在IBM-PC/XT上研制通用色谱数据处理系统

]本文在IBM-PC/XT微机上发展一种能对包括肩峰在内的各种不同峰形检测判别的通用色谱数据处理软件。实验表明,本软件不仅在色谱峰形的检测判别性能方面优于国外同类产品,而且能比较准确地用全谱图拟合法对重叠峰、肩峰进行定性和定量。     

色谱重叠峰分解的神经网络法

对于色谱图中两个相互重叠的峰, 本文提出了一种分解方法。首先在重叠峰的一阶导数曲线上取出五个无因次特征值, 然后用多层前传网来表达这五个特征值和重叠峰中子峰面积分率之间的关系。一系列实验的结果表明, 用神经网络方法所得子峰面积的准确度, 优于传统的垂线法及函数拟合法, 而且计算工作量较小, 可用于实时处理。     

非对称色谱峰的拟合与重叠峰的拟合解析

 ]利用色谱保留时间tR与色谱峰形模型参数tG、σ、τ间的线性关系、预测了气相色谱填充柱上非对称的和重迭的色谱峰的有关参数，并据此对这两类色谱峰进行了拟合和解析。与常用重叠峰解析方法如中垂线法，三角形法和切线法解析结果的对比证明，曲线拟合法在这些方法中具有最好的准确度。用曲线拟合法进行实际定量的结果表明，对于非对称峰，其定量的相对误差小于0.5％，而对于重叠峰的定量误差则在10％以内。     

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。     

三元重叠色谱峰面积的定量方法

本从色谱峰的ＥＭＧ模型出发，通过对重叠色谱峰的模拟和回归分析，提出了一种三元重叠色谱峰的面积的定量方法，三元重叠色谱峰的每一个峰面积可以由峰面积比和总面积求得，此法所需的数据都由实验色谱图上测得，峰面积计算结果的相对误差小于±５％，适用于相对峰谷为５０％－９５％的三元重叠色谱峰面积的定量。     

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。     

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。     

一阶和二阶导数相综合的色谱峰检测法

本文提出了一种介于一阶和二阶导数之间的色谱峰检测新方法，它能排除基线漂移的影响，具有抗噪声干扰能力，能判别重叠峰，还能够得色谱峰上各拐点，的位置并发现肩峰型重叠峰。该方法只需要设置一个起动参数即可自动进行峰检测，具有很强的自适应性和健壮性，极大地方便了用户。     

小波变换用于重叠色谱峰组分信息的提取

提出了一个小波变换用于提取重叠色谱中组分信息的理论公式，并将它应用于三组分和五组分重叠色谱实验数据的解析。结果表明：在定定分离度范围内，当相邻色谱峰峰宽相近时，根据此公式的计算结果，可以将各组分的信息从重叠色谱峰信号中提取出来。洒工作对小波变换用于重叠峰的解析具有重要意义。     

完全重叠色谱峰的二维微分色谱解析算法

利用完全重叠的色谱峰中同时消失的两组分的浓度变化速率差异，通过二维数据微分色谱法获取被掩盖组份的近似光谱，以解析完全重叠的色谱体系，将该法应用于维生素Ｃ和菸酸两组份完全重叠的二维色谱之分辨，结果令人满意，分辨光谱与标准光谱重合甚好。     

曲线拟合定量法在高效液相色谱手性分离中的应用

 首次将曲线拟合定量法用于解决高效液相色谱手性分离中重叠峰的定量问题。通过比较百树菊酯 8个立体异构体的实验谱图和拟合谱图 ,证明曲线拟合定量法与传统的中切法相比 ,可获得更令人满意的结果。     

Spectral quality enhancement as an aid to polymer characterisation

The limit to the information on the microstructure of polymers that may be obtained from their vibrational spectra is often set by overlapping bands, markedly broader than the spectrometer resolution. Following the initial pioneering work of Pohl and Hummel, using a simple curve fitting technique, mathematical methods of spectral quality enhancement have progressed very considerably. These methods are reviewed critically and new results are presented. The desirability of imposing some parameter constraints in curve fitting is demonstrated, and this has led to the development of methods for peak narrowing, as an aid to peak finding. The two important approaches, derivative spectroscopy and Fourier selfdeconvolution (FSD), are discussed in terms of their application to the complex of overlapping bands in the v(C-Cl) region of the infrared spectrum of poly(vinyl chloride). A development of the FSD method termed Fourier band isolation, is described and preliminary results indicate that it has considerable promise. The maximum entropy method is discussed briefly.     

化学谱图重叠峰检测及基线校正

本文提出一种谱峰曲线与其一个阶差分曲线相结合的算法，经宽松变换处理后，用于区分化学谱图中谱峰的终点是否真正落回到基线上，并由此建立了一种具有健壮性的重叠峰检测方法和及时准确的谱图基线校正方法。由于此算法的阈值参数可以固定，从而保证了重叠峰检测较少地受到人为的影响，进一步提高了化学谱图数据处理的自动化水平。     

Signal Processing in Normal Pulse Voltammetry by Means of Dedicated Mother Wavelet

In the work, a new signal processing algorithm is presented and applied for the transformation of the sigmoidal shaped curves, registered in normal pulse voltammetry (NPV), to the peak shaped curves. The method is based on the continuous wavelet transform (CWT) and specially constructed mother wavelet defined using the ideal wave‐shaped curve. Transformation of the signal, elimination of noises and separation of overlapping data can be achieved in one step by means of proposed procedure. The operation and effectiveness of the algorithm is presented using ideal, noised and overlapping simulated curves. The process of simultaneous determination of lead and indium as well as transformation of curves registered for elements' ions: lead, indium, thallium and cadmium is described. The obtained results show substantial improvement of the performance of NPV.     

多元曲线分辨-交替最小二乘法应用于延胡索药材指纹图谱中重叠峰分辨及延胡索乙素的含量测定

采用光谱相关色谱法对延胡索药材指纹图谱中的有效组分延胡索乙素峰进行确认;利用多元曲线分辨 交替最小二乘法（MCR-ALS）对延胡索乙素重叠峰簇进行解析,得到延胡索乙素的真实色谱峰,其光谱还原率大于0.999,并对其进行准确定量,该方法可作为指纹图谱的辅助方法,为中药的真伪鉴定和质量客观评价提供可靠依据;最后讨论了药材的炮制对延胡索乙素含量的影响。     

Synthesis,characterization, thermal behavior,and DFT calculation of solid 1,4-bis(3-carboxy-3-oxo-prop-1-enyl) benzene of some trivalent lanthanides

In this paper, the derivative thermogravimetry (DTG) curve displays an overlapping peak which consists of two subpeaks for the major oil-producing stage of Indonesian oil sand. This study was conducted to supplement the insufficiencies of the previous studies, which neglected or oversimplified the processing of the overlapping peak and did not determine the kinetic mechanism. First of all, we assume a two-component parallel reaction model to describe the mass-loss process of the major oil-producing stage (overall stage) to obtain the separated stages. Then, we present an asymmetric multi-peak fitting method, bi-Gauss, to separate the overlapping peak. Based on the results of the bi-Gauss method, the kinetic mechanism was obtained using the integral master plot method, followed by the determination of the activation energy by the integral iso-conversional non-linear (NL-INT) method. The results show that the bi-Gauss method can produce satisfactory fitting results. Moreover, the separated stages follow single mechanism; while the overall stage does not follow a single mechanism and the mechanisms of the front and back segments of the overall stage are in accordance with those of the separated stages, which prove the reliability of the two-component parallel reaction model.     

Resolution method for overlapping peaks based on the fractional-order differential

Equations between the differential order and the maximum of the fractional-order differential for the specified peak signals are developed based on the variation of the maximum of the specified peak signals at different orders. Also, equations between the differential order and the zero-crossing of the fractional-order differential of the specified peak signals are proposed according to the variation of the zero-crossing of the specified peak signals at different orders. Characteristic paramters of the Gaus- sian peak, Lorentzian peak, and Tsallis peak can be estimated using estimator I and estimator II which are obtained by the equations above. As a result, a new method is presented to resolve the overlapped peaks signal. Firstly, a fractional-order differential of the specified peak signals is obtained with the fractional-order differentiation filter. Then, characteristic paramters of the specified peak signals can be extracted using estimator I and estimator II. Finally, the Tsallis peak is used as a model to assign the overlapping peak signals correctly. Experimental results show that the proposed method is efficient and effective for the simulated overlapping peaks and detected overlapping voltammetric peak signals.     

交流示波极谱法中电流—电位曲线的研究——Ⅲ.电流-电位曲线示波极谱络合滴定法

利用交流示波极谱法中i_f-E曲线来指示滴定终点的容量分析方法,叫做i_f-E曲线示波极谱滴定法。本文研究i_f-E曲线示波极谱络合滴定法。     

基于无基底扣除的数据趋势累积谱峰检测算法

谱峰的检测分析在色谱技术研究中具有十分重要的作用,但在色谱数据采集、传输的过程中,不同程度的噪声干扰给谱峰检测带来了极大的困难。目前传统的谱峰检测算法普遍通过基底扣除的方式对谱峰的形态进行预定义,将谱峰分为单峰、重叠峰等多个种类。针对不同种类的谱峰采用不同的检测方法,这就导致了传统的谱峰检测算法具有高复杂度、低自动化程度以及容易失真等缺点。因此,该文从另一个角度出发提出了一种新型的谱峰检测算法。该算法取消基底扣除以及谱峰分类这一步骤,直接在源数据曲线的基础上进行谱峰检测,主要分为离散差分、趋势累积以及遍历寻峰3个步骤。首先通过信号量表征数据升降趋势;然后进行数据趋势累积,根据累积总和定位谱峰,采用三点定位的方式,即峰起点、极值点和峰终点描述一个谱峰的位置;最后根据遍历排序的方式进行谱峰的筛选。此外,通过谱峰扣除的方式得到曲线基底部分。采用C语言设计编写了算法程序,并对多个动态比表面积分析仪测定的色谱图进行了检测分析,结果显示使用该算法可以精准区分谱峰部分与基底部分,受数据曲线毛刺、震荡等噪声干扰很小,谱峰的三点定位十分准确,且不受其复杂形态的影响,具有很强的普适性。与其他算法相比,该算法定位准确,结构清晰,具有较好的稳定性以及可靠性。该文报道了无基底扣除以及趋势累积等新型谱峰检测思想在吸脱附色谱曲线中的应用,证明了其在吸脱附色谱峰检测中的有效性和良好的应用前景。