Caesium carbonate supported on hydroxyapatite‐encapsulated Ni0.5Zn0.5Fe2O4 nanocrystallites as a novel magnetically basic catalyst for the one‐pot synthesis of pyrazolo[1,2‐b]phthalazine‐5,10‐diones

A novel nanomagnetic basic catalyst of caesium carbonate supported on hydroxyapatite‐coated Ni_0.5Zn_0.5Fe₂O₄ magnetic nanoparticles (Ni_0.5Zn_0.5Fe₂O₄@HAP‐Cs₂CO₃) was prepared. This new catalyst was fully characterized using Fourier transform infrared spectroscopy, transmission and scanning electron microscopy, X‐ray diffraction and vibrating sample magnetometry techniques, and then the catalytic activity of this catalyst was investigated in the synthesis of 1H‐pyrazolo[1,2‐b]phthalazine‐5,10‐dione derivatives. Also, Ni_0.5Zn_0.5Fe₂O₄@HAP‐Cs₂CO₃ could be reused at least five times without significant loss of activity and could be recovered easily by applying an external magnet. Thus, the developed nanomagnetic catalyst is potentially useful for the green and economic production of organic compounds. Copyright © 2015 John Wiley & Sons, Ltd.     

Direct Transformation of Arenols Based on C—O Activation

In the view of substrate availability, atomic efficiency and cost, directly using arenols as coupling partners in cross‐coupling, would be one of the most attractive goals. Up to date, many efforts have been made to activate the C—O bond of phenols with different strategies, for example, through in‐situ formed intermediates, through a catalytic reductive dearomatization‐condensation‐rearomatization sequence or catalytic deoxygenation. In this review, we summarized recent advances in cross‐couplings of arenols as the electrophiles via C—O activation.     

Nano-sized Cu(II) and Zn(II) complexes and their use as a precursor for synthesis of CuO and ZnO nanoparticles: A study on their sonochemical synthesis,characterization, and DNA-binding/cleavage,anticancer, and antimicrobial activities

Two new divalent copper (C1) and zinc (C2) chelates having the formulae [M(PIMC)₂] (where M = Cu(II), Zn(II) and PIMC = Ligand [(E)-3-(((3-hydroxypyridin-2-yl)imino)methyl)-4H-chromen-4-one] were obtained and characterized by several techniques. Structures and geometries of the synthesized complexes were judged based on the results of alternative analytical and spectral tools supporting the proposed formulae. IR spectral data confirmed the coordination of the ligands to the copper and zinc centers as monobasic tridentate in the enol form. Thermal analysis, UV-Vis spectra and magnetic moment confirmed the geometry around the copper center to be tetrahedral, square pyramidal and octahedral. Study of the binding ability of the synthesized compounds with Circulating tumor DNA (CT-DNA) bas been evaluated applying UV-Vis spectral titration and viscosity measurements. The copper and zinc oxides were achieved from the copper and zinc nano-particles structures Schiff base complexes as the raw material after calcination for 5 hr at 600°C. On the other hand, synthesized of C1 and C2 NPs were used as suitable precursors to the preparation of CuO and ZnO NPs. Finally, the synthesized of the two complexes exhibited enhanced activity against the tested bacterial (Staphylococcus aureus and Escherichia Coli) and fungal strains (Candida albicans and Aspergillus fumigatus) as compared to HPIMC. Among all these synthesized compounds, C1 exhibits good cleaving ability compared to other newly synthesized C2.     

Theory of chemical bonds in metalloenzymes XXII: a concerted bond-switching mechanism for the oxygen–oxygen bond formation coupled with one electron transfer for water oxidation in the oxygen-evolving complex of photosystem II

ABSTRACT

QM(UB3LYP)/MM(AMBER) calculations were performed for the locations of the transition structure (TS) of the oxygen–oxygen (O–O) bond formation in the S₄ state of the oxygen-evolving complex (OEC) of photosystem II (PSII). The natural orbital (NO) analysis of the broken-symmetry (BS) solutions was also performed to elucidate the nature of the chemical bonds at TS on the basis of several chemical indices defined by the occupation numbers of NO. The computational results revealed a concerted bond switching (CBS) mechanism for the oxygen–oxygen bond formation coupled with the one-electron transfer (OET) for water oxidation in OEC of PSII. The orbital interaction between the σ-HOMO of the Mn(IV)₄–O₍₅₎ bond and the π*-LUMO of the Mn(V)₁=O₍₆₎ bond plays an important role for the concerted O–O bond formation for water oxidation in the CaMn₄O₆ cluster of OEC of PSII. One electron transfer (OET) from the π-HOMO of the Mn(V)₁=O₍₆₎ bond to the σ*-LUMO of the Mn(IV)₄–O₍₅₎ bond occurs for the formation of electron transfer diradical, where the generated anion radical [Mn(IV)₄–O₍₅₎]^-? part is relaxed to the ?Mn(III)₄?…?O₍₅₎^- structure and the cation radical [O₍₆₎=Mn(V)₁]⁺ ? part is relaxed to the ⁺O₍₆₎–Mn(IV)₁? structure because of the charge-spin separation for the electron-and hole-doped Mn–oxo bonds. Therefore, the local spins are responsible for the one-electron reductions of Mn(IV)₄->Mn(III)₄ and Mn(V)₁->Mn(IV)₁. On the other hand, the O₍₅₎^- and O₍₆₎⁺ sites generated undergo the O–O bond formation in the CaMn₄O₆ cluster. The Ca(II) ion in the cubane- skeleton of the CaMn₄O₆ cluster assists the above orbital interactions by the lowering of the orbital energy levels of π*-LUMO of Mn(V)₁=O₍₆₎ and σ*-LUMO of Mn(IV)₄–O₍₅₎, indicating an important role of its Lewis acidity. Present CBS mechanism for the O–O bond formation coupled with one electron reductions of the high-valent Mn ions is different from the conventional radical coupling (RC) and acid-base (AB) mechanisms for water oxidation in artificial and native photosynthesis systems. The proton-coupled electron transfer (PC-OET) mechanism for the O–O bond formation is also touched in relation to the CBS-OET mechanism.     

Surface of Ru/Fe2O3 catalysts used in water-gas shift reaction studied by auger electron spectrometry

Summary Carbon deposits on the surface ofRu/Fe₂O₃ catalysts used in the water-gas shift reaction have been investigated by Auger Electron Spectrometry. A correlation has been found between the thickness of the carbon deposit and the catalytic activity in WGSR. The carbon deposit covers the metallic active centers and blocks their contact with reagents. The dotting of the iron oxide support with sodium has been found to reduce the amount of carbon deposit. .      

C72,La2@C72几何结构和电子性质的计算研究

采用密度泛涵理论(density functional theory,DFT)中的广义梯度近似(generally gradient approximation,GGA)对富勒烯C72和内掺金属La富勒烯La2@C72三种同分异构体的几何结构和电子结构进行研究.发现在C72的三种同分异构体中,满足独立五边形规则(isolated-pentagon-rule,IPR)的C72(D6d)结构最为稳定;在La2@C72三种同分异构体中,有着两对两两相邻五元环(twofused-pentagon)的La2@C72(#10611)结构最为稳定,而满足IPR的La2@C72(D6d)的结构变成了最不稳定结构.从能级图和态密度图分析得知,笼子稳定性的变化与La原子的原子轨道与C72原子轨道之间的杂化有关.Mulliken电荷分析得知,La2@C72(#10611)的两个La原子共转移了约3个电子给C72,并且,它们几乎分布在整个C笼上,形成的电子结构为La23+@C3-72.净自旋分析得知,La2@C72(#10611)中La原子磁性完全淬灭.     

980 nm激发下Er3+/Yb3+共掺杂ZrO2-Al2O3粉末的上转换发光特性

通过固相反应法制备了Er3+/Yb3+共掺杂ZrO2-Al2O3粉末的样品,并对样品在980nm激光激发下的上转换发光特性进行了研究.从发射光谱可以发现,在可见光范围内有3个强的发光带,一个位于654nm附近的红光带和两个分别位于545nm、525nm附近的绿光带,分别对应于Er3+离子的以下辐射跃迁:4F9/2→4I15/2、4S3/2→4I15/2、2H11/2→4I15/2.其中又以Er3+离子的4F9/2→4I15/2跃迁产生的红色荧光辐射最强.对其上转换发光机制进行了分析,发现这三个发光过程都是双光子过程.对样品粉末进行了XRD检测,发现ZrO2主要以立方相为主,并且计算得到了这种立方结构的晶格常数.Al2O3固溶于ZrO2中,Al3+嵌入ZrO2后产生氧空位,导致ZrO2晶体的对称性降低,这种结构变化更有利于提高上转换效率,即上转换发光强度增强.     

SEPARATING SCN~- FROM DESULPHURIZATION WASTE SOLUTION OF COCKING PLANT BY D241 RESIN

1. INTRODUCTION In the process of coking plant, about 30%~35% sulfur is transformed to H2S and some other sulfide, which form impurity in coal gas together with NH3 and HCN. Only 0.1% H2S containing in air can lead to die, so it is very important to carry on desulphurization and decyanation with coal gas [1~3]. Currently desulphurization and decyanation craft technique have Dry Oxidation Technology, Wet Oxidation Technology and Liquid Absorption Technology [2] three main kinds. The…     

(Ni0.8Zn0.2Fe2O4)epoxy-PZT双层膜中的磁电效应

讨论了Ni_0.8Zn_0.2Fe₂O₄ (NZFO)与锆钛酸铅(PZT)的双层膜结构样品的磁电(ME)效应.NZFO粉料由溶胶-凝胶法制成，再经900℃热压，并高温烧结.在该双层膜中测量到了很强的磁电相互作用.发现横向的磁电效应比纵向效应大一个数量级，并且随NZFO烧结温度的提高而增加.当烧结温度从950℃上升到1380℃时，横向ME电压系数(α_E)的最大值变化范围为25.6 mV Am^-2≤α_E≤199.6 mV Am^-2.理论分析显示NZFO-PZT双层膜样品中ME效应源于NZFO与PZT之间相对良好的磁电耦合. 关键词： 镍铁氧体 PZT 热压法 ME效应     

Li3N、Mg3N2、Ca3N2催化作用的比较和分析

 Li₃N、Mg₃N₂和Ca₃N₂是高温高压下以hBN为原料合成cBN的催化剂。在实验中发现它们对常压高温下生成hBN的反应也表现出催化作用。对比了三种氮化物催化效果的差异，发现三种氮化物都只有在熔融状态下才能表现出催化效果，以及三种氮化物对生成hBN反应的催化效果与它们在高温高压下合成cBN反应的催化效果次序相似。提出了对合成hBN有催化作用的化合物也将对合成cBN表现出催化作用的观点。