Kalman滤波用于酶反应动力学的研究

采用卡尔曼滤波研究酶反应动力学及分析，依据酶存在下过氧化氢放出氧的反应建立了扩展Ｋａｌｍａｎ滤波模型，用滤波处理确定了反应速率与起始速率浓度的关系，并估算出酶反应动力学参数Ｋｍ。     

Kalman滤波法校正火焰原子吸收光谱干扰

本文将Ｋａｌｍａｎ滤波法应用于原子吸收光谱中，对光谱严重叠加的锰和镓进行了校正，讨论了波长测量点的选取技术对实际结果的影响。１６个合成样品的测定结果表明该法简单，有效。     

Kalman滤波用于荧光,吸收,导数与同步光谱的研究

将Ｋａｌｍａｎ滤波用于常规荧光、同步荧光、导数荧光、吸收光谱及导数光谱，实现了不经分离对苯酚与间苯二酚混合物及复方药物制剂的同时测定。结果良好，操作简便。     

基体归一定量技术在激光烧蚀-等离子体质谱法锆石原位多元素分析中的应用

探讨了内标法和基体归一法校准的基本原理。基体归一校准法的基本步骤为:先用简单外标法测得样品中尽可能全的主、次、痕量元素含量,氧化物加和后进行100%归一,得到灵敏度校正系数,对所有元素的测定结果进行修正。修正结果的可靠性在很大程度上取决于测定元素是否"完全"。由于锆石的基体元素组成简单且易于测定,很适合用基体归一法校准。在激光剥蚀-电感耦合等离子体质谱法(LA-ICP-MS)微区原位分析中,应用基体归一校准法的最大优点是:可以避免预先用其它微区分析技术对未知样品中的内标元素进行定量。该技术可适用于具有环带结构、难以找到均匀分布的内标元素的地质样品的元素空间分布测定。在高分辨ICP-MS(Element2)和NewWave-UV-213激光系统上,应用基体归一定量技术同时分析了锆石中主、次、痕量共54种元素。对未知锆石样品的分析,基体归一法与内标法结果的一致性令人满意。分析德国蛇纹岩标准玻璃ATHO-G中相对误差<25%的有52个元素,<10%的有36个元素;大多数元素的相对标准偏差<10%。     

黄芪中痕量元素的形态分析

对不同产地中药黄芪中铁、锰、铜及锌4种痕量元素存在的形态及其含量进行研究。文中叙述了分离各种形态的方法及其试液,包括样品中测定痕量元素总量的试液,水煎液的可溶态和悬浮态的试液,可溶态试液中有机形态、无机形态、稳定形态和不稳定形态的试液,以及水煎药渣中4种元素测定溶液等8种试液的制备方法。采用电感耦合等离子体原子发射光谱法测定了各试液中4种痕量元素的含量。以可溶无机形态的试液为基体,用标准加入法作回收试验,测得4种元素的回收率在97.6%～102.0%之间。     

XRF检验标准物质中痕量元素的匀性

本文讨论了用Ｘ射线荧光光谱检验标准物质中痕量元素的均匀性时，可根据峰和背景强度确定能否用ＸＲＦ进行检验，以及相应于一定精度度要求的浓度下限（可检浓度），并以大米和岩石标准物质为例，计算了Ｃ－的可检浓度。还指出，作为均匀性检验量应采用浓度或净强度，尤其是对于痕量元素，最后说明了样品基体对可检浓度和最小样品量的影响。     

ICP－AES分析中用Kalman滤波法校正光谱干扰时波长定位误差对结果的影响及消除

本工作以Ｋａｌｍａｎ滤波技术为光谱干扰校正方法，选择典型的光谱干扰为例，系统研究了波长定位误差影响滤波结果准确性的规律性，提出了改善波长定位精度的途径。对于谱线重叠干扰的校正，波长定位精度一般应优于０．１ｐｍ；利用新息序列零均白噪音特性建立指示函数优化扫描光谱峰位，大大提高了波长定位精度，保证了滤波结果的准确性。     

ICP—AES分析中用Kalman滤波法校正光谱干扰时波长定位误差对结果的…

本工作以Ｋａｌｍａｎ滤波技术为光谱干扰校正方法，选择典型的光谱干扰为例，系统研究了波长定位误差影响滤波结果准确性的规律性，提出了改善波长定位精度的途径。对于谱线重叠干扰的校正，波长定位精度一般应优于０．１ｐｍ；利用新息序列零均白噪音特性建立指示函数优化扫描光谱峰位，大大提高了波长定位精度，保证了滤波结果的准确性。     

高分辨电感耦合等离子体质谱法测定镍基单晶高温合金中36种痕量元素

基于高分辨电感耦合等离子体质谱法(HR-ICP-MS)的质谱干扰消除技术,对镍基单晶高温合金中36种痕量元素检测的质谱条件、基体干扰、质谱干扰与同位素选择进行了研究。取样品0.100 0 g,用体积比为3∶1的盐酸-硝酸混合酸10 mL、氢氟酸1 mL溶解,用水定容至250 mL。通过复杂基体质谱干扰计算判定、共存元素干扰消除,确定了待测元素的同位素和分辨模式,将镍基单晶高温合金中痕量元素准确测定的元素种类确定为36种。采用标准加入法进行定量分析,36种痕量元素的检出限(3s)为0.004～6.000μg·L^-1。方法用于分析国际标准物质,得到的测定值与认定值基本一致。方法用于镍基单晶高温合金样品分析,36种痕量元素的检出量为0.000 001 0%～0.018%。     

超声雾化电感耦合等离子体原子发射光谱法测定高纯锡锭中痕量杂质元素

建立了高纯锡锭中砷、锑、镉等12种痕量杂质元素的超声雾化－ICP－AES测定方法，考察了基体对杂质元素的干扰影响，采用HCl H2O2沸不浴蒸干排Sn处理，使样品90％的Sn基体挥发与待测元素分离消除基体干扰，方法快速、准确、具有比气动雾化更低的检出限，回收率为88％－103％，RSD均小于5％。     

Optimisation of plasma techniques for trace analysis of refractory metals

Besides atomic absorption spectrometry, the plasma techniques can be seen as state-of-the-art instrumentation in an industrial laboratory for the analysis of trace elements today. For the analysis of refractory metals, e.g. Mo and W, the determination limits which can be reached by ICP-AES techniques are mainly restricted by the spectral background of the matrix. Advantages and disadvantages of sequential and simultaneous detection as well as different methods of evaluation, such as Kaiman filtering and multiple component spectral fitting, are discussed. The results are compared with trace matrix separation techniques and on-line coupling of ion chromatography with ICP-AES and ICP-MS. Furthermore, the limitations of all techniques with respect to their applicability for routine analysis, especially the complexity of sample preparation, degree of automation, time consumption and cost are shown. With respect to the detection capability, TMS with ICP-MS end determination is the most powerful technique, but for routine analysis simultaneous multielement determination from the matrix is favourable.     

Multicomponent-analysis computations based on kalman filtering

A theoretical introduction to the use of Kalman filtering in analytical chemistry is based on multicomponent-analysis computations with the non-recursive least-squares estimation method as a starting point. An initial value for the computation of the error covariance matrix is given and some new practical applications (determination of number of components, estimation of constant systematic error) are derived and demonstrated. Theory and practice suggest a new possible design for experimental measurements and novel applications of on-line computation and computer control. The excellent performance of the Kalman filter algorithm is demonstrated.     

Kalman滤波-流动注射化学发光法同时测定痕量铌和钽的研究

流动注射化学发光（Flow injection-chemiluminescence,简称FI-CL）是基于流动注射（FI）进样技术与化学发光（CL）定量分析结合的痕量分析技术,具有仪器简单、操作方便及易于自动化等特点,从而在分析痕量元素方面取得了较大进展,尤其在痕量金属元素快速分析方面更具有优势.     

The Kalman filter in analytical chemistry

During the past ten years, the means by which more information can be extracted from experimental data have become an important area of research in analytical chemistry. Digital filters have been demonstrated to have a number of applications to analytical problems. These techniques typically involve a least-squares fit of experimental data to some model of the process being filtered. One method for filtering experimental data is based on the Kalman filter, a recursive, linear digital filter first developed for use in navigation, but now used in many fields. This paper discusses the implementation of Kalman filters in analytical chemistry. The principles of state-space digital filtering are reviewed, and the development of state/space models is discussed. Discussion is focused on the discrete Kalman algorithms. Two examples are provided to demonstrate the operation of the discrete Kalman filtering algorithm. Similarities between Kalman filtering and weighted least-squares methods are considered, and the specific advantages and disadvantages of linear and nonlinear Kalman filtering approaches are evaluated. To illustrate the range of problems which benefit from use of the filter, a comprehensive literature survey of the application of Kalman filtering to chemical problems is provided.     

Study on the Determination of Nine Trace Metal Elements in BOEING Aircraft Engine Oil by ICP-AES

There are a few trace metal elements and a lot of organic matrix in aircraft engine oil. In order to decrease the disturbance of organic matrix and the loss of trace elements, the engine oil sample added with activated carbon powder (SP) is digested with dry digestion method.     

电感耦合等离子体原子发射光谱分析中自适应卡尔曼滤波法研究

将自适应卡尔曼滤波（ＡＫＦ）用于ＩＣＰ－ＡＥＳ信号处理，并对影响滤波的因素进行了探讨，对于一些典型光谱干扰，测定的回收率为８５－１０５％。在选择了合适的初始参数条件下，ＡＫＦ法分析结果优于常规卡尔曼滤波（ＮＫＦ）法。     

卡尔曼滤波紫外光度法同时测定饮料中苯甲酸及糖精的研究

在酸性条件下，用乙醚萃取、蒸干乙醚后，用ＮａＨＣＯ３溶解残渣，从复杂的样品中分离出苯甲酸和糖精，测定它们在２４５～２８１ｎｍ之间的紫外吸收，运用卡尔曼滤波算法计算两者的浓度，用新息序列监测干扰物质分离的程度。此法简化了许多分离手续，用于饮料分析，结果满意。     

Aspects of application of Kalman filtering in multicomponent spectrophotometry

It is shown theoretically and experimentally that the reliability of the analytical results obtained by Kalman filtering in multicomponent spectrophotometry can be judged by means of the normalized autocorrelation coefficient (NAC) of the innovation sequence. Variations of the initial values of the concentration vector X(0), the error covariance matrix P(0), and the measurement noise variance R over a wide range do not show a substantial effect on the computed results. The effect of the rounding-off errors associated with application of different forms of the equation for calculation of the error covariance matrix is also discussed.     

Simultaneous determination of seven trace impurities (Al, As, Cr, Fe, Ti, V and Zr) in high-purity nickel metal and nickel oxide by coprecipitation and inductively coupled plasma-atomic emission spectrometry

Nickel is not coprecipitated with lanthanum hydroxide in ammonium hydroxide solution because it forms rapidly soluble nickel ammine complexes. This behaviour is used for the separation of Ni matrix from trace elements. These are simultaneously and quantitatively coprecipitated with lanthanum hydroxide at pH 10.0 and separated from the Ni matrix. Seven trace elements (Al, As, Cr, Fe, Ti, V and Zr) in Ni metal and 3 certified elements (Cr, Fe and Ti) in a standard reference material of nickel oxide have been simultaneously determined by inductively coupled plasma-atomic emission spectrometry (ICP-AES).     

钛锡钼钨同时测定多元统计与滤波分辨法比较

采用多元线性回归、主成份回归、偏最小二乘、目标因子分析和自适应滤波等多元统计及滤波分辨法,借金属离子-苯基荧光酮PF-CTMAB显色体系同时测定钼钨钛锡四组分,结果良好。并进行了方法比较。