环流装置的液相流型和下降管中的液相返混

本文用任意波形的液相浓度信号输入,时间域曲线拟合法,研究环流装置的液相流型和下降管中的液相局部返混系数。实验结果表明,上升管用活塞流模型、下降管用部份返混流模型可以较好地描述该系统的液相流动。几种方法的比较结果证明,时间域曲线拟合法比矩量法和修正矩量法优越;下降管液相局部返混系数随液速增加而增加,砂粒粒径对液相返混系数影响较大。     

酰胺水化作用的富里埃红外光谱研究及其SCFPPP计算

本文用富里埃红外光谱仪研究了酰胺水化作用引起的红外光谱变化。用SCFPPP方法对五种酰胺进行了计算。含水酰胺的羰基伸缩振动频率向低波数的位移与酰胺和水分子间的氢键强度成正比。其氢键强度与羰基上氧原子的净电荷密度成正比,与酰胺分子的HOMO轨道能量成反比。     

红外付里叶变换光谱及其在分析化学上的应用

(一)红外付里叶变换光谱付里叶变换(FT)是发生在自然界里最普通的变换之一。人们驾驭了这个变换的特点并已经将它用到了脑照相术、x-射线晶体学、雷达网络设计、红外光谱、核磁共振、离子回旋共振质谱、电化学、图象辨认和信息处理等领域中。时间域的强度谱与频率域的强度谱,在数学上是互为付里叶变换的。用某种实验手段首先取得时间域的强度谱,而后再以Cooley-Tukeyf快速付里叶变换算法用计算机将其计算成人们所熟悉的频率域的强度谱,已成为波谱学常用的一种技术。红外付里叶变换光谱(FT-IR)就是利用干     

蘇聯四十年來在高分子化合物化學發展方面的主要階段

只是在蘇維埃政權年代里,高分子化合物領域才得到迅速的發展。 但是它的起源是許多著名的俄國科學家的工作,他們開始了這一领域的研究并以自己的工作策劃了基本的路綫,這些路綫在以後取得了巨大的發展。關於異丁烯和甲醛聚合的工作,在用金属鈉作為聚合的引發劑方面的研究,和在     

多相催化中测定速率参数的理论模型

木文提出了一个多相催化中反应物与生成物动态行为的理论模型,用以测定各速率参数.如反应系一级不可逆反应,并且反应物与生成物在催化剂表面上处于吸附平衡状态,则将可获得解析解.对于可逆反应以及包含传质效应及吸附速度等因素的反应,则可运用矩量分析,富里埃分析或传递函数法计算参数.文中对于流出物与生成物相互搭界以及非线型吸附问题均作了理论和方法上的处理。     

丙三醇浓溶液Tg附近协同松弛的量热研究

利用差示扫描量热法测量了丙三醇水溶液Tg前后的比热容. 通过曲线拟合获得AGF模型参数. 研究结果表明, 该模型很好地预测了(Tg+20 K)以下体系的结构松弛时间. 协同重排活化能(Δμ')和协同重排域尺寸(z*)的分析结果表明, 只有选择比聚合物大得多的某一协同重排位形数, 用AGF方法得到的z*才具有物理意义. 作为材料常数的Δμ' 随体系水含量的增加而逐渐降低. 用Donth方法得到的丙三醇水溶液的协同重排域长度尺度(ξCRR)随着水含量的增加逐渐降低, 且其变化趋势可与Δμ'的分析结果相符. 但用AGF方法和Donth方法得到的协同重排域尺寸不能统一.     

水中天然有机物富里酸的光催化氧化研究

以粉末态TiO2为催化剂对水中天然有机物富里酸（FA）进行了光催化氧化的研究，考察了在光催化-超滤反应器中直接光氧化、曝气条件、错流速度、催化剂浓度、初始pH等因素对富里酸氧化的影响。结果表明，光催化氧化明显优于直接光氧化对富里酸的影响，另外在空气曝气、pH减小以及增大错流速度的条件下均能有效提高富里酸的去除率。     

三峡库区水体溶解有机质的荧光光谱特性

利用荧光发射和三维荧光光谱(EEM)研究了三峡库区(TGRA)长江干流及嘉陵江、乌江两支流水体溶解有机质(DOM)的荧光特性.结合采样段面溶解有机碳(DOC)、氧化还原电位(ORP)、pH等参数,考察了干流、两支流及其汇合后各水体DOM的荧光指数f450/500和类腐殖酸与类富里酸强度比值rC/D变化,分析了类腐殖酸、类富里酸及类蛋白质在库区支流与干流、上游与下游水体的来源、组成、分布及环境行为.实验表明: 干流水体中DOM以类富里酸、类蛋白质荧光有机质为主;嘉陵江水体DOM以类蛋白质为主,富里酸次之; 在朝天门与长江汇合后,类蛋白峰强减弱而类腐殖酸有一定增加;乌江以类富里酸为主,汇合干流后,富里酸和类蛋白质峰增强;库区上游水体DOM主要受嘉陵江影响;干流DOM受陆源性影响.初步揭示了水体DOM的EEM特性与库区水质参数的相关性,为水体监测与分析提供参考.     

吸光度减技术在混合物分析中的应用

混合物的光谱是其组份光谱的叠加,直接对它进行解析是十分困难的,所以光谱工作者要在化学分离上耗费大量精力。富里埃变换红外光谱仪及其它计算机化的红外光谱仪器具有被称为吸光度减的功能,可用以进行光谱之间的带权相减。它在一定程度上代替了化学分离,把各组份的光谱从混合物光谱中一一“剥离”开来。此技术可广泛用于混合物分析和涉及混合物的研究工作。Koenig曾对此技术的应用作过     

玉米秸秆堆腐过程中形成富里酸的结构分析

采用傅里叶变换红外光谱及＾１Ｈ和＾１３Ｃ核磁共振波谱对玉米秸秆堆腐过程中形成的富里酸的结构进行了表征。结果表明,玉米秸秆腐解过程中形成的富里酸包括羧基或羰基基团,芳香结构,烷基片断和碳水化合物结构。     

基于小波的恒电量瞬态响应信号的滤波处理

利用小波变换的阈值法对恒电量响应信号进行滤波处理, 同时与传统的时域和频域的滤波方法进行分析比较, 并且讨论了小波变换的分解层数对恒电量响应信号滤波效果的影响. 结果表明, 利用小波变换可以在时域和频域同时对恒电量响应信号取得良好的去噪效果. 这不仅能提高时域曲线拟合的精度, 还大大地提高了恒电量频谱解析的可靠性. 在实际应用中, 小波变换的分解层数取5～7层可以收到满意的效果.     

Curve fitting to asymmetrical chromatograms by the extended Kalman filter in frequency domain

An algorithm is presented to perform curve fitting on the basis of the Fourier transform of a signal. The curve fitting has been done with the exponentially modified Gaussian model, obtained when convolving a Gaussian distribution and an exponential decay function. The parameter estimation has been carried out by means of the two-dimensional extended Kalman filter. The goodness-of-fit has been characterized by the trace of the covariance matrix of the estimated parameters. The precision of the estimated parameters obtained by fitting either in time or frequency domain is compared.     

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。     

可见吸收光谱线型参数分析法测定十二烷基硫酸钠临界胶束浓度

于浓度相同的结晶紫（CV）溶液中,加入不同浓度的十二烷基硫酸钠（SDS）组成一系列含有相同浓度CV和不同浓度SDS的混合溶液。在可见光区内对每一混合溶液测定其吸收值时,可见随SDS浓度的逐步递增,在CV-单聚体吸收峰的吸收值逐渐减少;而在CV-二聚体吸收峰的吸收值逐渐增加,且随CV-二聚体浓度增加而出现的CV-二聚体与CV-单聚体的吸收光谱线相互严重重叠,光谱形状也发生渐变。运用分光光度计所配备的Origin 7．5软件中储存的高斯多峰拟合法,可自动进行重叠光谱的解析和各光谱参数（包括y0,A1,A2,ω1,ω2,xc1及xc2）的拟合计算。文中还证示,每一参数与SDS浓度之间有明显的相关性,在两者之间所作的曲线上可找到明显的转折点,与转折点相对应的、在横坐标上的SDS浓度值即为SDS的临界胶束浓度（CMC）值。文中首次报道了用吸收光谱的半峰宽对SDS浓度作图所得曲线上的转折点求得SDS的CMC值。     

Elimination of non-uniform, extra-device flow effects in membrane adsorbers

Commercial use of membrane adsorbers in the biotechnology industry is increasing. Here the system time lag created by membrane adsorber peripherals and the membrane adsorber flow distribution headers has been modeled using an anion exchange membrane and bovine serum albumin (BSA). The system time lag was modeled as a zero order and first order time lag. The zero and first order time lags have been removed from the breakthrough curve. The method used does not involve fitting a mathematical expression to the breakthrough curve. Further no assumptions are made regarding the shape of the breakthrough curve in the absence of the time lag. The method has been used to calculate the Langmuir isotherm parameters.The membrane capacity was found to be twice as large as the capacity determined after removal of the time lag. The Langmuir constant was five times as large for the system without accounting for the time lag. Errors in fitting isotherm parameters can significantly impact frontal analysis and membrane adsorber scale-up. The Langmuir isotherm calculated under dynamic conditions with the system time lag removed, was in agreement with the static adsorption isotherm.     

THE DETERMINATION OF PERIODICITIES IN SHORT-TERM TIME-SERIES DATA IN THE PRESENCE OF HIGH FREQUENCY NOISE AND LONG-TERM TREND

The presence of periodicities in biological data may often be obscured by superposition of a background trend or high frequency oscillations. A method of least squares curve fitting was utilized to remove the trend in signal level. Subsequent removal of higher frequency noise utilizing smoothing convolution functions allows the determination of rhythmic components. A new “noise” convolution function gives a measure of the noise in data containing both signal and noise and allows the estimation of a limit above which an observed oscillation is considered significant. The effects of treating data with these convolution functions are discussed with reference to amplitude-frequency response curves. The results of data analysis utilizing convolution functions are compared with results obtained utilizing a moving interval Fourier technique (Blume, 1965). The convolution analysis have the advantages that they are easily programmed and rapidly calculated by programmable calculators, give results relatively insensitive to the length of convolution interval, and allow estimation of the variation in period and amplitude of the rhythm investigated.     

USING ELECTROPHORESIS TO DETERMINE ZETA POTENTIAL OF MICELLES AND CRITICAL MICELLE CONCENTRATION

A heterodyne laser Doppler electrophoresis method for measuring the zeta potential of a surfactant micelle has been developed. Details of the method and results obtained will be presented in this paper. In comparison with the tracer electrophoresis method used in determining the zeta potential of a surfactant micelle, this method is much time saving and less laborious. The zeta potential values of one anionic and three cationic surfactant micelles have been determined by using this method. From the zeta potential versus concentration curve, one can determine the micellar dissociation concentration and the critical mi cellar concentration of a surfactant. The values obtained agree quite well with the surface tension measurement. The surfactant systems were studied in the presence and absence of NaCI. The zeta potential appears to decrease with the increase of NaCI concentration.     

Fitting Lorentzian peaks with evolutionary genetic algorithm based on stochastic search procedure

A global search technique for curve fitting based on evolutionary random search was modified and applied for quantifying a combination of Gaussian and Lorentzian peaks. This stochastic search procedures based on randomized operators is a modified Monte Carlo method. The proposed method tested on self obtained several overlapped Lorentzian peaks with random noise, Lennard particles in three dimensions and discrete mathematical functions previously used for optimization in literature. It was found to be the proposed method is suitable for complex and large scale optimization. The results of the new method have been compared with those obtained by two peak fitting programs. Developed method was found to be very fast and thus it is time saving.     

凝胶渗透色谱法峰加宽改正问题——Ⅱ.一种有效的解Tung方程的迭代法

本文运用一种病态线性方程组的迭代法解出 Tung方程。此法对定h及变h的 Gauss 核及 Gram-Charlier 核都是有效的,对窄分布样品的峰加宽改正也很适合。并与 Ishige 及 Smit等提出的迭代法作了比较。最后讨论了求积公式、归一化、对称化和GPC实验谱图的峰加宽改正问题。     

Comparison of Curve Fitting Models for Ligand Binding Assays

In the case of ligand binding assays the relationship between instrumental response and analyte concentration is non-linear, usually either hyperbolic or sigmoidal. As it is not possible to calibrate an assay at all the levels to be measured a suitable method of constructing a concentration-response relationship (the standard curve), based on a limited number of carefully spaced standards is required. The method should be robust and operator independent. The two main approaches that have been used involve empirical and mechanistic (theoretical) models. Empirical models utilise any mathematical function(s) that appears to have the characteristics of the experimentally derived assay data. Empirical models require no understanding of the principles of the assay. Mechanistic models make assumptions about the physico-chemical processes involved in the assay procedure. In practice either single function or spline models are used. The curve fitting solution may be explicit (in the case of spline interpolation), or by least-squares curve fitting regression methods, including polynomial and logistic equations, the latter involving many iterations. Examples of good curve fitting selection are presented and contrasted with inappropriate models in a number of common assay formats.