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31.
The calibration performance of partial least squares for one response variable (PLS1) can be improved by elimination of uninformative variables. Many methods are based on so-called predictive variable properties, which are functions of various PLS-model parameters, and which may change during the variable reduction process. In these methods variable reduction is made on the variables ranked in descending order for a given variable property. The methods start with full spectrum modelling. Iteratively, until a specified number of remaining variables is reached, the variable with the smallest property value is eliminated; a new PLS model is calculated, followed by a renewed ranking of the variables. The Stepwise Variable Reduction methods using Predictive-Property-Ranked Variables are denoted as SVR-PPRV. In the existing SVR-PPRV methods the PLS model complexity is kept constant during the variable reduction process. In this study, three new SVR-PPRV methods are proposed, in which a possibility for decreasing the PLS model complexity during the variable reduction process is build in. Therefore we denote our methods as PPRVR-CAM methods (Predictive-Property-Ranked Variable Reduction with Complexity Adapted Models). The selective and predictive abilities of the new methods are investigated and tested, using the absolute PLS regression coefficients as predictive property. They were compared with two modifications of existing SVR-PPRV methods (with constant PLS model complexity) and with two reference methods: uninformative variable elimination followed by either a genetic algorithm for PLS (UVE-GA-PLS) or an interval PLS (UVE-iPLS). The performance of the methods is investigated in conjunction with two data sets from near-infrared sources (NIR) and one simulated set. The selective and predictive performances of the variable reduction methods are compared statistically using the Wilcoxon signed rank test. The three newly developed PPRVR-CAM methods were able to retain significantly smaller numbers of informative variables than the existing SVR-PPRV, UVE-GA-PLS and UVE-iPLS methods without loss of prediction ability. Contrary to UVE-GA-PLS and UVE-iPLS, there is no variability in the number of retained variables in each PPRV(R) method. Renewed variable ranking, after deletion of a variable, followed by remodelling, combined with the possibility to decrease the PLS model complexity, is beneficial. A preferred PPRVR-CAM method is proposed. 相似文献
32.
Chromatographic separation techniques and data handling methods for herbal fingerprints: a review 总被引:2,自引:0,他引:2
As herbal medicines have an important position in health care systems worldwide, their current assessment and quality control are a major bottleneck. Over the past decade, major steps were taken not only to improve the quality of the herbal products but also to develop analytical methods ensuring their quality. Nowadays, chromatographic fingerprinting is the generally accepted technique for the assessment and quality control of herbal products. This paper briefly considers the evolution of the regulations and guidelines on the quality control of herbal medicines, and reviews the established analytical techniques for herbal fingerprinting with an emphasis on the most recent developments, such as miniaturized techniques, new stationary phases, analysis at high temperatures and multi-dimensional chromatography. Accessory to the new analytical techniques, the chemometric data handling techniques applied are discussed. Chemometrics provide scientists with useful tools in understanding the huge amounts of data generated by the analytical advances and prove to be valuable for quality control, classification and modelling of, and discrimination between herbal fingerprints. 相似文献
33.
The stereospecific syntheses of the four isomers of 6-formyl-5,6-epoxy hexanoic acid methyl ester , , and from Z-deoxy-D-ribose have allowed the preparation of methyl esters of LTA4, , and its three unnatural isomers. 相似文献
34.
We report a source of free electron pulses based on a field emission tip irradiated by a low-power femtosecond laser. The electron pulses are shorter than 70 fs and originate from a tip with an emission area diameter down to 2 nm. Depending on the operating regime we observe either photofield emission or optical field emission with up to 200 electrons per pulse at a repetition rate of 1 GHz. This pulsed electron emitter, triggered by a femtosecond oscillator, could serve as an efficient source for time-resolved electron interferometry, for time-resolved nanometric imaging and for synchrotrons. 相似文献
35.
We study three same-spin-state fermions of mass M interacting with a distinguishable particle of mass m in the unitary limit where the interaction has a zero range and an infinite s-wave scattering length. We predict an interval of mass ratio 13.384相似文献
36.
Yvan Notay 《Numerical Linear Algebra with Applications》2010,17(1):73-96
Two‐grid methods constitute the building blocks of multigrid methods, which are among the most efficient solution techniques for solving large sparse systems of linear equations. In this paper, an analysis is developed that does not require any symmetry property. Several equivalent expressions are provided that characterize all eigenvalues of the iteration matrix. In the symmetric positive‐definite (SPD) case, these expressions reproduce the sharp two‐grid convergence estimate obtained by Falgout, Vassilevski and Zikatanov (Numer. Linear Algebra Appl. 2005; 12 :471–494), and also previous algebraic bounds, which can be seen as corollaries of this estimate. These results allow to measure the convergence by checking ‘approximation properties’. In this work, proper extensions of the latter to the nonsymmetric case are presented. Sometimes approximation properties for the SPD case are summarized in loose terms; e.g.: Interpolation must be able to approximate an eigenvector with error bound proportional to the size of the eigenvalue (SIAM J. Sci. Comp. 2000; 22 :1570–1592). It is shown that this can be applied to nonsymmetric problems too, understanding ‘size’ as ‘modulus’. Eventually, an analysis is developed, for the nonsymmetric case, of the theoretical foundations of ‘compatible relaxation’, according to which a Fine/Coarse partitioning may be checked and possibly improved. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
37.
The performance of large-aperture hydrophone arrays to detect and localize blue and fin whales' 15-85 Hz signature vocalizations under ocean noise conditions was assessed through simulations from a normal mode propagation model combined to noise statistics from 15 960 h of recordings in Saguenay-St. Lawrence Marine Park. The probability density functions of 2482 summer noise level estimates in the call bands were used to attach a probability of detection/masking to the simulated call levels as a function of whale depth and range for typical environmental conditions. Results indicate that call detection was modulated by the calling depth relative to the sound channel axis and by modal constructive and destructive interferences with range. Masking of loud infrasounds could reach 40% at 30 km for a receiver at the optimal depth. The 30 dB weaker blue whale D-call were subject to severe masking. Mapping the percentages of detection and localization allowed assessing the performance of a six-hydrophone array under mean- and low-noise conditions. This approach is helpful for optimizing hydrophone configuration in implementing passive acoustic monitoring arrays and building their detection function for whale density assessment, as an alternative to or in combination with the traditional undersampling visual methods. 相似文献
38.
Andrzej Wolan Justyna A. Kowalska-Six Holisoa Rajerison Michèle Césario Marie Cordier Yvan Six 《Tetrahedron》2018,74(38):5248-5257
Two types of bicyclic N-cyclopropyl glycine ester derivatives have been prepared and put under scrutiny as possible precursors of azomethine ylides. The results demonstrate that they can indeed participate in 1,3-dipolar cycloaddition reactions with dipolarophiles, as illustrated in the cases of phenyl vinyl sulfone, N-phenylmaleimide, diethyl fumarate and diethyl maleate. The relative configurations of the major diastereoisomers produced are consistent with the predicted generation of azomethine ylide species, reacting in concerted cycloaddition processes. This unprecedented way of generating such 1,3-dipoles provides access to functionalised pyrrolizidine and pyrrolidine derivatives, that would be difficult to make directly by more classic methods. It was also found that using phenyl vinyl sulfone or N-phenylmaleimide as the dipolarophile reactant, a domino nucleophilic conjugate addition/1,3-dipolar cycloaddition process may operate competitively. 相似文献
39.
Robust cross-validation of linear regression QSAR models 总被引:1,自引:0,他引:1
Konovalov DA Llewellyn LE Vander Heyden Y Coomans D 《Journal of chemical information and modeling》2008,48(10):2081-2094
A quantitative structure-activity relationship (QSAR) model is typically developed to predict the biochemical activity of untested compounds from the compounds' molecular structures. "The gold standard" of model validation is the blindfold prediction when the model's predictive power is assessed from how well the model predicts the activity values of compounds that were not considered in any way during the model development/calibration. However, during the development of a QSAR model, it is necessary to obtain some indication of the model's predictive power. This is often done by some form of cross-validation (CV). In this study, the concepts of the predictive power and fitting ability of a multiple linear regression (MLR) QSAR model were examined in the CV context allowing for the presence of outliers. Commonly used predictive power and fitting ability statistics were assessed via Monte Carlo cross-validation when applied to percent human intestinal absorption, blood-brain partition coefficient, and toxicity values of saxitoxin QSAR data sets, as well as three known benchmark data sets with known outlier contamination. It was found that (1) a robust version of MLR should always be preferred over the ordinary-least-squares MLR, regardless of the degree of outlier contamination and that (2) the model's predictive power should only be assessed via robust statistics. The Matlab and java source code used in this study is freely available from the QSAR-BENCH section of www.dmitrykonovalov.org for academic use. The Web site also contains the java-based QSAR-BENCH program, which could be run online via java's Web Start technology (supporting Windows, Mac OSX, Linux/Unix) to reproduce most of the reported results or apply the reported procedures to other data sets. 相似文献
40.
Mangelings D Tanret I Meert V Eeltink S Schoenmakers PJ Kok WT Vander Heyden Y 《Journal of chromatographic science》2007,45(9):578-586
Polymeric methacrylate-based monoliths are evaluated in capillary electrochromatography (CEC) and pressurized capillary electrochromatography (p-CEC) for their potential in pharmaceutical analysis. Using a given polymerization mixture as a basis for the monolith synthesis, different mobile phase pH at constant organic modifier concentrations are tested in both CEC and p-CEC. The test set consists of basic, acidic, amphoteric, and neutral compounds, which are mainly pharmaceuticals. Because of the mainly hydrophobic character of the stationary phase, the interactions are largest when the compounds appear in an uncharged state, but some ion-exchange phenomena with negatively charged compounds can also be observed. In CEC, acidic substances are most retained at low pH. For amphoteric and neutral compounds, no preference regarding analyzing pH can be derived from these experiments. For basics, a high pH is chosen, but a reduced solvent strength is needed to enhance the retention of these compounds. The retention mechanism in p-CEC can also be assigned to both hydrophobic and ionic interactions. For acidic, amphoteric, and neutral compounds, acceptable retention is seen. For the basic compounds, the retention with a mobile phase containing 50% organic modifier is low, as in CEC. However, when the organic modifier content in the mobile phase is decreased, retention increases and the selectivity of the stationary phase is more pronounced. This mode of operation presents a possibility for separating some test mixtures, thus some potential for pharmaceutical analysis is seen. More efforts are needed to obtain higher efficiencies and better peak shapes, which might be solved by a further optimization of both the stationary phase synthesis and the mobile phase composition. 相似文献