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421.
de Vlieger JS Giezen MJ Falck D Tump C van Heuveln F Giera M Kool J Lingeman H Wieling J Honing M Irth H Niessen WM 《Analytica chimica acta》2011,698(1-2):69-76
In this paper we describe the hyphenation of high temperature liquid chromatography with ICP-MS and ESI-MS for the characterization of halogen containing drug metabolites. The use of temperature gradients up to 200°C enabled the separation of metabolites with low organic modifier content. This specific property allowed the use of detection methods that suffer from (significant) changes in analyte response factors as a function of the organic modifier content such as ICP-MS. Metabolites of two kinase inhibitors (SB-203580-Iodo and MAPK inhibitor VIII) produced by bacterial cytochrome P450 BM3 mutants and human liver microsomes were identified based on high resolution MS(n) data. Quantification was done using their normalized and elemental specific response in the ICP-MS. The importance of these kinds of quantification strategies is stressed by the observation that the difference of the position of one oxygen atom in a structure can greatly affect its response in ESI-MS and UV detection. 相似文献
422.
Mimi J. den Uijl Peter J. Schoenmakers Bob W.J. Pirok Maarten R. van Bommel 《Journal of separation science》2021,44(1):88-114
Recent applications of retention modelling in liquid chromatography (2015–2020) are comprehensively reviewed. The fundamentals of the field, which date back much longer, are summarized. Retention modeling is used in retention‐mechanism studies, for determining physical parameters, such as lipophilicity, and for various more‐practical purposes, including method development and optimization, method transfer, and stationary‐phase characterization and comparison. The review focusses on the effects of mobile‐phase composition on retention, but other variables and novel models to describe their effects are also considered. The five most‐common models are addressed in detail, i.e. the log‐linear (linear‐solvent‐strength) model, the quadratic model, the log–log (adsorption) model, the mixed‐mode model, and the Neue–Kuss model. Isocratic and gradient‐elution methods are considered for determining model parameters and the evaluation and validation of fitted models is discussed. Strategies in which retention models are applied for developing and optimizing one‐ and two‐dimensional liquid chromatographic separations are discussed. The review culminates in some overall conclusions and several concrete recommendations. 相似文献
423.
Vermoortele F Maes M Moghadam PZ Lennox MJ Ragon F Boulhout M Biswas S Laurier KG Beurroies I Denoyel R Roeffaers M Stock N Düren T Serre C De Vos DE 《Journal of the American Chemical Society》2011,133(46):18526-18529
Para-disubstituted alkylaromatics such as p-xylene are preferentially adsorbed from an isomer mixture on three isostructural metal-organic frameworks: MIL-125(Ti) ([Ti(8)O(8)(OH)(4)(BDC)(6)]), MIL-125(Ti)-NH(2) ([Ti(8)O(8)(OH)(4)(BDC-NH(2))(6)]), and CAU-1(Al)-NH(2) ([Al(8)(OH)(4)(OCH(3))(8)(BDC-NH(2))(6)]) (BDC = 1,4-benzenedicarboxylate). Their unique structure contains octahedral cages, which can separate molecules on the basis of differences in packing and interaction with the pore walls, as well as smaller tetrahedral cages, which are capable of separating molecules by molecular sieving. These experimental data are in line with predictions by molecular simulations. Additional adsorption and microcalorimetric experiments provide insight in the complementary role of the two cage types in providing the para selectivity. 相似文献
424.
Maarten M. J. Smulders Marko M. L. Nieuwenhuizen Tom F. A. de Greef Dr. Paul van der Schoot Prof. Dr. Albertus P. H. J. Schenning Dr. E. W. Meijer Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(1):362-367
To study the supramolecular polymerisation mechanisms of a self‐assembling system, concentration‐ and temperature‐dependent measurements can both be used to probe the transition from the molecular dissolved state to the aggregated state. In this report, both methods are evaluated to determine their effectiveness in identifying and quantifying the self‐assembly mechanism for isodesmic and cooperative self‐assembling systems. It was found that for a rapid and unambiguous determination of the self‐assembly mechanism and its thermodynamic parameters, temperature‐dependent measurements are more appropriate. These studies allow the acquisition of a large data set leading to an accurate determination of the self‐assembly mechanism and quantification of the different thermodynamic parameters that describe the supramolecular polymerisation. For a comprehensive characterisation, additional concentration‐dependent measurements can be performed. 相似文献
425.
426.
The original Erds-Ko-Rado problem has inspired much research. It started as a study on sets of pairwise intersecting k-subsets in an n-set, then it gave rise to research on sets of pairwise non-trivially intersecting k-dimensional vector spaces in the vector space V (n, q) of dimension n over the finite field of order q, and then research on sets of pairwise non-trivially intersecting generators and planes in finite classical polar spaces. We summarize the main results on the Erds-Ko-Rado problem in these three settings, mention the Erds-Ko-Rado problem in other related settings, and mention open problems for future research. 相似文献
427.
Maarten K. Jongkind Theo van Kessel Dr. Marjolein E. Z. Velthoen Nic. Friederichs Prof. Dr. Bert M. Weckhuysen 《Chemphyschem》2020,21(15):1665-1674
The Cr/SiO2 Phillips catalyst has taken a central role in ethylene polymerization ever since its discovery in 1953. This catalyst is unique compared to other ethylene polymerization catalysts, since it is active without the addition of a metal-alkyl co-catalyst. However, metal-alkyls can be added for scavenging poisons, enhancing the catalyst activity, reducing the induction period and altering polymer characteristics. Despite extensive research into the working state of the catalyst, still no consensus has been reached. Here, we show that by varying the type of metal-alkyl co-catalyst and its amount, the Cr redox chemistry can be tailored, resulting in distinct catalyst activities, induction periods, and polymer characteristics. We have used in-situ UV-Vis-NIR diffuse reflectance spectroscopy (DRS) for studying the Cr oxidation state during the reduction by tri-ethyl borane (TEB) or tri-ethyl aluminum (TEAl) and during subsequent ethylene polymerization. The results show that TEB primarily acts as a reductant and reduces Cr6+ with subsequent ethylene polymerization resulting in rapid polyethylene formation. TEAl generated two types of Cr2+ sites, inaccessible Cr3+ sites and active Cr4+ sites. Subsequent addition of ethylene also revealed an increased reducibility of residual Cr6+ sites and resulted in rapid polyethylene formation. Our results demonstrate the possibility of controlling the reduction chemistry by adding the proper amount and type of metal-alkyl for obtaining desired catalyst activities and tailored polyethylene characteristics. 相似文献
428.
429.
Kaveh Sookhak Lari Maarten van Reeuwijk Čedo Maksimović 《Heat and Mass Transfer》2013,49(8):1191-1203
We report on RANS simulations of high Schmidt number turbulent mass transfer due to a first-order reaction on the surface of a d-type rough wall. We find that for low reaction coefficients, the additional surface area of the rough wall causes an increased mass transfer in comparison with a smooth wall. However, when the reaction coefficient is high, the mass transfer becomes lower than for a smooth wall. A detailed analysis shows that the mass transport in the cavity is dominated by diffusion which becomes the limiting factor at high reaction coefficients. A conceptual model, which is in good agreement with the simulations, highlights that the influence of geometry roughness is not confined to the roughness Reynolds number for molecular-diffusion-dominated cavities. 相似文献
430.