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Criterion for quantifying the reliability of analytical results in method development and evaluation
An important characteristic in judging analytical results for their suitability for a particular use is the reliability of the results. A procedure is developed for quantifying the reliability in a single measure, the maximum total error. This measure comprises both the bias and the precision of the results, and takes account of the statistical uncertainty of these estimates. The applicability of the procedure in method development and method evaluation is illustrated by means of a practical example, the flow-injection determination of orthophosphate. 相似文献
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The quantitative validation of the results of a flow-injection determination of penicillin in pharmaceutical formulations is described. The validation procedure is done by using VALID, which is a generally applicable validation program based on an expert system program. The automated penicillin assay is based on the enzymatic hydrolysis of the penicillin to the corresponding penicilloic acid, which reacts with iodine generated on-line; the iodine consumption is detected amperometrically. The method is evaluated for applicability in pharmaceutical quality control. The complete validation procedure is described. During the program run, the system evaluates the calibration procedure, the drift of the analytical systemm and the effect of the sample matrix. The reliability of the flow-injection method is estimated by evaluating the maximum total error (MTE), which includes both random error and systematic error. The latter was assessed by comparing of the results of the flow-injection method with the results obtained by titration with mercury(II) as the reference method. The user requirement for the assay was an MTE of 10%. The validation procedure showed that the analytical method complied with the requirements for the major part of the concentration range (0.066–0.25 mM). 相似文献
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Garcia Ruano JL Alemparte C Martin Castro AM Adams H Rodriguez Ramos JH 《The Journal of organic chemistry》2000,65(23):7938-7943
The behavior of (Z)-3-p-tolylsulfinylacrylonitrile (1) as a chiral dienophile has been evaluated from its reactions with furan and acyclic dienes. Electrostatic interactions of the cyano group with the sulfinyl one restrict the conformational mobility around the C-S bond, thus controlling the pi-facial selectivity, which is almost complete in all cases, the approach of the diene from the less-hindered face of the dienophile (that bearing the lone electron pair) in the predominant rotamer being the favored one. The regioselectivity is also completely controlled by the cyano group. Additionally, the reactivity of compound 1 as well as its endo-selectivity are both higher than those observed for the corresponding (Z)-3-sulfinylacrylates, thus proving the potential of sulfinylnitriles as chiral dienophiles. 相似文献
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Dr. Laura Orian Lando P. Wolters Prof. Dr. F. Matthias Bickelhaupt 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(40):13337-13347
A mechanistic density functional theory study of acetylene [2+2+2] cyclotrimerization to benzene catalyzed by RhI half metallocenes is presented. The catalyst fragment contains a heteroaromatic ligand, that is, the 1,2‐azaborolyl (Ab) or the 3a,7a‐azaborindenyl (Abi) anions, which are isostructural and isoelectronic to the hydrocarbon cyclopentadienyl (Cp) and indenyl (Ind) anions, respectively, but differ from the last ones on having two adjacent carbon atoms replaced with a boron and a nitrogen atom. The better performance of either the classic hydrocarbon or the heteroaromatic catalysts is found to depend on the different mechanistic paths that can be envisioned for the process. The present analyses uncover and explain general structure–reactivity relationships that may serve as rational design principles. In particular, we provide evidence of a reverse indenyl effect. 相似文献
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EI Rodriguez Martinez CI Barriga-Paulino MI Zapata CC Chinchilla AM López-Jiménez CM Gómez 《BMC neuroscience》2012,13(1):104-23
ABSTRACT: BACKGROUND: The peri-adolescent period is a crucial developmental moment of transition from childhood to emergent adulthood. The present report analyses the differences in Power Spectrum (PS) of the Electroencephalogram (EEG) between late childhood (24 children between 8 and 13 years old) and young adulthood (24 young adults between 18 and 23 years old). RESULTS: The narrow band analysis of the Electroencephalogram was computed in the frequency range of 0--20 Hz. The analysis of mean and variance suggested that six frequency ranges presented a different rate of maturation at these ages, namely: low delta, delta-theta, low alpha, high alpha, low beta and high beta. For most of these bands the maturation seems to occur later in anterior sites than posterior sites. Correlational analysis showed a lower pattern of correlation between different frequencies in children than in young adults, suggesting a certain asynchrony in the maturation of different rhythms. The topographical analysis revealed similar topographies of the different rhythms in children and young adults. Principal Component Analysis (PCA) demonstrated the same internal structure for the Electroencephalogram of both age groups. Principal Component Analysis allowed to separate four subcomponents in the alpha range. All these subcomponents peaked at a lower frequency in children than in young adults. CONCLUSIONS: The present approaches complement and solve some of the incertitudes when the classical brain broad rhythm analysis is applied. Children have a higher absolute power than young adults for frequency ranges between 0-20 Hz, the correlation of Power Spectrum (PS) with age and the variance age comparison showed that there are six ranges of frequencies that can distinguish the level of EEG maturation in children and adults. The establishment of maturational order of different frequencies and its possible maturational interdependence would require a complete series including all the different ages. 相似文献
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Inside Cover: New Concepts for Designing d10‐M(L)n Catalysts: d Regime,s Regime and Intrinsic Bite‐Angle Flexibility (Chem. Eur. J. 36/2014)
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New Concepts for Designing d10‐M(L)n Catalysts: d Regime,s Regime and Intrinsic Bite‐Angle Flexibility
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Lando P. Wolters Dr. Willem‐Jan van Zeist Prof. Dr. F. Matthias Bickelhaupt 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(36):11370-11381
Our aim is to understand the electronic and steric factors that determine the activity and selectivity of transition‐metal catalysts for cross‐coupling reactions. To this end, we have used the activation strain model to quantum‐chemically analyze the activity of catalyst complexes d10‐M(L)n toward methane C?H oxidative addition. We studied the effect of varying the metal center M along the nine d10 metal centers of Groups 9, 10, and 11 (M=Co?, Rh?, Ir?, Ni, Pd, Pt, Cu+, Ag+, Au+), and, for completeness, included variation from uncoordinated to mono‐ to bisligated systems (n=0, 1, 2), for the ligands L=NH3, PH3, and CO. Three concepts emerge from our activation strain analyses: 1) bite‐angle flexibility, 2) d‐regime catalysts, and 3) s‐regime catalysts. These concepts reveal new ways of tuning a catalyst’s activity. Interestingly, the flexibility of a catalyst complex, that is, its ability to adopt a bent L‐M‐L geometry, is shown to be decisive for its activity, not the bite angle as such. Furthermore, the effect of ligands on the catalyst’s activity is totally different, sometimes even opposite, depending on the electronic regime (d or s) of the d10‐M(L)n complex. Our findings therefore constitute new tools for a more rational design of catalysts. 相似文献
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