- Selective removal of nitroaromatic compounds from wastewater in an integrated zero valent iron (ZVI) reduction and ZVI/H2O2 oxidation process
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In this study, an integrated system comprised of zero-valent iron (ZVI) reduction and ZVI-based Fenton oxidation processes (ZVI-ZVI/H2O2) was applied for the selective removal of nitroaromatic compounds (NACs) from 2,4-dinitroanisole (DNAN) producing wastewater. For the ZVI reduction process, at a hydraulic retention time (HRT) of 6 h and neutral pH of 7.2, removal efficiencies of 2,4-dinitroanisole (DNAN), 2,4-dinitrophenol (DNP) and 2,4-dinitrochlorobenzene (DNCB) were as high as 81.3 ± 3.6%, 80.6 ± 1.8% and 90.9 ± 3.5%, respectively, demonstrating the excellent performance of ZVI. For the ZVI/H2O2 oxidation process, the optimal pH and H2O2 dosage were found to be 3.0 and 100 mmol L-1, respectively. Under these optimal conditions, NACs and their degradation intermediates could be removed selectively and effectively in the coupled ZVI reduction and ZVI/H2O2 oxidation process, as was indicated by the low UV254 value of 0.104 ± 0.003 and the low TOC removal efficiency of 32.4 ± 0.7% in the effluent. Ferrous ions could be generated in situ through the corrosion of the metal iron in both the ZVI reduction process and the ZVI/H2O2 oxidation process, giving rise to a potent Fenton-type reaction. In addition, the enhanced Fenton reaction with the aid of reaction between Fe0 and Fe3+ was probably due to the presence of Fe0 in the ZVI/H2O2 oxidation process, which promoted the utilization efficiency of the Fenton catalyst, i.e., Fe2+. Compared to the sequential ZVI reduction and homogeneous Fenton oxidation process (ZVI-Fe2+/H2O2), the low consumption of iron shavings, the reduced H2O2 consumption and the low yield of ferric sludge made the integrated ZVI-ZVI/H2O2 process promising for the treatment of NAC containing wastewater.
- Liu, Jianguo,Ou, Changjin,Han, Weiqing,Faheem,Shen, Jinyou,Bi, Huiping,Sun, Xiuyun,Li, Jiansheng,Wang, Lianjun
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Read Online
- Co/Cu bimetallic ZIF as New heterogeneous catalyst for reduction of nitroarenes and dyes
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Nowadays one of the great challenges is to design new bimetallic catalysts with enhanced catalytic activity, selectivity and recycling properties. In this work, the preparation of new Co/Cu bimetallic Zeolitic Imidazolate Framework (Co-Cu/ZIF) as an efficient catalyst for the reduction of nitro compounds and organic dyes is described. Co-Cu/ZIF was characterized with different techniques such as SEM, TEM, XRD, XPS, TGA, FT-IR and UV–vis absorption indicating formation of entirely uniform cubic particles. Using this catalyst, structurally different aromatic nitro compounds were reduced efficiently to corresponding amines in excellent yields. Kinetic studies revealed that the reduction rates of nitrophenol isomers follow 3-NP > 4-NP > 2-NP order. The catalytic activity of Co-Cu/ZIF was further investigated in the reduction of organic dyes such as methyl orange (MO) and rhodamine B (RhB). This catalyst was recycled for at least ten runs in the reduction of 4-nitrophenol without a noticeable decrease in activity and reused catalyst was characterized.
- Gholinejad, Mohammad,Naghshbandi, Zhwan,Sansano, José M.
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Read Online
- UiO-66/btb/Pd as a stable catalyst reduction of 4-nitrophenol into 4-aminophenol
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In order to synthesize highly sparse nanoparticles, UiO-66-NH2 can be utilized as an appropriate support. It has great surface area, which is functionalized by 1,3-bis(dimethylthiocarbamoyloxy)benzene compounds that can act as the powerful performers, hence, the Pd (II) is a complex without aggregate over the UiO-66-NH2 microspheres structures (UiO-66/btb/Pd). Nitro-aromatic pollution in industrial waste streams threat wellbeing of water resources. The produced UiO-66/btb/Pd nanocatalyst showed appropriate catalytic activity for reduce nitro-aromatic compounds in aqueous solution. XRD, EDS, SEM, FT-IR, and TEM were utilized for characterizing the nanostructures UiO-66/btb/Pd.
- Kiani, Zahra,Zhiani, Rahele,Khosroyar, Susan,Motavalizadehkakhky, Alireza,Hosseiny, Malihesadat
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- Efficient reduction of nitro compounds and domino preparation of 1-substituted-1H-1,2,3,4-tetrazoles by Pd(ii)-polysalophen coated magnetite NPs as a robust versatile nanocomposite
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A new, versatile, and green methodology has been developed for the efficient NaBH4-reduction of nitroarenes as well as the domino/reduction MCR preparation of 1-substituted-1H-1,2,3,4-tetrazoles using Pd(ii)-polysalophen coated magnetite NPs as an efficient heterogeneous magnetically recyclable nanocatalyst. Polysalophen was firstly prepared based on a triazine framework with a high degree of polymerization, then coordinated to Pd ions and, finally, the resulting hybrid was immobilized on magnetite NPs. The catalyst was characterized by various instrumental and analytical methods, including GPC, DLS, N2adsorption-desorption, TGA, VSM, TEM, HRTEM, EDX, XPS, XRD, and ICP analyses. The catalyst possesses dual-functionality including the reduction of nitroarenes and the construction of tetrazole rings all in one stepviaa domino protocol. High to excellent yields were obtained for both nitro reduction and the direct preparation of 1-substituted-1H-1,2,3,4-tetrazoles from nitro compounds. Insight into the mechanism was conducted by XPSin situas well as DLSin situalong with several control experiments. Recyclability of the catalyst was studied for 6 consecutive runs along with metal leaching measurements in each cycle.
- Xu, DaPeng,Xiong, Meilu,Kazemnejadi, Milad
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p. 12484 - 12499
(2021/04/14)
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- Cyclic (Alkyl)(amino)carbene Ligand-Promoted Nitro Deoxygenative Hydroboration with Chromium Catalysis: Scope, Mechanism, and Applications
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Transition metal catalysis that utilizes N-heterocyclic carbenes as noninnocent ligands in promoting transformations has not been well studied. We report here a cyclic (alkyl)(amino)carbene (CAAC) ligand-promoted nitro deoxygenative hydroboration with cost-effective chromium catalysis. Using 1 mol % of CAAC-Cr precatalyst, the addition of HBpin to nitro scaffolds leads to deoxygenation, allowing for the retention of various reducible functionalities and the compatibility of sensitive groups toward hydroboration, thereby providing a mild, chemoselective, and facile strategy to form anilines, as well as heteroaryl and aliphatic amine derivatives, with broad scope and particularly high turnover numbers (up to 1.8 × 106). Mechanistic studies, based on theoretical calculations, indicate that the CAAC ligand plays an important role in promoting polarity reversal of hydride of HBpin; it serves as an H-shuttle to facilitate deoxygenative hydroboration. The preparation of several commercially available pharmaceuticals by means of this strategy highlights its potential application in medicinal chemistry.
- Zhao, Lixing,Hu, Chenyang,Cong, Xuefeng,Deng, Gongda,Liu, Liu Leo,Luo, Meiming,Zeng, Xiaoming
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supporting information
p. 1618 - 1629
(2021/01/25)
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- DFNS/PEI/Cu Nanocatalyst for Reduction of Nitro-aromatic Compounds
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Abstract: Nitro-aromatic pollution in industrial waste streams threat wellbeing of water resources. This study investigates the performance of a copper-based nano catalyst to reduce nitro-aromatic compounds in aqueous solution. Anchoring Cu NPs within the nano spaces of a fibrous silicate with high surface area, and simple accessibility of active sites were successfully established by a facile approach to produce a novel nanocatalyst (DFNS/PEI/Cu). DFNS displayed different properties such as dandelion-like shape, high surface area, and simple availability of active sites. Immobilization of the Cu NPs on DFNS nanospheres not only prevented their aggregation, but also considerably improved the availability of the catalytic active sites. The DFNS/PEI/Cu nanocatalyst demonstrated great catalytic activities for the reduction of nitro compounds under green conditions. Our findings show fibrous DFNS and Cu NPs as a helpful platform for the fabrication of noble metal-based affordable nanocatalyst for many catalytic applications. Graphic Abstract: DFNS/PEI/Cu nanocatalyst as a new adsorbents for the reduction of nitro compounds[Figure not available: see fulltext.]
- Moradi, Marjan,Rastakhiz, Nahid,Ghaedi, Mehrorang,Zhiani, Rahele
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p. 1653 - 1662
(2020/10/20)
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- CoPd Nanoalloys with Metal–Organic Framework as Template for Both N-Doped Carbon and Cobalt Precursor: Efficient and Robust Catalysts for Hydrogenation Reactions
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In this work, a series of metal–organic framework (MOF)-derived CoPd nanoalloys have been prepared. The nanocatalysts exhibited excellent activities in the hydrogenation of nitroarenes and alkenes in green solvent (ethanol/water) under mild conditions (H2 balloon, room temperature). Using ZIF-67 as template for both carbon matrix and cobalt precursor coating with a mesoporous SiO2 layer, the catalyst CoPd/NC@SiO2 was smoothly constructed. Catalytic results revealed a synergistic effect between Co and Pd components in the hydrogenation process due to the enhanced electron density. The mesoporous SiO2 shell effectively prevented the sintering of hollow carbon and metal NPs at high temperature, furnishing the well-dispersed nanoalloy catalysts and better catalytic performance. Moreover, the catalyst was durable and showed negligible activity decay in recycling and scale-up experiments, providing a mild and highly efficient way to access amines and arenes.
- Zhu, Jie,Xu, Deng,Ding, Lu-jia,Wang, Peng-cheng
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p. 2707 - 2716
(2021/01/21)
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- Highly selective hydrogenation of halogenated nitroarenes over Ru/CN nanocomposites by: In situ pyrolysis
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A highly chemoselective and recyclable ruthenium catalyst for the hydrogenation of halogenated nitroarenes has been prepared via the simple in situ calcination of a mixture of melamine, glucose and ruthenium trichloride. Superfine Ru particles (2.3 ± 0.3 nm) were obtained and highly dispersed in the nitrogen-doped carbon matrix. The Ru/CN catalyst smoothly transforms a variety of halogenated nitroarenes to the corresponding haloanilines with high intrinsic activity (e.g. TOF = 1333 h-1 for p-chloronitrobenzene) and selectivity of more than 99.6percent. Furthermore, through an analysis of the products in the reaction process, it was concluded that there are two parallel reaction pathways (a direct pathway and an indirect pathway) for the hydrogenation of aromatic nitro compounds over the Ru/CN catalyst, and the direct pathway was proved to be dominant in catalyzing the intermediates. This journal is
- Yue, Shengnan,Wang, Xueguang,Li, Shaoting,Sheng, Yao,Zou, Xiujing,Lu, Xionggang,Zhang, Chunlei
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p. 11861 - 11869
(2020/07/28)
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- Synthesis and characterization of a novel TEMPO?FeNi3/DFNS-laccase magnetic nanocomposite for the reduction of nitro compounds
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Water is an essential substance for life on earth and for all living things. Plants and animals need almost pure water to live; if it is contaminated with harmful chemicals and micro organisms, it will be impossible for them to survive. This study has tried to investigate the performance of catalyst to reduce nitro-aromatic combinations in the attendance of NaBH4 solution duo to the hydrogen source. TEMPO?FeNi3/DFNS-laccase MNPs was prepared, and its features were reviewed using SEM, TEM, XRD, TGA, VSM, AFM, and FTIR. Then, its strength as a nanocatalyst for removal of nitro-aromatic combinations was tested in contact time, initial concentration, the effects of pH and nanocatalyst amount was study. The results of this research proved that TEMPO?FeNi3/DFNS-laccase MNPs has a good return in removal of nitro-aromatic combinations, as its easy synthesis and reliable recovery.
- Mehrzad, Jamshid,Motavalizadehkakhky, Alireza,Saberi, Shima,Zhiani, Rahele
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p. 27297 - 27304
(2020/09/01)
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- Enhanced catalytic activity of natural hematite-supported ppm levels of Pd in nitroarenes reduction
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In this work, Pd NPs supported on amine-modified natural hematite have been prepared and characterized. Using this simple catalyst, nitroaromatic compounds as a major cause of industrial pollution were reduced to corresponding amines with ppm levels of Pd in the presence of designer surfactant TPGS-750-M and NaBH4 at room temperature in aqueous media. Synergistic effect between hematite and Pd is responsible for the observed enhanced catalytic activity. This catalyst was recycled for at least four times with a small decrease in the activity.
- Gholinejad, Mohammad,Shojafar, Mohammad,Sansano, José M.
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p. 2033 - 2043
(2020/04/07)
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- Cost-effective bio-derived mesoporous carbon nanoparticles-supported palladium catalyst for nitroarene reduction and Suzuki–Miyaura coupling by microwave approach
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A new heterogeneous catalyst was synthesized by immobilizing Pd on areca nut kernel-derived carbon nanospheres (CNSs). The CNSs, without any further activation processes, accommodated 3% of Pd on their surface. The new Pd/CNS material was used for the reduction of nitroarenes and Suzuki–Miyaura coupling of bromoarenes with aryl boronic acids. The reactions were conducted under microwave irradiation at 160 °C using 12 mol% of Pd/CNS (0.36% actual Pd content). The reduction of nitroarenes into their respective amino compounds was achieved in 10–20 min (conversion up to 100%); by contrast, the Suzuki–Miyaura reactions yielded up to 98% at 150 °C with 10 mol% of Pd/CNS catalyst. The products were identified using gas chromatography and nuclear magnetic resonance spectroscopy. The catalyst was isolated from reaction mixture and reused without any significant loss in the activity. Thus, the present work introduces one-pot-derived porous CNSs as efficient catalytic support to Pd, establishing an alternative to existing Pd/C in terms of cost and efficiency.
- Supriya,Ananthnag, Guddekoppa S.,Shetti, Vijayendra S.,Nagaraja,Hegde, Gurumurthy
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- Palladium Nanoparticles on a Creatine-Modified Bentonite Support: An Efficient and Sustainable Catalyst for Nitroarene Reduction
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Creatine as the nitrogen-rich, green and cheap compound is used for modification of natural bentonite and the resulting material is employed for the stabilization of Palladium nanoparticles having an average diameter of 3 nm. This new material bento-crt@Pd is characterized using different techniques such as X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), solid state UV-vis, scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), and energy-dispersive X-ray spectroscopy (EDX). This green catalyst promotes efficient reduction of aromatic nitro compounds in aqueous media. By using this catalyst nitroarenes having electron donating as well as electron withdrawing groups were reduced efficiently to their corresponding amines at room temperature. The catalyst can be recycled seven times and the reused catalyst was characterized by TEM and XPS.
- Gholinejad, Mohammad,Rasouli, Zahra,Najera, Carmen,Sansano, José M.
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p. 1122 - 1129
(2019/09/06)
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- Synergistic Effects of ppm Levels of Palladium on Natural Clinochlore for Reduction of Nitroarenes
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Augmenting the modified naturally occurring clay clinochlore with ppm amounts of palladium leads to a new and very effective reagent for the reduction of numerous aromatic nitro species. When palladium nanoparticles are supported on pyridyltriazole-modified clinochlore, iron within clinochlore acts synergistically with palladium to catalyze the reduction of a wide variety of nitroarenes at room temperature in aqueous media. Based on E-factor calculations, the catalyst system is found to be in line with green chemistry standards and can be recycled up to five times.
- Gholinejad, Mohammad,Oftadeh, Erfan,Shojafar, Mohammad,Sansano, José M.,Lipshutz, Bruce H.
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p. 4240 - 4248
(2019/09/06)
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- N-Heterocyclic Carbene-Modified Au–Pd Alloy Nanoparticles and Their Application as Biomimetic and Heterogeneous Catalysts
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The preparation of water-soluble, N-heterocyclic-carbene-stabilized Au–Pd alloy nanoparticles by a straightforward ligand exchange process is presented. Extensive analysis revealed excellent size retention and stability over years in water. The alloy nanoparticles were applied as biomimetic catalysts for aerobic oxidation of d-glucose, for which monometallic Au and Pd nanoparticles showed no or negligible activity. The alloy nanoparticles were further applied as titania-supported heterogeneous catalysts for the mild hydrogenation of nitroarenes and the semihydrogenation of 1,2-diphenylacetylene with a solvent-dependent selectivity switch between E- and Z-stilbene.
- Tegeder, Patricia,Freitag, Matthias,Chepiga, Kathryn M.,Muratsugu, Satoshi,M?ller, Nadja,Lamping, Sebastian,Tada, Mizuki,Glorius, Frank,Ravoo, Bart Jan
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supporting information
p. 18682 - 18688
(2018/11/23)
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- A capping agent dissolution method for the synthesis of metal nanosponges and their catalytic activity towards nitroarene reduction under mild conditions
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We report a general strategy for the synthesis of metal nanosponges (M = Ag, Au, Pt, Pd, and Cu) using a capping agent dissolution method where addition of water to the M@BNHx nanocomposite affords the metal nanosponges. The B-H bond of the BNHx polymer gets hydrolysed upon addition of water and produces hydrogen gas bubbles which act as dynamic templates leading to the formation of nanosponges. The rate of B-H bond hydrolysis has a direct impact on the final nanostructure of the materials. The metal nanosponges were characterized using powder XRD, electron microscopy, XPS, and BET surface area analyzer techniques. The porous structure of these nanosponges offers a large number of accessible surface sites for catalytic reactions. The catalytic activity of these metal nanosponges has been demonstrated for the reduction of 4-nitrophenol where palladium exhibits the highest catalytic activity (k = 0.314 min?1). The catalytic activity of palladium nanosponge was verified for the tandem dehydrogenation of ammonia borane and the hydrogenation of nitroarenes to arylamines in methanol at room temperature. The reduction of various substituted nitroarenes was proven to be functional group tolerant except for a few halogenated nitroarenes (X = Br and I) and >99% conversion was noted within 30-60 min with high turnover frequencies (TOF) at low catalyst loading (0.1 mol%). The catalyst could be easily separated out from the reaction mixture via centrifugation and was recyclable over several cycles, retaining its porous structure.
- Ghosh, Sourav,Jagirdar, Balaji R.
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p. 17401 - 17411
(2019/01/03)
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- Platinum nanoparticles onto pegylated poly(lactic acid) stereocomplex for highly selective hydrogenation of aromatic nitrocompounds to anilines
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A stereocomplexed poly(lactic acid)-polyethyleneglycol copolymer was synthesized and successfully used as recyclable support for Pt nanoparticles, generated by the metal vapor synthesis technique. The confinement of the Pt nanoparticles were determined by thermal analysis. Hydrogenation reactions of chlorinated aromatic nitro compounds, containing other reducible functional groups, to the corresponding anilines occurred with the latter supported Pt nanoparticles in MeOH under very mild reaction conditions (i.e. 30?°C, p(H2)?=?5.0?bar). The covalently attached polyethyleneglycol polymer significantly increased the catalytic activity of the supported Pt nanoparticles compared to an analogous catalytic system which did not contain polyethyleneglycol but the same sized Pt nanoparticles.
- Oberhauser, Werner,Evangelisti, Claudio,Tiozzo, Cristina,Bartoli, Mattia,Frediani, Marco,Passaglia, Elisa,Rosi, Luca
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- Generation of Cu nanoparticles on novel designed Fe3O4@SiO2/EP.EN.EG as reusable nanocatalyst for the reduction of nitro compounds
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In this work, copper nanoparticles loaded on Fe3O4@SiO2, which we have named Fe3O4@SiO2/EP.EN.EG@Cu for short, have been designed, prepared and characterized by XRD, FTIR, TEM, SEM, EDS, TGA, ICP, successfully. The catalytic performance was investigated in the reduction of aromatic nitro compounds in the presence of NaBH4 aqueous solution as the source of hydrogen at 50°C. The Fe3O4@SiO2/EP.EN.EG@Cu catalyst was readily removed from the reaction mixture by applying an external magnet and reused for five times without significant loss of catalytic activity.
- Rajabzadeh, Maryam,Eshghi, Hossein,Khalifeh, Reza,Bakavoli, Mehdi
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p. 19331 - 19340
(2016/03/01)
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- Chemoselective transfer hydrogenation of nitroarenes by highly dispersed Ni-Co BMNPs
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Highly dispread Ni-Co bimetallic nanoparticles (Ni-Co BMNPs) are synthesized and applied as an efficient catalyst in the chemoselective transfer hydrogenation of nitroarenes (CTH) using hydrazine hydrate as the hydrogen donor. The BMNPs can efficiently catalyze the reduction reaction without any additives under mild conditions with high TOF. Significantly higher activity is achieved when compared with corresponding single-component catalysts, optimal composition of the Ni-Co BMNPs was screened which was proved to be crucial in both the selectivity and yields. Excellent performance of Ni-Co BMNPs can be ascribed to the improved dispersion of active sites on the BMNPs surface (compared with Ni NPs) and the electron transfer from cobalt to nickel.
- Zhang, Jia-Wei,Lu, Guo-Ping,Cai, Chun
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- Transfer hydrogenation of nitroarenes with hydrazine at near-room temperature catalysed by a MoO2 catalyst
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We present an experimental and computational study of the elementary steps of hydrazine hydrogen transfer on crystalline MoO2, and demonstrate its unique bifunctional metallic-basic properties in a catalytic hydrogenation reaction. Density functional theory (DFT) calculations suggest that the stepwise hydrogen transfer via the prior cleavage of the N-H bond rather than the N-N bond, is the key step to create the dissociated hydride and proton species on the dual Mo and O sites, marking its difference with common oxides. Crystalline MoO2 shows exceptionally high chemoselectivity toward the nitro reduction over C=C, C≡C, and C≡N groups at room temperature and lower, down to 0 °C, rendering it as a promising catalytic material for hydrogenation reactions.
- Zhang, Chaofeng,Lu, Jianmin,Li, Mingrun,Wang, Yehong,Zhang, Zhe,Chen, Haijun,Wang, Feng
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p. 2435 - 2442
(2016/05/19)
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- Preparation and characterization of Ni/mZSM-5 zeolite with a hierarchical pore structure by using KIT-6 as silica template: An efficient bi-functional catalyst for the reduction of nitro aromatic compounds
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Ni/mZSM-5 and Ni/H-mZSM-5 were synthesized as hierarchical (micro/meso porous) ZSM-5 zeolites by an indirect template method for the first time. The resulting zeolite materials exhibited significantly enhanced diffusional properties in comparison to purely microporous zeolite materials. The structural and morphological characterization of the prepared catalysts was investigated using XRD, BET, atomic absorption spectroscopy, FT-IR, 27Al-MAS NMR, SEM, TEM, XPS and DRS-UV techniques. These hierarchical zeolites were used as acid-metal bi-functional heterogeneous catalysts for hydride transfer in the reduction of nitro aromatic compounds. In these reactions, NaBH4 was used as a reducing agent. Excellent yields at room temperature and very short reaction times in aqueous media conditions were obtained. Reusability experiments showed the excellent stability of Ni/mZSM-5 and Ni/H-mMZSM-5 and the catalysts could be reused 7 times without much loss of activity in reduction of nitro aromatic compounds. Surprisingly, the acid form of Ni/H-mZSM-5 showed much higher activity than that of Ni/mZSM-5. High yield, short reaction time, green solvent (water), room temperature, no by-product, the easy reusability of catalysts and the low amounts of catalyst required are some of the advantages of these catalysts.
- Mazaheri, Omid,Kalbasi, Roozbeh Javad
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p. 34398 - 34414
(2015/04/27)
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- Magnetically separable core-shell iron oxide@nickel nanoparticles as high-performance recyclable catalysts for chemoselective reduction of nitroaromatics
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A magnetically separable core-shell iron oxide@nickel (IO@Ni) nanocatalyst was synthesized by reduction of Ni2+ ions in the presence of iron oxide (Fe2+, Fe3+) by a simple one-pot synthetic route using NaBH4 as a reducing agent and starch as a capping agent. The synthesized nanoparticles (NPs) were characterized by several techniques such as X-ray diffraction (XRD), high resolution transmission electron microscopy (HR-TEM), selected area electron diffraction (SAED), and energy dispersive X-ray spectroscopy (EDS). The core-shell iron oxide@nickel nanoparticles (IO@NiNPs) were found to have excellent activity for the hydrogenation reactions of aromatic nitro compounds under mild conditions using water as a green solvent. Excellent chemoselectivity and recyclability up to 30 cycles for the nitro group reduction was demonstrated.
- Rathore, Puran Singh,Patidar, Rajesh,Shripathi,Thakore, Sonal
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p. 286 - 295
(2015/02/02)
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- Compositions for Treatment of Cystic Fibrosis and Other Chronic Diseases
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The present invention relates to pharmaceutical compositions comprising an inhibitor of epithelial sodium channel activity in combination with at least one ABC Transporter modulator compound of Formula A, Formula B, Formula C, or Formula D. The invention also relates to pharmaceutical formulations thereof, and to methods of using such compositions in the treatment of CFTR mediated diseases, particularly cystic fibrosis using the pharmaceutical combination compositions.
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Paragraph 0569
(2015/09/22)
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- Fabrication of Ruthenium Nanoparticles in Porous Organic Polymers: Towards Advanced Heterogeneous Catalytic Nanoreactors
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A novel strategy has been adopted for the construction of a copolymer of benzene-benzylamine-1 (BBA-1), which is a porous organic polymer (POP) with a high BET surface area, through Friedel-Crafts alkylation of benzylamine and benzene by using formaldehyde dimethyl acetal as a cross-linker and anhydrous FeCl3 as a promoter. Ruthenium nanoparticles (Ru NPs) were successfully distributed in the interior cavities of polymers through NaBH4, ethylene glycol, and hydrothermal reduction routes, which delivered Ru-A, Ru-B, and Ru-C materials, respectively, and avoided aggregation of metal NPs. Homogeneous dispersion, the nanoconfinement effect of the polymer, and the oxidation state of Ru NPs were verified by employing TEM, energy-dispersive X-ray spectroscopy mapping, cross polarization magic-angle spinning 13C NMR spectroscopy, and X-ray photoelectron spectroscopy analytical tools. These three new Ru-based POP materials exhibited excellent catalytic performance in the hydrogenation of nitroarenes at RT (with a reaction time of only ≈30 min), with high conversion, selectivity, stability, and recyclability for several catalytic cycles, compared with other traditional materials, such as Ru@C, Ru@SiO2, and Ru@TiO2, but no clear agglomeration or loss of catalytic activity was observed. The high catalytic performance of the ruthenium-based POP materials is due to the synergetic effect of nanoconfinement and electron donation offered by the 3D POP network. DFT calculations showed that hydrogenation of nitrobenzene over the Ru (0001) catalyst surface through a direct reaction pathway is more favorable than that through an indirect reaction pathway.
- Mondal, John,Kundu, Sudipta K.,Hung Ng, Wilson Kwok,Singuru, Ramana,Borah, Parijat,Hirao, Hajime,Zhao, Yanli,Bhaumik, Asim
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supporting information
p. 19016 - 19027
(2016/01/26)
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- Nickel nanoparticles as efficient catalyst for electron transfer reactions
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The catalytic efficiency of nickel nanoparticles was investigated in some electron transfer reactions. The nanoparticles brought about rapid roomtemperature reduction of a number of nitro aromatics in an aqueous medium with high chemoselectivity and also helped to speed up redox reaction of Fe(CN)-36and S2O-23. In addition, interesting results were obtained for microwave assisted decolourization of azo dye. The reactions were monitored through UV-Vis spectroscopy. The present study has additional advantages of reusability of catalysts and aqueous medium. The ultimate goal was to assess the suitability of low cost nanocatalyst for electron transfer reactions under aqueous conditions. Springer Science+Business Media New York 2013.
- Rathore, Puran Singh,Patidar, Rajesh,Rathore, Sonika,Thakore, Sonal
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p. 439 - 446
(2014/06/24)
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- Selective reduction of halogenated nitroarenes with hydrazine hydrate in the presence of Pd/C
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A large variety of halogenated nitroarenes have been selectively reduced with hydrazine hydrate in the presence of Pd/C to give the corresponding (halogenated) anilines in good yield.
- Li, Fang,Frett, Brendan,Li, Hong-Yu
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p. 1403 - 1408
(2014/06/23)
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- COMPOSITIONS FOR TREATMENT OF CYSTIC FIBROSIS AND OTHER CHRONIC DISEASES
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The present invention relates to pharmaceutical compositions comprising an inhibitor of epithelial sodium channel activity in combination with at least one ABC Transporter modulator compound of Formula A, Formula B, Formula C, or Formula D. The invention also relates to pharmaceutical formulations thereof, and to methods of using such compositions in the treatment of CFTR mediated diseases, particularly cystic fibrosis using the pharmaceutical combination compositions.
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- Excellent catalytic properties over nanocomposite catalysts for selective hydrogenation of halonitrobenzenes
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A partially reduced Pt/γ-Fe2O3 magnetic nanocomposite catalyst (Pt/γ-Fe2O3-PR) exhibited excellent catalytic properties in the selective hydrogenation of 2, 4-dinitrochlorobenzene and iodonitrobenzenes. The selectivity to 4-chloro-m-phenylenediamine (4-CPDA), meta-iodoaniline (m-IAN), and para-iodoaniline (p-IAN) reached 99.9%, 99.8%, and 99.4%, respectively, at complete conversion of the substrates. The hydrodehalogenation of 4-CPDA and IANs was fully suppressed for the first time over Pt/γ-Fe2O3-PR. It was found that CO chemisorption on the Pt nanoparticles deposited on the partially reduced γ-Fe2O3 and Fe3O4 nanoparticles was very weak, implying a weak tendency of the electronic back-donation from the Pt nanoparticles to the π* antibonding orbitals of the adsorbed molecules. We believe that this is a cause of the superior selectivity to the haloanilines in the hydrogenation reactions of interest over the Pt/γ-Fe2O3-PR catalyst.
- Liang, Minghui,Wang, Xiaodong,Liu, Hongquan,Liu, Haichao,Wang, Yuan
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p. 335 - 342
(2008/12/20)
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- QUINOXALINES AS B RAF INHIBITORS
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The invention relates to chemical compounds of the formula (I) or pharmaceutically acceptable salts thereof, which possess B Raf inhibitory activity and are accordingly useful for their anti cancer activity and thus in methods of treatment of the human or animal body. The invention also relates to processes for the manufacture of said chemical compounds, to pharmaceutical compositions containing them and to their use in the manufacture of medicaments of use in the production of an anti-cancer effect in a warm blooded animal such as man.
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Page/Page column 70
(2010/11/08)
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- One-pot reductive conversion of nitroarenes to N-arylacetamides mediated by metallic samarium
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Nitroarenes can be reduced and then converted to N-arylacetamides by metallic samarium in the presence of acetic anhydride, acetic acid and methanol in excellent yields by a one pot-procedure.
- Zhang, Yandong,Zhang, Yongmin
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p. 596 - 598
(2007/10/03)
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- Efficient reductions of nitroarenes with SnCl2 in ionic liquid
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Mild, eco-friendly and fast reductions of nitroarenes to aminoarenes have been accomplished using stannous chloride dihydrate in ionic liquid tetrabutylammonium bromide (TBAB) that provides unsolvated nucleophilic bromide ion. Improved yields, lower reaction time, generality, and a less demanding work-up procedure are the notable features of this protocol.
- De, Prithwiraj
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p. 1835 - 1837
(2007/10/03)
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- First and efficient method for reduction of aliphatic and aromatic nitro compounds with zinc borohydride as pyridine zinc tetrahydroborato complex: A new stable ligand-metal borohydride
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Pyridine zinc tetrahydroborate, [(Py)Zn(BH4)2], as a new stable ligand-metal borohydride, is prepared quantitatively by complexation of 1:1 zinc borohydride and pyridine at room temperature. This reagent efficiently reduces different aromatic and aliphatic nitro compounds to their primary amines in refluxing THF. In addition, the reduction shows chemoselectivity for aliphatic nitro compounds over the aromatic nitro compounds.
- Zeynizadeh, Behzad,Zahmatkesh, Karam
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p. 267 - 271
(2007/10/03)
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- Indium Mediated Reduction of Nitro and Azide Groups in the Presence of HCl in Aqueous Media
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Indium mediated reduction of azide and nitro groups in the presence of HCl (1.5 equiv based on indium) at room temperature in aqueous THF successfully provided the corresponding amine in high to quantitative yields. Under the some reaction conditions, selective reduction of azide and nitro group in the presence of vinyl group could be accomplished.
- Lee, Jung Gyu,Choi, Kyung Il,Koh, Hun Yeong,Kim, Youseung,Kang, Yonghan,Cho, Yong Seo
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- Rapid and inexpensive method for reduction of nitroarenes to anilines
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Nitroarenes are reduced to corresponding anilines in good yields using ferric chloride - Zinc - Dimethyl formamide - water system.
- Desai,Swami,Hapase
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p. 1033 - 1036
(2007/10/03)
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- Triazinyl reactive dyestuffs in which triazinyl group is further substituted with a beta-chloroethylsulfonyl- or vinylsulfonylbutyrylamino moiety
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Reactive dyes of the formula STR1 in which D is the radical of an organic dye of the monoazo, polyazo, metal complex azo, anthraquinone, phthalocyanine, formazan, azomethine, dioxazine, phenazine, stilbene, triphenylmethane, xanthene, thioxanthrone, nitroaryl, naphthoquinone, pyrenequinone or perylenetetracarbimide series, R is hydrogen or substituted or unsubstituted C1-4 -alkyl, X is a substituent which is detachable as an anion, B is a radical of the formula STR2 R1 and R2, independently of each other, are hydrogen or substituted or unsubstituted C1-4 -alkyl or phenyl, A is a substituted or unsubstituted aliphatic or aromatic bridge member, Y is a --CO--Z or --SO2 --Z radical, Z is an aliphatic, aromatic or heterocyclic reactive radical, and n is 1 or 2, are suitable for dyeing or printing cellulose-containing and nitrogen-containing materials and in high dyeing yield produce dyeings and prints having good fastness properties.
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- GRAPHITE CATAlYZED REDUCTION OF AROMATIC AND ALIPHATIC NITRO COMPOUNDS WITH HYDRAZINE HYDRATE
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Aromatic and aliphatic nitro compounds were readily reduced to amino compounds in excellant yields with graphite and hydrazine hydrate.
- Han, Byung Hee,Shin, Dae Hyun,Cho, Sung Yun
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p. 6233 - 6234
(2007/10/02)
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- Azo reactive dyestuffs having an aryl-triazinyl-aryl diazo component
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Optionally metallized azo dyestuffs which in the form of the free acid correspond to the formula STR1 wherein K is the radical of a benzene, naphthalene, pyrazolone, pyridone, pyrimidone, acetoacetic acid arylide or aminopyrazole coupling component; A is a non-ionic substituent; X is STR2 wherein W is a direct bond or a bridge member to a C atom of the benzene or naphthalene nucleus or the coupling component K; R is hydrogen or C1 -C4 -alkyl; B is a direct bond or a bridge member, especially -CO- or -SO2 -, to a C atom of Q; Q is a reactive radical; m is 0, 1 or 2; n is 0, 1 or 2; p is 0 or 1; q is 0, 1 or 2; and r is 0 or 1; and their use for the dyeing and printing of natural and regenerated cellulose fibre materials such as cotton and rayon, as well as natural and synthetic polyamide fibre materials, for example those of wool, silk, poly-ε-caprolactam or polycondensate of hexamethylene-diamine and adipic acid. The dyeings obtained, espeically those on cotton and rayon, are distinguished by good fastness properties, especially fastness to wet processing and to light.
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- Process for the monoacylation of an aromatic primary diamine
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A process for the monoacylating of an aromatic primary diamine containing no anionic water-solubilizing group, preferably m-phenylene or p-phenylenediamine, which comprises reacting an acylating agent in aqueous medium with a mineral acid salt, preferably the hydrochloric acid salt, of the diamine wherein the reaction mixture is maintained at a pH of from 1.5 to 3.5 during the addition and reaction of the acylating agent.
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