Ru Cl Research Articles

Interactions of arene ruthenium(II) complexes [η6-(C6H6)Ru(pprip)Cl]+ and [η6-(C6H6)Ru(H2iiP)Cl]+ with RNA triplex poly(U)•poly(A)*poly(U).

Two arene ruthenium(II) complexes [η6-(C6H6)Ru(pprip)Cl]PF6 (Ru1; pprip = 2-(3-phenyl-1H-pyrazol-4-yl)-imidazolo[4,5-f][1,10]phenanthroline) and [η6-(C6H6)Ru(H2iiP)Cl]PF6 (Ru2; H2iiP = 2-(indole-3-yl)-imidazolo[4,5-f][1,10]phenanthroline) have been synthesized and characterized in this work. Binding properties of Ru1 and Ru2 with the triplex RNA poly(U)•poly(A)*poly(U) were investigated by spectrophotometry and spectrofluorometry as well as viscosimetry. Analysis of spectroscopic titrations and viscosity measurements show that the two complexes bind with the triplex through intercalation, while the binding affinity for Ru2 toward the triplex is stronger than that for Ru1. Melting experiments indicate that the stabilizing effects of Ru1 and Ru2 toward the triplex differ from each other. Under the conditions used herein, Ru1 only stabilizes the Hoogsteen base-paired strand (third strand) without affecting stabilization of the Watson-Crick base-paired strand (the template duplex) of the triplex, while Ru2 stabilizes both the template duplex and the third strand. Although the two complexes prefer to stabilizing the third strand rather than the template duplex, the third-strand stabilization effect of Ru2 is stronger than that of Ru1. The obtained results of this work reveal that the planarity of the intercalative ligands plays an important role in the triplex stabilization by arene Ru(II) complexes.

A luminescent thermosensitive coating for a non-invasive and in-situ study of thermal polarization in hollow fiber membranes

A new non-invasive method to evaluate the thermal polarization is herein proposed for hollow fiber (HFs) membranes during the Direct Contact Membrane Distillation (DCMD) process. The goal was reached by using a temperature-sensitive phosphorescent molecular probe such as Tris(phenanthroline) ruthenium(II) chloride (Ru(phen)3) and an infrared camera (IR) camera, to map, in-situ, the thermal profile directly at the membrane surface which is in contact with the hot feed water solution. The molecular probe was immobilized, by means of a perfluoropolyether (PFPE)-based coating, on the surface of a polypropylene HF in order to obtain a thermosensitive polymerized coating. The produced HFs were fully characterized in order to demonstrate the successful embodiment of the molecular probe on the surface of the membrane and their suitability, in terms of pore size, hydrophobicity and stability, for DCMD application. The luminescent activity of the immobilized Ru(phen)3 complex was measured by a bifurcated optical fiber, one branch was used to excite the molecular probe and the other branch was able to constantly monitor the molecular emission which was dependent on the temperature along the HF surface. The HFs were tested in DCMD at different feed temperatures (40 °C, 50 °C, 60 °C) and constant conditions of streams flow rate and distillate temperature (Qf = 90 L/h; Qp = 24 L/h; Tp = 13 °C). The obtained results clearly demonstrated the possibility of studying the thermal polarization phenomenon occurring during DCMD, with the temperature profile developed on the HF surface monitored, for the first time, at molecular level using a non-invasive technique. This approach can shed the light on better understanding this phenomenon and the possible strategies for its mitigation and counteraction.

Carbohydrate effect of novel arene Ru(II) phenanthroline-glycoconjugates on metastatic biological processes

Novel water-soluble half-sandwich ruthenium(II) polypyridyl-glycoconjugates [Ru(p-cymene)Cl{N-(1,10-phenanthroline-5-yl)-β-glycopyranosylamine}][Cl] (glycopyranosyl = d-glucopyranosyl (1), D-mannopyranosyl (2), L-rhamnopyranosyl (3) and l-xylopyranosyl (4)) have been synthesized and fully characterized. Their behaviour in water under physiological conditions has been studied by nuclear magnetic resonance spectroscopy, revealing their hydrolytic stability. Interactions of the novel compounds with duplex-deoxiribonucleic acid (dsDNA) were investigated by different techniques and the results indicate that, under physiological pH and saline conditions, the metal glycoconjugates bind DNA in the minor groove and/or through external, electrostatic interactions, and by a non-classical, partial intercalation mechanism in non-saline phosphate buffered solution. Effects of compounds 1–4 on cell viability have been assessed in vitro against two human cell lines (androgen-independent prostate cancer PC-3 and non-tumorigenic prostate RWPE-1), showing moderate cytotoxicities, with IC50 values higher than those found for free ligands [N-(1,10-phenanthroline-5-yl)-β-glycopyranosylamine] (glycopyranosyl = d-glucopyranosyl (a), D-mannopyranosyl (b), L-rhamnopyranosyl (c) and l-xylopyranosyl (d)) or corresponding metal-aglycone. Cell viability was assayed in the presence and absence of the glucose transporters (GLUTs) inhibitor [N4-{1-(4-cyanobenzyl)-5-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl}-7-fluoroquinoline-2,4-dicarboxamide] (BAY-876), and the results point to a negligible impact of the inhibition of GLUTs on the cytotoxicity caused by Ru(II) compounds 1–4. Remarkably, glycoconjugates 1–4 potently affect the migration pattern of PC-3 cells, and the wound healing assay evidence that the presence of the carbohydrate and the Ru(II) center is a requisite for the anti-migratory activity observed in these novel derivatives. In addition, derivatives 1–4 strongly affect the matrix metalloproteinase MMP-9 activities of PC-3 cells, while proMMP-2 and especially proMMP-9 were influenced to a much lesser extent.

Study on antitumor activity of three ruthenium arene complexes in vitro

Three ruthenium arene complexes, namely {[(η6-p-cymene)Ru(Cl)]2(dpb)}(PF6)2 (1), [(η6-p-cymene)Ru(dpb)Cl](PF6) (2) and [(η6-p-cymene) Ru(dpb)py](PF6) (3) (dpb = 2,3-bis(2-pyridyl)benzo-quinoxaline, py = pyridine), were synthesized and their antitumor properties were introduced. Complexes 1-3 were characterized by 1H NMR, MS, and elemental analysis. As a binuclear ruthenium structure, the absorption of metal ligand electron transfer (MLCT) of 1 extended to 700 nm. Complex 1 was significantly hydrolyzed under dark conditions. The cytotoxicity in vitro study showed that complexes 1 and 2 are more toxic to human lung cancer cells (A549) and human cervial cancer cells (Hela) than cisplatin. Moreover, there was almost no cross-resistance between complex 1-2 and cisplatin. Under the irradiation at 478 nm, complexes 1-3 all produced singlet oxygen (1O2), and the 1O2 quantum yield of complex 1 in PBS is the highest among complexes 1-3. Complex 1 also produced 1O2 under 600 nm light irradiation. DNA gel electrophoresis showed that 1 caused the photocleavage of plasmid DNA. The hydrolysis rate of complex 1 was accelerated under light (λ > 600 nm). And the phototoxicity of complex 1 to Hela cells under light (λ > 600 nm) was much greater than its dark toxicity, which may be due to its generation of 1O2 and the promotion of its hydrolysis under long-wave light irradiation.

Point defects in two-dimensional RuCl3

Defects are crucial in determining a variety of material properties especially in low dimensions. In this work, we study point defects in monolayer \ensuremath{\alpha}-phase Ruthenium (III) chloride $(\ensuremath{\alpha}-\mathrm{Ru}{\mathrm{Cl}}_{3})$, a promising candidate to realize quantum spin liquid with nearly degenerate magnetic states. Our first-principles simulations reveal that Cl vacancies, Ru vacancies, and oxygen substitutional defects are the most energetically stable point defects. Besides, these point defects break the magnetic degeneracy: Cl vacancies and oxygen substitutional defects energetically favor the zigzag-antiferromagnetic configuration while Ru vacancies favor the ferromagnetic configuration, shedding light on understanding the observed magnetic structures and further defect engineering of magnetism in monolayer $\ensuremath{\alpha}-\mathrm{Ru}{\mathrm{Cl}}_{3}$. We further calculated their electronic structures and optical absorption spectra. The polarization symmetry of optical responses provides a convenient signature to identify the point defect types and long-range magnetic orders.

Half-Sandwich Ruthenium Complexes with Hydrazone Ligands: Preparation, Structure, and Catalytic Activity in Cyanosilylether Synthesis under an Air Atmosphere.

A new class of N,O-coordinate half-sandwich ruthenium complexes supported by hydrazone ligands with a general formula of [Ru(η6-p-cymene)Cl(L)] have been obtained in moderate to excellent yields conveniently. These air- and moisture-stable ruthenium complexes exhibited excellent catalytic activity in cyanosilylether synthesis under mild reaction conditions. Under the catalysis of ruthenium, various cyanosilylethers with different substituents were obtained through a one-pot reaction of trimethylsilyl cyanide with carbonyl substrates, with good to excellent yields. Excellent catalytic efficiency, a wide substrate range, and mild reaction conditions made this type of ruthenium catalyst have potential for industrial application. All of the half-sandwich ruthenium complexes have been well described by infrared, nuclear magnetic resonance, and EA analysis. Molecular structures of ruthenium complexes 1 and 4 were confirmed by single-crystal X-ray analysis.

A Molecularly Imprinted Polymer-Based Electrochemical Sensor for Heart Failure Detection

The number of Heart Failure (HF) patients is increasing every year, which suggests that early BNP detection is necessary. It is highly desired to look for a new sensor because the Brain Natriuretic Peptide (BNP) has the potential to be a cardiac biomarker for the diagnosis of HF. Due to this, the goal of this study was to create and develop a novel electrochemical sensor for BNP detection based on Molecularly Imprinted Polymer (MIP) rather than an antibody. The modification of carbon Screen Printed Electrode (SPCE) using functionalized-multiwall carbon nanotube/tris (bipyridine) ruthenium (II) chloride (f-MWCNTs/Ru) composites has the advantage of improving the electrode's electron transfer process, as effectively shown by the Cyclic Voltammogram (CV). Pyrrole (Py) and pyrrole-3-carboxylic acid (Py3C) were used as a copolymeric matrix to create the BNP recognition sites. BNP and two monomers were electropolymerized together in a single step by CV method. Differential Pulse Voltammetry (DPV) was used to determine the optimum conditions for the MIP-based BNP sensor, including the Py: Py3C ratio, the number of electropolymerizations, the rebinding pH, and the rebinding time. The DPV results of the new MB labeled NPs revealed directly proportional to the concentrations of rebinding BNP from 10 to 500 pg.cm-3 under optimal conditions, making them acceptable for the detection of both chronic and acute HF. This approach provides an improved detection range and may provide a novel and efficient platform for protein biomarkers.

Determination of Antithyroid Drug Propylthiouracil with Ru (III) in Pharmaceutical Formulations and its Characterization

Background: Background: Sulfur serves as a versatile element and an essential constituent of pharmaceutical industries, natural compounds, proteins, and biological systems. One of the fundamental constituents of sulfur is thiouracil, which forms several derivatives, including 6- methylthiouracil, 6-methyl-2-thiouracil, and 6-propylthiouracil. These derivatives act as effective chelating agents and can form complexes with metal ions. : Compared with other metals, ruthenium possesses unique chemical properties that make it an ideal therapeutic agent. Therefore, this study reports on the propylthiouracil: Ru(III) complex, considering these essential facts. Methods: An equimolar amount of ruthenium trichloride 3.34 x 10-5 M was added to various aliquots ranging from 0.4 mL to 8.8 mL of 3.26 x 10−5 M propylthiouracil. The volume was adjusted to 10 mL with double distilled water. After letting the solution stand for 10 min, we recorded the absorbance of different sets at λmax 376 nm. The Beer-Lambert's law graph demonstrated linearity in the concentration range of 3.18 x101 μgmL-1 to 7.96 x102 μgmL-1, with a linear regression equation of Y = 0.0354 + 0.1109 X. We determined the effective molar absorptivity (ε) to be 6.609 x 102 Lmole-1 cm-1, and the relative standard deviation (RSD %) was ± 0.34%. Results: At room temperature, a yellow-colored complex of propylthiouracil: Ru(III) was formed within 10 min, with a λmax of 376 nm and constant color intensity for 24 h. We confirmed and characterized the formed complex using FTIR, ESR, 1HNMR, thermal analysis, magnetic susceptibility, and powder X-ray. Conclusion: This approach is notable for its precision, accuracy, rapidity, cost-effectiveness, and applicability in tablet form. The novel propylthiouracil: Ru(III) complex offers several advantages, including stability, low absorbance, and no interference with water-soluble ions, eliminating the need for an organic solvent to extract the reaction product. Therefore, this approach could be recommended for quality control in the pharmaceutical industry.

Base-Free Transfer Hydrogenation Catalyzed by Ruthenium Hydride Complexes of Coumarin-Amide Ligands

Two sets of Ru(II) complexes, [Ru–Cl] (1–3) and [Ru–H] (4–6), supported with coumarin-amide-based ligands have been synthesized and characterized. In these complexes, the coumarin-amide-based ligands show different coordination modes: N–N, N–O, and N–N–O as confirmed by the crystallographic studies. While [Ru–Cl] complexes (1–3) required the presence of a base for promoting the transfer hydrogenation (TH), the corresponding [Ru–H] complexes (4–6) acted as excellent catalysts for the base-free TH of assorted carbonyl compounds. The [Ru–H] complexes (4–6) provided a nearly quantitative yield of the corresponding alcohols by using isopropanol both as a solvent and a hydrogen source. TH of a few biologically relevant substrates such as furfural, nicotinaldehyde, vanillin, isovanillin, chalcone, and 3,6-dihydroxyflavone illustrated the noteworthy catalytic performance of the [Ru–H] complexes. The entire catalytic procedure including reagents, solvents, and conditions was evaluated with the help of the CHEM21 green metrics toolkit to assess the ‘green credentials’ of the catalysis.

Activation mechanism of ruthenium etching by Cl-based radicals in O2/Cl2 plasma

The Ru etching mechanism was investigated using O2/Cl2 plasma with O, ClO, and Cl radicals. The etch rate drastically increased with a 10%–20% addition of Cl2 to O2 and was lower when using pure O2 or Cl2-rich gas in an ECR etcher. Experimental results indicate that chemical reactions involving Cl-based radicals contributed to the etching reactions. The chemical role of the Cl-based radicals was investigated by density functional theory simulations. The hypothesis tested was that O, ClO, and Cl adsorb on the RuO2 surface when it is irradiated with O-rich plasma. The reactivities of the topmost Ru atoms, where O, ClO, and Cl adsorbed, were compared in terms of the d-band structures. The ClO and Cl were found to enhance the reactivity of the Ru atoms more than O. These findings suggest that Cl-based radicals activate surface Ru atoms, resulting in the formation of volatile RuO4 or RuCl x O y .

Coordination of Ru(II)-Arene Fragments to Dipyridophenazine Ligands Leads to the Modulation of Their In Vitro and In Vivo Anticancer Activity

Despite extensive research on the anticancer properties of Ru complexes with dipyrido[3,2-a:2',3'-c]phenazine (dppz) ligands, their in vivo efficacy is rarely investigated. Aiming to understand whether the coordination of certain half-sandwich Ru(II)-arene fragments might improve the therapeutic potential of dppz ligands, we prepared a series of Ru(II)-arene complexes with the general formula [(η6-arene)Ru(dppz-R)Cl]PF6, where the arene fragment was benzene, toluene, or p-cymene and R was -NO2, -Me, or -COOMe. All compounds were fully characterized by 1H and 13C NMR spectroscopy and high-resolution ESI mass-spectrometry, and their purity was verified by elemental analysis. The electrochemical activity was investigated using cyclic voltammetry. The anticancer activity of dppz ligands and their respective Ru complexes was assessed against several cancer cell lines, and their selectivity toward cancer cells was assessed using healthy MRC5 lung fibroblasts. The substitution of benzene with a p-cymene fragment resulted in a more than 17-fold increase of anticancer activity and selectivity of Ru complexes and significantly enhanced DNA degradation in HCT116 cells. All Ru complexes were electrochemically active in the biologically accessible redox window and were shown to markedly induce the production of ROS in mitochondria. The lead Ru-dppz complex significantly reduced tumor burden in mice with colorectal cancers without inducing liver and kidney toxicity.

Visible light photocrosslinking of sugar beet pectin for 3D bioprinting applications

Herein, we report the hydrogelation of sugar beet pectin (SBP) via visible light-mediated photocrosslinking and its applications in extrusion-based 3D bioprinting. Rapid hydrogelation (<15 s) was achieved by applying 405 nm visible light to an SBP solution in the presence of tris(bipyridine)ruthenium(II) chloride hexahydrate ([Ru(bpy)3]2+) and sodium persulfate (SPS). The mechanical properties of the hydrogel could be tuned by controlling the visible light irradiation time and concentrations of SBP, [Ru(bpy)3]2+, and SPS. High-fidelity 3D hydrogel constructs were fabricated by extruding inks containing 3.0 wt% SBP, 1.0 mM [Ru(bpy)3]2+, and 1.0 mM SPS. Human hepatoblastoma (HepG2) cells encapsulated in SBP hydrogels remained viable and metabolically active after 14 d of culture. Overall, this study demonstrates the feasibility of applying SBP and a visible light-mediated photocrosslinking system to the 3D bioprinting of cell-laden constructs for tissue engineering applications.

Access to Bis(σ‐B−H) Complexes of Ruthenium Bearing Monoaryl Borate and Borane Ligands

AbstractA series of ruthenium bis(σ‐B−H) borate complexes 1–4 have been prepared by a salt‐elimination protocol using lithium monoaryl trihydroborates Li[ArBH3] (R=Ph, 3,5‐(CF3)2C6H3, o‐tol or Mes) and the corresponding metal halide Cp*Ru(PCy3)Cl. All of these bis(σ‐B−H) borate complexes are stable at room temperature and isolated in good yields (70–92 %). Additionally, treatment of 4 with the hydride abstracting agent B(C6F5)3 generated rare cationic bis(σ‐B−H) borane complex 5. Crystallographic characterization data are provided for 3 and 5. All these new complexes were fully characterized by multinuclear NMR spectroscopy and elemental analysis.

Ruthenium(II)–Arene Complexes with Glycosylated NHC-Carbene Co-Ligands: Synthesis, Hydrolytic Behavior, and Binding to Biological Molecules

Ruthenium(II) complexes with a three-legged piano-stool structure based on an arene ring, an N-heterocyclic carbene (NHC)-carbene ligand with a peracetylated glucose moiety and two chlorides or one bidentate ligand, were prepared and characterized by spectroscopy and crystallography. In one case, the sugar substituent is replaced by an ethyl. The chirality of the sugar results in the formation of two diastereomers that interconvert through rotations around the Ccarbene–Ru and Carene–Ru bonds. In water, the complexes undergo a series of equilibrium hydrolysis steps involving the Ru–Cl bonds. The Ru–arene bond and the sugar acetyls are also partially hydrolyzed, and the selectivity of the process is governed by the nature of the arene and the pH of the solution. The reactivity of the compounds was studied against model nucleophiles and biological macromolecules. In the former case, mass experiments demonstrated a variety of binding modes with a trend reflecting the stability in aqueous environment. In the latter case, protein crystallography was used to characterize the preferential binding sites of one of the complexes. The X-ray structure of the adduct formed upon reaction of one representative complex with hen egg white lysozyme contains a Ru center, which retains the carbene ligand, close to the side chain of Asp119. In the adduct with bovine pancreatic ribonuclease, there are two protein molecules in the asymmetric unit. In one molecule, two Ru centers are located close to the side chains of His105 and of His119, which is the protein active site. In the second molecule, only one Ru center was found in the proximity of the side chain of His105. The Ru complexes also interact with calf-thymus DNA, although without displacing the intercalating probe EB. Finally, the complexes are essentially inactive against the human ovarian carcinoma A2780 cells, the cisplatin-resistant A2780cis cells, and the human embryonic kidney HEK293T cells.

Simple synthesis of water-soluble ruthenium carry CDs as admirable probe for improved environment and biological applications

Metal-doped carbon dots (M-CDs) are brand-new 0-D nanomaterial that affords multiple guaranteed properties because of metals in between tiny carbon matrices. However, preparing M-CDs without aggregation of metals is very challenging. Here, we proposed a new tactic method to prepare highly water-soluble ruthenium Ru(Ⅱ)-holding CDs (Ru@CDs) through a one-step microwave-assisted approach with quantum yield of 19.21% using ruthenium chloride and ethylene diamine without any solvents. The optical, surface, structural, and morphological features were deeply evaluated with the support of UV–vis, photoluminescence, Fourier-transform infrared, Raman, X-ray diffraction, transmission electron microscope, and X-ray photoelectron spectroscopy techniques. The excellent photoluminescent and water-soluble properties of Ru@CDs were employed to individually detection of dual carcinogenic environmental toxic metal ions through the photoluminescence technique. They detected the lower limit of 0.128 μM as Cr6+ and 0.328 μM as Hg2+ in the aqueous environment, which was very low compared to CDs. Followed by Ru@CDs, embedded cost-efficient filter paper was fabricated for real-time visual recognition of Cr6+ and Hg2+ ions in water. Significantly, Ru@CDs show good cytotoxicity and effective growth inhibition against cancer cells compared to CDs. So, the Ru@CDs were employed as an effective bioimaging agent selectively. To conclude, facile synthesized Ru@CDs explore its multifunctional quality as a better environmental pollutant detector and bioimaging agent.

“Half-Sandwich” Ruthenium Complexes with Alizarin as Anticancer Agents: In Vitro and In Vivo Studies

Upon exploration of the chemistry of the combination of ruthenium/arene with anthraquinone alizarin (L), three new complexes with the general formulas [Ru(L)Cl(η6-p-cymene)] (C1), [Ru(L)(η6-p-cymene)(PPh3)]PF6 (C2), and [Ru(L)(η6-p-cymene)(PEt3)]PF6 (C3) were synthesized and characterized using spectroscopic techniques (mass, IR, and 1D and 2D NMR), molar conductivity, elemental analysis, and X-ray diffraction. Complex C1 exhibited fluorescence, such as free alizarin, while in C2 and C3, the emission was probably quenched by monophosphines and the crystallographic data showed that hydrophobic interactions are predominant in intermolecular contacts. The cytotoxicity of the complexes was evaluated in the MDA-MB-231 (triple-negative breast cancer), MCF-7 (breast cancer), and A549 (lung) tumor cell lines and MCF-10A (breast) and MRC-5 (lung) nontumor cell lines. Complexes C1 and C2 were more selective to the breast tumor cell lines, and C2 was the most cytotoxic (IC50 = 6.5 μM for MDA-MB-231). In addition, compound C1 performs a covalent interaction with DNA, while C2 and C3 present only weak interactions; however, internalization studies by flow cytometry and confocal microscopy showed that complex C1 does not accumulate in viable MDA-MB-231 cells and is detected in the cytoplasm only after cell permeabilization. Investigations of the mechanism of action of the complexes indicate that C2 promotes cell cycle arrest in the Sub-G1 phase in MDA-MB-231, inhibits its colony formation, and has a possible antimetastatic action, impeding cell migration in the wound-healing experiment (13% of wound healing in 24 h). The in vivo toxicological experiments with zebrafish indicate that C1 and C3 exhibit the most zebrafish embryo developmental toxicity (inhibition of spontaneous movements and heartbeats), while C2, the most promising anticancer drug in the in vitro preclinical tests, revealed the lowest toxicity in in vivo preclinical screening.

Two-dimensional ruthenium nanoparticles between graphite layers: The effect of reduction temperature

A mixture of graphite powder and ruthenium chloride (III) anhydrous was treated at 723 K under 0.3 MPa chlorine for 3 days, followed by reduction under 40 kPa of hydrogen for 1 h to produce ruthenium metal particles intercalated between graphite layers (Ru-GIC). The structures of ruthenium particles depended on the reduction temperatures. Sheet-like ruthenium particles with 1–3 nm thickness and 10 to several hundred nm width containing numerous irregularly shaped holes with round edge, were formed by reduction at 573 K. A Ru-GIC sample treated at 653 K possessed two-dimensional ruthenium nanosheets with hexagonal holes (straight lines intersect at an angle of 120°) in a similar range of thickness and width. On the other hand, Ru-GIC samples reduced at 773 and 823 K showed two-dimensional plate morphology with a thickness of 1–4 nm. In addition, ruthenium nanoparticles supported on the graphite surface (Ru/Gmix) were also prepared from a slurry of ruthenium chloride (III) hydrate and graphite powder by impregnation and hydrogen reduction. The ruthenium particles in Ru/Gmix were spherical at about 3.6 nm, and the reduction temperature did not affect their particles size. Both Ru-GIC and Ru/Gmix samples were evaluated for cinnamaldehyde (CAL) hydrogenation in supercritical carbon dioxide solvent at 323 K, and they were active to produce cinnamyl alcohol (COL) and hydrocinnamaldehyde (HAL). However, Ru-GIC samples showed higher COL selectivity than Ru/Gmix prepared at the same reduction temperature, and COL selectivity over Ru-GIC increased with the reduction treatments at 773 and 823 K.

Reversible Chromism of Tethered Ruthenium(II) Complexes in the Solid State.

Tethered ruthenium(II) complexes [Ru(η6:κ1-arene:N)Cl2] (where arene:N is 2-aminobiphenyl (1) and 2-benzylpyridine (2)) can convert into their open-tethered chlorido counterparts [Ru(η6-arene:NH)Cl3], 1·HCl and 2·HCl, at room temperature via solid-state reaction in the presence of HCl vapors. The reaction is accompanied by a change in color, is fully reversible, and crystallinity is maintained in both molecular materials. Organoruthenium tethers are presented as nonporous materials capable of capturing and releasing HCl reversibly in the crystalline solid state.

Array electrochemiluminescence device with ultra-high sensitivity and selectivity for rapid visualized monitoring of trace radon in environment

The World Health Organization has reported radioactive Rn gas as the second leading cause of lung cancer and gives an extreme limit to indoor Radon (Rn) concentration as 100 Bq/m3. To realize rapid and accurate Rn monitoring, we report an efficient visualized electrochemiluminescence (ECL) device for Rn detection with the lowest limit of detection (0.9 Bq/m3/3.6 Bq h m−3) compared to known Rn detection methods and the shortest measurement time (less than 5 h) among non-pump methods. In detail, an efficient Rn probe is prepared by Au nanoparticles, Pb2+ aptamer, as well as NH2-ssDNA co-reactant and then modified on ITO electrodes to obtain Rn detection devices. With tris(2,2′-bipyridyl)ruthenium(II)chloride (Ru(bpy)3Cl2) as an ECL emitter, the devices can exhibit ultra-high sensitivity and selectivity to trace Rn in environment via the ECL quenching caused by 210Pb, the relatively stable decay product of Rn. Furthermore, ECL imaging technology can be applied to realize the visualized Rn detection. An efficient up-response ECL detector was also invented to support this detection device to achieve accurate Rn detection in environment. This work reports noble gas ECL detection for the first time and provides an efficient strategy for rapid and accurate monitoring of trace Rn in environment.

Preparation of ruthenium oxide catalyst for oxygen evolution reaction in HT-PAWE by pulsed electrodeposition

Despite the fact that the technique of proton exchange membrane water electrolysis (PEMWE) dominates the market because of its low temperature of operation, platinum as a catalyst renders it relatively expensive. In this work, we demonstrated a recyclable ruthenium catalyst with high stability, high oxygen evolution reaction (OER) performance and low onset potential. In particular, instead of PEMWE, the technique of high temperature phosphoric acid water electrolysis (HT-PAWE) was used, with ruthenium oxide as its anode catalyst and a high operation temperature to decrease the amount of noble metals being used. Ruthenium was chosen in this study due to its excellent catalytic activity. The possibility of recycling and reusing noble metals would ease the problem of high cost. Homemade ruthenium catalyst in this study exhibited an outstanding OER performance including high stability and high current density than those of commercial platinum catalyst. Linear sweep voltammetry (LSV) test results showed that a maximum current density of 190 mA/cm2 was reached at only 1.5VSCE.For this experiment, ruthenium (III) chloride hydrate (RuCl3·3H2O) was used as the precursor, and potassium chloride (KCl) and hydrochloric acid (HCl) acted as the supporting electrolyte. Pulsed electrodeposition was chosen to achieve a better control in particle size and distribution of the catalyst over selected specimens. After electrodeposition, the specimens underwent thermal treatment for increasing stability in catalyst particles. Scanning electron microscopy (SEM), linear sweep voltammetry (LSV) and cyclic voltammetry (CV) were used to observe the morphology and to analyze the OER performance of the specimens, respectively. Types of catalyst carrier, electrodeposition potential and duration, and thermal treatment temperature were studied. As a result, all four parameters affected the morphologies and electrochemical performances of the tested specimens.