A comparison of quantitative nuclear magnetic resonance methods: internal,external, and electronic referencing

The performance of three quantitative NMR methods was compared in terms of short‐term and long‐term precision and accuracy, robustness, linear range, and general applicability. The Internal Reference method employs a reference material co‐dissolved with sample; the External Reference method employs a reference material contained in a separate solution; and the third method, known as Electronic REference To access In vivo Concentrations (ERETIC), employs an externally calibrated digital reference peak. The Internal Reference method results were the most precise and remained stable within 0.1% for at least 4 weeks. The results from the External Reference and ERETIC methods were practically equivalent to each other during this time. These methods exhibited small differences relative to the standard set by the Internal Reference method and slightly lower precision, establishing them as practical alternatives to the Internal Reference method. In contrast to the Internal Reference method, the External Reference and ERETIC methods possess several advantages that address peak overlap, flexibility of calibration, and duration of applicability. The study was designed such that each spectrum contained the information needed to compare the three methods while all other variables were kept constant. Applicability of pulse width compensation is addressed. ERETIC software compensation and minor adjustments to 90° pulse width were concluded to be unnecessary for this system. Although each of the methods was applied here to specifically calculate and compare chemical purity values, this evaluation applies generally to absolute quantitation by NMR. Copyright © 2013 John Wiley & Sons, Ltd.     

Use of 2, 3-Butanedione Monoxime for Homogeneous Precipitation of Nickel (II)

Abstract

The solid monoxime of 2, 3-butanedione is a more convenient material than liquid dione for the homogenous generation of DMG. 2, 3-butanedione dioxime. Determinations of Ni in steels and in pure Ni(II) solutions have shown the optimum pH and order of adding reagents. Gravimetric and/or an EDTA titrimetric finish are possible for a method of reliability within ± 0.2 mg of Ni in 50–150 mg Ni. The solid has the same character and filterability as that from the 1960 dione method of Salesin and Gordon¹.     

Electron Capture Determination of Propoxyphene from Human Plasma

Abstract

A procedure for the determination of propoxyphene (α-d-dimethylamino-1, 2 -diphenyl-3 -methyl-2 -propionoxybutane) in plasma is reported. The method is based on the electron capture characteristics of propoxyphene. The plasma is rendered basic to generate the free amine and extracted with ether. The extract is analyzed by gas chromatography using a 4 foot OV-225 column. An internal standard of imipramine hydrochloride is used to quantitate the propoxyphene. This internal standard is carried through the entire procedure. The ratio of the peak heights of propoxyphene to imipramine is compared to ratios obtained from standards placed in plasma and treated in the same manner as the samples. Six subjects were given propoxyphene at different time intervals, and the data are presented concerning these subjects.     

钒的一个特别灵敏指示反应

本文研究了钒（V）在乙酸介质中催化溴酸钾氧化钙试剂羧酸钠盐的褪色反应。本方法的灵敏度为2.5×101?g/ml,与同类方法相比为最高,测定范围为0～4ngV/25ml。本法已用于水样中超痕量钒测定。     

同步扫描－固体基质室温磷光法同时测定痕量对位三联苯和间位三联苯的研究

本文提出了一种新的测定间三联苯和对三联苯的同步扫描－ＳＳ－ＲＴＰ法。固体基质选用慢速定量滤纸，重原子盐为Ｔｌ２ＳＯ４。以激发单色器和发射单色器的波长差△λ＝１８０ｎｍ进行同步扫描，其同步特征峰间三联苯为４５０ｎｍ，对三联苯为４９０ｎｍ（均指发射波长）。间三联苯可直接由该特征峰的高度进行定量测定。对三联苯在４９０ｎｍ处的特征峰略受间三联苯同步拖尾的影响，其峰值信号需加校正。间三联苯和对三联苯的线性范围分别为０．４６～９２ｎｇ／斑点和０．４６～４６ｎｇ／斑点     

由压痕蠕变试验确定材料的蠕变性能参数

研究由平头压痕蠕变试验来确定受压材料蠕变性能参数的可行性。利用有限元蠕变分析确定在定压痕应力下的压痕蠕变率,重点放在稳定压痕蠕变率和受压材料蠕变性能参数的关系上。详细地研究了压头形状、大小和宏观约束对压痕蠕变响应的影响:当压头的尺寸和受压材料为同一数量级时,宏观约束将有十分明显的影响。提出两种方法来由压痕蠕变试验来确定受压材料蠕变性能参数,并给出了算例,结果有利于准确认识平头压痕蠕变试验,从而拓宽其应用范围。     

光谱导数Kalman滤波同时测定苯酚-邻氯苯酚和2,4二氯苯酚

文中提出了一个新的、稳定的光谱导数Kalman滤波紫外分光光度法同时定量分析方法,并且成功地将其应用于极难分辨的苯酚-邻氯苯酚和2,4二氯苯酚三组分混合体系的同时测量.选择分析光谱导数的原因是其不仅包含着吸光度,还包括在指定波长位置变化趋向等更多的信息量,这样更利于在吸收峰重叠的位置捕捉有较大差异的信号.利用Kalman滤波可以解决由光谱导数而引起的噪声放大问题,也可以过滤源于实验的噪声以及来自传递模型误差.在260～290 nm区间测量了30组浓度各自在1～10 mg·L-1范围的苯酚-邻氯苯酚和2,4二氯苯酚标准混合溶液紫外吸收光谱图.利用分段延伸高次多项式回归模拟求导准确获得吸光度导数,并且利用偏最小二乘法将其制作成Kalman滤波标准工作系数矩阵.通过随机线性离散系统的Kalman滤波器最优平滑计算,对混合体系中的各组分进行定量分析.回收实验显示出,光谱导数Kalman滤波分析法应用于本实验的极难分辨的三组分体系,得到了非常高的回收率,并且在整个实验范围内光谱导数Kalman滤波分析法具有非常好的稳定性.     

Cd-Sn(0.2)-Zn三元合金高压相图的测定

 为了验证三元合金高压相图的计算结果，本文采用高压DTA方法，测定了Cd-Sn-Zn三元系中x_Sn=20 at.%截面的高压垂直截面相图，实验压力为0、0.5、1.0、1.5 GPa。测得的常压相图（p=0 GPa）中其液相线与H. J. Bray的实验结果完全相符，所得高压相图与常压相图比较，在p=1.5 GPa时低共晶点上移了大约35 K，共析组成向富锌端移动了大约8%。     

The Intrusion of the Meissen Pluton (Elbe Valley-Zone): Evidence from Geochemical and Isotopic Data

Abstract

Geochemical and mineralogical investigations of plutonic rocks from the Meiβen massif indicate different magmatic evolution trends of the Freital sequence as well as for the central part of the complex Constant ε-Nd_T-345 values of ?1.5 of the Freital sequence and major/trace element data point to a fractional crystallization process. Based on ε-Nd values, ¹⁴⁷Sm/¹⁴⁴Nd ratios as well as on geochemical data affinities to alkali basalts cannot be excluded.

Analogous conclusions have been drawn regarding mineral chemical data [10] and cathodoluminescence spectra of apatite [13]. Assimilation of old continental crust, reflected by relics of apatite and zircon, may be the reason that the ε-Nd values plot at the lower end of the “mantle array”. The pyroxene-monzodiorite from Gröba belongs to the same source environment as the Freital sequence (Nd-characteristics).

The geological evolution of the central part of the studied plutonic complex is completely different to the Freital sequence: most of the intrusions show signatures of open system fractionation processes. The ε-Nd_T-345 value of ?1.46 of the Leuben monzonite indicates a narrow relation to the Freital sequence, whereas the ε-Nd_T-345 value of +2.27 of the Spitzgrund monzonite either reflects the derivation of another basic material then the Freital-type or the participation of other mixing component(s) from geologically young crust.

Fabric and mineral chemical investigations of the porphyry-like granite GII point to a mixing process of basic xenocrysts, resembling the corresponding minerals of the Freital sequence, and granite melts [10]. Large amounts of old zircon cores [11] indicate the inheritance of continental crust components by the Hauptgranit. Isotopic investigations on various granitic samples (GII, Hauptgranit and Riesensteingranit) reflect an increasing trend towards the crustal source(s) of their parental melts. The ε-Nd_T-345 values are ?3.75, ?4.16 and ?6.13, respectively.

Chemical parameters and the ε-Nd_T value of the Riesensteingranit agree with data of granites from the Saxonian Granulite Massif (see e.g. Wand et al. [8]; von Quadt, 1992). Thus, it may be possible that both granite types derived from similar sources.