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PARTICLE & PARTICLE SYSTEMS CHARACTERIZATION · 2021 ·Vol. 38 ·期 11 ·2100193 · IF 3.31

Converting an Almost Noncytotoxic Ru(II) Complex with Photolabile Ligands into a Highly Efficient PACT Agent

Shuang Qi,Zhihui Jin,Yuanjun Hou,Chao Li,Xuesong Wang,Qianxiong Zhou

Ru(II) complexes with weak ligand fields may undergo light-induced ligand dissociation, and the resulted Ru(II) aqua complexes may bind with biomolecules such as DNA, showing potential as photoactivated chemotherapy (PACT) agents. However, Ru(II) complexes with efficient PACT activity are still rare. Some Ru(II) complexes exhibit efficient photoinduced ligand dissociation but poor cytotoxicity. It is speculated that the low nuclear accumulation levels may account for their low PACT efficacy. In order to confirm this hypothesis, the almost noncytotoxic [Ru(7-OCH 3 -dppz)(4-OCH 3 -py) 4 ](PF 6 ) 2 (Ru1) is loaded on nucleus-targeted C 5 N 2 nanoparticles (NPs). Compared with the free Ru1, Ru1–C 5 N 2 NPs exhibit significantly increased cellular uptake and nuclear accumulation. Therefore, Ru1–C 5 N 2 NPs show efficient PACT activity toward various cancer cell lines (including cisplatin-resistant one) with half maximal inhibitory concentration (IC 50 ) values of 0.18 × 10 −6 –0.29 × 10 −6 m and phototoxicity index (IC 50 dark /IC 50 light ) values above 137 under both normoxic and hypoxic conditions. Moreover, Ru1–C 5 N 2 NPs also exhibit efficient PACT activity toward cisplatin-resistant 3D multicellular tumor spheroids upon two-photon irradiation (800 nm). The same strategy is also feasible to greatly improve the PACT activity of [Ru(7-OCH 3 -dppz)(py) 4 ] 2+ , which itself only has a medium effect. The results may provide new sights for developing efficient Ru(II) PACT agents.

CAS / MDL: 25249-54-1 9003-39-8
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ACS Applied Materials & Interfaces · 2021 · IF 9.229

Ru-Embedded Highly Porous Carbon Nanocubes Derived from Metal–Organic Frameworks for Catalyzing Reversible Li2O2 Formation

Le Wei,Yong Ma,Yuting Gu,Xuzhou Yuan,Ying He,Xinjian Li,Liang Zhao,Yang Peng,Zhao Deng

Rechargeable lithium–oxygen batteries (LOBs) have attracted increasing attention due to their high energy density but highly rely on the development of efficient oxygen catalysts for reversible Li2O2 deposition/decomposition. Herein, highly porous carbon nanocubes with a specific surface area up to 1600 m2 g–1 are synthesized and utilized to tightly anchor Ru nanoparticles for using as the oxygen-cathode catalyst in LOBs, achieving a low charge/discharge potential gap of only 0.75 V, a high total discharge capacity of 17,632 mA h g–1, and a superb cycling performance of 550 cycles at 1000 mA g–1. Comprehensive ex situ and operando characterizations unravel that the outstanding LOB performance is ascribed to the highly porous catalyst structure embedding rich active sites that synergistically function in reducing overpotentials, suppressing parasitic reactions, accommodating reaction products, and promoting mass and charge transportation.

CAS / MDL: 57-09-0 693-98-1
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JOURNAL OF THE ENERGY INSTITUTE · 2021 · IF 6.186

Hydrodeoxygenation of lignin-derived phenolic compounds over Ru/TiO2–CeO2 catalyst prepared by photochemical reduction method

Riyang Shu,Zhuojie Zhong,Hongyun You,Zhipeng Tian,Ying Chen,Longlong Ma

Hydrodeoxygenation (HDO) is an important pathway for lignin-oil upgradation to produce high quality liquid fuels, in which the high-active catalyst is the key point to achieve a high HDO efficiency. In this study, Ru/TiO 2 , Ru/CeO 2 and Ru/TiO 2 –CeO 2 catalysts were synthesized by a novel photochemical method with a high Ru dispersion and used for the HDO of lignin-derived phenolic compounds. Among these three catalysts, Ru/TiO 2 –CeO 2 showed a better performance than Ru/TiO 2 and Ru/CeO 2 . And guaiacol was transformed into cyclohexane with conversion and product selectivity close to 100 % at 230 °C under 1 MPa hydrogen atmosphere. Ru/TiO 2 –CeO 2 took the advantages of Ru/TiO 2 and Ru/CeO 2 , namely high Ru metal dispersion, plenty of medium strength acid sites and abundance of oxygen vacancy , which promoted the guaiacol adsorption and the HDO catalytic activity . Moreover, Ru/TiO 2 –CeO 2 catalyst showed an effective upgrading of other lignin-derived phenolic compounds. And the lignin-oil also enabled to be upgraded efficiently, producing a high content of hydrocarbons and alkylphenols.

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Sustainable Energy & Fuels · 2021 ·Vol. 5 ·期 11 ·2871-2876 · IF 6.367

Highly dispersed Ru nanoparticles on a bipyridine-linked covalent organic framework for efficient photocatalytic CO2 reduction

Ziling Liu,Yaqi Huang,Shuqing Chang,Xiaoli Zhu,Yanghe Fu,Rui Ma,Xinqing Lu,Fumin Zhang,Weidong Zhu,Maohong Fan

The visible-light driven photocatalytic conversion of CO2 into valuable hydrocarbons is a highly attractive approach for sustainable carbon cycle to solve the worldwide environmental and energy problems. Herein, highly dispersed Ru nanoparticles (NPs) are confined in a photosensitizing bipyridine-linked covalent organic framework (TpBpy) to facilely construct Ru@TpBpy composites. The resulting Ru@TpBpy catalysts exhibit significantly enhanced activities for CO2 reduction under visible-light irradiation, giving the maximum HCOOH production rate of 172 μmol gcat−1 h−1 over 0.7 wt% Ru@TpBpy. The interactions between Ru NPs and TpBpy can not only enhance the visible-light harvesting, but also restrain the recombination of photo-generated charges efficiently and facilitate the electron transfer through Ru NPs, thereby improving the photocatalytic performance for CO2 reduction. The current work provides a promising pathway to construct efficient photocatalysts with highly dispersed metallic NPs confined into photosensitizing COFs via utilizing the coordination microenvironments and also expands the application of COF-based materials.

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Journal of Energy Chemistry · 2021 · IF 9.676

Tuned selectivity and enhanced activity of CO2 methanation over Ru catalysts by modified metal-carbonate interfaces

Qiaojuan Wang,Yating Gao,Chantsalmaa Tumurbaatar,Tungalagtamir Bold,Fei Wei,Yihu Dai,Yanhui Yang

Carbonate-modified metal-support interfaces allow Ru/MnCO 3 catalyst to exhibit over 99% selectivity, great specific activity and long-term anti-CO poisoning stability in atmospheric CO 2 methanation. As a contrast, Ru/MnO catalyst with metal-oxide interfaces prefers reverse water–gas shift rather than methanation route, along with a remarkably lower activity and a less than 15% CH 4 selectivity. The carbonate-modified interfaces are found to stabilize the Ru species and activate CO 2 and H 2 molecules. Ru-CO* species are identified as the reaction intermediates steadily formed from CO 2 dissociation, which show moderate adsorption strength and high reactivity in further hydrogenation to CH 4 . Furthermore, carbonates of Ru/MnCO 3 are found to be consumed by hydrogenation to form CH 4 and replenished by exchange with CO 2 , which are in a dynamic equilibrium during the reaction. Modification with surface carbonates is proved as an efficient strategy to endow metal-support interfaces of Ru-based catalysts with unique catalytic functions for selective CO 2 hydrogenation.

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MATERIALS RESEARCH BULLETIN · 2020 · IF 4.019

Enhanced activity of Ru-Ir nanoparticles over SiC for hydrogenation of levulinic acid at room-temperature

Jingru Wang,Shanhui Zhu,Yunwei Wang,Yingyong Wang,Guoqiang Jin,Xili Tong,Xiangyun Guo

The hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL) under mild condition is a promising but challenging process. Herein, SiC supported Ru-Ir bimetallic catalyst exhibit enhanced catalytic activity for aqueous hydrogenation of LA into GVL under mild conditions. Comparing with monometallic Ir 3 /SiC and Ru 3 /SiC, the conversion of LA over bimetallic Ru 0.5 -Ir 2.5 /SiC catalyst increase from 51.2 % and 45.9% to 100% at 25 °C and 0.2 MPa of H 2 pressure. The enhanced catalytic activity of Ru 0.5 -Ir 2.5 /SiC catalyst originates from the electronic synergistic effect among Ru, Ir and SiC. Due to the electron transfer, electron-richened Ir nanoparticles show stronger ability for H 2 dissociation, and the SiC surface produces more active sites to accommodate hydrogen species that spill over from Ir and Ru. The adsorption and hydrogenation of LA molecules occur on the surface of SiC.

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ChemElectroChem · 2020 ·Vol. 7 ·期 20 ·4239-4244 · IF 4.154

Electrochemiluminescence of Ru(bpy)32+/Oxamic Hydrazide and its Application for Selective Detection of 4-Nitrobenzaldehyde

Fan Yuan,Mohamed Ibrahim Halawa,Xiangui Ma,Abubakar Abdussalam,Baohua Lou,Guobao Xu

Graphical Shine and detect : Oxamic hydrazide (OHA) can dramatically increase the electrochemiluminescence (ECL) intensity of Ru(bpy) 3 2+ on glassy carbon electrode (GCE). 4-Nitrobenzaldehyde (4-NBA) can react with OHA to form a hydrazone product through nucleophilic addition, inducing a significant quenching on the ECL intensity of the developed Ru(bpy) 3 2+ /OHA system. Based on this, a sensing platform of 4-NBA was constructed. Oxamic hydrazide (OHA) was utilized as an efficient coreactant of Ru(bpy) 3 2+ for the first time, which can dramatically increase the electrochemiluminescence (ECL) intensity of Ru(bpy) 3 2+ on glassy carbon electrode (GCE). 4-nitrobenzaldehyde (4-NBA), a nitroaromatic compound, has mutagenic and carcinogenic toxicity on humans′ genome and causes a serious impact on the environment. Hence, the detection of its level in biological and environmental samples is of great significance. Interestingly, 4-NBA was found to induce a dramatic quenching for the ECL intensity of the developed Ru(bpy) 3 2+ /OHA system owing to the formation of hydrazone product through the nucleophilic addition reaction with OHA. Under optimal conditions, the ECL decreasing value of Ru(bpy) 3 2+ /OHA in the presence of 4-NBA is linear in the range of 20 μM to 800 μM with a limit of detection (LOD) of 1.09 μM (signal-to-noise 3 : 1). Finally, this strategy enabled the detection of 4-NBA in tap water with satisfactory recoveries from 97.84 % to 103.56 %.

CAS / MDL: 87-69-4
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KOREAN JOURNAL OF CHEMICAL ENGINEERING · 2020 ·Vol. 37 ·期 2 ·224-230 · IF 2.69

Selective oxidation of 5-formyloxymethylfurfural to 2, 5-furandicarboxylic acid with Ru/C in water solution

Si Zhihao,Zhang Xin,Zuo Miao,Wang Tao,Sun Yong,Tang Xing,Zeng Xianhai,Lin Lu

2, 5-furandicarboxylic acid (FDCA) is a one of the most promising biomass-derived chemicals to substitute the non-renewable terephthalic acid as the monomer for producing polyethyleneterephthalate. At present, the oxidation of HMF is regarded as a prevalent way to prepare FDCA. Nevertheless, the isolation and storage of HMF is still a challenge. Herein, based on the higher stability of 5-formyloxymethylfurfural (FMF) than 5-hydroxymethylfurfural (HMF), we present an effective preparation route to prepare FDCA by substituting HMF with FMF as feedstock. A complete conversion of FMF and a 93.55% selectivity of FDCA were obtained in the mixed solvent of water and 1, 2-dioxane using Ru/C as catalyst and O 2 as oxidant. An improved process was developed for preparing FDCA using FMF as feedstock. The investigation of conversion pathway showed that FMF and HMF were simultaneously oxidized to 2, 5-diformylfuran (DFF) in a case of the existence of the reversible equilibrium between FMF and HMF. Then DFF was oxidized to 5-formyl-2-furancarboxylic acid (FFCA). Subsequently, FFCA was oxidized to FDCA. In this process, the oxidation of FFCA to FDCA was determined as the rate-determining step. Furthermore, appropriate alkalinity favored the selectivity of FDCA and the conversion of FMF.

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SENSORS AND ACTUATORS B-CHEMICAL · 2020 · IF 7.1

A sensitive electrochemiluminescence immunoassay for glycosylated hemoglobin based on Ru(bpy)32+ encapsulated mesoporous polydopamine nanoparticles

Pei Zhang,Yao Zhang,Xin Xiong,Yao Lu,Nengqin Jia

A sensitive electrochemiluminescence (ECL) immunosensor was successfully fabricated utilizing Ru(bpy) 3 2+ -doped mesoporous polydopamine (MPDA) for subtle exploration of the diabetes biomarker glycosylated hemoglobin (HbA1c). In this protocol, with the advantages of relatively large specific surface area and good biocompatibility, MPDA nanoparticles are capable of loading more Ru(bpy) 3 2+ to greatly amplify the ECL efficiency during the existence of trinpropylamine (TPA) as common coreactant. The acquired Ru(bpy) 3 2+ @MPDA nanoparticles are used as a beneficial substrate for immobilizing aptamer, thereby specifically recognizing the targeting substance HbA1c as much as possible with high selectivity. It could be noted from the experimental results that the ECL intensity was evidently reduced as the proposed Ru(bpy) 3 2+ @MPDA ECL immunosensor captured HbA1c, which showed the principle of the ECL quenching determination. Under optimal experimental conditions, the prepared Ru(bpy) 3 2+ @MPDA ECL immunosensor exhibited wide linear range from 0.1% to 18.5% with the low detection limit (LOD) of 0.015% (S/N = 3) and the correlation coefficient (R 2 ) of 0.994. Moreover, the Ru(bpy) 3 2+ @MPDA immunosensor displayed high sensitivity and selectivity for detecting HbA1c. Therefore, the as-obtained Ru(bpy) 3 2+ @MPDA ECL immunosensor will open up a new promising platform for highly sensitive bioassay of HbA1c.

CAS / MDL: 62-31-7 102-69-2
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EUROPEAN JOURNAL OF MEDICINAL CHEMISTRY · 2020 · IF 5.573

Novel cyclometalated Ru(II) complexes containing isoquinoline ligands: Synthesis, characterization, cellular uptake and in vitro cytotoxicity

Jincan Chen,Jie Wang,Yuanyuan Deng,Baojun Li,Chengpeng Li,Yuxue Lin,Dongbin Yang,Huanyun Zhang,Lanmei Chen,Tao Wang

Two novel cyclometalated Ru(II) complexes containing isoquinoline ligand, [Ru(bpy) 2 (1-Ph-IQ)](PF 6 ), (bpy = 2,2′-bipyridine; 1-Ph-IQ = 1-phenylisoquinoline; RuIQ-1 ) and [Ru(phen) 2 (1-Ph-IQ)](PF 6 ) (phen = 1,10-phenanthroline; RuIQ-2 ) were found to show high cytotoxic activity against NCI–H460, A549, HeLa and MCF-7 cell lines. Notably, both of them exhibited IC 50 values that were an order of magnitude lower than those of clinical cisplatin and two structurally similar Ru(II)-isoquinoline complexes [Ru(bpy) 2 (1-Py-IQ)](PF 6 ) 2 ( Ru3 ) and [Ru(phen) 2 (1-Py-IQ)](PF 6 ) 2 ( Ru4 ) (1-Py-IQ = 1-pyridine-2-yl). The cellular uptake and intracellular localization displayed that the two cyclometalated Ru(II) complexes entered NCI–H460 cancer cells dominantly via endocytosis pathway, and preferentially distributed in the nucleus. Further investigations on the apoptosis-inducing mechanisms of RuIQ-1 and RuIQ-2 revealed that the two complexes could cause S, G2/M double-cycle arrest by regulating cell cycle related proteins. The two complexes also could reduce the mitochondrial membrane potential (MMP), promote the generation of intracellular ROS and trigger DNA damage, and then lead to apoptosis-mediated cell death . More importantly, RuIQ-2 exhibits low toxicity both towards normal HBE cells in vitro and zebrafish embryos in vivo . Accordingly, the developed complexes hold great potential to be developed as novel therapeutics for effective and low-toxic cancer treatment.

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JOURNAL OF NANOPARTICLE RESEARCH · 2020 ·Vol. 22 ·期 5 ·1-13 · IF 2.132

Photocatalytic synthesis of N2/H2O to ammonia on coal based GO/SiO2 supported Ru composite catalyst

Maimaiti Halidan,Wang Shixin,Awati Abuduheiremu,Xu Bo

Graphene oxide/silica (GO/SiO 2 ) containing various inorganic particles is obtained by using the Xinjiang Wucaiwan coal as carbon source and silicon source. The ruthenium/graphene oxide/silica (Ru/GO/SiO 2 ) composite was prepared by loading Ru nanoparticles on the surface of GO/SiO 2 . Then, the photocatalytic ammonia synthesis performance was investigated while characterizing the structure of Ru/GO/SiO 2 . On the one hand, the Ru can be sufficiently dispersed to make the surface plasmon resonance (SPR) effect enhance significantly. On the other hand, the quantum confinement effect of the defect structure on the Ru/GO/SiO 2 can effectively separate electron and hole, and it can participate in the reducing/oxidizing reaction of photocatalytic ammonia synthesis.

CAS / MDL: 16940-66-2
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RSC Advances · 2020 ·Vol. 10 ·期 28 ·16515-16525 · IF 3.119

Ru/g-C3N4 as an efficient catalyst for selective hydrogenation of aromatic diamines to alicyclic diamines

Junya Cao,Fenggang Han,Liguo Wang,Xiaoyu Huang,Yan Cao,Peng He,Huanhuan Yang,Jiaqiang Chen,Huiquan Li

A series of Ru/g-C3N4 materials with highly dispersed Ru were firstly prepared by an ultrasonic impregnation method using carbon nitride as a support. The catalysts were characterized by various techniques including BET and elemental analysis, ICP-AES, XPS, XRD, CO2-TPD and TEM. The results demonstrated that Ru/g-C3N4 materials with a mesoporous structure and highly dispersed Ru were successfully prepared. The chemo-selective hydrogenation of p-phenylenediamine (PPDA) to 1,4-cyclohexanediamine (CHDA) over Ru/g-C3N4 as a model reaction was investigated in detail. PPDA conversion of 100% with a CHDA selectivity of more than 86% could be achieved under mild conditions. It can be inferred that the carbon nitride support possessed abundant basic sites and the Ru/g-C3N4-T catalysts provided suitable basicity for the aromatic ring hydrogenation. Compared to the N-free Ru/C catalyst, the involvement of nitrogen species in Ru/g-C3N4 remarkably improved the catalytic performance. In addition, the recyclability of the catalyst demonstrated that the aggregation of Ru nanoparticles was responsible for the decrease of the catalytic activity. Furthermore, this strategy also could be expanded to the selective hydrogenation of other aromatic diamines to alicyclic diamines.

CAS / MDL: 106-50-3 10049-08-8
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