三线性分解方法用于激发-发射矩阵荧光数据中一阶瑞利散射的扣除

由于荧光分析具有检测灵敏度高、数据容易获得等优点,近年来二阶张量校正方法与激发-发射矩阵荧光光谱技术的联用正受到人们越来越多的关注.但是,在三维荧光分析中,经常出现的一阶瑞利散射干扰往往容易导致建立的三线性模型存在较大的偏离,进而直接影响复杂体系中感兴趣组分的定性、定量分析.针对该问题,我们提出了一种基于对组分数不敏感的三线性分解算法扣除一阶瑞利散射干扰的新思路.该方法的特点是根据一阶瑞利散射分别在水平切片矩阵和侧面切片矩阵所处位置相同,沿I-模和J-模同时构建含一阶瑞利散射的三维数据阵,利用三线性分解算法对此各自建模,将一阶瑞利散射当作一个响应组分或因子拟合后从三维数据阵中扣除掉.通过对模拟和实际三维激发发射矩阵荧光光谱实验数据进行讨论,结果表明该方法能有效地扣除体系中的一阶瑞利散射干扰.改进后的方法不仅操作简单,而且不受组分数选取不当的困扰.另外,由于同时从两个方向进行一阶瑞利散射扣除,因此不会出现因边缘瑞利散射峰形不完整而扣除不完全的情况.该方法为三维荧光光谱的无损分析提供了新思路,为进一步进行三维荧光光谱的定量分析奠定了良好的基础.     

三维荧光校正法直接测定尿液中的利血平

利用化学计量学三维数据校正方法中的交替三线性分解算法(ATLD)和自加权交替三线性分解算法(SWATLD), 不经化学分离, 对采用激发-发射矩阵荧光法所得到的三维响应数据阵进行三线性成分分解, 再基于标样已知浓度, 利用简单回归法直接测定尿液中利血平(Reserpine)的含量. 结果表明, 当体系的主要组分数取3时, 两种方法均可迅速、 快捷地得到待测物的浓度, 有效地解决了荧光法定量测定时未知背景及干扰物光谱严重重叠而引起的问题.     

三线性分解方法用于光谱数据中背景漂移的扣除

在光谱测量中, 通常会发生光谱背景漂移现象. 引起光谱背景漂移的因素有很多, 如仪器的背景噪声变化, 测量时环境温度的变化, 光源如氙灯的使用时间等等. 针对三维光谱数阵, 发展了一种基于交替三线性分解(ATLD)算法的化学计量学方法用来处理光谱背景漂移问题. 该方法在进行三线性分解时, 对待光谱背景漂移与感兴趣组分一样, 将其单独当作一个组分或因子来考虑, 并将其从分解得到的相应矩阵中提取出来, 构建一个光谱背景漂移阵, 然后从三维原始响应数阵中将其减掉, 从而达到成功扣除光谱背景漂移的目的. 采用发展的方法处理2组模拟数据和2组实验数据, 都获得了满意的结果. 另外, 对于非线性较严重的背景漂移, 通过再进行一次扣除, 即“二次扣除”, 也达到了理想的效果. 该方法有望发展成为一种很有潜力的光谱预处理技术.     

正交信号校正-插值-RBF法同时测定原料油中的铁、镍、钒

提出了一种解析分光光度同时测定数据的正交信号校正-插值-RBF(OSC-Interp-RBF)网络方法。该法将光谱阵用浓度阵正交,滤除光谱与浓度阵无关的信号,再用一维线性插值处理使训练集样本对待辩识空间形成较好的覆盖,使RBF网络能够更有效地提取信息,从而提高预测的准确性。将该算法用于模拟原料油中铁、镍、钒的测定数据解析及实际样的组分浓度预测的结果表明,对于合成样预测结果与组分实际浓度的相对误差,及对于实际样预测结果与按常规测定方法获得的结果的相对误差,绝对值均小于10%,结果令人满意。     

用Procrustes旋转-相关光谱数据分解同时光度测定硝酸根和亚硝酸根的探讨

输入具有相同光谱轮廓但不同浓度试样的吸光度数据，通过对相关光谱的分解及Procrustes旋转，可在无需校正试样的情况下获得试样中的组分数、纯组分光谱轮廓和各组分的相对浓度等信息，本文探索将此方法应用于NO-2及NO-3的同时光度测定，获得较好的结果。     

化学计量学方法在动力学过程分析中的应用

提出了一种公因子分析的新方法。通过这一方法，对一个动力学体系，我们能够从两个不同的波长范围或反应时间范围的数据阵中获得共同组分的数目和它们的光谱或浓度曲线。将这一方法结合正交投影（OPR）技术，成功地应用于聚苯胺掺杂质子酸反应体系数据阵的解析，获得了这一过程中聚苯胺本征态及掺杂后两个新生结构的光谱和浓度变化曲线。基于解析结果可以推断：聚苯胺质子酸掺杂可能生成PANHn^n （α）、PANHn^a (β）两个不同结构的产物，他们间可相互转化。     

用Procrustes旋转—相关光谱数据分解同时光度测定硝酸根和亚硝酸…

输入具有相同光谱轮廓但不同浓度试样的吸光度数据，通过对相关谱的分解及Ｐｒｏｃｒｕｓｔｅｓ旋转，可在无需校正试样的情况下获得工样中的组分数、纯组分光谱轮廓和各组分的相对浓度等信息。本文探索将此 方法应用于ＮＯ＾－２及ＮＯ＾－３的同时光度测定，获得较好的结果。     

偏最小二乘—分光光度法同时测定邻硝基苯酚,间硝基苯酚和对硝基苯酚

１引言同分异构体由于具有相似的结构，在多数情况下，其紫外－可见光谱严重重叠，影响其同时测定。偏最小二乘法（ＰＬＳ）通过对已知标准混合物测量，利用数学模型，借助于矩阵的正交分解途径，将浓度矩阵与量测矩阵分解为一列正交阵与行正交阵之积，具有较强的数据解析功能，可避免矩阵示逆困难，消除组分间的相互作用。本文将ＰＬＳ法用于吸收峰完全重叠的邻硝基苯酚，间硝基苯酚和对硝基苯酚三组分体系分析，结果表明，本法准确可靠，操作简便。２实验部分２．１仪器和试剂ＵＶ－２５０型紫外可见分光光计（日本岛津）。ＡＳＴ－４８６…     

阿司匹林合成过程的在线拉曼光谱研究

利用在线拉曼光谱的方法,跟踪阿司匹林合成反应过程的实验.直接观测到反应过程中体系的拉曼光谱随时间的变化,用小波变换的方法去除光谱的本底之后, 又利用多波长线性回归的方法对实验数据进行实时的处理,得到了实验中各组分的相对浓度随时间的变化.     

小波变换结合多维偏最小二乘方法用于近红外光谱定量分析

将小波变换和多维偏最小二乘法相结合用于近红外光谱定量校正模型的建立。首先将原始光谱进行小波变换分解，得到系列小波细节系数，通过选取一组受外界因素少、信息强的小波系数组成三维光谱阵，然后再采用多维偏最小二乘法建立校正模型。实验结果表明，该方法所建近红外校正模捌的预测能力更强，并更具稳健性。     

Simultaneous determination of vitamin B12 and its derivatives using some of multivariate calibration 1 (MVC1) techniques

Resolution of binary mixtures of vitamin B12, methylcobalamin and B12 coenzyme with minimum sample pre-treatment and without analyte separation has been successfully achieved by methods of partial least squares algorithm with one dependent variable (PLS1), orthogonal signal correction/partial least squares (OSC/PLS), principal component regression (PCR) and hybrid linear analysis (HLA). Data of analysis were obtained from UV-vis spectra. The UV-vis spectra of the vitamin B12, methylcobalamin and B12 coenzyme were recorded in the same spectral conditions. The method of central composite design was used in the ranges of 10-80mgL(-1) for vitamin B12 and methylcobalamin and 20-130mgL(-1) for B12 coenzyme. The models refinement procedure and validation were performed by cross-validation. The minimum root mean square error of prediction (RMSEP) was 2.26mgL(-1) for vitamin B12 with PLS1, 1.33mgL(-1) for methylcobalamin with OSC/PLS and 3.24mgL(-1) for B12 coenzyme with HLA techniques. Figures of merit such as selectivity, sensitivity, analytical sensitivity and LOD were determined for three compounds. The procedure was successfully applied to simultaneous determination of three compounds in synthetic mixtures and in a pharmaceutical formulation.     

偏最小二乘法-BP 神经网络用于多组分药物测定

先将输入向量采用偏最小二乘法进行成分分析,再与ＢＰ神经网络法相结合,用于测定甲硝唑,头孢唑啉钠,维生素Ｂ６三给分。三给分的平均回收率及ＲＳＤ分别为９９．３％,０．７１％;９９．１％,０．９３％;９９．３％,２．８％。     

Determination of vitamin B5 in human urine by high-performance liquid chromatography coupled with mass spectrometry

In the present work, we have developed a simple and rapid liquid chromatography/mass spectrometry (LC/MS) method for the identification and quantification of vitamin B5 in human urine. Urine was spiked with vitamin B5 internal standard, hopantenic acid (HOPA), and then diluted with the LC mobile phase prior to its analysis by LC/MS. The quantification was performed in single ion monitoring mode. The calibration curve was linear (r2 = 0.999) between 0.25 to 10 microg/mL. With a limit of detection of 0.1 microg/mL the method was sensitive enough to determine low levels of vitamin B5 in urine. The overall quantitative efficiency of the method was evaluated by spiking urine samples with four different concentrations of vitamin B5; the intra-assay coefficient of variation was below 5% and the recoveries were between 96 to 108%. The results of the present study show that the proposed method is selective and sensitive enough for the quantification of vitamin B5 in urine.     

多元校正紫外光度法同时测定甲硝唑与维生素B6

本文报道多元校正紫外光度法同时测定甲硝唑和维生素B6。首先在0．1mol／LHCl溶液中对甲硝唑和维生素B6两组分混合溶液进行分光光度法测定,然后将所得的重叠光谱数据经计算机采集后,分别用化学计量学方法中的偏最小二乘法（PLS）和主成分回归法（PCR）进行处理,并用于药物样品的测定,获得了较好的定量分析结果。该法甲硝唑和维生素B6的线性范围分别为1．0～28．0mg／L和1．0～28．0mg／L,检出限分别为0．568mg／L和0．364mg／L。     

偏最小二乘法用于同步荧光法同时测定维生素B1,维生素B2和维生素B6

本文将偏最小二乘法结合同步荧光扫描技术对含维生素Ｂ１，Ｂ２和Ｂ６的混合物进行了同时测定。对同步荧光法的测定条件及△λ的选择进行了试验和讨论，比较了△λ分别为６５ｎｍ和３０ｎｍ时的计算结果。所建立的方法用于复合维生素Ｂ片等药片叶Ｂ１，Ｂ２和Ｂ６孤同时测定，获较满意的结果。     

Phyllohydroquinone (Vitamin K1 H2) and Phylloquinone (Vitamin K1): Purification and Spectral Analysis

Abstract

Simple procedures for the preparation of pure phyllohydroquinone and phylloquinone are described. Phylloquinone is reduced by sodium dithionite and the reduced vitamin is purified by reverse phase high performance liquid chromatography. The essential spectral properties of the pure vitamins in ethanol and methanol are cited. The data provide a convenient spectral method for the accurate determination of the absolute concentrations of the oxidized and reduced vitamins and the rates of oxidation of the reduced vitamin. Pure, dry phyllohydroquinone may be safely stored at -70[ddot]C under nitrogen for a period of months. The stability of Phyllohydroquinone in methanol at 25.0 ± 0.1[ddot]C is also reported.     

Studying the Glycan Moiety of RNase B by Means of Raman and Raman Optical Activity

Raman and Raman optical activity (ROA) spectroscopy are used to study the solution‐phase structure of the glycan moiety of the protein ribonuclease B (RNase B). Spectral data of the intact glycan moiety of RNase B is obtained by subtracting high‐quality spectral data of RNase A, the non‐glycosylated form of the RNase, from the spectra of the glycoprotein. The remaining difference spectra are compared to spectra generated from Raman and ROA data of the constituent disaccharides of the RNase glycan, achieving convincing spectral overlap. The results show that ROA spectroscopy is able to extract detailed spectral data of the glycan moieties of proteins, provided that the non‐glycosylated isoform is available. Furthermore, good comparison between the full glycan spectrum and the regenerated spectra based on the disaccharide data lends great promise to ROA as a tool for the solution‐phase structural analysis of this structurally elusive class of biomolecules.     

Determination of Vitamin B1 in Pharmaceutical Preparations by Flow-injection Analysis with Biamperometric Detection

IntroductionVitamin B1(VB1),also called thiamine,is animportant biomolecule,widely existing in beans,cere-al and meat,etc.So far,the application of spectropho-tometry[1,2],fluorimetry[3,4],high performance liquidchromatography[5],chemiluminescence[6]or potentiom-etry[7]for the determination of VB1has been reported.These methods have drawbacks,such as low selectivi-ty,elaborate procedures needed and a long responsetime.The dead-stop end-point biamperometry by usingtwo platinum foil electrodes…     

基于能量重分配的波长偏移校正方法

针对原子光谱分析中波长偏移问题,提出了一种基于能量重分配原理实现波长偏移校正的方法.用抛物线插值法对能量密度分布进行反演,以谱图相似度为判断指标,通过三分法确定最佳偏移量,并根据最佳偏移量与能量密度分布对光谱强度进行重新计算,实现了亚像素级别的波长校正.对微型光纤光谱仪与单道扫描光谱仪获得的谱图进行了算法验证,使Eu元素的背景噪音平均降低了48%,Mo元素的信号稳定度由20%改善至约5%.该方法对具有结构化特征的谱图具有较好的适用性,且无须寻峰算法配合使用,有助于提高光谱分析精确度.     

Common components and specific weights analysis: a tool for monitoring the molecular structure of semi-hard cheese throughout ripening

Twelve semi-hard (Raclette) cheeses, belonging to four brand products, namely A (n = 3), B (n = 3), C (n = 3) and D (n = 3), were produced during summer period and ripened at an industrial scale. Tryptophan, riboflavin and vitamin A fluorescence spectra were scanned on the 12 cheeses at 2, 30 and 60 days of ripening. The physico-chemical analyses were performed only at the end of the ripening stage (60 days). Common components and specific weights analysis (CCSWA) were applied on the four data tables. CCSWA showed that the common component 1 (q₁), discriminating cheeses labelled A, B and C from those labelled D, expressed 94.4 and 59% of the inertia of vitamin A and tryptophan fluorescence spectra and a less amount for riboflavin fluorescence spectra and physico-chemical data (24.2 and 13.2%, respectively). Common component 3 (q₃), differentiating between cheeses labelled B and those labelled A and C, explained 34.6 and 23.9% of the inertia of the physico-chemical data and tryptophan fluorescence spectra, respectively, and a tiny part of the inertia of riboflavin and vitamin A fluorescence spectra (3.2 and 0.7%, respectively). The CCSWA showed its ability to describe the overall information collected from fluorescence and physico-chemical data tables and to extract relevant information at the molecular level throughout ripening of the investigated semi-hard cheeses.