBA = methylbenzylammonium), with unique magnetic properties is reported. (R/S‐MBA)3Ru2Br9 is composed of a surface‐shared octahedron dimer separated by chiral cations and crystallizes into the Sohncke space group of P212121. The crystal structures, chiroptical, magnetic properties, and magnetic circular dichroism of (R/S‐MBA)3Ru2Br9 are systematically investigated. Owing to the strong antiferromagnetic coupling between the Ru atom through bromine bridge in the [Ru2Br9]3− dimer and the weak ferromagnetic coupling between the neighboring [Ru2Br9]3− dimer, (R/S‐MBA)3Ru2Br9 exhibits antiferromagnetic property with Néel temperature at 7 K. Considering the unique magnetic property of ruthenium, together with the rapid progress of antiferromagnetic spintronics and optospintronics recently, this work provides a novel multifunctional lead‐free chiral magnetic candidate toward chiral optoelectronics and antiferromagnetic spintronics. [ABSTRACT FROM AUTHOR]

A production route for 99mTc and 101Tc using the (γ,p) reaction was considered. For an electron beam with energy of 40 MeV and power of 10 kW, distributions of produced 99mTc and 101Tc were obtained. For the optimized target (0.5 g) configurations, values of 99mTc specific activities of 9.53 GBq/g (0.26 Ci/g) for a one-stage setup and of 1.77 GBq/g (0.049 Ci/g) for a two-stage setup were obtained. For 101Tc, the corresponding values were 6.51 GBq/g (0.18 Ci/g) and 1.24 GBq/g (0.033 Ci/g). [ABSTRACT FROM AUTHOR]

[Ru(bipy)2(dpphen)]Cl2 (where bipy = 2,2′-bipyridine and dpphen = 2,9-diphenyl-1,10-phenanthroline) (complex 1) is a sterically strained compound that exhibits promising in vitro photocytotoxicity on an array of cell lines. Since lung adenocarcinoma cancer remains the most common lung cancer and the leading cause of cancer deaths, the current study aims to evaluate the plausible effect and uptake of complex 1 on human alveolar carcinoma cells (A549) and mesenchymal stem cells (MSC), and assess its cytotoxicity in vitro while considering its effect on cell morphology, membrane integrity and DNA damage. MSC and A549 cells showed similar rates of complex 1 uptake with a plateau at 12 h. Upon photoactivation, complex 1 exhibited selective, potent anticancer activity against A549 cells with phototoxicity index (PI) values of 16, 25 and 39 at 24, 48 and 72 h, respectively. This effect was accompanied by a significant increase in A549-cell rounding and detachment, loss of membrane integrity and DNA damage. Flow cytometry experiments confirmed that A549 cells undergo apoptosis when treated with complex 1 followed by photoactivation. In conclusion, this present study suggests that complex 1 might be a promising candidate for photochemotherapy with photoproducts that possess selective anticancer effects in vitro. These results are encouraging to probe the potential activity of this complex in vivo. [ABSTRACT FROM AUTHOR]

Novel full-sandwich (η5-Cp)-Ru-paraphenylene complexes with the general formula [(η5-Cp)nRu(η6-L)](PF6)n where n = 1–3 and L = biphenyl, p-terphenyl and p-quaterphenyl, were synthesized and characterized by means of spectroscopic and analytical techniques. The structures of the complexes [(η5-Cp)Ru(η6-biphenyl)](PF6) (1), [(η5-Cp)Ru(η6-terphenyl)](PF6) (3) and [(η5-Cp)2Ru(η6-terphenyl)](PF6)2 (4) was determined by X-ray single crystal methods. The interaction of the complexes [(η5-Cp)Ru(η6-quaterphenyl)]Cl, (6)Cl, and [(η5-Cp)2Ru(η6-quaterphenyl)]Cl2, (7)Cl2, with the DNA duplex d(5′-CGCGAATTCGCG-3′)2 was studied using NMR techniques. The results showed that both complexes interacted non-specifically with both the minor and major grooves of the helix. Specifically, (6)Cl exhibited partial binding through intercalation between the T7 and T8 bases of the sequence without disrupting the C–G and A–T hydrogen bonds. Fluorometric determination of the complexes' binding constants revealed a significant influence of the number of connected phenyl rings in the paraphenylene ligand (L) on the binding affinity of their complexes with the d(5′-CGCGAATTCGCG-3′)2. The complexes (6)Cl and (7)Cl2 were found to be highly cytotoxic against the A549 lung cancer cell line, with complex (6) being more effective than (7) (IC50 for (6)Cl: 17.45 ± 2.1 μΜ, IC50 for (7)Cl2: 65.83 ± 1.8 μΜ) and with a selectivity index (SI) (SI for (6)Cl: 1.1 and SI for (7)Cl2: 4.8). [ABSTRACT FROM AUTHOR]

New complex [RuLCl2(PPh3)] (L=N,N‐bis(2‐hydroxy‐5‐nitrobenzaldehyde)‐2,2'‐diaminodiethylamine) was prepared and characterized analytically and was employed as a luminescent chemosensor for the detection of anions. The results show that [RuLCl2(PPh3)] can detect HSO4− and AcO− selectively and in sequential order in H2O‐CH3CN (8 : 2, v/v) at pH 7.0. The spectral binding, titration, and interference analyses reveal that the addition of HSO4− to [RuLCl2(PPh3)] results in an intense fluorescence emission (IF/I0=6.55). This shows that HSO4− interacts suitably with the complex to switch ON the fluorescence which could be explained by inhibition of a PET mechanism as the above addition forms [RuLCl(HSO4)(PPh3)] in the excited state. Selectivity interaction of complex [RuLCl2(PPh3)] with HSO4− results in the formation of [RuLCl(HSO4)(PPh3)] in water but the system exhibits negligible change in its emission except for AcO−, which enhances fluorescence intensity. For the addition of AcO− to [RuLCl2(PPh3)], the system [RuLCl(AcO)(PPh3)] is formed, however, the adding of HSO4− to [RuLCl(AcO)(PPh3)] does not show any change in the intensity, suggesting that there exists a logic gate function for the addition of HSO4− followed by AcO− to [RuLCl2(PPh3)]. This finding is interesting because [RuLCl2(PPh3)] can act as a fast selective chemosensor for the sequential detection of HSO4− and AcO−. [ABSTRACT FROM AUTHOR]

[Display omitted] New ruthenium(ii) and ruthenium(iii) complexes with 2,6-di- tert -butylphenol as the antioxidant moiety were synthesized, and their antioxidant and antiproliferative activities were evaluated. Electrochemical behaviour and the potential of these compounds to act as inhibitors of lipid peroxidation in biological systems were explored. [ABSTRACT FROM AUTHOR]

In the research field on severe accidents in nuclear power plant, a specific scenario correspond to accident with oxidative conditions for which damaged fuel can be highly oxidised with significant releases of ruthenium oxides. Ruthenium chemistry is complex, and the current knowledge has to be deepened to better assess ruthenium source term with potential radioactive releases to the environment as volatile ruthenium tetroxide. In this work, experimental studies are focused on ruthenium behaviour along a stainless-steel thermal gradient tube, with maximum temperature of 1200 °C, simulating the reactor cooling system in oxidizing conditions with mainly steam/air gas mixtures. Results showed that few % of ruthenium oxides (< 10% with SS tube) can reach low temperature, representative of containment temperature, even with low oxygen content in the carrier gas. The ruthenium revaporization process from the Ru deposits along the tube on mid-term was studied. Influence of carrier gas composition (steam %), flow rate and NOx feed are discussed. [ABSTRACT FROM AUTHOR]

We investigated a method to prevent RuO4 formation from a heated high-level liquid waste (HLLW) in a severe accident in a reprocessing facility. When the alkali or alkaline earth hydroxides were added in excess of the point of neutralization of HLLW, the amount of RuO4 released was significantly suppressed to less than 1% of that without hydroxide addition. Alkaline earth hydroxides would be more suitable for actual use, because alkali hydroxides enhance RuO4 release by an addition below the equivalent neutralization whereas alkaline earth hydroxides do not have such effect. [ABSTRACT FROM AUTHOR]

We synthesised star-shaped ruthenium(II) complexes containing one or five styryl-BODIPY units arranged around a central trisindazolylrutheniumcyclopentadienyl fragment. A symmetric complex was obtained following a five-fold Suzuki-Miyaura reaction of the pentabrominated key precursor while desymmetrisation was next achieved via a modular synthetic approach based on sequential chemoselective Suzuki-Miyaura reactions on a key building block bearing one iodophenyl and four bromophenyl groups. [ABSTRACT FROM AUTHOR]

Recent years have witnessed considerable work on the development of lead-free piezoelectric ceramic materials and their structure–property correlations. The development of piezo response is a strong function of phase evolution in these materials. In this work, we report the effect of Ru doping and consequent phase evolution on the maximization of piezoelectric response of polycrystalline lead-free barium titanate, depicted as Ba(RuxTi1-x)O3 (BRT). The samples were prepared in a narrow compositional range of 0 ≤ x ≤ 0.03 using the conventional solid-state reaction method. Ru doping increases the leakage current of BaTiO3 samples attributed to increased oxygen vacancy concentration due to substitution of Ti4+ by Ru3+. Detailed structural analysis reveals that samples exhibiting coexistence of tetragonal (space group: P4mm) and orthorhombic (space group: Amm2) structured phases near room temperature reveal relatively enhanced piezoelectric properties. The BRT sample with Ru content of 2 mol% yields a maximum longitudinal piezoelectric coefficient, d33 of ∼269 pC/N, a high strain value of 0.16% with a large remnant polarization of ∼19 µC/cm2 and a coercive field of 5.8 kV/cm. We propose that the '4d' orbital of Ruthenium plays a crucial role in improving the functional properties and in decreasing the ferroelectric Curie temperature. Our work provides clues into tailoring the phase evolution for designing lead-free piezoelectric materials with enhanced piezoelectric properties. [ABSTRACT FROM AUTHOR]

Ruthenium (Ru) has been regarded as one of the most promising alternatives to substitute Pt for catalyzing alkaline hydrogen evolution reaction (HER), owing to its inherent high activity and being the cheapest platinum‐group metal. Herein, based on the idea of strong metal–support interaction (SMSI) regulation, Ru/TiN catalysts with different degrees of TiN overlayer over Ru nanoparticles were fabricated, which were applied to the alkaline electrolytic water. Characterizations reveal that the TiN overlayer would gradually encapsulate the Ru nanoparticles and induce more electron transfer from Ru nanoparticles to TiN support by the Ru–N–Ti bond as the SMSI degree increased. Further study shows that the exposed Ru–TiN interfaces greatly promote the H2 desorption capacity. Thus, the Ru/TiN‐300 with a moderate SMSI degree exhibits excellent HER performance, with an overpotential of 38 mV at 10 mA cm−2. Also, due to the encapsulation role of TiN overlayer on Ru nanoparticles, it displays super long‐term stability with a very slight potential change after 24 h. This study provides a deep insight into the influence of the SMSI effect between Ru and TiN on HER and offers a novel approach for preparing efficient and stable HER electrocatalysts through SMSI engineering. [ABSTRACT FROM AUTHOR]

Ruthenium targets were prepared by vacuum hot pressing of ruthenium powder with different morphologies. Ruthenium films were then deposited on a SiO2/Si(100) substrate for different times by radio frequency (RF) magnetron sputtering. The relationship in terms of the microstructure and electrical properties between the ruthenium targets and resultant films at different conditions were studied by means of field-emission scanning electron microscopy (FE-SEM), X-ray diffraction (XRD), atomic force microscopy (AFM) and fourpoint probe. The results showed that parameters such as the average deposition rate, surface roughness, crystallisation properties and growth rate were directly related to the homogeneity of the microstructure of the ruthenium targets, but there was no correlation between the crystal orientations of the films and the targets. Moreover, the resistivity of ruthenium films was positively correlated with that of the ruthenium targets. [ABSTRACT FROM AUTHOR]

Herein, we report two biomimetic [Ru–Ru] analogs (Ru 2 ADTX(CO) 6 , X = Ts or Cbz), which contain the N -substituted azadithiolate (ADT) moiety of the native H-cluster, and their differential reactivity to the formic acid/carbon dioxide-hydrogen (FA/CO 2 –H 2) "carbon-neutral cycle" reaction. The results show that the strongly electron-withdrawing tosyl-substituted Ru 2 ADTTs(CO) 6 (1) exhibits a higher preference for CO 2 hydrogenation, while the donor-inductive carboxybenzyl-substituted Ru 2 ADTCbz(CO) 6 (2) favors FA dehydrogenation, supporting electronically- or sterically-substituted pendant amine bases in influencing the entry and exit of protons from the Ru–Ru active site and subsequent H 2 oxidation and generation. Furthermore, the propensity of TEA in FA dehydrogenation and DBU in CO 2 hydrogenation support the role of bases as sacrificial electron donors and co-reagents, respectively. In the CO 2 hydrogenation reaction, the P-ligands with more phosphorus atoms exhibited higher reactivity and final CO 2 conversion efficiency, indicating that the number of phosphorus atoms and the different electronic but isosteric substitutions on the P-ligands have significant effects on the reactivity of metal complexes. These results support the combination of the FA dehydrogenation of complex 2 and the CO 2 hydrogenation capability of complex 1 to construct an efficient FA/CO 2 –H 2 reversible reaction for a sustainable supply of energy and environmental CO 2 control. • A biomimetic [Ru–Ru] H-cluster system with differential reactivity to the FA/CO 2 –H 2 carbon-neutral cycle was constructed. • The electrosteric effect of the pendant amine substituent greatly affects the direction of the reaction. • The choice and ratio of base and P-ligand also has a significant impact on the performance of the reaction and its rate. [ABSTRACT FROM AUTHOR]

By rationally adjusting the coordination environment and constructing the more electron‐enriched active site in single‐atom catalysts, the effect of heterogenous peroxymonosulfate (PMS)‐based Fenton‐like reactions can be effectively improved, yet remains a severe challenge. In this study, the electron‐rich Ru dual‐atom site is successfully immobilized onto N‐doped carbon (Ru2N6‐C) for PMS activation in water purification. The presence of electron‐rich Ru dual‐atom sites not only provides more electrons for PMS but also facilitates the formation of a Yeager adsorption configuration on the catalyst surface, which enhances O─O bond cleavage and leads to an increase in •SO4− and •OH generation. Moreover, the Ru2N6‐C catalyst exhibits exceptional durability and reliability, achieving an ultra‐high efficiency with a turnover frequency of 153.95 min−1 M−1 for the naproxen degradation. A membrane reactor is further developed for the purification of wastewater, which is expected to provide a viable approach to controlling water pollution through the design of metal dual‐atom sites carbon‐based catalysts. [ABSTRACT FROM AUTHOR]

Ruthenium thin films were deposited by plasma enhanced atomic layer deposition (PEALD) using Ru(EtCp)2 and oxygen plasma on the modified silicon surface and SiO2/Si substrates. The substrate temperature has a significant impact on film growth. The GXRD and SIMS analysis have shown that at the substrate temperature T = 375°C there is a sharp change in the mechanisms of surface reactions, which leads to a change in the film composition from RuO2 at low temperatures to a pure Ru film at higher temperatures. This was confirmed by measurements of the electrical resistivity of Ru-based films. The lowest surface roughness ~1.5 nm was obtained at a film thickness of 29 nm deposited at 375°C on a SiO2/Si-substrate. The measured resistivity of the Ru film was 18–19 μΩ cm. Issues regarding the plasma-chemical etching of ruthenium and the spin-on of a low-k dielectric onto arrays of lines are taken into account. [ABSTRACT FROM AUTHOR]

Attaching a nitrene precursor to an intramolecular nucleophile allows for a catalytic asymmetric intramolecular oxyamination of alkenes in which the nucleophile adds in an endocyclic position and the amine in an exocyclic fashion. Using chiral‐at‐ruthenium catalysts, chiral γ‐aminomethyl‐γ‐lactones containing a quaternary carbon in γ‐position are provided in high yields (up to 99 %) and with excellent enantioselectivities (up to 99 % ee). DFT calculations support the possibility of both a singlet (concerted oxyamination of the alkene) and triplet pathway (stepwise oxyamination) for the formation of the predominant stereoisomer. γ‐Aminomethyl‐γ‐lactones are versatile chiral building blocks and can be converted to other heterocycles such as δ‐lactams, 2‐oxazolidinones, and tetrahydrofurans. [ABSTRACT FROM AUTHOR]

The efficient decomposition of ammonia to produce COx‐free hydrogen at low temperatures has been extensively investigated as a potential method for supplying hydrogen to mobile devices based on fuel cells. In this study, we employed dielectric barrier discharge (DBD) plasma, a non‐thermal plasma, to enhance the catalytic ammonia decomposition over supported Ru catalysts (Ru/Y2O3, Ru/La2O3, Ru/CeO2 and Ru/SiO2). The plasma‐catalytic reactivity of Ru/La2O3 was found to be superior to that of the other three catalysts. It was observed that both the physicochemical properties of the catalyst (such as support acidity) and the plasma discharge behaviours exerted significant influence on plasma‐catalytic reactivity. Combining plasma with a Ru catalyst significantly enhanced ammonia conversion at low temperatures, achieving near complete NH3 conversion over the 1.5 %‐Ru/La2O3 catalyst at temperatures as low as 380 °C. Under a weight gas hourly space velocity of 2400 mL gcat−1 h−1 and an AC supply power of 20 W, the H2 formation rate and energy efficiency achieved were 10.7 mol gRu−1 h−1 and 535 mol gRu−1 (kWh)−1, respectively, using a 1.5 %‐Ru/La2O3 catalyst. [ABSTRACT FROM AUTHOR]

The in-situ activation process alleviates the strong ruthenium-hydrogen and ruthenium-hydroxyl bonds, optimizing hydrogen and hydroxyl desorption energy. [Display omitted] • Partially oxidized Ru nanoparticles dispersed Ni 3 N nanosheet electrocatalyst was developed. • The in-situ electrochemical activation effectively promoted hydrogen evolution. • The controlled oxidation alleviates the strong Ru-H and Ru-OH bonds. • The catalysts show superior performance for HER and urea-assisted water splitting. The rational design of electrocatalysts with exceptional performance and durability for hydrogen production in alkaline medium is a formidable challenge. In this study, we have developed in-situ activated ruthenium nanoparticles dispersed on Ni 3 N nanosheets, forming a bifunctional electrocatalyst for hydrogen evolution and urea oxidation. The results of experimental analysis and theoretical calculations reveal that the enhanced hydrogen evolution reaction (HER) performance of O-Ru-Ni 3 N stems primarily from the optimized hydrogen adsorption and hydroxyl adsorption on Ru sites. The O-Ru-Ni 3 N on nickel foam (NF) electrode exhibits excellent HER performance, requiring only 29 mV to reach 10 mA cm−2 in an alkaline medium. Notably, when this O-Ru-Ni 3 N/NF catalyst is employed for both HER and urea oxidation reaction (UOR) to create an integrated H 2 production system, a current density of 50 mA cm−2 can be generated at the cell voltage of 1.41 V. This report introduces an energy-efficient catalyst for hydrogen production and proposes a viable strategy for anodic activation in energy chemistry. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: Chiral ruthenium‐catalyzed enantioselective hydrogenation of tetrapyridine‐type N‐heteroarenes was firstly developed. The partial reduction of adjacent tetraheteroaromatic substrates proceeded smoothly in the presence of phosphine‐free chiral cationic ruthenium diamine complexes, affording unprecedented high reactivity, enantioselecitivity and diastereoselectivity (up to 93% yield, >99% ee and 92 : 8 dr). The potential application of chiral tetradentate pyridine‐amine products as chiral ligands has been demonstrated in the Cu‐catalyzed asymmetric Friedel–Crafts alkylation reaction between indoles and nitroalkenes. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: Chiral ruthenium‐catalyzed enantioselective hydrogenation of tetrapyridine‐type N‐heteroarenes was firstly developed. The partial reduction of adjacent tetraheteroaromatic substrates proceeded smoothly in the presence of phosphine‐free chiral cationic ruthenium diamine complexes, affording unprecedented high reactivity, enantioselecitivity and diastereoselectivity (up to 93% yield, >99% ee and 92 : 8 dr). The potential application of chiral tetradentate pyridine‐amine products as chiral ligands has been demonstrated in the Cu‐catalyzed asymmetric Friedel–Crafts alkylation reaction between indoles and nitroalkenes. [ABSTRACT FROM AUTHOR]

The catalytic alkoxycarbonylation of alkenes is an attractive, atom‐efficient method for producing value‐added carboxylic esters. However, the conventional catalyst system for this reaction needs coordination with a noble metal, sensitive ligands and proton acid additives. Therefore, the design of a simple and efficient catalyst system without any acid additives under mild conditions is still a major challenge. In this work, a simple ruthenium/deep eutectic solvent catalytic system was developed to effectively catalyse the alkoxycarbonylation reaction without any sensitive ligands or acid additives under mild conditions. The conversion of 1‐hexene reached 99.0 %, and the ester selectivity was 99.1 %, much higher than that of Ruthenium carbonyl without deep eutectic solvent. The excellent performance of the catalytic system could be ascribed to the form of the ruthenium active species [Ru(CO)2Br3]− in the deep eutectic solvent. This innovative catalyst system presents a significant advancement in the alkoxycarbonylation reaction, eliminating the use of acid additives and delicate ligands. [ABSTRACT FROM AUTHOR]

Noble‐metal nanoboxes offer an attractive form of nanomaterials for catalytic applications owing to their open structure and highly efficient use of atoms. Herein, we report the facile synthesis of Ag−Ru core−shell nanocubes and then Ru nanoboxes with a hexagonal close‐packed (hcp) structure, as well as evaluation of their catalytic activity toward a model hydrogenation reaction. By adding a solution of Ru(acac)3 in ethylene glycol (EG) dropwise to a suspension of silver nanocubes in EG at 170 °C, Ru atoms are generated and deposited onto the entire surface of a nanocube. As the volume of the RuIII precursor is increased, Ru atoms are also produced through a galvanic replacement reaction, generating Ag−Ru nanocubes with a hollow interior. The released Ag+ ions are then reduced by EG and deposited back onto the nanocubes. By selectively etching away the remaining Ag with aqueous HNO3, the as‐obtained Ag−Ru nanocubes are transformed into Ru nanoboxes, whose walls are characterized by an hcp structure and an ultrathin thickness of a few nanometers. Finally, we evaluated the catalytic properties of the Ru nanoboxes with two different wall thicknesses by using a model hydrogenation reaction; both samples showed excellent performance. [ABSTRACT FROM AUTHOR]

New 1,2-azolylamidino complexes fac-[RuCl(DMSO)3(NHC(R)az*-κ²N,N)]OTf [R = Me (2), Ph (3); az* = pz (pyrazolyl, a), indz (indazolyl, b)] are synthesized via chloride abstraction from their corresponding precursors cis,fac-[RuCl2(DMSO)3(az*H)] (1) after subsequent base-catalyzed coupling of the appropriate nitrile with the 1,2-azole previously coordinated. All the compounds are characterized by ¹H NMR, 13C NMR and IR spectroscopy. Those derived from MeCN are also characterized by X-ray diffraction. Electrochemical studies showed several reduction waves in the range of −1.5 to −3 V. The electrochemical behavior in CO2 media is consistent with CO2 electrocatalytic reduction. The catalytic activity expressed as [icat(CO2)/ip(Ar)] ranged from 1.7 to 3.7 for the 1,2-azolylamidino complexes at voltages of ca. −2.7 to −3 V vs. ferrocene/ferrocenium. Controlled potential electrolysis showed rapid decomposition of the Ru catalysts. Photocatalytic CO2 reduction experiments using compounds 1b, 2b and 3b carried out in a CO2-saturated MeCN/TEOA (4 : 1 v/v) solution containing a mixture of the catalyst and [Ru(bipy)3]2+ as the photosensitizer under continuous irradiation (light intensity of 150 mW cm−2 at 25 °C, λ > 300 nm) show that compounds 1b, 2b and 3b allowed CO2 reduction catalysis, producing CO and trace amounts of formate. The combined turnover number for the production of formate and CO is ca. 100 after 8 h and follows the order 1b < 2b ≈ 3b. [ABSTRACT FROM AUTHOR]

Ruthenium dioxide is the most promising alternative to the prevailing but expensive iridium-based catalysts for the oxygen evolution reaction in proton-exchange membrane water electrolyzers. However, the under-coordinated lattice oxygen of ruthenium dioxide is prone to over-oxidation, and oxygen vacancies are formed at high oxidation potentials under acidic corrosive conditions. Consequently, ruthenium atoms adjacent to oxygen vacancies are oxidized into soluble high-valence derivatives, causing the collapse of the ruthenium dioxide crystal structure and leading to its poor stability. Here, we report an oxyanion protection strategy to prevent the formation of oxygen vacancies on the ruthenium dioxide surface by forming coordination-saturated lattice oxygen. Combining density functional theory calculations, electrochemical measurements, and a suite of operando spectroscopies, we showcase that barium-anchored sulfate can greatly impede ruthenium loss and extend the lifetime of ruthenium-based catalysts during acidic oxygen evolution, while maintaining the activity. This work paves a new way for designing stable and active anode catalysts toward acidic water splitting. Designing stable Ru-based catalysts for acidic oxygen evolution remains a challenge. Here, the authors propose an oxyanion protection strategy to prevent the formation of oxygen vacancies on the RuO2 surface by creating coordination-saturated lattice oxygen, thereby greatly enhancing the stability. [ABSTRACT FROM AUTHOR]

First and second generation of Grubbs catalysts (G1 and G2) were applied in the piperine olefin metathesis under different conditions. G1 was used in self-metathesis, G2 was implemented in both, self and cross-metathesis of piperine with eugenol. Results allowed to implicate about the main intermediate of the reaction and the position of olefin attachment to the catalyst, assuming that the reaction follows a pathway where 2A=B olefin leads to the formation of A=A and B=B. In addition, the results contributed to the studies of catalyst's reactivity when the olefin metathesis product required the high electronic effect of the N-heterocyclic of G2. In this paper, the highest activity of G2 in the olefin metathesis of eugenol was observed when the first intermediate was Ru-eugenol-moiety in the cross-metathesis of the piperine with eugenol. This demonstrates that the acidity of the new carbene in the intermediate species causes inactivity only in the reaction with piperine. [ABSTRACT FROM AUTHOR]

Green hydrogen production through the electrocatalytic hydrogen evolution reaction (HER) is a promising solution for transition from fossil fuels to renewable energy. To enable the use of a variety of electrolytes with different pH values, HER catalysts with pH universality are highly desirable but their performance remains mediocre. Herein, a pH‐universal HER catalyst composed of ruthenium nanoparticles decorated on amorphous Ni‐doped MoO3 (a–Ni–MoO3) nanowire support is reported, that is, Ru/a–Ni–MoO3, which achieves enhanced performance as compared to the commercial Ru/C catalyst. Electron transfer from Ru to a–Ni–MoO3 is identified by spectroscopic techniques, which results in a modified electronic structure of the Ru active sites with a reduced electron density of 4d states near the Fermi level. Density functional theory calculations further reveal that the modulated electronic structure weakens the interactions between the Ru active sites and the reaction intermediates, which facilitates the HER reaction steps including H intermediate desorption and water dissociation. Experimental and theoretical findings provide insight into enhancing pH‐universal HER performance through modulation of electrocatalyst electronic structure. [ABSTRACT FROM AUTHOR]

Ruthenium(II/III)-based compounds have gained significant interest due to the biocompatibility of ruthenium, its similarity to iron, and the possibility for structural diversification through the choice of ligands. In this contribution, two novel ligands, (2-(2-methoxyethoxy)ethyl nicotinate hydrochloride) and (2-[2-(2-methoxyethoxy)ethoxy]ethyl nicotinate hydrochloride) (pyCOO(CH2CH2O)nCH3: L2, n = 2; L3, n = 3), were synthesized and characterized via ESI-HRMS, as well as IR and NMR spectroscopies. Their structures were optimized at the B3LYP/6-311++G(d,p) level of theory, and NMR chemical shifts were predicted, along with the most important intramolecular interactions. Additionally, two neutral complexes of the general formula [RuCl2(η6-p-cym) (L-κN)] (L = L2: 2; L3: 3) and two cationic complexes of the general formula [RuCl(η6-p-cym)(L-κN)2][PF6] (L = L1: 4; L2: 5) were obtained and characterized. The optimization of the structures was performed at the B3LYP/6-31+G(d,p)(H,C,N,O,Cl)/LanL2DZ(Ru) level of theory. Structural features were described, and intramolecular stabilization interactions were outlined. [ABSTRACT FROM AUTHOR]

Cancer treatments, including traditional chemotherapy, have failed to cure human malignancies. The main reasons for the failure of these treatments are the inevitable drug resistance and serious side effects. In clinical treatment, only 5 percent of the 50 percent of cancer patients who are able to receive conventional chemotherapy survive. Because of these factors, being able to develop a drug and treatment that can target only cancer cells without affecting normal cells remains a big challenge. Since the special properties of cisplatin in the treatment of malignant tumors were accidentally discovered in the last century, metal anticancer drugs have become a research hotspot. Metal anticancer drugs have unique pharmaceutical properties, such as ruthenium metal drugs with their high selectivity, low toxicity, easy absorption by tumor tissue, excretion, and so on. In recent years, efficient and low-toxicity metal antitumor complexes have been synthesized. In this paper, the scientific literature on platinum (Pt), ruthenium (Ru), iridium (Ir), gold (Au), and other anticancer complexes was reviewed by referring to a large amount of relevant literature at home and abroad. [ABSTRACT FROM AUTHOR]

Brachytherapy with episcleral plaques is the most common primary tumor treatment for uveal melanoma. This study aimed to compare the risk of tumor recurrence and metastatic death between 2 frequently used ruthenium 106 plaque designs: CCB (20.2 mm) and CCA (15.3 mm). Data were obtained from 1387 consecutive patients treated at St. Erik Eye Hospital, Stockholm, Sweden between 1981 and 2022 (439 with CCA and 948 with CCB plaques). During the period, scleral transillumination was performed to delineate tumor margins before plaque insertion, but accurate plaque positioning was not verified after scleral attachment, and no minimum scleral dose was used. Patients treated with CCA plaques had smaller tumors than those treated with CCB plaques (mean diameter, 8.6 vs 10.5 mm; P <.001). There were no differences in patient sex, age, tumor distance to the optic disc, tumor apex dose, dose rate, or in rates of ciliary body involvement, eccentric plaque placement, or adjunct transpupillary thermotherapy (TTT). The average difference between plaque and tumor diameter was greater with the CCB plaque, and a smaller difference was an independent predictor of tumor recurrence. The 15-year incidence of tumor recurrence was 28% and 15% after treatment with CCA and CCB plaques, respectively (competing risk analysis, P <.001). Multivariate Cox regression analysis revealed a lower risk for tumor recurrence with CCB plaques (hazard ratio, 0.50). Similarly, patients treated with CCB plaques had a lower risk for uveal melanoma–related mortality (hazard ratio, 0.77). The risk for either outcome was not lower for patients treated with adjunct TTT. Uni- and multivariate time-dependent Cox regressions demonstrated that tumor recurrence was associated with uveal melanoma–related and all-cause mortality. Compared with 20-mm plaques, brachytherapy with 15-mm ruthenium plaques is associated with a higher risk for tumor recurrence and death. These adverse outcomes may be avoided by increasing safety margins and implementing effective methods to verify accurate plaque positioning. [ABSTRACT FROM AUTHOR]

The worldwide demand for clean water is rising worldwide, yet wastewater decontamination is actually limited by the presence of refractory organic and inorganic compounds, calling for more efficient treatment methods. Here we review the use of ruthenium-based catalysts for the removal or transformation of pollutants at a concentration range of 1.0–100 mg/L under acid or neutral conditions. We focus on catalytic oxidation and reduction, and on the environmental impact of ruthenium catalysts. We discuss electrooxidation, photocatalytic oxidation, activation of inert oxidants, hydrogen-assisted reduction, electroreduction, and N–O bond activation. [ABSTRACT FROM AUTHOR]

In this study, we compared carbene and pyridine substituted ligands {3‐Me‐1‐[2‐(CH2CH2SPh)]‐C7H4N2} (L1) and {2‐[(2,6‐iPr2‐C6H3)N=CH]‐6‐(MeO)C5H3N}(L2) for synthesis of ionic C,S‐ and N,N‐coordinated Ru (II) complexes [(κ2‐L1)RuCl(η6‐p‐cymene)]+Cl− (1), [(κ2‐L1)RuI(η6‐p‐cymene)]+I− (2), and [(κ2‐L2)RuCl(η6‐p‐cymene)]+Cl− (3), respectively. Stannylene ligand [{2,6‐(Me2NCH2)2C6H3}SnCl] (L3), as heavy carbene analog, was also used in this study to prepare neutral Sn‐coordinated Ru (II) complex [(κ1‐L3)RuCl2(η6‐p‐cymene)] (4). Finally, reaction of SnCl2 with 1, 3, and 4 was also studied to yield [(κ2‐L1)RuCl(η6‐p‐cymene)]+[SnCl3]− (5), [(κ2‐L2)RuCl(η6‐p‐cymene)]+[SnCl3]− (6), and [(κ1‐L3)RuCl (SnCl3)(η6‐p‐cymene)] (7). The catalytic activity of 1–7 was tested on aerobic oxidation of benzylamine. The effect of different ligands L1–3 as well as the effect of the SnCl3− moiety is discussed. [ABSTRACT FROM AUTHOR]

Two new ruthenium(II)-complexes, [Ru(Ang)((benzene)Cl2] (RuB-Ang) and [Ru(Ang)((p-cymene)Cl2] (RuC-Ang), were synthesized using andrographolide (Ang) as a ligand with [RuCl2(arene)]2 (arene = benzene or p-cymene) and characterized by various spectroscopic techniques. These techniques ascertained the formation of the complexes. An assessment of the antioxidant activity of the compounds indicated better scavenging activity against ABTS•+, DPPH•, O2−, NO• and OH− radicals. The cytotoxic activities of RuB-Ang and RuC-Ang have been evaluated against A549 (human lung) and HeLa (human cervical) cancer cell lines. The complexes exhibited superior anticancer activity to cisplatin and was non-toxic towards human umbilical vein endothelial (HUVEC) cells. The morphological changes of the HeLa and A549 cells with the complexes have been studied by AO-EB and DAPI staining methods. The cytotoxic nature of the compounds was RuC-Ang > RuB-Ang > cisplatin > ligand. [ABSTRACT FROM AUTHOR]

Mononuclear Ru-based compounds cis-RuII(dppm)2Cl2 (1) and trans-RuII(dppe)2Cl2 (4) were synthesized by treatment of RuIICl2(DMSO)4 with dppm or dppe, respectively (dppm = bis(diphenylphosphino) methane, dppe = 1,2-bis(diphenylphosphino) ethane, DMSO = dimethyl sulfoxide). Mononuclear Ru-based compounds trans-RuII(dppm)2Cl2 (2) and cis-RuII(dppe)2Cl2 (3) were obtained by reaction of RuIICl2(PPh3)3 with dppm or dppe, separately. These two pair of cis–trans isomers, cis/trans-RuII(dppm)2Cl2 and cis/trans-RuII(dppe)2Cl2, were characterized by electronic absorption spectra, infrared, elemental analysis, 1H NMR, 13C NMR, 31P NMR, and single-crystal X-ray diffraction analysis. Both the crystal structure data and electronic absorption spectra indicate that the cis-isomer is a more thermodynamically stable structure and has lower energy than the trans-isomer. The luminescence spectroscopic study and relative cell viability of 1–4 on HeLa cancer cells has been investigated. [ABSTRACT FROM AUTHOR]

The reaction of tris(pyridin‐2‐yl)amine with [CyRuCl2]2 (Cy = p‐isopropyltoluene or cymene) in refluxing diglyme led to the formation of cis‐[RuCl2{κ2‐(2‐py)3N}2]·CHCl3 (1a) after recrystallization from chloroform/pentane, or cis‐dichloridobis[tris(pyridin‐2‐yl)amine‐κ2N,N′]ruthenium(II) dichloromethane disolvate, [RuCl2(C15H12N4)2]·2CH2Cl2 or cis‐[RuCl2{κ2‐(2‐py)3N}2]·2CH2Cl2 (1b). Treatment of 1a with one equivalent of silver(I) hexafluoridoantimonate in dichloromethane gave [RuCl{κ2‐(2‐py)3N}{κ3‐(2‐py)3N}][SbF6]·CH2Cl2 (2a). Crystallization of 2a from chloroform provided chlorido[tris(pyridin‐2‐yl)amine‐κ2N,N′][tris(pyridin‐2‐yl)amine‐κ3N,N′,N′′]ruthenium(II) hexafluoridoantimonate chloroform monosolvate, [RuCl(C15H12N4)2][SbF6]·CHCl3 or [RuCl{κ2‐(2‐py)3N}{κ3‐(2‐py)3N}][SbF6]·CHCl3 (2b). Complex 2a reacted with a further equivalent of silver(I) hexafluoridoantimonate to give [Ru{κ3‐(2‐py)3N}2][SbF6]2 (3). The reaction of (2‐py)3N with [CyRuCl2]2 in dichloromethane followed by treatment with excess sodium hexafluoridoantimonate gave the known complex [CyRuCl{κ2‐(2‐py)3N}][SbF6] (4). Complex 2 is a rare example of a complex containing both κ2‐ and κ3‐(2‐py)3N. Intramolecular π‐stacking interactions determine the orientation of the free pyridyl in the κ2 complexes. An interesting encapsulation of methylene chloride hydrogen‐bonded tetramers was noted in one case. [ABSTRACT FROM AUTHOR]

The stable activity of catalysts is an important characteristic, which determines their suitability for industrial applications. The purpose of this study was to investigate the stability of ruthenium systems deposited on carbon under conditions simulating long-term operation in CO methanation. Two series of Ru/carbon catalysts were prepared and studied during CO methanation in a hydrogen-rich gas stream. Two graphitized carbons substantially differing in their surface area (23 and 1457 m2/g) were used as supports, and Ru loadings of 3 and 6 wt.% were applied. The stability of Ru/C catalysts was examined in a 240 h time-on-stream test. The samples were characterized by CO chemisorption, XRD, TEM, Raman spectroscopy, TG–MS studies and CO-TPD. The stability of the catalysts over 240 h in the CO + H2 mixture depended on the support type and Ru loading. The highest CO conversion and increased activity was observed for both catalysts with Ru dispersion above 80%. The tested systems were also resistant to carbon deposition. Interestingly, a similar level of activity was obtained for 3 wt.% Ru supported on the low surface area carbon. It is presumed that the similar activity observed for systems with such different ruthenium dispersion is related to the presence of active sites of different strength and structure on the surface of both small and large Ru particles. [ABSTRACT FROM AUTHOR]

CO2 methanation offers a promising route for converting CO2 into valuable chemicals and energy fuels at the same time as hydrogen is stored in methane, so the development of suitable catalysts is crucial. In this review, the performance of catalysts for CO2 methanation is presented and discussed, including noble metal-based catalysts and non-noble metal-based catalysts. Among the noble metal-based catalysts (Ru, Rh, and Pd), Ru-based catalysts show the best catalytic performance. In the non-noble metal catalysts, Ni-based catalysts are the best among Ni-, Co-, and Fe-based catalysts. The factors predominantly affecting catalytic performance are the dispersion of the active metal; the synergy of the active metal with support; and the addition of dopants. Further comprehensive investigations into (i) catalytic performance under industrial conditions, (ii) stability over a much longer period and (iii) activity enhancement at low reaction temperatures are anticipated to meet the industrial applications of CO2 methanation. [ABSTRACT FROM AUTHOR]

The molecular complexes of Re(4,4′-dcbpy)(CO)3Cl (dcbpy = dicarboxylicacid-2,2'-bipyridyl) and [Ru(dcbpy)3]2+ are co-assembled into UiO-66 scaffolds as structural imperfects for CO2 photocatalytic reduction (named as Re-Ru@U). The prepared catalysts are characterized by XRD, Fourier-Transform infrared (FTIR) spectra, X-ray photoelectron spectra (XPS) and N2 adsorption–desorption isotherms. The intact structure of molecular complexes within the matrix are monitored by 1H nuclear magnetic resonance (NMR) spectra through a totally digesting catalyst. The optical properties are studied via absorption and photoluminescence spectra, and the single-electron reduction in Re and Ru complexes is detected by electron paramagnetic resonance (EPR) spectra. An excellent photocatalytic performance is obtained with steady and sustained CO evolution and a turnover number (TON) value of 15 (11 h). The CO activity irradiating by single wavelength presents the absorption-intensity-dependent changing tendency, where the absorption intensity is superposed by Re and Ru complexes. The two radicals related to Re and Ru, respectively, are simultaneously detected in the Re-Ru@U catalyst. It is suggested that the ReC2 component serves as both a photosensitizer and a catalyst, and the RuC2 component works as an additional photosensitizer to supply the second electron for CO2 reduction. The co-assembling of dual metals Re and Ru in the matrix promotes the electron transfer from the reductive Ru centres to one-electron-reduced Re centres and accounts for the superior activity of CO evolution. Our results demonstrate a strategy to develop the multimetallic catalysts via facile assembling into MOF scaffolds to promote photocatalytic performance. [ABSTRACT FROM AUTHOR]

Hydrogen has emerged as an important candidate for clean energy, owing to its environmentally friendly advantages. Electrolytic hydrogen production stands out as the most promising technology for hydrogen production. Therefore, the design of highly efficient electrocatalysts is significant to drive the application of hydrogen technologies. Platinum (Pt)-based catalysts are famous for their outstanding performance in the hydrogen evolution reaction (HER). However, the expensive cost limits its wide application. Ruthenium (Ru)-based catalysts have received extensive attention due to their relatively lower cost and HER performance similar to that of Pt. Nevertheless, the performance of Ru-based catalysts is still unable to meet industrial demands. Therefore, improving HER performance through the modification of Ru-based catalysts remains significant. In this review, the reaction mechanism of HER is analyzed and the latest research progress in the modification of Ru-based electrocatalysts is summarized. From the reaction mechanism perspective, addressing the adsorption of intermediates on the Ru-based electrocatalyst surface, the adsorption–activation of interface water molecules, and the behavior of interface water molecules and proposing solutions to enhance performance of Ru-based electrocatalyst are the main findings, ultimately contributing to promoting their application in the field of electrocatalysis. [ABSTRACT FROM AUTHOR]

Electrical properties of pseudo‐vertical Schottky barrier diodes (pVSBDs) prepared on (113)–oriented boron‐doped diamond (BDD) layers using ruthenium (Ru) for both the ohmic and Schottky contacts are investigated. First, Ru ohmic contacts are evaporated on homoepitaxial BDD layers with different resistivity, and their specific contact resistance is measured using circular transfer length method structures after annealing at various temperatures up to 750 °C. Then, pVSBD structures are fabricated on the boron‐doped bilayer consisting of a lower, heavily boron‐doped layer ensuring an ohmic contact and an upper, lightly doped layer providing a rectifying Schottky contact. After necessary mesa etching, both contacts are formed by the Ru evaporation. The results show that Ru forms a stable ohmic contact with very low contact resistance (10−5–10−6 Ω cm2) when deposited on BDD layers with metallic conductivity. It also provides an acceptable Schottky contact on low‐doped (113) homoepitaxial BDD. Both contacts, which are made simultaneously, realize pVSBDs with low on‐state resistance and low forward voltage drop. However, the lower barrier of the ruthenium contacts results in higher leakage. Ru pVSBDs thus show a lower rectification ratio, higher leakage, and a worse ideality factor compared to analogical pVSBDs using molybdenum contacts. [ABSTRACT FROM AUTHOR]

Ruthenium complexes have gained significant attention due to the ruthenium similarity to iron, lower toxicity, and higher anticancer effectiveness than other compounds. In this contribution, five new isonicotinate-polyethylene glycol ester ligands were synthesised and characterised by NMR and IR spectroscopies. The corresponding Ru(II) complexes were also obtained, and their structure was investigated by traditional methods. The optimisation of structures was performed at B3LYP/6-31+G(d,p) level of theory for H, C, N and O atoms and B3LYP/LanL2DZ for Ru. The intramolecular stabilisation interactions were assessed through the natural bond orbital approach. The NMR chemical shifts were predicted by the gauge independent atomic orbital method and compared to the experimental values. High correlation coefficients and low mean absolute errors between these data sets proved that the predicted structures described well the experimental ones. The theoretical and experimental IR spectra were also compared, and differences in the most notable bands were described. One of the ligands (L5) and complexes (5) showed fluorescent properties due to methylisatoic moiety. The electronic spectra of this compound were modelled by the time dependent-density functional theory method. The difference of 11 nm between the experimental and the theoretical wavelength was explained by the interactions between the solvent and the solute. Further biological and theoretical studies are advised for this series of compounds. [ABSTRACT FROM AUTHOR]

The four-membered ruthenium(II) organometallics Ru(η2-RL)(PPh3)2(CO)(Cl) (1) where η2-RL = C6H2O-2-CHNHC6H4R(p)-3-Me-5 and R = CH3 reacts with 2-(2-hydroxyphenyl)benzothiazole (Hhpbt) and 2-(2-hydroxyphenyl)benzoxazole (Hhpbo) in refluxing ethanol to afford Ru(PPh3)2(CO)(hpbt)Cl (2) and Ru(PPh3)2(CO)(hpbo)Cl (3) respectively in excellent yield. In the course of these reactions, the Ru − C(aryl) bond in 1 is cleaved, and the RL ligand is no longer coordinated with the metal center in the products. The spectral (UV–vis, IR, 1H NMR) and electrochemical data of the complexes are reported. The identity of complex 2 has been established by single-crystal X-ray structure determination. The electronic structure and the absorption spectra of the complexes are scrutinized by DFT and TD-DFT analyses. The complexes were also tested for their ability to exhibit DNA-binding activity. [ABSTRACT FROM AUTHOR]

It has been over half a century since Barnett Rosenberg discovered the cytotoxic action of cisplatin, the platinum-based (Pt-based) drug that has almost eradicated the cases of testicular cancers. Despite this advancement, cancer continues to be widespread, highlighting the imperative for the development of more effective drugs to combat this disease. Most malignancies are initially responsive to anticancer treatments, but cancer cells gain resistance with time. The GRP78 pathway, a key regulator of cellular stress and resistance, is the focus of BOLD-100, a first-in-class ruthenium-based (Ru-based) anticancer drug. This medication inhibits cell survival by preventing stress-induced overexpression of GRP78 in tumour cells, suppressing drug resistance, survival and proliferation. The following article dictates the evolution and the current scenario of the Ru-based drug BOLD-100. [ABSTRACT FROM AUTHOR]

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Abstract Isomerization Metathesis (ISOMET) reaction is an emerging tool for “open loop” chemical recycling of polyethylene to propylene. Novel, latent N‐Alkyl substituted Cyclic(Alkyl)(Amino)Carbene (CAAC)–ruthenium catalysts (5a‐Ru, 3b‐Ru – 6c‐Ru) are developed rendering “inverted” chemical structure while showing enhanced ISOMET activity in combination with (RuHCl)(CO)(PPh3)3 (RuH) double bond isomerization co‐catalyst. Systematic investigations reveal that the steric hindrance of the substituents on nitrogen and carbon atom adjacent to carbene moiety in the CAAC ligand have significantly improved the catalytic activity and robustness. In contrast to the NHC‐Ru and CAAC‐Ru catalyst systems known so far, these systems show higher isomerization metathesis (ISOMET) activity (TON: 7400) on the model compound 1‐octadecene at as low as 3.0 bar optimized pressure, using technical grade (3.0) ethylene. The propylene content formed in the gas phase can reach up to 20% by volume.