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101.
Building a calibration model with detection and quantification capabilities is identical to the task of building a regression model. Although commonly used by analysts, an application of the calibration model requires at first careful attention to the three components of the regression triplet (data, model, method), examining (a) the data quality of the proposed model; (b) the model quality; (c) the LS method to be used or a fulfillment of all least-squares assumptions. This paper summarizes these components, describes the effects of deviations from assumptions and considers the correction of such deviations: identifying influential points is the first step in least-squares model building, the calibration task depends on the regression model used, and finally the least squares LS method is based on assumptions of normality of errors, homoscedasticity, independence of errors, overly influential data points and independent variables being subject to error. When some assumptions are violated, the ordinary LS is inconvenient and robust M-estimates with the iterative method of reweighted least-squares must be used. The effects of influential points, heteroscedasticity and non-normality on the calibration precision limits are also elucidated. This paper also considers the proper construction of the statistical uncertainty expressed as confidence limits predicting an unknown concentration (or amount) value, and its dependence on the regression triplet. The authors' objectives were to provide a thorough treatment that includes pertinent references, consistent nomeclature, and related mathematical formulae to show by theory and illustrative examples those approaches best suited to typical problems in analytical chemistry. Two new algorithms, calibration and linear regression written in s-plus and enabling regression triplet analysis, the estimation of calibration precision limits, critical levels, detection limits and quantification limits with the statistical uncertainty of unknown concentrations, form the goal of this paper. 相似文献
102.
Makarević J Jokić M Frkanec L Katalenić D Zinić M 《Chemical communications (Cambridge, England)》2002,(19):2238-2239
Some bis (amino acid) oxalamide gelators form common thermo-reversible gels with various organic solvents but also gels of exceptional thermal stability with some solvents of medium and low polarity; the latter gels can be heated up to 50 degrees C higher temperatures than the bp of the solvent without apparent gel-to-sol transition. 相似文献
103.
104.
Arsov Z Schara M Strancar J 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2002,157(1):52-60
Using EPR spectroscopy a typical lateral domain structure was detected in the membranes of spin-labeled bovine erythrocyte ghosts. The spectral parameters were determined by decomposing the EPR spectrum into three spectral components and tuned by a hybrid-evolutionary-optimization method. In our experiments the lateral domain structure and its properties were influenced by the variation in the temperature and by the addition of n-butanol. The specific responses of the particular domain types were detected. For the most-ordered domain type a break was seen in the temperature dependence of its order parameter, while the order parameters of the two less-ordered domain types exhibited a continuous decrease. Below the break-point temperature the alcohol-induced membrane fluidity variation is mainly a consequence of the change in the proportions of the least- and the most-ordered domain type and not the change of the domain-type ordering or dynamics (with n-butanol concentration). On the other hand, the fluidity variation above the break-point temperature arises from both types of changes. Interestingly, the proportion of the domain type that has its order parameter between that of the least- and the most-ordered domain type remains almost constant with concentration as well as with temperature, which implies its stability. Such characterization of the lateral membrane domain structure could be beneficial when considering the lipid-protein interactions, because it can be assumed that the activity of the membrane-bound enzyme depends on the properties of the particular domain type. 相似文献
105.
Milan Kučera 《Czechoslovak Mathematical Journal》1999,49(3):449-474
Variational inequalities
are studied, where K is a closed convex cone in
, 3, B
is a × matrix, G is a small perturbation, a real parameter. The assumptions guaranteeing a Hopf bifurcation at some 0 for the corresponding equation are considered and it is proved that then, in some situations, also a bifurcation of periodic solutions to our inequality occurs at some I 0. Bifurcating solutions are obtained by the limiting process along branches of solutions to penalty problems starting at 0 constructed on the basis of the Alexander-Yorke theorem as global bifurcation branches of a certain enlarged system. 相似文献
106.
In this paper the Mossbauer spectra of a chromite at 140K 200K and 298K were measured. Next nearest neighbor effects were
used to explain the spectra of the chromite, and multiple doublets of Fe2+ ions on the A sites were caused by the different cation combinations on 12 next nearest neighbor B sites. The quandrupole
splitting of each of mult iple Fe2+ doublets decreases with increasing temperature. 相似文献
107.
108.
Milan Marhol 《Fresenius' Journal of Analytical Chemistry》1967,231(4):265-272
Summary Uranium or thorium separations from a number of various ions were studied by means of cation exchangers containing phosphorus in their functional group. These ion exchangers adsorb selectively only UO2
2+ or Th4+ ions from the mixture studied in a medium of >0.4 N nitric or hydrochloric acid. Several di- and trivalent cations are not sorbed under these conditions. In the absence of UO2
2+ and Th4+ ions, Me2+ may be more easily separated quantitatively from Me3+ in 0.2 N nitric or hydrochloric acid than with cation exchangers containing the -SO3H group.
Zusammenfassung Die quantitative Trennung von UO2 2+ oder Th4+ von einer Reihe anderer Ionen wurde mit Hilfe phosphorhaltiger Kationenaustauscher untersucht. Diese Ionenaustauscher sorbieren selektiv nur UO2 2+ oder Th4+-Ionen aus einem Medium von >0,4 N HNO3 oder HCl. Eine Reihe verschiedener zwei- und dreiwertiger Kationen wird unter diesen Bedingungen nicht sortiert. Bei Abwesenheit von UO2 2+- und Th4+-Ionen kann man Me2+ in 0,2 N HNO3- oder HCl-Lösung quantitativ von Me3+ trennen, und zwar leichter als mit -SO3H-haltigen Austauschern.相似文献
109.
A method has been developed for the quantitative coulometric permanganatometric micro-determination of hydrogen peroxide. The end-point is ascertained by the colour changes of the indicators ferroin, and nitro-ferroin respectively 相似文献
110.
An algorithm for encoding long strings of building blocks, like 4 DNA bases (adenine-A, cytosine-C, thymine-T, and guanidine-G), 20 natural amino acids (from Alanine Ala to Valine-Val, plus the stop triplet), or all 64 possible base triplets (from AAA to TTT), into "zigzag" or "spectrum-like" representations is suggested. The new encoding scheme can be derived in the 3-, 2-, or 1-dimensional form depending on the user's wishes. The only information, besides the string for which the "spectrum-like" representation is sought, is the initial positioning of the complete set of units from which the string is composed, i.e., four positions for A, C, G, and T, or 20 positions for natural amino acids plus stop, etc. This initial positioning can be initialized in either the 3-, 2-, or 1-D form. As an illustration of the suggested encoding scheme of the visual and chemometric comparison of the first 10 exon strings of the beta globin gene of 10 different species, each string consisting of about 100 basic amino acids long is shown. 相似文献