电感耦合等离子体原子发射光谱分析中光谱干扰校正卡尔曼滤波法研究

本文利用电感耦合等离子体原子发射光谱多色仪的扫描功能,用卡尔曼滤波法对各种光谱干扰进行校正。结果表明,该法能处理各种类型光谱干扰,不需要样品基体匹配,其测定回收率明显优于在峰法和离峰法,具有简便、准确等优点。     

A note on smoothed estimating functions

The kernel estimate of regression function in likelihood based models has been studied in Staniswalis (1989,J. Amer. Statist. Assoc.,84, 276–283). The notion of optimal estimation for the nonparametric kernel estimation of semimartingale intensity (t) is proposed. The goal is to arrive at a nonparametric estimate of ₀=(t ₀) for a fixed pointt ₀ [0, 1]. We consider the estimator that is a solution of the smoothed optimal estimating equation is the optimal estimating function as in Thavaneswaran and Thompson (1986,J. Appl. Probab.,23, 409–417).     

AnL 1 smoothing spline algorithm with cross validation

We propose an algorithm for the computation ofL ₁ (LAD) smoothing splines in the spacesW _M (D), with . We assume one is given data of the formy _i =(f(t _i ) + _i , i=1,...,N with {itt_i} _i=1 ^{N D} , the _i are errors withE( _i )=0, andf is assumed to be inW _M . The LAD smoothing spline, for fixed smoothing parameter0, is defined as the solution,s , of the optimization problem (1/N) _i=1 ^N ¦y _i –g(t _i ¦+J _M (g), whereJ _M (g) is the seminorm consisting of the sum of the squaredL ₂ norms of theMth partial derivatives ofg. Such an LAD smoothing spline,s , would be expected to give robust smoothed estimates off in situations where the _i are from a distribution with heavy tails. The solution to such a problem is a thin plate spline of known form. An algorithm for computings is given which is based on considering a sequence of quadratic programming problems whose structure is guided by the optimality conditions for the above convex minimization problem, and which are solved readily, if a good initial point is available. The data driven selection of the smoothing parameter is achieved by minimizing aCV() score of the form .The combined LAD-CV smoothing spline algorithm is a continuation scheme in 0 taken on the above SQPs parametrized in, with the optimal smoothing parameter taken to be that value of at which theCV() score first begins to increase. The feasibility of constructing the LAD-CV smoothing spline is illustrated by an application to a problem in environment data interpretation.     

卡尔曼滤波析相光度法同时测定锰铁铜锌镉的研究——5-Br-PADAP—Triton X-100体系

运用卡尔曼滤波递推法,以2-(5-溴-2-吡啶偶氮)—5-二乙氨基苯酚(5-Br-PADAP)为显色剂,建立了同时测定锰、铁、铜、锌、镉析相光度法.在pH9.0硼酸-氢氧化钠介质中,胶束溶液在95℃加热1h,配合物被Triton X-100相完全富集,最大吸收峰分别为锰566nm、铁556nm、铜560nm、锌562nm、镉557nm,工作曲线范围除镉为0～8μg/5ml外,其余均为0～10μg/5ml.应用于大米中锰铁铜锌镉的同时测定,结果满意.     

改进的单纯形优化法用于混合稀土的同时测定

本文应用改进的单纯形优化法较好地弥补了目前在分析化学计量学中得到广泛应用的卡尔曼滤波法所存在的不足，交法应用于混合稀土的同时测定中，获得了满意的结果，结果准确度较卡尔滤波法的有显著的提高。     

ICP—AES卡尔曼滤波同时测定铁基体中26种痕量元素

本文利用电感耦合等离子体原子发射光谱（ＩＣＰ－ＡＥＳ）多色仪的扫描功能，用Ｃ语言编制了Ｋａｌｍａｎ滤波程度软件包，用该软件包对铁基体中２６种痕量元素进行了回收率试验，并对标准碳素钢样中１３种痕量元素进行了测定，结果表明Ｋａｌｍａｎ滤波完全适用于复杂谱线基体中的多种元素同时分析。     

卡尔曼滤波光谱法用于化学平衡研究

提出了光谱法与卡尔曼滤波及因子分析相结合的新方法以研究化学平衡,将复杂的化学平衡视为特殊的多组分混合体系,其中各物种在不同介质中存在相互的平衡,卡尔曼滤波及因子分析被用作有效的化学计量学分辨工具,从光谱数据中提取信息,已用于确定所存在的物种数目和浓度以及平衡常数,本文以部分三苯甲烷试剂为例确定其酸碱平衡常数。     

Nondifferential optimization via adaptive smoothing

The problem of minimizing a nondifferential functionx f(x) (subject, possibly, to nondifferential constraints) is considered. Conventional algorithms are employed for minimizing a differential approximationf off (subject to differentiable approximations ofg). The parameter is adaptively reduced in such a way as to ensure convergence to points satisfying necessary conditions of optimality for the original problem.This research was supported by the UK Science and Engineering Research Council, the National Science Foundation under Grant No. ECS-8121149, and the Joint Services Electronics Program, Contract No. F49620-79-C-0178.     

A simple optimization strategy based on Rs-minimum and information theory of chromatography

Summary A simple optimization method based on the well-known Rs-minimum method and on the information theory of FUMI Φ is proposed. Resolution (Rs), peak area and height (or width) are the only parameters necessary for the calculation of the information Φ and information flow ϑ. The most precise analysis can be selected as the chromatogram having maximal ϑ. Mobile phase composition, column length, flow rate, detection wavelength, amount of internal standard, etc. can be optimized by this method.     

Influence of Light Scattering by Residual Alumina Nanoparticles on the Analysis of Surfactants Adsorption Using Spectroscopy

The adsorption of a surfactant mixture, based on an anionic surfactant, sodium dodecyl benzenesulfonate (SDBS) and a nonionic surfactant (Triton X-100, or TX100), on alumina nanoparticles was determined by solution depletion method combined with spectrometric measurement. It is shown that the light scattering, originated from the residual adsorbent alumina particles in the supernatant after centrifugation separation, interferes with the measurements of absorbance of the surfactant molecules, and therefore constitutes an error source for determination of the surfactant concentration in the supernatant by spectrometric means. The intensity of this light scattering, namely the influence of the residual alumina nanoparticles upon the surfactant adsorption, was related to the surfactant adsorption and its equilibrium concentration and varied among a batch. In this paper we report a Kalman filter method in order to eliminate the variational scattering background caused by non-separated residual alumina nanoparticles in each supernatant. This method is of interest as it is simple, easy to carry out and of high precision.