联用色谱数据的局部分辨

提出了一种对二维数据严重重叠峰中待测组份进行分辨的新方法：子窗口分析法（ｓｕｂｗｉｎｄｏｗ ａｎａｌｙｓｉｓ，ＳＡ）。该方法充分利用重叠区信息，成功地解析出严重重叠峰中待测组份的光谱，进而利用正交投影求得待测组份色谱曲线．这种对二维数据进行局部分辨的方法，降低了对色谱分离条件的要求，可直接应用于未知组份的定性定量分析。     

正交投影用于一维重叠色谱峰分辨及背景扣除

对于两组份色谱重叠峰体系,当以小组份色谱峰作为干扰时,本文利用正交投影方法,通过构造正交投影矩阵,利用原始信号及其投影与背景之间的内在关系来确定真实背景,从而将背景干扰予以扣除,使含背景干扰的一维重叠色谱峰得以分辨。模拟研究表明,对于两组份色谱峰重叠体系当以小色谱峰为干扰时本文方法具有很好的分辨效果,对于完全重叠峰,即使其峰分离度为零能得到满意的结果。     

模差渐进投影法解析重叠色谱峰

提出了一种鉴别重叠色谱峰类型的化学计量学方法——模差渐进投影(MDEP)法。该方法利用二维色谱数据中相邻两个色谱流出点的光谱矢量模的和与该两个矢量和的模之差,建立模差-时间(dm-t)曲线判断非纯色谱峰的纯组分区,同时判定第二组分色谱流出点和倒数第二组分色谱结束点。分别以纯组分区的光谱矢量建立正交阵对该色谱峰进行投影运算,得到投影后转换色谱。该转换色谱消除了纯组分区所对应化合物的色谱和光谱信息。对转换色谱重复上述操作至整个色谱峰的模差-时间曲线均为0时终止,得到重叠色谱峰各组分的色谱流出点和结束点。利用上述结果,采用不包含待测组分光谱信息的该重叠峰二维色谱数据建立正交矩阵对该色谱峰进行投影运算,获得待测组分的相似色谱图。通过比对分析即可得到该组分在重叠色谱峰中的光谱和色谱信息。依次操作,即可获得重叠色谱峰中各组分的光谱和色谱信息。采用模差渐近投影法对4组分模拟重叠二维色谱峰及杜香挥发油GC-MS的重叠色谱峰进行了解析,方法简便、结果准确。     

二维色谱／光谱重叠峰的定性定量方法研究（Ⅰ）：水中多种酚二维色谱／ …

探讨了ＨＥＬＰ法在水中酚类色谱重叠峰的分辨与定性定量分析中的应用。实验结果表明，各组分浓度比为１：５０的范围内分辨光谱与真实光谱十分吻合。     

完全重叠色波二维谱的解析新方法

提出一种新的完全重叠色波二维谱解析方法。对于两组分色谱－光谱数据阵，只要在重叠区中存在单组分区，就能解得各组分的纯色谱和纯光谱，这种方法将求解纯谱问题转化为优化问题，再用数值遗传算法寻找最优解．本法用于２，４－二硝基苯酚和３，５－二硝基苯甲酸的合成实验以及四环素的杂质分析都得到满意的结果．     

直观推导式演进特征投影法解析多环芳烃的重叠色谱峰

用高效液相色谱法(HPLC)测定多环芳烃时,因芴、苊和菲,茚(1,2,3-cd)芘和苯并(g,h,i)苝的色谱峰严重重叠而影响测定结果。本研究用高效液相色谱-二极管阵列检测器(DAD)和荧光检测器(FLD)测定多环芳烃,在激发波长λex=230nm,发射波长λem=300～500nm范围内采集重叠峰的HPLC-FLD二维色谱数据,再用直观推导式演进特征投影法(HELP)解析它们的重叠色谱峰,分辨结果令人满意。该方法对重叠组分的分辨下限为0.02mg/L。结果表明,用二维色谱荧光数据解析色谱重叠峰,灵敏度更高,可用于环境样品中多环芳烃的测定。     

二维重叠色谱峰解析方法的比较

利用渐进因子分析方法(EFA)和固定尺寸移动窗口因子分析方法(FSMWEFA)与局部正交投影方法(LOPA)相结合,用于模拟的HPLC—DAD二维数据解析。通过比较谱峰部分重叠、光谱完全重叠、色谱拖尾3种情况的结果显示,在谱峰部分重叠和色谱拖尾两种情况下两种方法都可以较好的解析重叠峰。但是在光谱完全重叠时,前一种方法不能得出正确的结论,而后一种方法仍能得到满意的结果。     

二维色谱/光谱重叠峰的定性定量方法研究(Ⅰ)——水中多种酚二维色谱/光谱重叠峰的分辨与定性定量

探讨了HELP法在水中酚类色谱重叠峰的分辨与定性定量分析中的应用.实验结果表明,各组分浓度比为1∶50的范围内分辨光谱与真实光谱十分吻合.在10-4～10-6g/mL的浓度范围内分辨色谱的定量结果线性关系良好.分辨下限3.0×10-7g/mL,相对标准偏差为5.0%.     

正交投影用于多波长色谱重叠峰分析

 将正交投影分辨 (OPR)技术用于多波长色谱重叠峰分辨 ,当色谱峰中最大重叠度小于或等于波长数时 ,用这一方法能从多波长色谱重叠峰中获得完全真解。基于双波长色谱分析 ,提出了一种新的色谱重叠峰中背景校正、组分数和纯组分信号区确定以及各组分重叠情况的分析方法 ,即双波长特征信息分析 (DWCI)。该法被成功的用于三组分双峰和双组分单峰重叠色谱的分析。     

联用色谱数据的双窗口因子分析

利用组分光谱的特征信息,发展了一种能直接对联用色谱重叠峰中组分进行定性定量分析的新方法──双窗口因子分析（dualwindowfactoranalysis,DWPA）。该法可从多组分重叠峰中定性目标组分,且在未经其它组分的分辨下可直接对目标组分的光谱、色谱进行分辨。因此更适应于联用色谱对复杂体系中待测组分的定性定量分析。用该法成功地对4组分重叠峰进行了分析,实验结果令人满意。     

Quantification of components in overlapping peaks from capillary electrophoresis by using continues wavelet transform method

The application of continues wavelet transform (CWT) for resolving overlapping peaks from capillary electrophoresis (CE) is described. Overlapping peaks can be resolved easily by transforming experimental signals into their wavelet coefficients. The proposed method was applied for the determination of benzoic acid and salicylic acid in overlapping peaks from CE. The composition of the two acids in Zuguangsan, a traditional Chinese patent medicine, was determined. The quantification results are satisfactory. CWT has been shown to be a practicable approach for resolving overlapping peaks and for quantitative determining coeluted compounds in overlapping peaks from CE. The quantification results obtained from CWT were compared with those obtained from numerical differentiation method. CWT has been shown prior to numerical differentiation method for processing experimental signals which contain noise.     

Application of Multivariate curve resolution-alternating least square methods on the resolution of overlapping CE peaks from different separation conditions

Discussed in this paper is the development of a new strategy to improve resolution of overlapping CE peaks by using second-order multivariate curve resolution with alternating least square (second-order MCR-ALS) methods. Several kinds of organic reagents are added, respectively, in buffers and sets of overlapping peaks with different separations are obtained. Augmented matrix is formed by the corresponding matrices of the overlapping peaks and is then analyzed by the second-order MCR-ALS method in order to use all data information to improve the precision of the resolution. Similarity between the resolved unit spectrum and the true one is used to assess the quality of the solutions provided by the above method. 3,4-Dihydropyrimidin-2-one derivatives (DHPOs) are used as model components and mixed artificially in order to obtain overlapping peaks. Three different impurity levels, 100, 20, and 10% relative to the main component, are used. With this strategy, the concentration profiles and spectra of impurities, which are no more than 10% of the main component, can be resolved from the overlapping peaks without pure standards participant in the analysis. The effects of the changes in the components spectra in the buffer with different organic reagents on the resolution are also evaluated, which are slight and can thus be ignored in the analysis. Individual data matrices (two-way data) are also analyzed by using MCR-ALS and heuristic evolving latent projections (HELP) methods and their results are compared with those when MCR-ALS is applied to augmented data matrix (three-way data) analysis.     

偏最小二乘吸光光度法同时测定钡和锶的研究

二溴对甲基偶氮甲磺（ＤＢＭ－ＭＳＡ）在磷酸介质中能与Ｂａ（Ⅱ）、Ｓｒ（Ⅱ）形成稳定的络合物。研究了该显色体系的反应条件以及应用偏最小二乘法（ＰＬＳ）处理两者叠吸收峰,建立了光度法同时测定Ｂａ（Ⅱ）和Ｓｒ（Ⅱ）的方法。方法用于合成试样和除氧剂试样中两元素含量的测定,结果满意。     

H-point standard additions method for resolution of overlapped chromatographic peaks with a conventional fluorescence detector. Determination of phenol and cresols in waters

Summary The H-Point Standard Additions Method (HPSAM) is proposed in order to resolve overlapping peaks in liquid chromatography by using a conventional fluorescence detector. The method uses as analytical signals the heights or the areas obtained at two previously selected emission wavelengths, and good results are obtained for highly overlapping peaks with highly overlapping fluorescence spectra. The principal benefits of the method are the ease of finding the required wavelengths, its insensitivity to changes in the retention time of the peak from one injection to another, and the possibility of using it in highly or only partially overlapping peaks. We have applied the method to the determination of phenol and cresols in water, resolving by the proposed method the overlapping peaks ofm- andp-cresol.     

A two-dimensional immune algorithm for resolution of overlapping two-way chromatograms

A two-dimensional immune algorithm is proposed for resolving the multicomponent overlapping two-way data matrices. The method is a development of the one-dimensional immune algorithm proposed elsewhere. When the inner product of vectors is expanded to the similar operation on matrices, the 1D immune algorithm can be expanded to the 2D algorithm which is suitable for the analysis of two-way data matrices. Both simulated and experimental two-way data sets were investigated by the method, and the results prove that the 2D immune algorithm is an effective tool for resolving the overlapping two-way signals. The effect of noise on the recoveries is also discussed.     

A two-dimensional immune algorithm for resolution of overlapping two-way chromatograms

A two-dimensional immune algorithm is proposed for resolving the multicomponent overlapping two-way data matrices. The method is a development of the one-dimensional immune algorithm proposed elsewhere. When the inner product of vectors is expanded to the similar operation on matrices, the 1D immune algorithm can be expanded to the 2D algorithm which is suitable for the analysis of two-way data matrices. Both simulated and experimental two-way data sets were investigated by the method, and the results prove that the 2D immune algorithm is an effective tool for resolving the overlapping two-way signals. The effect of noise on the recoveries is also discussed.     

Local resolution of two-way data from multicomponent equilibria

A self-modeling curve resolution (SMCR) method is proposed to calculate concentration and spectral profiles for the two-way spectral data from an equilibrium containing several chemical components. The proposed method has three main distinctive steps: (i) fixed size moving window evolving factor analysis (FSMWEFA) is used to identify the selective and zero concentration regions for a desired component, (ii) orthogonal projection resolution (OPR) is used to calculate its concentration profile and (iii) the component striping is done directly to resolve other components. The results of simulated and real polyprotic acid dissociation equilibria showed that the proposed combined method performs well even in situation when the successive stepwise equilibrium constants are close to each other. The applicability of method for resolving the triprotic acid system with rank deficiency due full spectral overlapping of two involved chemical species also is shown.     

基于积分渐进展开的气相色谱重叠峰快速解析法

论文提出用积分渐进展开解析气相色谱重叠峰,该方法有3个主要步骤：首先将谷峰或肩峰分成两个积分区域,得到一个子区域的积分方程和一个重叠峰面积的代数方程;然后用数值积分求出这两个方程计算中所需要的峰面积,再用积分渐进公式将积分方程展开成代数方程;最后,将这两个方程与峰高约束方程联立后,得到一个非线性代数方程组,用Gauss-Seidel迭代可以快速求解方程组,方程收敛的最大迭代次数不超过20次。仿真和实验结果表明,解析的峰高和峰面积误差均很小,峰面积最大误差低于6.44%,峰高的最大误差约为6.80%。由于该算法精度高,效率高,所以这个方法可以用于气相色谱重叠峰和一般色谱峰的实时在线解析。