Asymmetric epoxidation of alkenes by a chiral manganese(III) salen complex anchored onto a functionalised hexagonal mesoporous silica

A Jacobsen-type catalyst was anchored onto an amine functionalised hexagonal mesoporous silica (HMS) through the diimine bridge fragment of the complex. The new heterogeneous catalyst, as well as the precedent materials, were characterised by elemental analyses, FTIR-DRIFT, UV-vis, porosimetry and XPS which showed that the complex was successfully anchored. This material was active in the epoxidation of styrene and α-methylstyrene in dichloromethane at 0°C using, respectively, m-CPBA/NMO and NaOCl. With the former substrate no asymmetric induction was found in the epoxide, whereas with the latter substrate higher %ee was found than in homogeneous phase. Using the latter experimental conditions, catalyst reuse led to no significant loss of catalytic activity and enantioselectivity. © 2005 Elsevier B.V. All rights reserved.

Symmetric and asymmetric evaluation of the Tokamap in comparison with direct symplectic integration

Comparing the Poincaré plots of the Tokamap and the underlying Hamiltonian system reveals large differences. This stems from the particular choice of evaluation of the singular perturbations present in the system (a series of δ functions). A symmetric evaluation approach is proposed and shown to yield results that almost perfectly match the Hamiltonian system. © 2005 The American Physical Society.

Bio-inspired carbon electro-catalysis for the oxygen reduction reaction

We report the synthesis, characterisation and catalytic performance of two nature-inspired biomass-derived electro-catalysts for the oxygen reduction reaction in fuel cells. The catalysts were prepared via pyrolysis of a real food waste (lobster shells) or by mimicking the composition of lobster shells using chitin and CaCO3 particles followed by acid washing. The simplified model of artificial lobster was prepared for better reproducibility. The calcium carbonate in both samples acts as a pore agent, creating increased surface area and pore volume, though considerably higher in artificial lobster samples due to the better homogeneity of the components. Various characterisation techniques revealed the presence of a considerable amount of hydroxyapatite left in the real lobster samples after acid washing and a low content of carbon (23%), nitrogen and sulphur (<1%), limiting the surface area to 23 m2/g, and consequently resulting in rather poor catalytic activity. However, artificial lobster samples, with a surface area of ≈200 m2/g and a nitrogen doping of 2%, showed a promising onset potential, very similar to a commercially available platinum catalyst, with better methanol tolerance, though with lower stability in long time testing over 10,000 s.

Risk, seasonality and the asymmetric behaviour of stock returns

For some time there has been a puzzle surrounding the seasonal behaviour of stock returns. This paper demonstrates that there is an asymmetric relationship between systematic risk and return across the different months of the year for both large and small firms. In the case of both large and small firms systematic risk appears to be priced in only two months of the year, January and April. During the other months no persistent relationship between systematic risk and return appears to exist. The paper also shows that when systematic risk is priced, the size of the systematic risk premium is higher for large firms than for small firms and varies significantly across the months of the year.

Directional bend sensor based on an asymmetric modification of the fiber cladding by femtosecond laser

A femtosecond laser was used to modify a part of the cladding of a standard LPG bend sensor. The device produced wavelength shifts depending upon the direction of bend, thus making a shape sensor.

Long period grating directional bend sensor based on asymmetric index modification of cladding

A long period grating (LPG) written in a standard optical fibre was modified by using a femtosecond laser to induce an asymmetric change in the cladding's refractive index. This device produced blue and red wavelength shifts depending on the orientation of applied curvature, with maximum sensitivities of -1.6 nm m and +3.8 nm m, suggesting that this type of LPG may be useful as a shape sensor.

Strong localization of whispering gallery modes in an optical fiber via asymmetric perturbation of the translation symmetry

Recently introduced Surface Nanoscale Axial Photonics (SNAP) is based on whispering gallery modes circulating around the optical FIber surface and undergoing slow axial propagation. In this paper we develop the theory of propagation of whispering gallery modes in a SNAP microresonator, which is formed by nanoscale asymmetric perturbation of the FIber translation symmetry and called here a nanobump microresonator. The considered modes are localized near a closed stable geodesic situated at the FIber surface. A simple condition for the stability of this geodesic corresponding to the appearance of a high Q-factor nanobump microresonator is found. The results obtained are important for engineering of SNAP devices and structures.

Asymmetric advertising impact

Companies under pressure from stakeholders to meet profit expectations are often tempted to cut advertising expenses, particularly in times of economic difficulties. However, firms may not fully grasp the actual impact of such drastic cuts. Indeed, the general assumption is that advertising effects are symmetric: the numerical sales impact of budget increase or decrease would be the same in absolute value. Our paper addresses this gap by developing a new model based on multivariate time-series analysis (VAR models) to capture these asymmetric dynamic relationships. Our results show that advertising models are improved by allowing the capture of these asymmetric patterns.

Performance impact of asymmetric filtered 40Gb/s RZ DPSK system:tight optical filtering considerations

We present the impact of Asymmetric filtering of strong (e.g. 35 GHz) optical filters on the performance of 42.7 Gb/s 50% RZ-DPSK systems. The performance is evaluated when offsetting the filter by substantial amounts and it is found that with an offset of almost half the bit rate there is a significant improvement in the calculated Q.

Characterization of asymmetric filtered 40 Gb/s RZ-DPSK system-strong filtering considerations

We present the impact of frequency offsetting of strong (e.g. 35 GHz) optical filters on the performance of 42.7 Gb/s 50% RZ-DPSK systems. The performance is evaluated when offsetting the filter by substantial amounts and it is found that with an offset of almost half the bit rate there is a significant improvement in the calculated 'Q' (> 1 dB). We deployed balanced, constructive single ended and destructive single ended detection, so that we could investigate the physical origins of the penalty reduction of asymmetric filtering of 42.7 Gb/s 50% RZ-DPSK system.

Phosphorus catalysis in the pyrolysis behaviour of biomass

Phosphorus is a key plant nutrient and as such, is incorporated into growing biomass in small amounts. This paper examines the influence of phosphorus, present in either acid (HPO) or salt ((NH)PO) form, on the pyrolysis behaviour of both Miscanthus × giganteus, and its cell wall components, cellulose, hemicellulose (xylan) and lignin (Organosolv). Pyrolysis-gas chromatography-mass spectrometry (PY-GC-MS) is used to examine the pyrolysis products during thermal degradation, and thermogravimetric analysis (TGA) is used to examine the distribution of char and volatiles. Phosphorus salts are seen to catalyse the pyrolysis and modify the yields of products, resulting in a large increase in char yield for all samples, but particularly for cellulose and Miscanthus. The thermal degradation processes of cellulose, xylan and Miscanthus samples occur in one step and the main pyrolysis step is shifted to lower temperature in the presence of phosphorus. A small impact of phosphorus was observed in the case of lignin char yields and the types of pyrolysis decomposition products produced. Levoglucosan is a major component produced in fast pyrolysis of cellulose. Furfural and levoglucosenone become more dominant products upon P-impregnation pointing to new rearrangement and dehydration routes. The P-catalysed xylan decomposition route leads to a much simpler mixture of products, which are dominated by furfural, 3-methyl-2-cyclopenten-1-one and one other unconfirmed product, possibly 3,4-dihydro-2-methoxy-2H-pyran or 4-hydroxy-5,6-dihydro-(2H)-pyran-2-one. Phosphorus-catalysed lignin decomposition also leads to a modified mixture of tar components and desaspidinol as well as other higher molecular weight component become more dominant relative to the methoxyphenyl phenols, dimethoxy phenols and triethoxy benzene. Comparison of the results for Miscanthus lead to the conclusion that the understanding of the fast pyrolysis of biomass can, for the most part, be gained through the study of the individual cell wall components, provided consideration is given to the presence of catalytic components such as phosphorus.

Long period grating directional bend sensor based on asymmetric index modification of cladding

A long period grating (LPG) written in a standard optical fibre was modified by using a femtosecond laser to induce an asymmetric change in the cladding's refractive index. This device produced blue and red wavelength shifts depending on the orientation of applied curvature, with maximum sensitivities of -1.6 nm m and +3.8 nm m, suggesting that this type of LPG may be useful as a shape sensor.