Electronic Structures, (d-p)π Conjugation Effects, and Spectroscopic Properties of Polyoxometalates: M6O19 2− (M=Cr, Mo, W)

The electronic structures and bonding of isopoly oxometalates M₆O₁₉ ^2– (M=Cr, Mo, W) have been investigated by using ab initio and relativistic density functional methods. We have discussed the role of the central oxygen atom and the (d-p) conjugation interactions between the metal and bridging oxygen atoms. It is found that there exist 12 three-centered two-electron (d-p-d) bonds for the three M₄(-O)₄ planar rings in M₆O₁₉ ^2– ions and these hexametalates are considered to have quasi-aromaticity. The (d-p) conjugation effects play essential role in stabilizing these cluster compounds, and the reduced (d-p) conjugation effects account for the instability of the isopoly oxochromate ion, Cr₆O₁₉ ^2–. The vibrational spectra and electronic spectra of M₆O₁₉ ^2– ions are evaluated and assigned theoretically and the calculated spectra are in fairly good agreement with the measured experimental results.     

19F-NMR-spektroskopischer Nachweis und Berechnung der statistischen Bildung der gemischten Clusteranionen [(Mo6BrCl)F]2−, n = 0 – 8

¹⁹F NMR Spectroscopic Evidence and Calculation of the Statistical Formation of Mixed Cluster Anions [(Mo₆Br Cl )F ]^2?, n = 0 – 8 The complete system of the innersphere mixed clusters (Mo₆BrCl)⁴⁺ is formed by exchange of innersphere bound Clⁱ against outersphere bound Br^a on tempering the solid [(Mo₆Cl)Br] at 500°C for 16 h. After conversion with conc. HCl into (H₃O)₂[(Mo₆BrCl)Cl] and precipitation of the outer Cl^a with AgBF₄ in ethanol, treatment with tetrabutylammonium(TBA)fluoride yields (TBA)₂ [(Mo₆BrCl)F], a mixture of 22 different species. According to the sets of chemical equivalent fluorine atoms in total 55 ¹⁹F nmr signals are expected, which are really observed in the high resolution 1D-¹⁹F-nmr spectrum. Using increments of chemical shifts, peak intensities and multiplet structures as well as the 2D-¹⁹F/¹⁹F-COSY spectrum the complete and unambiguous assignment of all resonances is achieved. From the measured integral intensities the distribution of the different compounds is determined, revealing statistical formation of the geometrical isomers.     

Reaction of a 5α-bromo-6β,19-epoxysteroid with BF3·Et2O/Ac2O: An evidence of a cyclic bromonium cation

Treatment of 3β-acetoxy-5-bromo-6β,19-epoxy-5α-androstan-17-one with Ac₂O and BF₃·OEt₂, produced the cleavage of the epoxy moiety and migration of the bromine atom to afford 3β,19-diacetoxy-6α-bromo-5-hydroxy-5β-androst-17-one in high yield.     

Evaluation of the reactivity of new activated difluoroaromatic compounds

To evaluate the reactivity of new difluroroaromatic compounds in nucleophilic substitution, the positive charges on carbon atoms of C−F bonds were calculated using the quantum-chemical semiempirical PM3 method. A correlation between the charges calculated and the chemical shifts in the¹⁹F NMR spectra was established. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 623–625, April, 1998.     

正则地稳定环和模的稳定同构

设R是一个含幺结合环。如果任意两个稳定同构的有限生成投射R－模均是同构的，则称R是强Hermitian环；如果对任意正则元a,b∈R且aR bR=R,均存在y∈R使得a by可逆，则称R是正则地稳定环。本文证明了环R是强Hermitian环，当且仅当对任意自然数n有Mn(R)是正则地稳定环。还给出了正则地稳定环的一些性质和刻画。     

BaAl12O19高温热稳定材料制备方法

ＢａＡｌ１２Ｏ１９是一种被用于高温催化燃烧的β－Ａｌ２Ｏ３型材料．在其制备过程中可采用柠檬酸盐无定形前驱体法．它在１３０℃的分解反映出硝酸盐与自由羰基的相互作用；３６０℃的分解对应于柠檬酸盐的氧化；在８００℃时，ＢａＣＯ３分解并生成ＢａＡｌ２Ｏ４．ＢａＡｌ２Ｏ４的产生并没有抑制ＢａＡｌ１２Ｏ１９的形成．形成ＢａＡｌ１２Ｏ１９的另一条途径是γ－Ａｌ２Ｏ３同分散相Ｂａ２＋之间的反应     

Insecticidal activity of residual Bt protein at the second trophic level

Since the first commercial release of transgenic crop expressing genes from Bacillus thuringiensis (Bt), there have been concerns about its potential impact on the environment. Research has focused on the ecological effects from second exposure to Bt prot…     

可压Euler方程的格子Boltzmann方法:二维情形

根据微观和宏观之间的质量、动量和能量守恒原理，构建了一个可用于模拟可压流体的D2V19格子Boltzmann模型，利用Chapman—Enskog分析可从该模型推导出宏观流体力学方程-Euler方程．利用该模型对三种典型激波管进行数值模拟并与Riemann解析解进行比较和分析，发现该模型能较好的捕捉激波，精度令人满意，证明了该模型对可压流体的适用性．该模型适用于气体多方指数为任意值的系统．     

蓬莱19-3油田溢油事件及其应急管理综述

当今社会并不太平,不管是自然因素还是人为因素,都引发了各种类型的突发事件。频繁发生的突发事件对人们的生命财产造成了极大的损失。蓬莱19-3油田溢油事件的发生不仅造成了比较严重的经济、环境和社会影响,还会推动我国的石油发展战略以及海洋石油开发技术,并会将中国的应急管理引向一个新的方向。本文将从中国的应急管理、蓬莱19-3油田溢油事件造成的影响以及启示三个方面,深入分析此次事故带来的影响。     

Electrospun Aspirin/Eudragit/Lipid Hybrid Nanofibers for Colon-targeted Delivery Using an Energy-saving Process

Both electrospinning apparatus and their commercial pro-ducts are extending their applications in a wide variety of fields. However, very limited reports can be found about how to implement an energy-saving process and in turn to reduce the production cost. In this paper, a brand-new type of coaxial spinneret with a solid core and its electrospinning methods are developed. A novel sort of medicated Eudragit/lipid hybrid nanofibers are gene-rated for providing a colon-targeted sustained release of aspirin. A series of characterizations demonstrates that the as-prepared hybrid nanofibers have a fine linear morphology with the aspirin/lipid separated from the matrix Eudragit to form many tiny islands. In vitro dissolution tests exhibit that the hybrid nanofibers are able to effectively prevent the release of aspirin under an acid condition (8.7%±3.4% for the first two hours), whereas prolong the drug release time period under a neutral condition(99.7±4.2% at the se-venth hour). The energy-saving mechanism is discussed in detail. The prepared aspirin-loaded hybrid nanofibers can be further transferred into an oral dosage form for potential application in counte-ring COVID-19 in the future.