An adaptive pruning algorithm for the discrete L-curve criterion

We describe a robust and adaptive implementation of the L-curve criterion. The algorithm locates the corner of a discrete L-curve which is a log–log plot of corresponding residual norms and solution norms of regularized solutions from a method with a discrete regularization parameter (such as truncated SVD or regularizing CG iterations). Our algorithm needs no predefined parameters, and in order to capture the global features of the curve in an adaptive fashion, we use a sequence of pruned L-curves that correspond to considering the curves at different scales. We compare our new algorithm to existing algorithms and demonstrate its robustness by numerical examples.     

Reservoir operations optimization via fuzzy criterion decision processes

In this paper, we propose the treatment of complex reservoir operation problems via our newly developed tool of fuzzy criterion decision processes. This novel approach has been shown to be a more flexible and useful analysis tool especially when it is desirable to incorporate an expert’s knowledge into the decision models. Additionally, it has been demonstrated that this form of decision models will usually result in an optimal solution, which guarantees the highest satisfactory degree. We provide a practical exemplification procedure for the models presented as well as an application example.     

The Pharmacophore Hypothesis of Novel Inhibitors for Aurora A Kinase

A three-dimensional pharmacophore model was developed from a series of inhibitors of Aurora A kinase to discover new potent anti-cancer agents using the HypoGen module in the Catalyst software. The pharmacophore model was developed based on the structure of 20 currently available inhibitors, which were carefully selected from the literature. The best hypothesis （Hypo 1） was defined by four features： one hydrogen-bond donor and three hy- drophobic points, with the best correlation coefficient of 0.909, the lowest rms deviation of 1.563, and the highest cost difference of 99.075. The Hypo 1 was then validated by a test set consisting of 24 compounds and by a cross-validation of 95% confidence level through randomizing the data using the CatScramble program, which suggested that a predictive pharmacophore model had been successfully obtained.     

Simplex-optimization with a new criterion. Applications to dual-column ion chromatography

A new optimization criterion for chromatography is presented. It was designed to evaluate the quality of chromatograms in a way similar to human estimation. Selectivity, efficiency, and time of analysis as well as the number of peaks were taken into account. The criterion has been tested in comparison with expert estimations and some modern criteria. A better agreement of the new criterion with human estimation of chromatographic quality compared to some literature criteria is shown. A number of successful optimization runs has been performed using the criterion together with simplex optimization.     

Determination of clindamycin in animal plasma by high-performance liquid chromatography combined with electrospray ionization mass spectrometry

A method for the quantification of clindamycin in animal plasma using high-performance liquid chromatography combined with electrospray ionization mass spectrometry (LC/ESI-MS/MS) is presented. Lincomycin is used as the internal standard. The sample preparation includes a simple deproteinization step with trichloroacetic acid. Chromatographic separation is achieved on an RP-18 Hypersil column using gradient elution with 0.01 M ammonium acetate and acetonitrile as mobile phase. Good linearity was observed in the range 0-10 microg ml(-1). The limit of quantification of the method is 50 ng ml(-1) and the limit of detection is 1.3 ng ml(-1). The method was shown out to be of use for pharmacokinetic studies of clindamycin formulations in dogs.     

Generalized criterion of solvent polarity as a tool for control of chromatographic process

The generalized (reductive) criterion of solvent polarity was obtained by the method of multiparametric optimization of the Snyder index P", Hildebrand parameter _T , permittivity _r , and solvatochromism parameter E _T (30). Possibilities of employing this criterion for estimation of the elution power of normal and reversed mobile phases used in high-performance liquid chromatography were considered.     

Screening,library-assisted identification and validated quantification of fifteen neuroleptics and three of their metabolites in plasma by liquid chromatography/mass spectrometry with atmospheric pressure chemical ionization

A liquid chromatographic/mass spectrometric assay with atmospheric pressure chemical ionization (APCI-LC/MS) is presented for the fast and reliable screening and identification and for the precise and sensitive quantification of 15 neuroleptic (antipsychotic) drugs and three of their relevant metabolites in plasma. It allows confirmation of the diagnosis of a neuroleptic overdose and monitoring of psychiatric patients' compliance. The neuroleptics amisulpride, bromperidol, clozapine, droperidol, flupenthixol, fluphenazine, haloperidol, melperone, olanzapine, perazine, pimozide, risperidone, sulpiride, zotepine and zuclopenthixol and the pharmacologically active metabolites norclozapine, clozapine N-oxide and 9-hydroxyrisperidone were extracted from plasma using solid-phase extraction and were separated on a Merck LiChroCART column with Superspher 60 RP Select B as the stationary phase. Gradient elution was performed using aqueous ammonium formate and acetonitrile. After screening and identification in the scan mode using the authors' new LC/MS library, the neuroleptics were quantified in the selected-ion mode. The quantification assay was fully validated. It was found to be selective and proved to be linear from sub-therapeutic to over therapeutic concentrations for all analytes. The corresponding reference levels are listed. The accuracy and precision data were within the required limits. The analytes were stable in frozen plasma for at least 1 month. The method was successfully applied to several authentic plasma samples from patients treated or intoxicated with various neuroleptics. The validated LC/MS assay has proved to be appropriate for the isolation, separation, screening, identification and quantification of various neuroleptics in plasma for clinical toxicology and therapeutic drug monitoring purposes.     

Validation of an analytical method to determine trace metal impurities in fluoride compounds by flame atomic absorption spectroscopy

 The development of an analytical method for the determination of some heavy metals (Fe, Cu, Co, Zn and Ni) in fluoride compounds [Cu(BF₄)₂, Sn(BF₄)₂, Pb(BF₄)₂ and HBF₄] by flame atomic absorption spectroscopy is described. This method is to be used as a routine analytical method in an industrial quality control laboratory. To this end the "performance characteristics" of an instrumental analytical method such as matrix effects, sensitivity, linearity, detection and quantitation limits, precision and accuracy were evaluated for every system under study. The results of these investigations showed that non-spectral interferences (due to the presence of large concentrations of major metals such as Cu, Sn and Pb) were observed. Nevertheless it was possible to define a matrix concentration interval where matrix effects were not statistically significant, and therefore a direct calibration approach could be used as the calibration tool whenever the major metal concentration was not higher than 40×10^–3 kg l^–1. A guide to the developement of an analytical method for trace metal determination is provided. General tools for quality control have been used in order to show how an analytical method can be tested daily and evaluated in a convenient manner. Received: 29 January 1997 Accepted: 11 March 1997     

直键与弯键的对称性判据

一穹键的提出人们认为,杂化轨道(HAO)角函数的最大值方向(亦即HAO的方向)指向与之键合的原子,这样形成的化学键称为“直键”。但环丙烷分子中的三个碳原子构成三元环,有60°的键角。而任意两个正交的S-P杂化轨道之间的夹角θ都不可能小于90°,因而形成C-C键的HAO,不可能指向键合原子,环上的C-C键不可能是直键,而是“弯键”(BentBond)。通常,人们认为张力分子环上的键是弯键,其他的键为直键。     

To what extent can an uncertainty calculation be general?

 It is argued that results of uncertainty calculations in chemical analysis should be taken into consideration with some caution owing to their limited generality. The issue of the uncertainty in uncertainty estimation is discussed in two aspects. The first is due to the differences between procedure-oriented and result-oriented uncertainty assessments, and the second is due to the differences between the theoretical calculation of uncertainty and its quantication using the validation (experimental) data. It is shown that the uncertainty calculation for instrumental analytical methods using a regression calibration curve is result-oriented and meaningful only until the next calibration. A scheme for evaluation of the uncertainty in uncertainty calculation by statistical analysis of experimental data is given and illustrated with examples from the author's practice. Some recommendations for the design of corresponding experiments are formulated.