A novel arylation of arylacetic acid esters using tertiary arylamines and TiCl4

The reactions of arylacetic acid esters with tertiary arylamines in the presence of TiCl₄ give α-arylated products in 65-90% yields, as well as 10-20% yields of the corresponding benzidines.     

含有偏好的DEA-BWM评价方法研究

针对传统的DEA模型在评估过程中并未考虑决策者对相关指标权重的偏好,将最优最差方法(BWM)嵌入到传统DEA模型中,基于决策者偏好排序的判断矩阵,构建一种含有偏好的DEA-BWM评价方法。首先在保持传统DEA方法的优势基础上,构建了CCR-BWM评价模型对各DMU进行评价。同时考虑为了便于各决策单元在统一权重基础上相互比较,构建了CSW-BWM公共权重模型。另外考虑决策单元自评和互评,构建了NCE-BWM中立型交叉效率。然后采用min-max方法分别将上述三种多目标评价模型转换为单目标线性规划进行求解。最后,选择一组算例对三种模型的有效性与合理性进行验证。     

A stream tube model for miscible flow

A simple theoretical model is described for deriving a 1-dimensional equation for the spreading of a tracer in a steady flow at the field scale. The originality of the model is to use a stochastic appoach not in the 3-dimensional space but in the 1-D space of the stream tubes. The simplicity of calculation comes from the local relationship between permeability and velocity in a 1-D flow. The spreading of a tracer front is due to local variations in the cross-sectional area of the stream tubes, which induces randomness in travel time. The derived transport equation is averaged in the main flow direction. It differs from the standard dispersion equation. The roles of time and space variables are exchanged. This result can be explained by using the statistical theory of Continuous Time Random Walk instead of a standard Random Walk. However, the two equations are very close, since their solutions have the same first and second moments. Dispersivity is found to be equal to the product of the correlation length by the variance of the logarithm of permeability, a result similar to Gelhar's macrodispersion.Nomenclature A total cross-section area of the sample - C (resident) concentration of tracer - D,D ^* dispersion coefficient - F flux of tracer - G probability distribution function for permeability in the stream-tube segments - I tracer intensity (mass crossing a surface per unit time) - K permeability - L length of the medium - M number of stream tubes in the medium - N number of segments along a stream tube - P pressure - Q total flow rate in the sample - a length of an elementary stream-tube segment - g probability distribution function for permeability in the space - i, j indices, tube numbers - q flow rate in each stream tube - s variable cross-section area of a stream tube - t, t time - u front velocity - x space variable in the flow direction - small local variation in time - , _t longitudinal, transverse dispersivity - porosity of the porous medium - correlation length in the permeability field - viscosity of the fluid - time for filling an elementary stream tube segment - standard deviation of a stochastic variable - probability distribution of arrival times (Gaussian)     

LOWLAD: a locally weightedL 1 smoothing spline algorithm with cross validated choice of smoothing parameters

The computation ofL ₁ smoothing splines on large data sets is often desirable, but computationally infeasible. A locally weighted, LAD smoothing spline based smoother is suggested, and preliminary results will be discussed. Specifically, one can seek smoothing splines in the spacesW _m (D), with [0, 1] ⁿ D. We assume data of the formy _i =f(t _i )+ _i ,i=1,..., N with {t _i } _i=1 ^N D, the _i are errors withE( _i )=0, andf is assumed to be inW _m . An LAD smoothing spline is the solution,s , of the following optimization problem

AnL 1 smoothing spline algorithm with cross validation

We propose an algorithm for the computation ofL ₁ (LAD) smoothing splines in the spacesW _M (D), with . We assume one is given data of the formy _i =(f(t _i ) + _i , i=1,...,N with {itt_i} _i=1 ^{N D} , the _i are errors withE( _i )=0, andf is assumed to be inW _M . The LAD smoothing spline, for fixed smoothing parameter0, is defined as the solution,s , of the optimization problem (1/N) _i=1 ^N ¦y _i –g(t _i ¦+J _M (g), whereJ _M (g) is the seminorm consisting of the sum of the squaredL ₂ norms of theMth partial derivatives ofg. Such an LAD smoothing spline,s , would be expected to give robust smoothed estimates off in situations where the _i are from a distribution with heavy tails. The solution to such a problem is a thin plate spline of known form. An algorithm for computings is given which is based on considering a sequence of quadratic programming problems whose structure is guided by the optimality conditions for the above convex minimization problem, and which are solved readily, if a good initial point is available. The data driven selection of the smoothing parameter is achieved by minimizing aCV() score of the form .The combined LAD-CV smoothing spline algorithm is a continuation scheme in 0 taken on the above SQPs parametrized in, with the optimal smoothing parameter taken to be that value of at which theCV() score first begins to increase. The feasibility of constructing the LAD-CV smoothing spline is illustrated by an application to a problem in environment data interpretation.     

Measurements of HO2 uptake coefficient on aqueous (NH4)2SO4 aerosol using aerosol flow tube with LIF system

The γ(HO₂) was elevated with increase of Cu(II) concentrations in aqueous (NH₄)₂SO₄ aerosol. The threshold of Cu(II) concentration was 10^-3 mol/L for the dramatic increase of γ(HO₂) to 0.1, suggesting sensitive γ(HO₂) value to concentration of transition metal ions in aerosol.     

Evidence of a phase transition of RbHCO3 from high-resolution solid-state 13C and 87Rb NMR by comparison with KHCO3

A variable-temperature high-resolution 13C and 87Rb solid-state NMR study of powder rubidium hydrogencarbonate, RbHCO3, is presented for the first time. At ambient temperature, RbHCO3 is formed by centrosymmetric dimers linked by hydrogen bonds, but almost no information is available on this compound concerning proton disorder and the low-temperature phase. However, potassium hydrogencarbonate, KHCO3, which has an isomorphic structure for the high temperature phase, was well studied: it undergoes a non-ferroic, non-ferroelectric phase transition at Tc = 318 K between two monoclinic structures. The protons are disordered in an asymmetric double-well potential in the low-temperature phase, and the double-well potential becomes symmetric in the high-temperature phase. By comparison with recent solid-state NMR experimental results on KHCO3, we show that RbHCO3 undergoes a phase transition at Tc approximately 245 K, and give evidence that the proton dynamic disorder in both compounds is very similar.     

石墨炉原子吸收法中热解涂层石墨管在无标准分析法测定环境样品中铬的应用

本文探讨了热解涂层石墨管测定铬的最佳实验条件,研究了各种酸和干扰物质的基体效应,提出用浓氨水为基体改进剂克服高氯酸的干扰。比较了各原子化温度时的理论和实验特征量。使热解涂层石墨管有可能用于无标准分析法测定各种环境样品中的铬。     

石墨炉原子吸收法测定钒的研究

本文比较了在标准石墨管,热解涂层和全热解石墨管中钒的吸收信号形状。用全热解石墨管和EDTA铵盐作基体改进剂,直接测定水系沉积物中痕量钒。方法的特征量为61pg/0.0044A。     

原子吸收光谱法测定拉伸断口铬镍钼钛钢样品中主成分

研究了毫克级铬镍钼风样品中主成分镍的火焰原子吸收光谱法（FAAS法）和铬、钼、钒、钛、铝的塞曼恒温平台石墨炉原子吸收光谱法（ZSTPF－AAS法）。采用了微波溶样技术作为防污染样品预处理技术，采用石墨管硅涂层改进技术提高了仪器的测试精度。其中铬、镍、钼、钒、钛、铝的相对标准偏差分别为2.7%,0.97%,8.6%,7.3%,1.7%,7.3%。其加标回收率分别为96.5%,97%,96.7%,93%,98%,91%。通过分析，发现在较低温度下铬镍钼钛钢断面上有轻微的钼偏析现象，可能是拉伸断裂的主要化学影响因素。