Tutorial review on validation of liquid chromatography–mass spectrometry methods: Part II

This is the part II of a tutorial review intending to give an overview of the state of the art of method validation in liquid chromatography mass spectrometry (LC–MS) and discuss specific issues that arise with MS (and MS–MS) detection in LC (as opposed to the “conventional” detectors). The Part II starts with briefly introducing the main quantitation methods and then addresses the performance related to quantification: linearity of signal, sensitivity, precision, trueness, accuracy, stability and measurement uncertainty. The last section is devoted to practical considerations in validation. With every performance characteristic its essence and terminology are addressed, the current status of treating it is reviewed and recommendations are given, how to handle it, specifically in the case of LC–MS methods.     

Free hypermodules: a categorical approach

Abstract

In category theory, the existence of free objects is very important, especially free modules that play an important role in homological algebra. Although algebraic hyperstructures are a natural extension of algebraic structures, due to the major difference between them, study-free objects in algebraic hyperstructures become very difficult. In this article, we provide a categorical approach for the construction of free hypermodules. In fact, by considering appropriate morphisms between hypermodules, we characterize free hypermodules from three different perspectives.     

Correlating conductivity and Seebeck coefficient to doping within crystalline and amorphous domains in poly(3-(methoxyethoxyethoxy)thiophene)

Molecular doping of conjugated polymers (CPs) plays a vital role in optimizing organic electronic and energy applications. For the case of organic thermoelectrics, it is commonly believed that doping CPs with a strong dopant could result in higher conductivity (σ) and thus better power factor (PF). Herein, by investigating thermoelectric performance of a polar side-chain bearing CP, poly(3-(methoxyethoxyethoxy)thiophene) (P3MEET), vapor doped with fluorinated-derivative of tetracyanoquinodimethane FnTCNQ (n = 1, 2, 4), we show that using strong dopants can in fact have detrimental effects on the thermoelectric performance of CPs. Despite possessing higher electron affinity, doping P3MEET with F4TCNQ only results in a σ (27.0 S/cm) comparable to samples doped with other two weaker dopants F2TCNQ and F1TCNQ (26.4 and 20.1 S/cm). Interestingly, F4TCNQ-doped samples display a marked reduction in the Seebeck coefficient (α) compared to F1TCNQ- and F2TCNQ-doped samples from 42 to 13 μV/K, leading to an undesirable suppression of the PF. Structural characterizations coupled with Kang-Snyder modeling of the α–σ relation show that the reduction of α in F4TCNQ-doped P3MEET samples originates from the generation of low mobility carrier within P3MEET's amorphous domain. Our results demonstrate that factors such as dopant distribution and doping efficiency within the crystalline and amorphous domains of CPs should play a crucial role in advancing rational design for organic thermoelectrics.     

紧急疏散中最优抗出错路径选择模型与算法

疏散路径选择是紧急疏散中的重要问题，为了减小疏散人在紧急疏散过程中由于路径选择错误带来的损失，提出一对起讫点间最优抗出错路径选择模型。给出路径出错系数的定义，用以度量疏散人路径选择错误带来的疏散效率损失，并且设计了求解最优抗出错路径的DAE算法，证明该算法的时间复杂度为O（ mn2）。结果表明，选择最优抗出错路径作为疏散路径，能够有效地抵抗由于疏散人路径选择错误带来的损失，对提高突发事件下的疏散效率具有实际意义。     

退火对PECVD制备的掺磷硅薄膜及其电阻温度系数影响的研究

本文对采用PECVD技术制备的不同掺杂比掺磷硅薄膜在不同退火时间和温度下的结构和电阻温度系数进行了研究。拉曼散射光谱结果表明:未退火样品主要为非晶/微晶混合相;当退火温度从500℃上升到700℃,薄膜结构呈现出先向非晶相转变,后完全晶化的趋势,与此同时,电阻率和电阻温度系数随掺杂浓度及退火温度的增加而单调减小。文中我们采用Lu的模型对上述实验结果进行了解释,认为由Si-P键构成的晶界势垒高度的变化是上述实验结果的根本原因。     

Estimation of the Coefficient of Multiple Determination

Assume that we have iid observations on the random vector X = (X ,...,X ) following a multivariate normal distribution N (,) where both R and (p.d.) are unknown. Let denote the multiple correlation coefficient between X and (X ,...,X ). The parameter = , called the multiple coefficient of determination, indicates the proportion of variability in X explained by its best linear fit based on (X ,..., X ). In this paper we consider the point estimation of under the ordinary squared error loss function. The usual estimators (MLE, UMVUE) have complicated risk expressions and hence it is quite difficult to get exact decision-theoretic results. We therefore follow the asymptotic decision theoretic approach (as done by Ghosh and Sinha (1981, Ann. Statist., 9, 1334-1338)) and study Second Order Admissibility of various estimators including the usual ones.     

Some pairs of adjoint functors involving track homotopy categories

K. A. Hardie and K. H. Kamps investigated the track homotopy categoryH _B over a fixed spaceB ([1]). They have introduced two pairs of adjoint functors:P _B N _B andm _* m ^*, whereP _B :H _B →H ^B , andm _*:H _A →H _B for a fixed mapm:A→B. We have introduced a split fibration of categoriesL:H _b →H _B and provedL J, J L in [2]. This paper first extendsP _B N _B to for any fixed mapb: . Moreover we also extend these results to obtain two pairs of adjoint functors involving track homotopy categoriesH _b andH ^b whereH ^b is the dual ofH _b . One of our results isN _b P _b . This differs fromP _B N _B . Supported by National Natural Science Foundation of China