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601.
Maes A Meyns T Sustronck B Maes D De Backer P Croubels S 《Journal of mass spectrometry : JMS》2007,42(5):657-663
The aim of this study was to develop a rapid and sensitive method for the quantification of cefquinome in animal plasma and bronchoalveolar lavage (BAL) fluid using high-performance liquid chromatography combined with electrospray tandem mass spectrometry (LC-ESI-MS/MS). Cefadroxil is used as internal standard. For plasma, the sample preparation includes a simple deproteinization step with a Microcon filter. This allows detecting the unbound cefquinome concentration, which is correlated with the concentration in other body fluids, such as BAL fluid. To be able to detect the total plasma concentration, deproteinization with acetonitrile, followed by a back-extraction of actonitrile with dichloromethane was performed. The BAL fluid is centrifuged to precipitate floating particles. Chromatographic separation is achieved on a PLRP-S column using 0.005% formic acid and methanol as mobile phase. For plasma, good linearity was observed in the range of 5-2500 ng ml(-1) for both the unbound and total concentration. The response in BAL fluid was linear in the range of 4-1000 ng ml(-1). The limit of quantification (LOQ) was set at 5.00 ng ml(-1) for plasma and at 4.00 ng ml(-1) for BAL fluid. The limit of detection (LOD) was 3.12 ng ml(-1) and 0.41 ng ml(-1) for the unbound and total concentration in plasma, respectively, and was 1.43 ng ml(-1) for BAL fluid. The method was shown to be of use in a pharmacokinetic study in pigs, where the correlation between cefquinome concentrations in plasma and BAL fluid of pigs was studied. 相似文献
602.
Hermans I Breynaert E Poelman H De Gryse R Liang D Van Tendeloo G Maes A Peeters J Jacobs P 《Physical chemistry chemical physics : PCCP》2007,9(39):5382-5386
In this contribution, the formation and immobilisation of chromium(iii) hydroxyoxide colloids is investigated. Nano-sized Cr(iii) colloids are generated in situ upon reduction of Cr(vi), dosed to a stirred reactor. The growth of the elementary colloids by the consumption of solved Cr is kinetically unfavorable compared to their aggregation to larger secondary particles, the size of which depends on the concentration of the building block colloids. This aggregation process can be steered by simple process parameters such as dosing rate and concentration of the Cr(vi). The Cr(iii) colloids are immobilised in situ on a support material via precipitation chromatography. Upon drying, the initially amorphose hydroxyoxides are gradually transformed into crystalline Cr(2)O(3) nanoparticles, mainly located at the external surface of the support. This approach opens new opportunities for the synthesis of supported metal oxide catalysts. 相似文献
603.
604.
E. Kunnen G.T. BarkemaC. Maes D. ShamiryanA. Urbanowicz H. StruyfM.R. Baklanov 《Microelectronic Engineering》2011,88(5):631-634
This work proposes an extended model that describes the propagation of damage in porous low-k material exposed to a plasma. Recent work has indicated that recombination and diffusion play a more dominant role than VUV light [1], [2], [3], [4] and [5] in oxygen plasma induced damage. Especially at low depths, the radical concentration is determined by the number of radicals that disappear back into the plasma while the final depth of damage is defined by recombination of oxygen atoms. A logarithmic equation has been proposed to describe the behavior as a function of time. In this work this equation is extended to take diffusion into account, next to recombination. The results are in agreement with experimental data and one-dimensional random walk theory calculations. 相似文献
605.
606.
Kumauchi M Kaledhonkar S Philip AF Wycoff J Hara M Li Y Xie A Hoff WD 《Journal of the American Chemical Society》2010,132(44):15820-15830
PAS domains form a divergent protein superfamily with more than 20?000 members that perform a wide array of sensing and regulatory functions in all three domains of life. Only nine residues are well-conserved in PAS domains, with an Asn residue at the start of α-helix 3 showing the strongest conservation. The molecular functions of these nine conserved residues are unknown. We use static and time-resolved visible and FTIR spectroscopy to investigate receptor activation in the photosensor photoactive yellow protein (PYP), a PAS domain prototype. The N43A and N43S mutants allow an investigation of the role of side-chain hydrogen bonding at this conserved position. The mutants exhibit a blue-shifted visible absorbance maximum and up-shifted chromophore pK(a). Disruption of the hydrogen bonds in N43A PYP causes both a reduction in protein stability and a 3400-fold increase in the lifetime of the signaling state of this photoreceptor. A significant part of this increase in lifetime can be attributed to the helical capping interaction of Asn43. This extends the known importance of helical capping for protein structure to regulating functional protein kinetics. A model for PYP activation has been proposed in which side-chain hydrogen bonding of Asn43 is critical for relaying light-induced conformational changes. However, FTIR spectroscopy shows that both Asn43 mutants retain full allosteric transmission of structural changes. Analysis of 30 available high-resolution structures of PAS domains reveals that the side-chain hydrogen bonding of residue 43 but not residue identity is highly conserved and suggests that its helical cap affects signaling kinetics in other PAS domains. 相似文献
607.
de Smit E Cinquini F Beale AM Safonova OV van Beek W Sautet P Weckhuysen BM 《Journal of the American Chemical Society》2010,132(42):14928-14941
The stability and reactivity of ?, χ, and θ iron carbide phases in Fischer-Tropsch synthesis (FTS) catalysts as a function of relevant reaction conditions was investigated by a synergistic combination of experimental and theoretical methods. Combined in situ X-ray Absorption Fine Structure Spectroscopy/X-ray Diffraction/Raman Spectroscopy was applied to study Fe-based catalysts during pretreatment and, for the first time, at relevant high pressure Fischer-Tropsch synthesis conditions, while Density Functional Theory calculations formed a fundamental basis for understanding the influence of pretreatment and FTS conditions on the formation of bulk iron carbide phases. By combining theory and experiment, it was found that the formation of θ-Fe(3)C, χ-Fe(5)C(2), and ?-carbides can be explained by their relative thermodynamic stability as imposed by gas phase composition and temperature. Furthermore, it was shown that a significant part of the Fe phases was present as amorphous carbide phases during high pressure FTS, sometimes in an equivalent amount to the crystalline iron carbide fraction. A catalyst containing mainly crystalline χ-Fe(5)C(2) was highly susceptible to oxidation during FTS conditions, while a catalyst containing θ-Fe(3)C and amorphous carbide phases showed a lower activity and selectivity, mainly due to the buildup of carbonaceous deposits on the catalyst surface, suggesting that amorphous phases and the resulting textural properties play an important role in determining final catalyst performance. The findings further uncovered the thermodynamic and kinetic factors inducing the ?-χ-θ carbide transformation as a function of the carbon chemical potential μ(C). 相似文献
608.
Riccardo Salvio Sven Krabbenborg Wouter J. M. Naber Aldrik H. Velders David N. Reinhoudt Wilfred G. van der Wiel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(33):8235-8240
The treatment of a suspension of graphite oxide (GO) with sodium azide leads to a material that, after reduction, features amino groups at the top and bottom of the sheets. These groups react through microcontact printing with an isothiocyanate monolayer on a silicon oxide substrate to form covalent bonds that strongly attach to the particles on the surface. With ultrasonication it is possible to obtain exfoliation of the sheets that are not covalently bound to the surface leaving single‐layer platelets attached to the substrate. The azido derivative can be also used to functionalize the graphene oxide with long alkylic chains through a click chemistry approach. This functionalization results in the exfoliation of this material in dimethylformamide. The novel materials were fully characterized by different techniques including IR spectroscopy, thermogravimetric analysis (TGA), scanning and transmission electron microscopy (SEM and TEM), X‐Ray photoelectron spectroscopy (XPS), and solid state NMR spectroscopy. The material with amino groups, after the reduction step, is conductive with a resistivity only approximately seven times larger than that of unprocessed graphite. This implies that after reduction of the GO, the conjugated sp2 network is largely restored. We consider this to be an important step towards a chemical approach for forming conducting large‐area platelet films of single‐layer graphene. 相似文献
609.
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
610.