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121.
In the presence of n-Bu4NBr acting as phase-transfer reagent, n-Bu4N+ salts of organophosphoryl polyoxotungstate derivatives [RP(O)]2X
n+W11O39
(8–n)– [R = PhCH2CH2P(O), X = P, Si; R = C6H11P(O); X = Ge, Ga] have been prepared and characterized by elemental analysis, i.r., 31P- and 183W-n.m.r. spectroscopy. According to the elemental analysis and spectroscopic data, the hybrid anions consist of an -[XW11O39] framework on which are grafted two equivalent organophosphoryl groups through P—O—W bridges; these new species still retain the Keggin structure. The six-line 183W spectrum indicates that hybrid anions possess C
s symmetry in MeCN. 相似文献
122.
β-Trifluoroacetyl vinyl ethers ROCHCHCOCF3 react smoothly as dienophiles with α,β-unsaturated carbonyl compounds to give the unexpected 2-alkoxyl-5-trifluoroacetyl-3,4-dihydro-2H pyrans. These products are formed by elimination and addition of the alcohol to the products of the normal hetero Diels-Alder reaction (2-alkoxyl-3-trifluoroacetyl-2,3-dihydro-2H pyrans). In contrast, 1,3-dipolar cycloaddition of ROCHCHCOCF3 with ArCHN(O)Me proceeds via a Z-endo transition state to give regio- and stereospecific 4-trifluoroacetyl substituted isoxazolidines and their derivatives. 相似文献
123.
Yao Zhu Siyuan Fang Shaoqin Chen Youjie Tong Chunling Wang Yun Hang Hu 《Chemical science》2021,12(16):5825
Photocatalytic ethane conversion into value-added chemicals is a great challenge especially under visible light irradiation. The production of ethyl hydroperoxide (CH3CH2OOH), which is a promising radical reservoir for regulating the oxidative stress in cells, is even more challenging due to its facile decomposition. Here, we demonstrated a design of a highly efficient visible-light-responsive photocatalyst, Au/WO3, for ethane oxidation into CH3CH2OOH, achieving an impressive yield of 1887 μmol gcat−1 in two hours under visible light irradiation at room temperature for the first time. Furthermore, thermal energy was introduced into the photocatalytic system to increase the driving force for ethane oxidation, enhancing CH3CH2OOH production by six times to 11 233 μmol gcat−1 at 100 °C and achieving a significant apparent quantum efficiency of 17.9% at 450 nm. In addition, trapping active species and isotope-labeling reactants revealed the reaction pathway. These findings pave the way for scalable ethane conversion into CH3CH2OOH as a potential anticancer drug.Highly efficient visible-light driven photocatalytic oxidation of ethane into ethyl hydroperoxide was realized for the first time over Au/WO3. 相似文献
124.
125.
MingZhuLIU ShengYiZHANG YuHuaSHEN MingLiangZHANG 《中国化学快报》2004,15(10):1249-1252
Selenium nanoparticles were prepared by a reverse microemulsion system. Sodium selenosulfate was used as selenium source. The results showed that hydrochloric acid concentration and reaction temperature had great influence on the morphology of products. The crystalline selenium nanowires and amorphous selenium nanorods were obtained in given condition. 相似文献
126.
127.
Group theoretic methods are presented for the transformations of integrals and the evaluation of matrix elements encountered in multiconfigurational self-consistent field (MCSCF) and configuration interaction (CI) calculations. The method has the advantages of needing only to deal with a symmetry unique set of atomic orbitals (AO) integrals and transformation from unique atomic integrals to unique molecular integrals rather than with all of them. Hamiltonian matrix element is expressed by a linear combination of product terms of many-center unique integrals and geometric factors. The group symmetry localized orbitals as atomic and molecular orbitals are a key feature of this algorithm. The method provides an alternative to traditional method that requires a table of coupling coefficients for products of the irreducible representations of the molecular point group. Geometric factors effectively eliminate these coupling coefficients. The saving of time and space in integral computations and transformations is analyzed. © 1994 by John Wiley & Sons, Inc. 相似文献
128.
采用二硫化碳重结晶富勒烯混合物或二硫化碳二次抽提烟灰以提取高富勒烯(higherfulerenes,Cn,n>70)。产物经高效液相色谱分析,高富勒烯的含量从1%分别提高到4%和6%;经激光飞行时间质谱证明,产物中除含主要成分C60和C70以外,还含有C76、C78、C82、C84以及更高碳原子的富勒烯。 相似文献
129.
碳氟链与碳氢链表面活性剂在固液界面上的吸附 总被引:1,自引:0,他引:1
全氟辛酸及其钠盐和十二烷基硫酸钠在R972上的吸附等温线均为S型或LS型,指示固液界面吸附过程中有表面疏水缔合物生成.碳氟表面活性剂的饱和吸附量显著高于碳氢表面活性剂的饱和吸附量.加电解质于液相使各体系吸附量上升.对于碳氟表面活性剂,甚至引起吸附等温线类型变化.例如,不加电解质时全氟辛酸在R972上的吸附等温线为S型,而加入HCl(c=0.05mol·dm-3)使吸附等混线变成LS型.全氟辛酸比全氟辛酸钠在R972上的吸附更强.几种表面活性剂在R972上的吸附均随温度升高而减少。应用两阶段吸附模型及通用吸附等温线公式可以很好地解释所得实验结果. 相似文献
130.
Useful methodology is described for the synthesis of dehydroalanine residues (II) within peptides. The unnatural amino acid (Se)-phenylselenocysteine (I) can be incorporated into growing peptide chains via standard peptide synthesis procedures. Subsequent oxidative elimination affords a dehydroalanine at the desired position. The oxidation conditions are mild and tolerate functionalities commonly found in peptides, including variously protected cysteine residues. To illustrate its utility, cyclic lanthionines have been synthesized by this method. 相似文献