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951.
Hang Xu Chun‐Shuai Cao Han‐Shi Hu Shi‐Bin Wang Jin‐Cheng Liu Peng Cheng Nikolas Kaltsoyannis Jun Li Bin Zhao 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(18):6083-6088
Assembled from [Th48Ni6] nanocages, the first transition‐metal (TM)‐thorium metal–organic framework (MOF, 1 ) has been synthesized and structurally characterized. 1 exhibits high solvent and acid/base stability, and resistance to 400 kGy β irradiation. Notably, 1 captures ReO4? (an analogue of radioactive 99TcO4?, a key species in nuclear wastes) with a maximum capacity of 807 mg g?1, falling among the largest values known to date. Furthermore, 1 can enrich methylene blue (MB) and can also serve as an effective and recyclable catalyst for CO2 fixation with epoxides; there is no significant loss of catalytic activity after 10 cycles. Theoretical studies with nucleus‐independent chemical shifts and natural bond orbital analysis reveal that the [Th6O8] clusters in 1 have a unique stable electronic structure with (d–p)π aromaticity, partially rationalising 1 ′s stability. 相似文献
952.
953.
Density functional theory was employed to investigate rhodium(I)‐catalyzed C–C bond activation of siloxyvinylcyclopropanes and diazoesters. The B3LYP/6‐31G(d,p) level (LANL2DZ(f) for Rh) was used to optimize completely all intermediates and transition states. The computational results revealed that the most favorable pathway was the channel forming the methyl‐branched acyclic product p1 in path A (cyclooctadiene (cod) as the ligand), and the oxidative addition was the rate‐determining step for this channel. It proceeded mainly through the complexation of diazoester to rhodium, rhodium–carbene formation, coordination of siloxyvinylcyclopropane, oxidative addition (C2–C3 bond cleavage) of siloxyvinylcyclopropane, carbene migratory insertion, β‐hydrogen elimination and reductive elimination. The complexation of diazoester to rhodium occurred prior to the coordination of siloxyvinylcyclopropane. Also, the role of the ligands cod, chlorine and 1,4‐dioxane, the effect of di‐rhodium catalyst and the solvent effect are discussed in detail. 相似文献
954.
An efficient and practical route to β‐keto sulfones has been developed through heterogeneous oxidative coupling of oxime acetates with sodium sulfinates by using an MCM‐41‐supported Schiff base‐pyridine bidentate copper (II) complex [MCM‐41‐Sb,Py‐Cu (OAc)2] as the catalyst and oxime acetates as an internal oxidant, followed by hydrolysis. The reaction generates a variety of β‐keto sulfones in good to excellent yields. This new heterogeneous copper (II) catalyst can be easily prepared via a simple procedure from readily available and inexpensive reagents and exhibits the same catalytic activity as Cu (OAc)2. MCM‐41‐Sb,Py‐Cu (OAc)2 is also easy to recover and is recyclable up to eight times with almost consistent activity. 相似文献
955.
Yulya N. Biglova Rauilya N. Malikova Svetlana F. Petrova Sergey P. Ivanov Ilshat M. Sakhautdinov Akhat G. Mustafin 《国际化学动力学杂志》2019,51(5):311-320
The kinetics of nucleophilic fullerene cyclopropanation by halomethyl ketones with a diterpene fragment has been studied by the Bingel method, and the influence of the biologically active cyclopropanating agent on the process has been estimated. It has been revealed that favorable conditions for carrying out the reaction result in maximum monofunctionalized methanofullerenes formation with the maximum yield. 相似文献
956.
Josué M. Silla Laize A.F. Andrade Matheus P. Freitas 《Magnetic resonance in chemistry : MRC》2019,57(7):373-379
The Perlin effect and its analog for fluorinated compounds (the fluorine Perlin-like effect) manifest on one-bond C─H (C─F for the fluorine Perlin-like effect) spin–spin coupling constants (SSCCs) in six-membered rings. These effects can be useful to probe the stereochemistry (axial or equatorial) of the C─H and C─F bonds, respectively. The origin of these effects has been debatable in the literature as being due to hyperconjugative interactions, dipolar effects, and induced current density. Accordingly, a variety of model compounds has been used to probe such effects since the cyclohexanone carbonyl group and the endocyclic heteroatom lone pairs play different roles on the above-mentioned effects. Thus, the 1JC─F SSCC in fluorinated lactams and lactones were theoretically studied to gain further insight on the nature of the fluorine Perlin-like effect. In addition, because the intramolecular α-effect has recently gained attention for its importance in the reactivity and stereoelectronic interactions in peroxide compounds, some fluorinated 1,2-dioxanes and 1,2-dithianes were studied to evaluate the role of the α-effect on the behavior of 1JC─F SSCCs. Differently from fluorinated ketones and ethers, the fluorine Perlin-like effect in the amides and esters cannot be explained by hyperconjugative or dipolar interactions alone, because the resonance in these groups affect the 1JC─F values. The O─O and S─S-containing systems exhibit a strong fluorine Perlin-like effect, but unlike the α-effect, this behavior cannot be explained neither by hyperconjugation nor by dipolar interactions alone; the spatial proximity of the C─F and O─O/S─S bonds is proposed to affect the magnitude of the 1JC─F SSCC. 相似文献
957.
Based on rigorous analysis of finite element method (FEM), moment method (MoM), and curves fitting techniques, a set of closed-form formulas for the characteristic impedance and the primary (L and C) parameters of the shielded split ring line, are presented. The general expressions give a good accuracy for a wide-range of discontinuity angles and are suitable for all shielded split ring lines which have an outer–inner conductors radius ratio between 2 and 10. These expressions can be easily implemented in CAD simulation tools, to design many components as RF resonators, filters, transmission lines, for wireless communication and probes for material characterization. The results of the design of an RF resonator using the shielded split ring line are presented. 相似文献
958.
La2O3对TiAl合金激光熔覆γ/Cr7C3/TiC 复合材料涂层组织与性能的影响 总被引:3,自引:0,他引:3
研究了添加不同含量稀土氧化物La2O3对TiAl合金预涂NiCr-Cr3C2混合粉末激光熔覆复合材料涂层组织、耐磨性及抗氧化性能的影响,分析了La2O3的作用机理。结果表明,激光熔覆涂层的组织主要由大量较规则初生块状Cr2C3,细小粒状或树枝状TiC以及γ/Cr2C3共晶组成;随着La2O3的加入,初生相明显细化、球化,共晶组织数量增多,适当的(质量分数4%)La2O3的添加能提高涂层的硬度、韧性和耐磨性,并改善其抗氧化性能。这主要是由于稀土元素对显微组织的细化和涂层的净化作用,显微组织的细化提高了涂层的强度、韧性和硬度,而涂层的净化可以降低其夹杂物的含量,进而提高氧化膜的致密性和附着性,这些都有利于提高其耐磨性和抗氧化性。 相似文献
959.
醋酸甲羟孕酮与β-环糊精包络作用的光谱研究及应用 总被引:1,自引:0,他引:1
用紫外吸收、荧光光谱法对水溶液中β-环糊精(β-CD)与醋酸甲羟孕酮(MA)主客体包络物的光谱行为进行了研究.利用改进的Benesi-Hildebrand法测定了包络物的形成常数,初步探讨了某些水溶性一元醇的引入对该包络物形成及荧光性质的影响,并提出了测定MA的高灵敏度荧光光度新方法,方法的最低检出限为8.9×10-9mol·L-1.用该法测定样品中MA的结果令人满意,回收率为97.9%~101.7%,平均回收率为99.9%(n=5) 相似文献
960.
本文研究了在阴-非离子表面活性剂SDS-TritonX-100存在下,用Cadion 2B分光光度法测定银,发现DMF介质的增溶、增敏、增稳效果均好.配合物的最大吸收波长为560nm,表现摩尔吸光系数为1.23×10~5L·mol~(-1)·cm~(-1),Ag(Ⅰ)在0—18μg/25ml范围内服从比耳定律.该方法操作简便、快速,选择性好,可直接用于废水中微量银的测定,结果满意. 相似文献