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41.
High-speed peak matching algorithm for retention time alignment of gas chromatographic data for chemometric analysis 总被引:5,自引:0,他引:5
A rapid retention time alignment algorithm was developed as a preprocessing utility to be used prior to chemometric analysis of large datasets of diesel fuel profiles obtained using gas chromatography (GC). Retention time variation from chromatogram-to-chromatogram has been a significant impediment against the use of chemometric techniques in the analysis of chromatographic data due to the inability of current chemometric techniques to correctly model information that shifts from variable to variable within a dataset. The alignment algorithm developed is shown to increase the efficacy of pattern recognition methods applied to diesel fuel chromatograms by retaining chemical selectivity while reducing chromatogram-to-chromatogram retention time variations and to do so on a time scale that makes analysis of large sets of chromatographic data practical. Two sets of diesel fuel gas chromatograms were studied using the novel alignment algorithm followed by principal component analysis (PCA). In the first study, retention times for corresponding chromatographic peaks in 60 chromatograms varied by as much as 300 ms between chromatograms before alignment. In the second study of 42 chromatograms, the retention time shifting exhibited was on the order of 10 s between corresponding chromatographic peaks, and required a coarse retention time correction prior to alignment with the algorithm. In both cases, an increase in retention time precision afforded by the algorithm was clearly visible in plots of overlaid chromatograms before and then after applying the retention time alignment algorithm. Using the alignment algorithm, the standard deviation for corresponding peak retention times following alignment was 17 ms throughout a given chromatogram, corresponding to a relative standard deviation of 0.003% at an average retention time of 8 min. This level of retention time precision is a 5-fold improvement over the retention time precision initially provided by a state-of-the-art GC instrument equipped with electronic pressure control and was critical to the performance of the chemometric analysis. This increase in retention time precision does not come at the expense of chemical selectivity, since the PCA results suggest that essentially all of the chemical selectivity is preserved. Cluster resolution between dissimilar groups of diesel fuel chromatograms in a two-dimensional scores space generated with PCA is shown to substantially increase after alignment. The alignment method is robust against missing or extra peaks relative to a target chromatogram used in the alignment, and operates at high speed, requiring roughly 1 s of computation time per GC chromatogram. 相似文献
42.
Jana Porubsk Bob Alince Theo G. M. van de Ven 《Colloids and surfaces. A, Physicochemical and engineering aspects》2002,210(2-3):223-230
The effects of cationic polyethylenimine (PEI) on the colloidal stability of anionic fines (microcrystalline cellulose or thermomechanical fines), fillers (clay) and their mixtures in deionized and tap water were investigated, using a photometric dispersion analyzer. Measurements confirmed that PEI flocculates all used materials by charge neutralization. As expected, higher additions of PEI lead to electrostatic stabilization of microcellulose and clay suspensions, but it was not possible to stabilize the suspension of fines using high additions of PEI. This is ascribed to the mechanical entanglements of fibrillar fines. In tap water, much more PEI is needed to reach optimum flocculation conditions than in deionized water. Heteroflocculation between PEI-coated clay and fines takes place with a rate which, for high fines concentration and a constant clay concentration, is independent of fines concentration. A theoretical model for the heteroflocculation of fines with PEI-coated clay has been developed, which explains the observed trends. In essence, clay particles can act as bridging agents for fines flocculation. 相似文献
43.
Tadeusz Bednarski 《Probability Theory and Related Fields》1981,58(3):397-405
Summary Solutions to minimax test problems between neighbourhoods generated by specially defined capacities are discussed. The capacities are superpositions of probability measures and concave functions, so the paper covers most of the earlier results of Huber and Rieder concerning minimax testing between -contamination and total variation neighbourhoods. It is shown that the Neyman-Pearson lemma for 2-alternating capacities, proved by Huber and Strassen, can be applied to test problems between noncompact neighbourhoods of probability measures. It turns out that the Radon-Nikodym derivative between the special capacities is usually a nondecreasing function of the truncated likelihood ratio of some probability measures. 相似文献
44.
Five chemical compounds, CuMoO4, Cu3Mo2O9, Cu2Mo3O10, Cu6Mo4O15, and Cu4?x Mo3O12 (0.10 ? x ? 0.40), were identified in the system Cu2OCuOMoO3 and characterized by DTA, X-ray powder patterns, ir spectra, and magnetic properties. Cupric molybdates CuMoO4 and Cu3Mo2O9 are stable in air up to 820 and 855°C, respectively, melting at these temperatures with simultaneous decomposition (oxygen loss). Congruent mp of cuprous molybdates Cu2Mo3O10 and Cu6Mo4O15, in argon, are 532 and 466°C, respectively. Nonstoichiometric phase Cu4?x Mo3O12 = Cu2+3Cu01?xMo6+3O12, melts in argon between 630 and 650°C depending on the value of x and at 525–530°C undergoes polymorphic transformation. Areas of coexistence of the above-mentioned phases are determined. The μeff of Cu2+ ions and θ values are: 1.80 B.M. and 28°K for CuMoO4, 1.71 B.M. and ? 12°K for Cu3Mo2O9, and 1.74 B.M. and ? 93°K for Cu4?xMo3O12. Below 200°K CuMoO4 becomes antiferromagnetic. Cu2Mo3O10 and Cu6Mo4O15 show weak temperature-independent paramagnetism. 相似文献
45.
Teresa Olszewska Maria J. Milewska Maria Gdaniec Tadeusz Połoński 《Tetrahedron: Asymmetry》2012,23(3-4):278-283
The crystal structures of several bicyclic N-nitrosamines indicate that they crystallize in the chiral (Sohncke) space group P212121 as conglomerates. This allows the resolution of these compounds by manual picking of the enantiomorphous crystals. The optical activity of the single crystals was confirmed by their CD spectra taken in KBr disks. The absolute configurations of the title nitrosamines were assigned by crystallographic measurements and by a comparison of their CD spectra with those of a reference compound resolved by classical methods. The observed Cotton effect signs, corresponding to the n–π1 transition, were correlated with the helicity of the inherently chiral nitrosamine chromophore. 相似文献
46.
A symmetric monoidal category naturally arises as the mathematical structure that organizes physical systems, processes, and composition thereof, both sequentially and in parallel. This structure admits a purely graphical calculus. This paper is concerned with the encoding of a fixed causal structure within a symmetric monoidal category: causal dependencies will correspond to topological connectedness in the graphical language. We show that correlations, either classical or quantum, force terminality of the tensor unit. We also show that well-definedness of the concept of a global state forces the monoidal product to be only partially defined, which in turn results in a relativistic covariance theorem. Except for these assumptions, at no stage do we assume anything more than purely compositional symmetric-monoidal categorical structure. We cast these two structural results in terms of a mathematical entity, which we call a causal category. We provide methods of constructing causal categories, and we study the consequences of these methods for the general framework of categorical quantum mechanics. 相似文献
47.
48.
Motasem Y. D. Alazaiza Su Kong Ngien Mustafa M. Bob Samira A. Kamaruddin Wan Mohd Faizal Ishak 《Transport in Porous Media》2017,117(1):103-123
Double porosity is a substantial microstructure characteristic in a wide range of geomaterials. It is a natural phenomenon that can be found in many types of soil, and it can result from biological, chemical or mechanical damage. In this paper, the influence of macro-pores on dense non-aqueous phase liquid (DNAPL) migration in double-porosity medium was investigated using light transmission visualization technique. Three experiments were carried out in two-dimensional flow chambers filled with a double-porosity medium composed of a mixture of local sand and sintered kaolin clay spheres arranged in a periodic manner. In each experiment, a different volumetric fraction of macro-pores and micropores was used. Tetrachloroethylene (PCE) was used to simulate DNAPL, and it was dyed using Oil-Red-O for better visualization. A predetermined amount of PCE was injected into the flow chambers and this amount was re-calculated using image analysis. A very strong correlation was found between the PCE amount injected and the amount calculated from image analysis in each experiment. The experiment was repeated by filling the flow chamber with silica sand to represent single-porosity medium. The results show that the macro-pores have a considerable effect on the PCE migration in double-porosity soil as the PCE movement was the fastest in the third experiment which contained the largest macro-pores volume. The accuracy of the method was validated using statistical analysis. The results show a slight difference between the means of the three experiments, indicating that the method is viable for monitoring NAPL migration in double-porosity medium under different volumetric fractions of macro-pores and micropores. 相似文献
49.
Prof. Juliusz Pernak Michał Niemczak Prof. Łukasz Chrzanowski Łukasz Ławniczak Przemysław Fochtman Katarzyna Marcinkowska Prof. Tadeusz Praczyk 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(34):12012-12021
This study focused on the synthesis and subsequent characterization of herbicidal ionic liquids based on betaine and carnitine, two derivatives of amino acids, which were used as cations. Four commonly used herbicides (2,4‐D, MCPA, MCPP and Dicamba) were used as anions in simple (single anion) and oligomeric (two anions) salts. The obtained salts were subjected to analyzes regarding physicochemical properties (density, viscosity, refractive index, thermal decomposition profiles and solubility) as well as evaluation of their herbicidal activity under greenhouse and field conditions, toxicity towards rats and biodegradability. The obtained results suggest that the synthesized herbicidal ionic liquids displayed low toxicity (classified as category 4 compounds) and showed similar or improved efficacy against weed compared to reference herbicides. The highest increase was observed during field trials for salts containing 2,4‐D as the anion, which also exhibited the highest biodegradability (>75 %). 相似文献
50.
Accurate quantification of polymer distributions is one of the main challenges in polymer analysis by liquid chromatography. The response of contemporary detectors is typically influenced by compositional features such as molecular weight, chain composition, end groups, and branching. This renders the accurate quantification of complex polymers of which there are no standards available, extremely challenging. Moreover, any (programmed) change in mobile‐phase composition may further limit the applicability of detection techniques. Current methods often rely on refractive index detection, which is not accurate when dealing with complex samples as the refractive‐index increment is often unknown. We review current and emerging detection methods in liquid chromatography with the aim of identifying detectors, which can be applied to the quantitative analysis of complex polymers. 相似文献