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81.
82.
Vikram Kestens Guy Auclair Katarzyna Drozdzewska Andrea Held Gert Roebben Thomas Linsinger 《Journal of Thermal Analysis and Calorimetry》2010,99(1):245-261
In this study, the use of differential scanning calorimetry (DSC) is demonstrated as a powerful technique that can provide
accurate thermodynamic property values of environmental contaminants such as polycyclic aromatic hydrocarbons (PAHs). In total,
47 high purity PAH certified reference materials were selected and analysed by DSC. Their onset melting temperature, enthalpy
of fusion and eutectic purity were calculated from the obtained melting endotherms. In addition, the entropy of fusion, which
was calculated from the onset melting temperature and enthalpy of fusion, is presented. All measurements were evaluated in
a metrologically rigorous manner, including measurement uncertainties. 相似文献
83.
Gert de Cooman Matthias C.M. Troffaes Enrique Miranda 《Journal of Mathematical Analysis and Applications》2008,340(2):982-999
This paper deals with n-monotone functionals, which constitute a generalisation of n-monotone set functions. Using the notion of exactness of a functional, we introduce a new notion of lower and upper integral which subsumes as particular cases most of the approaches to integration in the literature. As a consequence, we can characterise which types of integrals can be used to calculate the natural extension (the lower envelope of all linear extensions) of a positive bounded charge. 相似文献
84.
Using a general approach which provides sequential optimality conditions for a general convex optimization problem, we derive necessary and sufficient optimality conditions for composed convex optimization problems. Further, we give sequential characterizations for a subgradient of the precomposition of a K-increasing lower semicontinuous convex function with a K-convex and K-epi-closed (continuous) function, where K is a nonempty convex cone. We prove that several results from the literature dealing with sequential characterizations of subgradients are obtained as particular cases of our results. We also improve the above mentioned statements. 相似文献
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88.
Frederik Detobel Veronika Fekete Wim De Malsche Selm De Bruyne Han Gardeniers Gert Desmet 《Analytical and bioanalytical chemistry》2009,394(2):399-411
The present paper provides a detailed analysis of the analyte-wall adsorption effects in nanochannels, including a random
walk study of the analyte-wall collision frequency, and uses these insights to estimate wall desorption times from chromatographic
experiments in nanochannels. Using coumarin dye analytes and using a methanol/water mixture buffered at pH 3 in 120-nm deep
channels, the surface desorption times on naked fused-silica glass were found to be maximally of the order of 60 to 150 μs,
while they were found to be on the order of 100 to 500 μs on a hydrophobically coated wall. These nonzero adsorption and desorption
times lead to an additional band broadening when conducting chromatographic separations. Shear-driven flows, requiring a noncoated
moving wall and a stationary coated wall, intrinsically turn out to be more prone to this effect than pressure-driven or electro-driven
flows for example. The present study also shows that, interestingly, the number of analyte-wall collisions increases with
the inverse of the channel depth and not with its second power, as would be expected from the Einstein–Smoluchowski relationship
for molecular diffusion. 相似文献
89.
Illa X De Malsche W Gardeniers H Desmet G Romano-Rodríguez A 《Journal of separation science》2010,33(21):3313-3318
Experimental measurements to study the retention capacity and band broadening under retentive conditions using micromachined non-porous pillar array columns fabricated in cyclo olefin polymer are presented. In particular, three columns with different depths but with the same pillar structure have been fabricated via hot embossing and pressure-assisted thermal bonding. Separations of a mixture of four coumarins using varying mobile phase compositions have been monitored to study the relation between the retention factor and the ratio of organic solvent in the aqueous mobile phase. Moreover, the linear relation between the retention and the surface/volume ratio predicted in theory has been observed, achieving retention factors up to k=2.5. Under the same retentive conditions, minimal reduced plate height values of h(min)=0.4 have been obtained at retention factors of k=1.2. These experimental results are compared with the case of non-porous and porous silicon pillars. Similar results for the plate heights are achieved while retention factors are higher than the non-porous silicon column and considerably smaller than the porous pillar column, given the non-porous nature of the used cyclo olefin polymer. The feasibility of using this polymer column as an alternative to the pillar array silicon columns is corroborated. 相似文献
90.
Jeff Op de Beeck Wim De Malsche Joris Vangelooven Han Gardeniers Gert Desmet 《Journal of chromatography. A》2010,1217(39):6077-6084
We report on the possibility to perform HDC in micropillar array columns and the potential advantages of such a system. The HDC performance of a pillar array column with pillar diameter = 5 μm and an interpillar distance of 2.5 μm has been characterized using both a low MW tracer (FITC) and differently sized polystyrene bead samples (100, 200 and 500 nm). The reduced plate height curves that were obtained for the different investigated markers all overlapped very well, and attained a minimum value of about hmin = 0.3 (reduction based on the pillar diameter), corresponding to 1.6 μm in absolute value and giving good prospects for high efficiency separations. The obtained reduced retention time values were in fair agreement with that predicted by the Di Marzio and Guttman model for a flow between flat plates, using the minimal interpillar distance as characteristic interplate distance. 相似文献