SO_4~(2-)/M_xO_y型固体超强酸在有机合成中的应用

SO2 -4 /MxOy(M =Ti,Zr,Fe)是一新型的固体超强酸催化剂 .综述了近年来SO2 -4 /MxOy 型催化剂在有机合成中的应用 ,并对其今后的发展趋势作了预测 .     

New labdane-type diterpenoids from Leonurus heterophyllus SW

Five new natural labdane-type diterpenoids (5-9), designated leoheteronins A-E, together with four known diterpenoids (1-4), two phytosterols as a mixture of beta-sitosterol and stigmasterol, and the flavone genkwanin (10) were isolated from the aerial parts of Leonurus heterophyllus SW. (Lamiaceae) collected in northern Vietnam. Compound 1 was isolated for the first time from a Leonurus species, and 10 is considered to be a chemotaxonomic marker of the Leonurus genus. Their structures were determined using spectroscopic analyses.     

Interval estimation of the critical value in a general linear model

Summary This paper concerns interval estimation of the critical value θ which satisfies under the general linear model,Y _i =μ(x _i )+ε _i (i=1,2,···), where for and the functional forms off _j ^′ s are known. From an asymptotic expansion it is shown that, under reasonable conditions, the limiting distribution of is normal. Thus in the large-sample case a confidence interval for θ can be obtained. Such a result is useful when one is interested in carrying out a retrospective analysis rather than designing the experiment (as in the Kiefer-Wolfowitz procedure). In Section 3 a sequential procedure is considered for confidence intervals with fixed width 2d. It is shown that, for a given stopping variableN, is also asymptotically normal asd→0. Thus the coverage probability converges to 1−α (preassigned) asd→0. An example of application in estimating the phase parameter in circadian rhythms is given for the purpose of illustration. Research partially supported by the NSF Grant DMS-8502346.     

Homo-dinuclear σ-alkynyl complexes: past, present and opportunities

Homo-dinuclear alkynyl complexes with a distinct metal–metal bond constitute a rapidly growing field, where the focus is placed on compounds based on ruthenium, molybdenum, tungsten or rhodium. Interesting characteristics of these complexes include paramagnetism, intense charge-transfer absorptions, tunable bridging ligands, which may not be easily accessible in mononuclear acetylide systems. These complexes have significant potential for use in both molecular electronics and supramolecular chemistry. In this short account, previous work in this area is assessed, and each of the major groups of complexes is discussed in terms of both the synthetic strategies and structural motifs.     

A novel trilinear decomposition algorithm： Three-dimension non-negative matrix factorization

Non-negative matrix factorization(NMF)is a technique for dimensionality reduction by placing non-negativity constraints onthe matrix.Based on the PARAFAC model,NMF was extended for three-dimension data decomposition.The three-dimension non-negative matrix factorization(NMF3)algorithm,which was concise and easy to implement,was given in this paper.The NMF3algorithm implementation was based on elements but not on vectors.It could decompose a data array directly without unfolding,which was not similar to that the traditional algorithms do.It has been applied to the simulated data array decomposition andobtained reasonable results.It showed that NMF3 could be introduced for curve resolution in chemometrics.     

二甲基甲酰胺中四种钕盐的电导

通过电导测量研究了四种钕盐：Nd(CF3SO3)3、Nd(ClO4)3、Nd(NO3)3和NdCl3在极性非质子溶剂DMF中的电导性质.利用线性拟合方法求得在25 ℃下Nd(CF3SO3)3和Nd(ClO4)3的极限摩尔电导率分别为278.8和 280.7 S•cm2•mol－1.用间接方法求得Nd(NO3)3 与NdCl3 的极限摩尔电导率分别为297.2和287.3 S•cm2 •mol－1.在25～65 ℃温度范围内，Nd(CF3SO3)3和Nd(ClO4)3的电导率随温度呈线性变化. Nd(NO3)3和NdCl3的电导行为表现出明显的离子缔合.     

Highly efficient visible-light photocatalytic ethane oxidation into ethyl hydroperoxide as a radical reservoir

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 g_cat⁻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 g_cat⁻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.     

Intact size-selected Au(n) clusters on a TiO2(110)-(1 x 1) surface at room temperature

Experiments in which mass-selected gold clusters were deposited on a surface have found that the catalytic properties depend strongly on cluster size. However, these experiments have not established definitively that the clusters maintain their size after deposition. We report here work in which we deposit low kinetic energy, mass-selected Aun+ (n = 1-8) clusters on a rutile TiO2(1 x 1) surface and use ultrahigh vacuum scanning tunneling microscopy (UHV-STM) to determine their size and shape.     

Preparation of ZnO colloids by aggregation of the nanocrystal subunits

Colloidal ZnO particles with narrow size distribution were prepared via a sol-gel process by base-catalyzed hydrolysis of zinc acetate. The morphology of ordered arrays of the particles was recorded by SEM. SEM also reveals that these uniform particles were composed of tiny ZnO subunits (singlets) sized of several nanometers. The size of the singlets, which is confirmed by X-ray diffraction and UV-vis absorption spectra, increases as the aging time is prolonged. The size-selective formation of colloids by aggregation of nanosized subunits is proposed to consist of two-stage growth by nucleation of nanosized crystalline primary particles and their subsequent aggregation into polycrystalline secondary colloids. The aggregates are all spherical because the internal rearrangement processes are fast enough. The ZnO colloids, i.e., the aggregates, tend to self-assemble into well-ordered hexagonal close-packed structures. Room-temperature photoluminescence was characterized for green and aged ZnO.