基于XRD-Rietveld全谱拟合技术定量分析花岗岩风化壳中矿物组成

XRD-Rietveld全谱拟合方法突破了传统XRD定量分析的众多技术局限,在解决复杂多相混合物的定量问题方面具有显著优势。将XRD-Rietveld全谱拟合方法引入风化壳矿物学研究,有助于解决长期以来地学界对风化壳中矿物组分缺乏准确定量认知的技术瓶颈。在制定专门针对风化样品的全谱拟合精修策略基础上,以广西玉林大容山地区的花岗岩风化壳为研究对象,对发育在两组不同岩性之上的风化剖面(剖面A和剖面B)进行了对比研究。结果表明,风化剖面A(母岩为粗粒黑云母花岗岩)的矿物组合及含量变化范围为：高岭石(6.05%～44.67%)+伊利石(15.85%～49.59%)+石英(29.72%～46.15%)+钾长石(12.04%～22.85%)+斜长石(24.33%～32.70%);风化剖面B(母岩为细粒黑云母花岗岩)的矿物组合及含量变化范围为：高岭石(3.12%～11.47%)+伊利石(13.95%～31.94%)+石英(26.60%～58.05%)+钾长石(13.70%～43.47%)+斜长石(17.95%～23.47%)。两组剖面的全谱拟合修正因子R_wp值<15且gof值<5,计算谱与原始谱拟合效果好,指示矿物定量数据可靠,且能与地质规律较好匹配。在地质意义上,本研究通过母岩原生矿物与次生矿物的含量同步变化,深入揭示了研究区内花岗岩的化学风化过程,厘定了长石类矿物在亚热带气候环境下所经历的长石→伊利石→高岭石演变序列。基于剖面A与剖面B中粘土矿物总量和矿物构成出现显著差异,研究认为在研究区内粗粒黑云母花岗岩比细粒黑云母花岗岩更易遭受强烈的化学风化作用。     

爆炸波中的混合不确定度量化方法

将认知不确定作为外层,偶然不确定作为内层,利用混合不确定理论处理爆炸波中的不确定度问题.分别使用非嵌入多项式混沌方法（NIPC）和Dempster-Shafer理论处理偶然不确定和认知不确定,用迎风格式求解确定系统.结果表明：NIPC和Dempster-Shafer结构为模型输入参数和初边值不确定性对输出响应量的影响提供一种有效方法,对各种建模与模拟不确定性评估和确认建模与模拟具有很好的参考价值.     

圆筒试验JWL状态方程参数的贝叶斯标定

在研究数值模拟的输入参数引入的不确定性时,通常需要人为给定每个输入参数的概率分布,且输入参数概率分布的选择可能会对分析结果产生直接影响。利用贝叶斯方法标定了圆筒试验JWL状态方程参数,得到了标定参数的估计值和后验分布,并研究了不同统计模型假设对标定参数的估计值和后验分布的影响。贝叶斯后验分布融合了基准试验的试验数据的信息,因此将其作为不确定度量化分析时输入参数的初始概率分布,可以尽量减少分布选择引入的认知不确定性。     

Mass selective separation applied to radioisotopes of cesium

A technique that uses the intrinsic mass‐based separation capability of a quadrupole mass spectrometer has been used to resolve spectral radiometric interference of two isotopes of the same element. In this work the starting sample was a mixture of ¹³⁷Cs and ¹³⁴Cs and was (activity) dominated by ¹³⁷Cs. This methodology separated and ‘implanted’ ¹³⁴Cs that was later quantified for spectral features and activity with traditional radiometric techniques. This work demonstrated a ¹³⁴Cs/¹³⁷Cs activity ratio enhancement of >4 orders of magnitude and complete removal of ¹³⁷Cs spectral features from the implanted target mass (i.e. 134). Copyright © 2016 John Wiley & Sons, Ltd.     

Linear quantification calibration of crystallinity at subpercent and its evaluation based on spectral and spatial information inherited in Raman chemical images

In this paper, the author reported two methods to extract spectral or spatial information inherited in the Raman chemical images for linear quantification calibration of crystallinity. The two approaches reported quantification results according to the spectral mean score of overall pixels or the spatial percentage of the pixels with a score greater than and equal to the threshold of the chemical images, respectively. From this study, it can be concluded that, first, sampling method for data collection in mapping has to be optimized to achieve linear quantification calibration through simple univariate analysis approaches. Second, the ordinary way of evaluating/validating a linear quantification technique by best linear correlation coefficient (R²) and root‐mean‐square error of calibration is disputable and has to be reconsidered. Lastly, with further consideration of root‐mean‐square relative error of calibration and predicted crystallinity at subpercent, it was found that the spectral mean score method cannot generate reliable quantification results at subpercent crystallinity. Copyright © 2014 John Wiley & Sons, Ltd.     

二元复杂共混体系组成的SEC-LS分析

提供了一种利用体积排阻色谱-光散射(SEC-LS)联用技术来解决二元复杂共混体系组成的定量分析问题.基于体积排除色谱的绝对定量化原则,首先从理论上分析了共混物的光散射响应因子与组成呈线性关系.通过分析六组复杂共混体系的光散射响应因子与组成的关系,验证了该线性关系确实存在.进而利用该线性关系计算了共混体系的组成.在某些共混体系中,通过光散射响应因子得出的组成比利用示差法得出的组成更加接近原料组成.通过分析这两种方法产生误差的来源,阐述了产生该现象的原因.     

Quantification of asenapine and three metabolites in human plasma using liquid chromatography-tandem mass spectrometry with automated solid-phase extraction: application to a phase I clinical trial with asenapine in healthy male subjects

The development and validation of methods for determining concentrations of the antipsychotic drug asenapine (ASE) and three of its metabolites [N-desmethylasenapine (DMA), asenapine-N(+) -glucuronide (ASG) and 11-O-sulfate-asenapine (OSA)] in human plasma using LC-MS/MS with automated solid-phase extraction is described. The three assessment methods in human plasma were found to be acceptable for quantification in the ranges 0.0250-20.0 ng/mL (ASE), 0.0500-20.0 ng/mL (DMA and OSA) and 0.250-50.0 ng/mL (ASG).     

Generation of anti-azoxystrobin monoclonal antibodies from regioisomeric haptens functionalized at selected sites and development of indirect competitive immunoassays

Azoxystrobin is a modern strobilurin fungicide used around the world to combat prime diseases affecting highly valuable crops. Accordingly, residues of this chemical are frequently found in food, even though mostly under maximum tolerated levels. We herein describe the development of an indirect competitive immunoassay for the determination of azoxystrobin residues. A panel of monoclonal antibodies displaying subnanomolar affinity to azoxystrobin was generated using, as immunizing haptens in mice, four functionalized derivatives carrying the same spacer arm located at different rationally chosen positions. This collection of antibodies was thoroughly characterized with homologous and heterologous antigens, and the immunoassay consisting of monoclonal antibody AZo6#49 and the coating conjugate OVA–AZb6, which displayed an IC₅₀ value of 0.102 μg L⁻¹ and a LOD of 0.017 μg L⁻¹, was eventually optimized. The response to different pH and ionic strength conditions of the specific assay was studied using a biparametric approach. In addition, the influence of Tween 20 and organic solvents over the assay parameters was also evaluated. After optimization, the developed immunochemical assay was applied to the analysis of azoxystrobin in spiked juices of relevant fruits and vegetables, showing excellent recoveries between 2 and 500 μg L⁻¹.     

Electrochemical Quantification of Mercury in Solutions Using Boron-doped Diamond Electrodes: Electrode Regeneration and Role of Gold and Impurities

Abstract

For determining Hg in solutions in the ppb to ppt range using boron-doped diamond (BDD) electrochemistry, the role of an added gold solution for enhanced sensitivity is investigated. Using differential pulse anodic stripping voltammetry (DPASV), peaks due to Cu and Ag as impurities from gold are identified. With the proper choice of the potential for deposition, effects of the impurities are minimized and an electrode regeneration procedure is devised and tested, resulting in reproducible slopes of the calibration curves in successive runs. The location and shift of the DPASV peak potentials with concentration are explained with the use of the Nernst equation.     

Evaluation of the ion trap MS performance for quantification of flavonoids and comparison to UV detection

The application of an ion trap mass spectrometer, usually employed for identification, has been here systematically evaluated for quantitative analysis of various conjugated forms of flavonoids and compared with UV quantification. Three MS methods were tested to assess the potential and limits of the ion trap for quantification of flavonoids: full‐scan experiment MS², isolated ion experiment MS, and full‐scan experiment MS. The test was performed using nine reference standards of flavonoids with six different aglycones: luteolin, apigenin, hypolaetin, 4′‐O‐methylhypolaetin, isoscutellarein and 4′‐O‐methylisoscutellarein in the form of 7‐O‐glucosides and diglucosides, mono or diacetylated, isolated from Sideritis scardica. The analytical characteristics of the tested MS methods were shown to be comparable to UV with regards to precision and accuracy, and superior for selectivity and sensitivity especially when using extracted ion chromatograms. Detection limits did not differ significantly between the MS methods but were significantly lower than those obtained with UV detection by one order of magnitude. Another issue addressed by these results was the choice of most suitable standard substances for quantification of flavonoids with various substituents attached when using MS. In UV detection, the nature of the aglycone is crucial for the absorbance properties, and various derivatives can be quantified with the available one with the same aglycone. Here, it was shown that in MS detection, one flavone derivative can be quantified using other available derivatives with similar substitution pattern with regards to attached and acetylated sugars, whereas the nature of the aglycone is not crucial. Copyright © 2012 John Wiley & Sons, Ltd.