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1.
Dr. Jordan Donat Mr. Patrick Dubourdeaux Dr. Martin Clémancey Dr. Julia Rendon Clara Gervasoni Mr. Morgan Barbier Jessica Barilone Dr. Jacques Pécaut Prof. Dr. Serge Gambarelli Prof. Dr. Pascale Maldivi Prof. Dr. Jean-Marc Latour 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(70):e202201875
Nitrene transfer reactions have emerged as one of the most powerful and versatile ways to insert an amine function to various kinds of hydrocarbon substrates. However, the mechanisms of nitrene generation have not been studied in depth albeit their formation is taken for granted in most cases without definitive evidence of their occurrence. In the present work, we compare the generation of tosylimido iron species and NTs transfer from FeII and FeIII precursors where the metal is embedded in a tetracarbene macrocycle. Catalytic nitrene transfer to reference substrates (thioanisole, styrene, ethylbenzene and cyclohexane) revealed that the same active species was at play, irrespective of the ferrous versus ferric nature of the precursor. Through combination of spectroscopic (UV-visible, Mössbauer), ESI-MS and DFT studies, an FeIV tosylimido species was identified as the catalytically active species and was characterized spectroscopically and computationally. Whereas its formation from the FeII precursor was expected by a two-electron oxidative addition, its formation from an FeIII precursor was unprecedented. Thanks to a combination of spectroscopic (UV-visible, EPR, Hyscore and Mössbauer), ESI-MS and DFT studies, we found that, when starting from the FeIII precursor, an FeIII tosyliodinane adduct was formed and decomposed into an FeV tosylimido species which generated the catalytically active FeIV tosylimide through a comproportionation process with the FeIII precursor. 相似文献
2.
摘要:目的 比对分析 2017—2019 年北京地区实验动物微生物及遗传质量监测结果,为实验动物产业发展提供参考。 方法 按照国家和地方现行实验动物检测标准,对北京地区实验动物生产单位进行抽检,并发布检测报告。按照报告数据,对此阶段小鼠、大鼠、豚鼠、地鼠、兔、犬、猴和小型猪共 8 个品种的实验动物按照品种、等级、单位等进行分类,分析质量问题,并与 2014—2016 年同期实验动物质量比对,分析变化趋势。 结果 2017—2019 年分别抽检动物 144、131 和 135 批次,检出不合格批次分别为 30、15 和 17 批。 不合格主要因素为兔、犬及猪免疫不达标(20 批) ,病原感染 20 批,未发现遗传变异。 与 2014—2016 年同期相比,未检出遗传问题相同,免疫不达标状况好转,但病原感染出现上升。 结论 通过质量分析比对,能够为实验动物产业健康发展提供数据支持。 相似文献
3.
Synthesis of Small‐Sized,Porous, and Low‐Toxic Magnetite Nanoparticles by Thin POSS Silica Coating
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Dr. Swee Kuan Yen D. Prathyusha Varma Wei Mei Guo Dr. Vincent H. B. Ho Dr. Vimalan Vijayaragavan Dr. Parasuraman Padmanabhan Prof. Kishore Bhakoo Prof. Subramanian Tamil Selvan 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(10):3914-3918
In this communication, we report the synthesis of small‐sized (<10 nm), water‐soluble, magnetic nanoparticles (MNPs) coated with polyhedral oligomeric silsesquioxanes (POSS), which contain either polyethylene glycol (PEG) or octa(tetramethylammonium) (OctaTMA) as functional groups. The POSS‐coated MNPs exhibit superparamagnetic behavior with saturation magnetic moments (51–53 emu g?1) comparable to silica‐coated MNPs. They also provide good colloidal stability at different pH and salt concentrations, and low cytotoxicity to MCF‐7 human breast epithelial cells. The relaxivity data and magnetic resonance (MR) phantom images demonstrate the potential application of these MNPs in bioimaging. 相似文献
4.
Dr. Nozomi Mihara Dr. Yasuyuki Yamada Dr. Hikaru Takaya Prof. Yasutaka Kitagawa Dr. Kazunobu Igawa Prof. Katsuhiko Tomooka Prof. Hiroshi Fujii Prof. Kentaro Tanaka 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(13):3369-3375
Development of supramolecular methods to further activate a highly reactive intermediate is a fascinating strategy to create novel potent catalysts for activation of inert chemicals. Herein, a supramolecular approach to enhance the oxidizing ability of a high-valent oxo species of a nitrido-bridged iron porphyrinoid dimer that is a known potent molecular catalyst for light alkane oxidation is reported. For this purpose, a nitrido-bridged dinuclear iron complex of porphyrin-phthalocyanine heterodimer 3 5+, which is connected through a fourfold rotaxane, was prepared. Heterodimer 3 5+ catalyzed ethane oxidation in the presence of H2O2 at a relatively low temperature. The site-selective complexation of 3 5+ with an additional anionic porphyrin (TPPS4−) through π–π stacking and electrostatic interactions afforded a stable 1:1 complex. It was demonstrated that the supramolecular post-synthetic modification of 3 5+ enhances its catalytic activity efficiently. Moreover, supramolecular conjugates achieved higher catalytic ethane oxidation activity than nitrido-bridged iron phthalocyanine dimer, which is the most potent iron-oxo-based molecular catalyst for light-alkane oxidation reported so far. Electrochemical measurements proved that the electronic perturbation from TPPS4− to 3 5+ enhanced the catalytic activity. 相似文献
5.
Elsye Agustina Jeungchoon Goak Suntae Lee Youngho Seo Jun-Young Park Naesung Lee 《ChemistryOpen》2015,4(5):613-619
Iron catalysts have been used widely for the mass production of carbon nanotubes (CNTs) with high yield. In this study, UV/visible spectroscopy was used to determine the Fe catalyst content in CNTs using a colorimetric technique. Fe ions in solution form red–orange complexes with 1,10-phenanthroline, producing an absorption peak at λ=510 nm, the intensity of which is proportional to the solution Fe concentration. A series of standard Fe solutions were formulated to establish the relationship between optical absorbance and Fe concentration. Many Fe catalysts were microscopically observed to be encased by graphitic layers, thus preventing their extraction. Fe catalyst dissolution from CNTs was investigated with various single and mixed acids, and Fe concentration was found to be highest with CNTs being held at reflux in HClO4/HNO3 and H2SO4/HNO3 mixtures. This novel colorimetric method to measure Fe concentrations by UV/Vis spectroscopy was validated by inductively coupled plasma optical emission spectroscopy, indicating its reliability and applicability to asses Fe content in CNTs. 相似文献
6.
A new dinuclear iron(Ⅲ) complex has been synthesized and structurally characterized by X-ray crystallography: [FeⅢ2(L)(C6H5COO)(SO4)(CH3OH)2]·CH3CN·CH3OH(1, H3 L = N,N'-bis(salicylidene)-1,3-diamino-2-propanol). Complex 1 belongs to orthorhombic space group Pna21 with a = 11.4400(8), b = 22.9705(2), c = 12.5712(9) , V = 3303.5(4) 3, Z = 4, F(000) = 1576, Dc = 1.531 g·cm–3, Mr = 761.36, μ = 1.007 mm–1, S = 1.014, the final R = 0.0505 and wR = 0.1018. The crystal packing is stabilized by intermolecular O–H···O hydrogen bonds, forming an extended one-dimensional chain structure. The temperature dependence of magnetic susceptibility measurement shows that antiferromagnetic interaction is propagated between the metal centers. Fit as dinuclear arrangement gave parameters of J = 19.7 cm-1, g = 1.89 and R2 = 0.9999. 相似文献
7.
李云晋 《大理学院学报:综合版》2004,3(4):1-3,8
根据现有考古资料,从考古学的角度,概述了洱海区域新石器时代文化遗址的分布与类型、文化特征及文化渊源,证实了该区域新石器文化是在古人类文化的基础上而产生,并不断地汲取其它文化因素,形成了自成一体的区域地方性新石器文化. 相似文献
8.
文章以调查典型县现状年灌溉用水定额为基础 ,以当地灌溉水可利用量为控制条件 ,采用逐级平衡的办法 ,制定吕梁区主要作物的灌溉用水定额 相似文献
9.
加强法制建设促进珠江上游经济环保整体发展 总被引:1,自引:0,他引:1
李克艳 《曲靖师范学院学报》2003,22(4):31-34
珠江上游南、北盘江流域水土流失严重,生态环境不断恶化,严重影响了该地区经济的可持续发展。法制建设在该地区环境保护中起着至关重要的作用,只有通过法律制度的不断创新和完善,才能为该地区的环境治理提供有效的法律保障,最终达到环境保护与经济发展的和谐统一。 相似文献
10.
研究了RE_Mg合金对固体粉末法硼、铬、铝共渗层成分、组织和性能的影响 .发现随着RE_Mg合金加入量的增加 ,渗层中Al2 O3的量不断增多 ,当RE_Mg合金加入量为 5 %时 ,渗层中出现连续致密分布的Al2 O3黑区组织 ,对此进行了性能测试和机理探讨 相似文献