分析测试中溶液体积测量的不确定度评定

对环境温度与溶液体积变动性的关系进行阐述.不确定度评定中要正确区分温度对容量器皿容积和对溶液体积的影响.溶液体积变动性的不确定度应根据其配制后温度的变化来评定,与容量器皿的校正温度无直接关系.文中对溶液体积不确定度评定中一些误区进行深入讨论.     

离子色谱法测定高纯硅溶胶成分标准物质中的钠、钾、钙、镁

研究了离子色谱法测定高纯硅溶胶成分标准物质中钠、钾、钙、镁的方法,实现了一次进样同时测定4种金属离子.分析了影响测量结果的主要因素,评定了测量不确定度.溶液稀释用容量器皿的不确定度、称量的不确定度以及样品处理的不确定度是测量结果不确定度的主要来源,并且容量的不确定度大于称量的不确定度.     

化学计量测试中不确定度评价的实例介绍

化学计量测试简单地说是为了不同的目的而采用不同的方法来确定测试结果的不确定度的方法,这些方法是多种多样的。因此对测试不确定度因素的分析也比较困难。另一方面确定不确定度的方法与测定结果的不确定度并不是一种简单直接的关系。论述了参照某一标准进行的小型测试的不确定度,也对一般性测试的实例进行了介绍。     

原子吸收光谱法测定铜阳极泥中Bi的不确定度评定

探讨了用原子吸收光谱法测定铜阳极泥中铋的不确定度的评定,阐述了测量结果不确定度主要来源于样品称量、试液定容体积和测量试液中铋的浓度产生的不确定度,计算了这些不确定的分量,最后计算出合成标准不确定度和扩展不确定度.通过评估,得出影响铋量测量不确定度的主要因素是测量试液中铋浓度时所引起的不确定度.     

火焰原子吸收光谱法测定空气中铬含量的不确定度评定

用火焰原子吸收光谱法测定空气中铬含量,评定了测定过程的不确定度,把不确定度分解为标准溶液及配制引入的不确定度、标准曲线拟合引入的不确定度和样品重复测定引入的不确定度等七个因素,系统分析并计算各不确定度分量和扩展不确定度.结果表明,其中采集样品引入的不确定度是主要影响因素,空气中铬含量为3.88 μg/m3时,扩展不确定度为0.12 μg/m3.     

ICP-AES测定糖果中铅质量分数的不确定度评定

建立了电感耦合等离子体发射光谱(ICP-AES)测定糖果中铅的相应数学模型, 对数学模型中各个参数进行不确定度来源分析, 分别对A类不确定度或B类不确定度进行评定. 对各不确定度分量合成和扩展, 得到铅质量分数的不确定度. 结果表明: 标准溶液的配制、标准曲线拟合线性方程及样品溶液的定容是不确定度的主要来源.     

Kragten法评估测量不确定度探讨

利用Kragten数值方法对医学检验中血清淀粉酶（amylase, AMY）活性浓度测量模型的合成标准不确定度（u_c）进行计算,得到的结果与基于不确定度传播率的方法（GUM）基本一致,方法间计算的偏差均来自与该测量模型输出量呈非线性的输入量的贡献.推导出了非线性输入量引入的不确定度分量的解析式,表明Kragten法和含一阶项的GUM法计算结果的相对偏差仅与各输入量的相对不确定度呈函数关系.考查了逐渐增大的样品体积相对不确定度值(u（V_S）/V_S)对Kragten法计算的u_c影响趋势,并与GUM法进行了比较.当相对不确定度的值增大而使测量结果非线性地取决于1个或多个输入量时,Kragten法仅给出了估计的标准不确定度,此时GUM法中的高阶项部分不应该被忽略.本研究对将Kragten法用于此类非线性模型的不确定度的评估,具有一定的参考和指导意义.     

化学计量测试中不确定度评价的实例介绍

化学计量计量测试简地说是为了不同的目的而采用不同的方法来确定测试结果的不确定度的方法，这些方法是多种多样的。因此对测试不确定度因素的分析也比较困难。另一方面确定不确定度的方法与测定结果的不确定度并不是一种简单直接的关系。论述了参照某一标准进行的小型测试的不确定度，也对一般性测试的实例进行了介绍。     

氢化物原子荧光光谱法测定土壤中的汞的不确定度评定

对氢化物原子荧光光谱法测定土壤中汞含量的不确定度进行了评定.根据其测定方法和测定程序,分析了产生不确定度的重要因素.通过不确定度评定得出不确定度分量的主要来源为样品制备过程带来的不确定度.其中,样品消解产生的不确定度最大,最小二乘法拟合校准曲线校准所产生的不确定度次之;而标准溶液稀释及样品重复性产生的不确定度较以上二者小很多.     

轻柴油馏程测量结果不确定度的评定

采用不确定度的A类评定和B类评定等方法,通过对轻柴油馏程测量过程分析,找出影响回收温度结果的各因素及它们之间的关系,对其结果的不确定度进行评定,得出轻柴油馏程各回收温度结果不确定度的标准计算和表示法.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

A carbanion induced synthesis of highly congested pyrazole and imidazole containing heterocycles

An efficient approach to the synthesis of highly congested di, penta and hexacyclic pyrazoles as well as imidazole fragment containing novel heterocyclic molecule has been developed through a carbanion induced transformation of suitably functionalized 2H-pyran-2-ones, benzo[h]chromene and thiochromeno[4,3-b]pyrans. Due to the presence of fluorescence, we report their prime application metal sensor as off/on switching in ferric ions.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Selective synthesis of 4,5-dihydroimidazo- and imidazo[1,5-a]quinoxalines via modified Pictet–Spengler reaction

An efficient tandem approach for the selective synthesis of 4,5-dihydroimidazo[1,5-a]quinoxalines 6a–g and imidazo[1,5-a]quinoxalines 7a–h by the reaction of 2-imidazolyl anilines 4a–c with aryl aldehydes 5a–k under mild reaction conditions is described. Introduction of electron releasing alkyl groups in substrates 4a–b was found to be instrumental for the success of the reaction.     

Understanding the Diels-Alder reactivity of 1,2-azaborine analogues

The Diels-Alder reactivity of 1,2-heteroborines (H₄C₄B(H)X, X?=?NH, PH, AsH; O, S, Se) has been computationally explored by means of Density Functional Theory (DFT) calculations. The influence of the HB?=?X fragment on the reactivity of the system has been quantitatively analyzed in detail by means of the so-called Activation Strain Model (ASM) of reactivity. It is found that the interaction between these species and the dienophile is significantly stronger than that computed for their all-carbon isoelectronic counterpart, benzene. In addition, the strain energy plays a key role in the observed reactivity trends. The role of the aromaticity strength of these heteroarenes on the reactivity is also assessed.