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61.
Ketoprofen (KP) is a nonsteroidal anti-inflammatory drug, which during UV irradiation rapidly transforms into benzophenone derivatives. Such transformation products may occur after topical application of KP, which is then exposed to sunlight resulting in a photo-allergic reaction. These reactions are mediated by the benzophenone moiety independently of the amount of allergen. The same reactions will also occur during wastewater or drinking water treatment albeit their effect in the aqueous environment is yet to be ascertained. In addition, only a few such transformation products have been recognised. To enable the detection and structural elucidation of the widest range of KP transformation products, this study applies complementary chromatographic and mass spectrometric techniques including gas chromatography coupled to single quadrupole or ion trap mass spectrometry and liquid chromatography hyphenated with quadrupole-time-of-flight mass spectrometry. Based on structural information gained in tandem and multiple MS experiments, and on highly accurate molecular mass measurements, chemical structures of 22 transformation products are proposed and used to construct an overall breakdown pathway. Among the identified transformation products all but two compounds retained the benzophenone moiety--a result, which raises important issues concerning the possible toxic synergistic effects of KP and its transformation products. These findings trigger further research into water treatment technologies that would limit their entrance into environmental or drinking waters. 相似文献
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Birgit G. Koehler 《国际化学动力学杂志》2001,33(5):295-309
This study combines Fourier transform infrared (FTIR) spectroscopy and temperature‐programmed desorption to examine the evaporation kinetics of thin films of crystalline nitric acid hydrates, solid amorphous H2O/HNO3 mixtures, H2O–ice, ice coated with HCl, and solid HNO3. IR spectroscopy measured the thickness of each film as it evaporated, either at constant temperature or during a linear temperature ramp (temperature‐programmed infrared, TPIR). Simultaneously, a mass spectrometer measured the rate of evaporation directly by monitoring the evolution of the molecules into the gas phase (temperature‐programmed desorption, TPD). Both TPIR and TPD data provide a measurement of the desorption rate and yield the activation energy and preexponential factor for desorption. TPD measurements have the advantage of producing many data points but are subject to interference from experimental difficulties such as uneven heating from the edge of a sample and sample‐support as well as pumping‐speed limitations. TPIR experiments give clean but fewer data points. Evaporation occurred between 170 and 215 K for the various films. Ice evaporates with an activation energy of 12.9 ± 1 kcal/mol and a preexponential factor of 1 × 1032±1.5 molec/cm2 s, in good agreement with the literature. The beta form of nitric acid trihydrate, β–NAT, has an Edes of 15.6 ± 2 kcal/mol with log A = 34.3 ± 2.3; the alpha form of nitric acid trihydrate, α–NAT, is around 17.7 ± 3 kcal/mol with log A = 37.2 ± 4. For nitric acid dihydrate, NAD, Edes is 17.3 ± 2 kcal/mol with log A = 35.9 ± 2.6; for nitric acid monohydrate, NAM, Edes is 13 ± 3 kcal/mol with log A = 31.4 ± 3. The α–NAT converts to β–NAT during evaporation, and the amorphous solid H2O/HNO3 mixtures crystallize during evaporation. The barrier to evaporation for pure nitric acid is 14.6 ± 3 kcal/mol with log A = 34.4 ± 3. © 2001 John Wiley & Sons, Inc. Int J Chem Kinet 33: 295–309, 2001 相似文献
64.
Michael Brieseck Walter Lengauer Birgit Gneiß Karin Wagner Stephanie Wagner 《Mikrochimica acta》2010,168(3-4):309-316
Measurement of the grain-size distribution of sintered hardmetals is indispensable in research and production. In this study we present a method consisting of etching hardmetals in order to remove the cobalt binder and to analyse the remaining tungsten-cobalt (WC) crystallites on the basis of scanning electron microscopy images subjected to a PC-based image analysis by use of MATLAB®. Sample preparation is easy and quick to perform, i.e. it does not require metallographic polishing. It consists of either deep etching of the cobalt binder of cut and optionally hand-ground surfaces or etching of fracture surfaces. Two different computational routines and one combination thereof are described. Two hardmetal grades with average WC grain sizes slightly larger as well as smaller than 200 nm were investigated. The results of the computer algorithms are compared to data obtained by manual linear intercept analysis. The analysis has good potential to avoid time-consuming metallographic preparation and pre-treatment for grain-size analysis, which is especially true for hardmetals with extremely fine grain size. 相似文献
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Birgit Effey J.A. Butcher Jr. R.L. Cappelletti 《Journal of magnetic resonance (San Diego, Calif. : 1997)》1998,132(2):266-273
The PASS MAS-NMR technique is capable of recovering full intensities of the central resonances of a spectrum by phase adjusting the spinning sidebands. This variant of the original PASS sequence by Dixon uses six π pulses instead of four. The addition of two π pulses provides more flexibility in choosing the spacing between pulses and therefore eliminates pulse overlap and receiver dead-time problems. The nonlinear, underdetermined PASS equations were solved using a graphical phasor method. All PASS sequences were successfully tested. A table of the six pulse delay times for different pitches is presented. 相似文献
68.
Shermin S. Goh Guilhem Chaubet Birgit Gockel Marie‐Caroline A. Cordonnier Hannah Baars Andrew W. Phillips Edward A. Anderson 《Angewandte Chemie (International ed. in English)》2015,54(43):12618-12621
Two enantioselective total syntheses of the nortriterpenoid natural product rubriflordilactone A are described, which use palladium‐ or cobalt‐catalyzed cyclizations to form the CDE rings, and converge on a late‐stage synthetic intermediate. These key processes are set up through the convergent coupling of a common diyne component with appropriate AB‐ring aldehydes, a strategy that sets the stage for the synthetic exploration of other members of this family of natural products. 相似文献
69.
We prove a Desch‐Schappacher type perturbation theorem for strongly continuous and locally equicontinuous one‐parameter semigroups which are defined on a sequentially complete locally convex space. 相似文献
70.
The remobilization of antimony and vanadium from previously loaded commercial granular ferric-hydroxide GEH material (intended for water treatment) was examined by using a sequential extraction procedure and three different leaching systems to evaluate their physicochemical mobility and potential availability under different simulated environmental conditions. A classical batch extraction, an extraction cell (EC) and rotating-coiled columns (RCC) were used as extraction systems.For each system it could be shown that the content of ion-exchangeable antimony and vanadium in previously loaded material is negligible (<1.5%). The oxyanions were sorbed strongly and could be predominantly remobilized through reducing agents, which means through dissolution of the iron (hydr)oxide matrix.The major advantages of dynamic systems in comparison to batchwise fractionation technique are the drastically reduced extraction time and the possibility of generating information to the leaching kinetics. It is shown that the efficiency of the three leaching systems is quite different employing Wenzel's sequential fractionation protocol. Only by working with RCC, the iron (hydr)oxide matrix was completely dissolved within four steps resulting in the total mobilization of antimony and vanadium. EC seems to be less suitable for leaching studies of Sb and V sorbed on iron(hydr)oxide. The remobilizable proportion of the several fractions was lower in comparison to batch and RCC and seems to be a result of an agglomeration of the GEH in the EC device. 相似文献