OH-radical induced degradation of hydroxybenzoic- and hydroxycinnamic acids and formation of aromatic products—A gamma radiolysis study

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.     

Pupils’ attitudes towards mathematics: a comparative study of Norwegian and English secondary students

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.     

Intertwining operators and the restriction of representations of rank-one orthogonal groups

We give a complete classification of intertwining operators (breaking symmetry operators  ) between spherical principal series representations of O(n+1,1)$O(n+1,1)$ and O(n,1)$O(n,1)$ together with explicit formulae of the distribution kernels. Further we use this to determine the breaking symmetry operators between their irreducible composition factors.     

Desorption kinetics of model polar stratospheric cloud films measured using Fourier Transform Infrared Spectroscopy and Temperature‐Programmed Desorption

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 × 10^32±1.5 molec/cm² s, in good agreement with the literature. The beta form of nitric acid trihydrate, β–NAT, has an E_des 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, E_des is 17.3 ± 2 kcal/mol with log A = 35.9 ± 2.6; for nitric acid monohydrate, NAM, E_des 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     

A straightforward method for analysing the grain-size distribution in tungsten carbide - cobalt hardmetals

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.     

A Six-Pulse PASS MAS-NMR Technique Solved by a Phasor Method

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.