Investigation of the quantitative properties of the quadrupole orthogonal acceleration time-of-flight mass spectrometer with electrospray ionisation using 3,4-methylenedioxymethamphetamine

This paper describes the investigation of the potential of a quadrupole orthogonal acceleration time-of-flight mass spectrometer (Q-TOF) equipped with an atmospheric pressure ionisation interface for quantitative measurements of small molecules separated by reversed phase liquid chromatography. To this end, the detection limits and linear dynamic range in particular were studied in an LC/MS/MS experiment using 3,4-methylenedioxymethamphetamine standards and 3,4-methylenedioxyethylamphetamine for internal standardisation. In a second phase, the experiment was repeated with real biological extracts (whole blood, serum, and vitreous humour). A calibration for 3,4-methylenedioxymethamphetamine and its metabolite 3,4-methylenedioxyamphetamine was prepared in each of these matrices again using 3,4-methylenedioxyethylamphetamine as internal standard. The resulting quantitative data were compared with those obtained by liquid chromatography with fluorescence detection for the same extracts. The Q-TOF results revealed excellent sensitivity and a linear dynamic range of nearly four decades (2-10 000 pg on-column, r(2) = 0.9998, 1/x weighting). Furthermore, all the calibration curves prepared in biological material were superimposable, LC/MS/MS and LC-fluorescence, and the quantitative results for actual samples compared very favourably. It was concluded that the Q-TOF achieves a linear dynamic range for quantitative LC/MS/MS work exceeding that of fluorescence detection and at much better absolute sensitivity. Copyright 1999 John Wiley & Sons, Ltd.     

Routine analysis by high precision gas chromatography/mass selective detector/isotope ratio mass spectrometry to 0.1 parts per mil

Stable isotope methods are potentially quite useful for validating natural or enhanced mineral degradation of contaminants. For this reason, a continuous flow gas chromatograph (GC), isotope ratio mass spectrometer (IRMS) has been coupled with a quadrupole mass selective detector (MSD) to allow simultaneous mass spectral and stable carbon isotope ratio data to be obtained from a single chromatographic analysis. This allows the target contaminant and any extra-cellular degradation intermediates to be both qualified and quantified. Previously acceptable limits of precision (0.3 parts per mil) are undesirable given the small fractionation observed during aerobic degradation. To further understand the fate of organic contaminants and to gain information about the metabolic degradative pathway employed by a microorganism, routine isotopic analyses on a range of analytes have been performed. Quantities of sample producing mass-44 ion beam signal (I(44)) of 2 x 10(-10) to 1 x 10(-8) A were analysed. When the IRMS was tuned for high sensitivity, ion source nonlinearities were overcome by peak height correction from an algorithm that was produced using known isotopic standards of varying concentrations. This led to sample accuracy of <0.01 per thousand and sample precision of 0.1 per thousand. Copyright 1999 John Wiley & Sons, Ltd.     

Structure of 72,74Se at high spin

Lifetimes of high spin states up to { }=22⁺ in the yrast positive parity bands have been measured to investigate the shape evolution with increasing spin in ^{72, 74}Se. The Q _t values derived from these measurements indicate that prolate shape stabilizes for ⁷²Se, while a triaxial shape develops for ⁷⁴Se at higher spins. Comparison of the observed trend in Q _t with spin for ^{72, 74}Se with that of the corresponding kryptones isotones emphasizes the stability provided by N=38 prolate shell gap even at high rotational frequency.     

电感耦合等离子体原子发射光谱法测定钛酸钡纳米粉体中7种杂质元素

钛酸钡纳米粉体样品用盐酸溶解,在所得样品溶液中用电感耦合等离子体原子发射光谱法测定了以氧化物存在于样品中的7种杂质元素(包括镁、锶、钾、钠、铝、硅及铁),对测定的光谱条件进行了试验并优化达到上述各元素的测定上限为0.1%(质量分数).测得方法的检出限(3S/b)为(单位μg·L-1):2.0(铝),1.0(铁),20.0(钾),0.2(镁),4.0(钠),3.0(硅)及0.5(锶).应用此方法分析了两件实样,所得结果的相对标准偏差(n=6)小于等于2.0%,对其中4种杂质元素(镁、钾、钠和锶)同时用HG/T 3587-1999标准中的方法作分析校核,所得结果与此方法结果一致.