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71.
An image processing approach originating from the proteomics field has been transferred successfully to the processing of data obtained with comprehensive two-dimensional gas chromatographic separations data. The approach described here has proven to be a useful analytical tool for unbiased pattern comparison or profiling analyses, as demonstrated with the differentiation of volatile patterns (“aroma”) from fruits such as apples, pears, and quince fruit. These volatile patterns were generated by headspace solid phase microextraction coupled to comprehensive two-dimensional gas chromatography (HS-SPME-GC × GC). The data obtained from GC × GC chromatograms were used as contour plots which were then converted to gray-scale images and analyzed utilizing a workflow derived from 2D gel-based proteomics. Run-to-run variations between GC × GC chromatograms, respectively their contour plots, have been compensated by image warping. The GC × GC images were then merged into a fusion image yielding a defined and project-wide spot (peak) consensus pattern. Within detected spot boundaries of this consensus pattern, relative quantities of the volatiles from each GC × GC image have been calculated, resulting in more than 700 gap free volatile profiles over all samples. These profiles have been used for multivariate statistical analysis and allowed clustering of comparable sample origins and prediction of unknown samples. At present state of development, the advantage of using mass spectrometric detection can only be realized by data processing off-line from the identified software packages. However, such information provides a substantial basis for identification of statistically relevant compounds or for a targeted analysis. 相似文献
72.
Rosa Perestrelo Sílvia Petronilho José S. Câmara Sílvia M. Rocha 《Journal of chromatography. A》2010,1217(20):3441-3445
An analytical methodology based on headspace solid phase microextraction (HS-SPME) combined with comprehensive two-dimensional gas chromatography—time-of-flight mass spectrometry (GC × GC–ToFMS) was developed for the identification and quantification of the toxic contaminant ethyl carbamate (EC) directly in fortified wines. The method performance was assessed for dry/medium dry and sweet/medium sweet model wines, and for quantification purposes, calibration plots were performed for both matrices using the ion extraction chromatography (IEC) mode (m/z 62). Good linearity was obtained with a regression coefficient (r2) higher than 0.981. A good precision was attained (R.S.D. <20%) and low detection limits (LOD) were achieved for dry (4.31 μg/L) and sweet (2.75 μg/L) model wines. The quantification limits (LOQ) and recovery for dry wines were 14.38 μg/L and 88.6%, whereas for sweet wines were 9.16 μg/L and 99.4%, respectively. The higher performance was attainted with sweet model wine, as increasing of glucose content improves the volatile compound in headspace, and a better linearity, recovery and precision were achieved. The analytical methodology was applied to analyse 20 fortified Madeira wines including different types of wine (dry, medium dry, sweet, and medium sweet) obtained from several harvests in Madeira Island (Portugal). The EC levels ranged from 54.1 μg/L (medium dry) to 162.5 μg/L (medium sweet). 相似文献
73.
Gilles Gasser Jonathan D. Carr Stephen J. Green Sean M. Cafferkey James H.R. Tucker 《Journal of organometallic chemistry》2010,695(2):249-3763
Two new ligand derivatives of ferrocene, namely N-4-[3,5-di-(2-pyridyl)-1,2,4-triazoyl]ferrocene carbimine (L1) and N-4-[3,5-di-(2-pyridyl)-1,2,4-triazoyl]ferrocene carbamide (L2), were synthesised in good yields by reacting the known compound 3,5-di-pyridine-2-yl-[1,2,4]triazol-4-ylamine (1) with ferrocenecarbaldehyde and chlorocarbonyl ferrocene, respectively. The structures of L1 and L2 were determined by X-ray crystallography. The complexation of L1 and L2 with CuI, AgI, ZnII and CdII was studied by NMR and UV-vis spectroscopies, as well as by electrochemistry, with titrations used to determine metal:ligand stoichiometries. The cyclic voltammograms of L1 and L2 and their respective complexes indicated reversible one-electron transfers corresponding to the Fc0/+ redox couple (Fc = ferrocene), with formal electrode potentials shifting to more positive values upon metal complexation. 相似文献
74.
本文在多类型复发间隔时间数据下,研究了一类广义半参数风险回归模型的参数估计问题,给出了该模型中未知参数和非参数函数的一种估计方法,并证明了估计量的相合性和渐近正态性.最后利用数值模拟来评估估计量在有限样本下的表现. 相似文献
75.
Frédérick Adam Didier Thiébaut Fabrice Bertoncini Marion Courtiade Marie-Claire Hennion 《Journal of chromatography. A》2010,1217(8):1386-1394
This paper reports the conditions of online hyphenation of supercritical fluid chromatography (SFC) with twin comprehensive two-dimensional gas chromatography (twin-GC × GC) for detailed characterization of middle distillates; this is essential for a better understanding of reactions involved in refining processes. In this configuration, saturated and unsaturated compounds that have been fractionated by SFC are transferred on two different GC × GC columns sets (twin-GC × GC) placed in the same GC oven. Cryogenic focusing is used for transfer of fractions into the first dimension columns before simultaneous GC × GC analysis of both saturated and unsaturated fractions. The benefits of SFC–twin-GC × GC are demonstrated for the extended alkane, iso-alkane, alkene, naphthenes and aromatics analysis (so-called PIONA analysis) of diesel samples which can be achieved in one single injection. For that purpose, saturated and unsaturated compounds have been separated by SFC using a silver loaded silica column prior to GC × GC analysis. Alkenes and naphthenes are quantitatively recovered in the unsaturated and saturated fractions, respectively, allowing their identification in various diesel samples. Thus, resolution between each class of compounds is significantly improved compared to a single GC × GC run, and for the first time, an extended PIONA analysis of diesel samples is presented. 相似文献
76.
Gaëlle Semard Valerie Peulon-Agasse Auguste Bruchet Jean-Philippe Bouillon Pascal Cardinaël 《Journal of chromatography. A》2010,1217(33):5449-5454
It is important to develop methods of optimizing the selection of column sets and operating conditions for comprehensive two-dimensional gas chromatography. A new method for the calculation of the percentage of separation space used was developed using Delaunay's triangulation algorithms (convex hull). This approach was compared with an existing method and showed better precision and accuracy. It was successfully applied to the selection of the most convenient column set and the geometrical parameters of second column for the analysis of 49 target compounds in wastewater. 相似文献
77.
Elizabeth M. Humston Joshua D. Knowles Andrew McShea Robert E. Synovec 《Journal of chromatography. A》2010,1217(12):1963-1970
Quality control of cacao beans is a significant issue in the chocolate industry. In this report, we describe how moisture damage to cacao beans alters the volatile chemical signature of the beans in a way that can be tracked quantitatively over time. The chemical signature of the beans is monitored via sampling the headspace of the vapor above a given bean sample. Headspace vapor sampled with solid-phase micro-extraction (SPME) was detected and analyzed with comprehensive two-dimensional gas chromatography combined with time-of-flight mass spectrometry (GC × GC–TOFMS). Cacao beans from six geographical origins (Costa Rica, Ghana, Ivory Coast, Venezuela, Ecuador, and Panama) were analyzed. Twenty-nine analytes that change in concentration levels via the time-dependent moisture damage process were measured using chemometric software. Biomarker analytes that were independent of geographical origin were found. Furthermore, prediction algorithms were used to demonstrate that moisture damage could be verified before there were visible signs of mold by analyzing subsets of the 29 analytes. Thus, a quantitative approach to quality screening related to the identification of moisture damage in the absence of visible mold is presented. 相似文献
78.
S. Abdalla 《Physica B: Condensed Matter》2011,406(3):584-587
The complicated structure of human blood has been characterized based on relaxation time, τ, and the Cole-Cole parameter, α, obtained from dielectric measurements. As previously reported by different authors, the experimental data show net deviation from the classical Debye model with certain distribution of relaxation times (Dτ). Plots of α versus width of the relaxation rate distribution of micro-particles inside the blood show that Dτ drastically affects the dielectric properties of the fluid. The mathematical function of Dτ is found to be Gaussian and we find that the α values of normal blood have net lower magnitude than that of diabetic blood. These results suggest that glucose in blood increases the broadness of the parameter α, which have significant importance in diabetic-biosensor manufacture. 相似文献
79.
In this paper we examine the various effects that workstations and rework loops with identical parallel processors and stochastic processing times have on the performance of a mixed-model production line. Of particular interest are issues related to sequence scrambling. In many production systems (especially those operating on just-in-time or in-line vehicle sequencing principles), the sequence of orders is selected carefully to optimize line efficiency while taking into account various line balancing and product spacing constraints. However, this sequence is often altered due to stochastic factors during production. This leads to significant economic consequences, due to either the degraded performance of the production line, or the added cost of restoring the sequence (via the use of systems such as mix banks or automated storage and retrieval systems). We develop analytical formulas to quantify both the extent of sequence scrambling caused by a station of the production line, and the effects of this scrambling on downstream performance. We also develop a detailed Markov chain model to analyze related issues regarding line stoppages and throughput. We demonstrate the usefulness of our methods on a range of illustrative numerical examples, and discuss the implications from a managerial point of view. 相似文献
80.
Gerber and Li (1981) formulated, using a Markov chain embedding, a system of equations that describes relations between generating functions of waiting time distributions for occurrences of patterns in a sequence of independent repeated experiments when the initial outcomes of the process are known. We show how this system of equations can be obtained by using the classical gambling team technique. We also present a form of solution of the system and give an example showing how first results of trials influence the probabilities that a chosen pattern precedes the remaining ones in a realization of the process. 相似文献