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61.
J. J. Berzas Nevado J. Rodríguez Flores G. Castaeda Pealvo 《Analytica chimica acta》1997,340(1-3):257-265
Two spectrophotometric methods for the determination of Ethinylestradiol (ETE) and Levonorgestrel (LEV) by using the multivariate calibration technique of partial least square (PLS) and principal component regression (PCR) are presented. In this study the PLS and PCR are successfully applied to quantify both hormones using the information contained in the absorption spectra of appropriate solutions. In order to do this, a calibration set of standard samples composed of different mixtures of both compounds has been designed. The results found by application of the PLS and PCR methods to the simultaneous determination of mixtures, containing 4–11 μg ml−1 of ETE and 2–23 μg ml−1 of LEV, are reported. Five different oral contraceptives were analyzed and the results were very similar to that obtained by a reference liquid Chromatographic method. 相似文献
62.
Mohammad Ali Karimi Mohammad Mazloum Ardakani Omran Moradlou Reza Behjatmanesh‐Ardakani Fatemeh Banifatemeh 《中国化学会会志》2007,54(1):15-21
Simultaneous kinetic‐spectrophotometric determination of a ternary mixture of hydrazine (HZ) and its derivatives by principal component regression (PCR) and partial least squares (PLS) calibration is described. The methods were based on the difference observed in the reduction rate of iron(III) with HZ, thiosemicarbazide (TSCZ) and phenylhydrazine (PHZ) in the presence of 2,2′‐bipyridine (Bpy). The colored complex of [Fe(Bpy)3]2+ was formed in sodium dodecyl sulfate (SDS) as micellar media, and then monitored at 520 nm. The results showed that simultaneous determination of HZ, TSCZ and PHZ could be performed in their concentration ranges of 1.0–70.0, 0.2–6.0 and 0.1–10.0 μg mL?1, respectively. The root mean squares errors of prediction (RMSEP) of HZ, TSCZ and PHZ were 0.719, 0.164 and 0.105 (for PLS) 0.788, 0.166 and 0.993 (for PCR), respectively. Both methods (PCR and PLS) were validated using a set of synthetic sample mixtures and then applied for simultaneous determination of HZ, TSCZ and PHZ in water samples. 相似文献
63.
64.
A conjugate-gradient method is developed for computing the Moore-Penrose generalized inverseA
of a matrix and the associated projectors, by using the least-square characteristics of both the method and the inverseA
. Two dual algorithms are introduced for computing the least-square and the minimum-norm generalized inverses, as well asA
. It is shown that (i) these algorithms converge for any starting approximation; (ii) if they are started from the zero matrix, they converge toA
; and (iii) the trace of a sequence of approximations multiplied byA is a monotone increasing function converging to the rank ofA. A practical way of compensating the self-correcting feature in the computation ofA
is devised by using the duality of the algorithms. Comparison with Ben-Israel's method is made through numerical examples. The conjugate-gradient method has an advantage over Ben-Israel's method.After having completed the present paper, the author received from Professor M. R. Hestenes his paper entitledPseudo Inverses and Conjugate Gradients. This paper treated the same subject and appeared in Communications of the ACM, Vol. 18, pp. 40–43, 1975. 相似文献
65.
The partial least squares (PLS-1) calibration model based on spectrophotometric measurement, for the simultaneous determination of CN− and SCN− ions is described. The method is based on the difference in the rate of the reaction between CN− and SCN− ions with chloramine-T in a pH 4.0 buffer solution and at 30 °C. The produced cyanogen chloride (CNCl) reacts with pyridine and the product condenses with barbituric acid and forms a final colored product. The absorption kinetic profiles of the solutions were monitored by measuring absorbance at 578 nm in the time range 20-180 s after initiation of the reaction with 2 s intervals. The experimental calibration matrix for partial least squares (PLS-1) calibration was designed with 31 samples. The cross-validation method was used for selecting the number of factors. The results showed that simultaneous determination could be performed in the range 10.0-900.0 and 50.0-1200.0 ng mL−1 for CN− and SCN− ions, respectively. The proposed method was successfully applied to the simultaneous determination of cyanide and thiocyanate in water samples. 相似文献
66.
《Electroanalysis》2002,14(24):1699-1706
An application of a partial least squares calibration method for the simultaneous voltammetric determination of indomethacin, acemethacin, piroxicam and tenoxicam is suggested. It was shown that it is possible to resolve complex mixtures of analytes even when they have strongly overlapped signals. In order to check the proposed method, statistical analysis of the results was performed by mean of hypothesis tests. The method developed was applied to the electrochemical reduction region of four anti‐inflammatory drugs and allowed the drugs to be quantified at concentrations between 0.52 and 4.09 μg mL?1 for acemethacin, 0.44 and 3.50 μg mL?1 for indomethacin, 0.43 and 3.40 μg mL?1 for piroxicam, and 0.42 and 3.30 μg mL?1 for tenoxicam with good results. The average absolute value of relative errors was 2.25%, 4.31%, 1.68% and 2.49%, respectively. 相似文献
67.
A novel near infrared (NIR) modeling method—Laplacian regularized least squares regression (LapRLSR) was presented, which can take the advantage of many unlabeled spectra to promote the prediction performance of the model even if there are only few calibration samples. Using LapRLSR modeling, NIR spectral analysis was applied to the online monitoring of the concentration of salvia acid B in the column separation of Salvianolate. The results demonstrated that LapRLSR outperformed partial least squares (PLS) significantly, and NIR online analysis was applicable. 相似文献
68.
Daniela P. Mesquita Cristiano Leal Jorge R. Cunha Adrian Oehmen A. Luís Amaral Maria A.M. Reis Eugénio C. Ferreira 《Analytica chimica acta》2013
The present study focuses on predicting the concentration of intracellular storage polymers in enhanced biological phosphorus removal (EBPR) systems. For that purpose, quantitative image analysis techniques were developed for determining the intracellular concentrations of PHA (PHB and PHV) with Nile blue and glycogen with aniline blue staining. Partial least squares (PLS) were used to predict the standard analytical values of these polymers by the proposed methodology. Identification of the aerobic and anaerobic stages proved to be crucial for improving the assessment of PHA, PHB and PHV intracellular concentrations. Current Nile blue based methodology can be seen as a feasible starting point for further enhancement. Glycogen detection based on the developed aniline blue staining methodology combined with the image analysis data proved to be a promising technique, toward the elimination of the need for analytical off-line measurements. 相似文献
69.
70.
Exhaled breath condensate is a promising, non-invasive, diagnostic sample obtained by condensation of exhaled breath. Starting from a historical perspective of early attempts of breath testing towards the contemporary state-of-the-art breath analysis, this review article focuses mainly on the progress in determination of non-volatile compounds in exhaled breath condensate. The mechanisms by which the aerosols/droplets of non-volatile compounds are formed in the airways are discussed with methodological consequences for sampling. Dilution of respiratory droplets is a major problem for correct clinical interpretation of the measured data and there is an urgent need for standardization of EBC. This applies also for collection instrumentation and therefore various commercial and in-house built devices are described and compared with regard to their design, function and collection parameters. The analytical techniques and methods for determination of non-volatile compounds as potential markers of oxidative stress and lung inflammation are scrutinized with an emphasis on method suitability, sensitivity and appropriateness. The relevance of clinical findings for each group of possible non-volatile markers of selected pulmonary diseases and methodological recommendations with emphasis on interdisciplinary collaboration that is essential for future development into a fully validated clinical diagnostic tool are given. 相似文献