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121.
Birgit Prüger Dr. Gretchen E. Hofmeister Prof. Dr. Christian Borch Jacobsen David G. Alberg Prof. Dr. Martin Nielsen Dr. Karl Anker Jørgensen Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(12):3783-3790
Transition‐metal‐free formal Sonogashira coupling and α‐carbonyl arylation reactions have been developed. These transformations are based on the nucleophilic aromatic substitution (SNAr) of β‐carbonyl sulfones to electron‐deficient aryl fluorides, producing a key intermediate that, depending on the reaction conditions, gives the aromatic alkynes or α‐aryl carbonyl compounds. The development of these reactions is presented and, based on investigations under basic and acidic conditions, mechanisms have been proposed. To develop the formal Sonogashira coupling further, a milder, two‐step protocol is also disclosed that expands the reaction concept. The scope of these reactions is demonstrated for the synthesis of Sonogashira and α‐carbonyl arylated products from a range of electron‐deficient aryl fluorides with a variety of functional groups and aryl‐, heteroaryl‐, alkyl‐, and alkoxy‐substituted sulfone nucleophiles. These transition‐metal‐free reactions complement the metal‐catalyzed versions in terms of substitution patterns, simplicity, and reaction conditions. 相似文献
122.
Birgit Brucher Jens Rudat Christoph Syldatk Oliver Vielhauer 《Chromatographia》2010,71(11-12):1063-1067
In this study we describe the enantioseparation of aromatic β3-amino acids by precolumn derivatization with o-phthaldialdehyde and N-isobutyryl-l-cysteine. Derivatization conditions were studied in detail for (R,S)-β-phenylalanine and (R,S)-β-tyrosine revealing a reaction time of 1 min and a molar ratio of the reagents β³-amino acid to o-phthaldialdehyde to N-isobutyryl-l-cysteine of 1:25:25 as optimal. The method was validated for (R,S)-β-phenylalanine in a bacterial cell extract. The analysis provided excellent specificity and reproducibility. The limit of quantification was 25 pmol per 0.5 μL injection. The method could be successfully transferred to the enantioseparation of other β³-amino acids. Enantioseparation of all studied compounds could be achieved in 4–11 min. 相似文献
123.
Soowhan Kim Jingling Yan Birgit Schwenzer Jianlu Zhang Liyu Li Jun Liu Zhenguo Yang Michael A. Hickner 《Electrochemistry communications》2010,12(11):1650-1653
As an alternative to Nafion® ion exchange membrane, an inexpensive commercially-available Radel® polymer was sulfonated, fabricated into a thin membrane, and evaluated for its performance in a vanadium redox flow battery (VRFB). The sulfonated Radel (S-Radel) membrane showed almost an order of magnitude lower permeability of VO2+ ions (2.07 × 10?7 cm2/min), compared to Nafion 117 (1.29 × 10?6 cm2/min), resulting in better coulombic efficiency (~ 98% vs. 95% at 50 mA/cm2) and lower capacity loss per cycle. Even though the S-Radel membrane had a slightly higher membrane resistance, the energy efficiency of the VRFB with the S-Radel membrane was comparable to that of Nafion because of its better coulombic efficiency resulting from the lower vanadium ion crossover. The S-Radel membrane exhibited good performance up to 40 cycles, but a decline in performance at later cycles was observed, likely as a result of membrane degradation. 相似文献
124.
125.
Birgit Krimmel Friederike Swoboda Sonja Solar Gottfried Reznicek 《Radiation Physics and Chemistry》2010,79(12):1247-1254
The OH-radical induced degradation of hydroxybenzoic acids (HBA), hydroxycinnamic acids (HCiA) and methoxylated derivatives, as well as of chlorogenic acid and rosmarinic acid was studied by gamma radiolysis in aerated aqueous solutions. Primary aromatic products resulting from an OH-radical attachment to the ring (hydroxylation), to the position occupied by the methoxyl group (replacement –OCH3 by ?OH) as well as to the propenoic acid side chain of the cinnamic acids (benzaldehyde formations) were analysed by HPLC–UV and LC–ESI–MS. A comparison of the extent of these processes is given for 3,4-dihydroxybenzoic acid, vanillic acid, isovanillic acid, syringic acid, cinnamic acid, 4-hydroxycinnamic acid, caffeic acid, ferulic acid, isoferulic acid, chlorogenic acid, and rosmarinic acid. For all cinnamic acids and derivatives benzaldehydes were significant oxidation products. With the release of caffeic acid from chlorogenic acid the cleavage of a phenolic glycoside could be demonstrated. Reaction mechanisms are discussed. 相似文献
126.
Birgit Pepin 《ZDM》2011,43(4):535-546
Comparing English and Norwegian pupils’ attitude towards mathematics, in this article I develop a deeper understanding of the factors that may shape and influence ‘pupil attitude towards mathematics’, and argue for it as a socio-cultural construct embedded in and shaped by students’ environment and context in which they learn mathematics. The theoretical framework leans on work by Zan and Di Martino (The Montana Mathematics Enthusiast, Monograph 3, pp. 157–168, 2007) to elicit Norwegian and English pupils’ attitude of mathematics as they experience it in their respective environments. Whilst there were differences which could be seen to be accounted for by differently ‘figured’ environments, there are also many similarities. It was interesting to see that, albeit based on a small statistical sample, in both countries students had a positive attitude towards mathematics in year 7/8, which dropped in year 9, and increased again in years 10/11. This result could be explained and compared with other larger scale studies (e.g. Hodgen et al. in Proceedings of the British Society for Research into Learning Mathematics. 29(3), 2009). The analysis of pupils’ qualitative comments (and classroom observations) suggested seven factors that appeared to influence pupil attitude most, and these had ‘superficial’ commonalities, but the perceptions that appeared to underpin these mentions were different, and could be linked to the environments of learning mathematics in their respective classrooms. In summary, it is claimed that it is not enough to identify the factors that may shape and influence pupil attitude, but more importantly, to study how these are ‘lived’ by pupils, what meanings are made in classrooms and in different contexts, and how the factors interrelate and can be understood. 相似文献
127.
Yosef E. Maruvka Nadav M. Shnerb Sorin Solomon Gur Yaari David A. Kessler 《Journal of statistical physics》2011,142(6):1302-1316
The inference of past demographic parameters from current genetic polymorphism is a fundamental problem in population genetics.
The standard techniques utilize a reconstruction of the gene-genealogy, a cumbersome process that may be applied only to small
numbers of sequences. We present a method that compares the total number of haplotypes (distinct sequences) with the model
prediction. By chopping the DNA sequence into pieces we condense the immense information hidden in sequence space into a function
for the number of haplotypes versus subsequence size. The details of this curve are robust to statistical fluctuations and
are seen to reflect the process parameters. This procedure allows for a clear visualization of the quality of the fit and,
crucially, the numerical complexity grows only linearly with the number of sequences. Our procedure is tested against both
simulated data as well as empirical mtDNA data from China and provides excellent fits in both cases. 相似文献
128.
We give a complete classification of intertwining operators (breaking symmetry operators ) between spherical principal series representations of O(n+1,1) and O(n,1) together with explicit formulae of the distribution kernels. Further we use this to determine the breaking symmetry operators between their irreducible composition factors. 相似文献
129.
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
130.