Über die Bestimmung der Oxalsäure

Analytical and Bioanalytical Chemistry -     

Raney-Co mediated reductive cyclization of an alpha,beta-unsaturated nitrile

An expedient, five step synthesis of caprolactam 1 is reported starting from natural L-homoserine. The key step is a chemoselective reductive cyclization of alpha,beta-unsaturated nitrile 10 mediated by Raney-Co type metals. This hydrogenation is extensively investigated in order to account for the observed product distribution and yields.     

Planar lattice gases with nearest-neighbor exclusion

We discuss the hard-hexagon and hard-square problems, as well as the corresponding problem on the honeycomb lattice. The case when the activity is unity is of interest to combinatorialists, being the problem of counting binary matrices with no two adjacent 1's. For this case, we use the powerful corner transfer matrix method to numerically evaluate the partition function per site, density and some near-neighbor correlations to high accuracy. In particular, for the square lattice, we obtain the partition function per site to 43 decimal places.     

The neural correlates of calculation ability in children: an fMRI study

Most studies investigating mental numerical processing involve adult participants and little is known about the functioning of these systems in children. The current study used functional magnetic resonance imaging (fMRI) to investigate the neural correlates of numeracy and the influence of age on these correlates with a group of adults and a group of third graders who had average to above average mathematical ability. Participants performed simple and complex versions of exact and approximate calculation tasks while in the magnet. Like adults, children activated a network of brain regions in the frontal and parietal lobes during the calculation tasks, and they recruited additional brain regions for the more complex versions of the tasks. However, direct comparisons between adults and children revealed significant differences in level of activation across all tasks. In particular, patterns of activation in the parietal lobe were significantly different as a function of age. Findings support previous claims that the parietal lobe becomes more specialized for arithmetic tasks with age.     

A new reagent for direct difluoromethylation

Molecular scaffolds containing alkylfluorine substituents are desired in many areas of chemical research from materials to pharmaceuticals. Herein, we report the invention of a new reagent (Zn(SO(2)CF(2)H)(2), DFMS) for the innate difluoromethylation of organic substrates via a radical process. This mild, operationally simple, chemoselective, and scalable difluoromethylation method is compatible with a range of nitrogen-containing heteroarene substrates of varying complexity as well as select classes of conjugated π-systems and thiols. Regiochemical comparisons suggest that the CF(2)H radical generated from the new reagent possesses nucleophilic character.     

Indication of reactor ν(e) disappearance in the Double Chooz experiment

The Double Chooz experiment presents an indication of reactor electron antineutrino disappearance consistent with neutrino oscillations. An observed-to-predicted ratio of events of 0.944±0.016(stat)±0.040(syst) was obtained in 101 days of running at the Chooz nuclear power plant in France, with two 4.25 GW(th) reactors. The results were obtained from a single 10 m(3) fiducial volume detector located 1050 m from the two reactor cores. The reactor antineutrino flux prediction used the Bugey4 flux measurement after correction for differences in core composition. The deficit can be interpreted as an indication of a nonzero value of the still unmeasured neutrino mixing parameter sin(2)2θ(13). Analyzing both the rate of the prompt positrons and their energy spectrum, we find sin(2)2θ(13)=0.086±0.041(stat)±0.030(syst), or, at 90% C.L., 0.017相似文献   

The determination of134Cs,137Cs,210Pb,226Ra and228Ra concentrations in nearshore marine sediments and seawater

Multi-radionuclide analyses of coastal marine sediments and seawater can be of considerable value in defining rates and mechanisms of nearshore processes. A preliminary study of¹³⁴Cs,¹³⁷Cs,²¹⁰Pb,²²⁶Ra and²²⁸Ra in the Clyde Sea Area has been performed. A summary of the marine geochemistries of these species and a detailed account of methods involved in their routine analysis are described.     

Free surface Stokes flows obstructed by multiple obstacles

Gravity‐driven Stokes flow down an inclined plane over and around multiple obstacles is considered. The flow problem is formulated in terms of a boundary integral equation and solved using the boundary element method. A Hermitian radial basis function (RBF) is used for the interpolation of the free surface, generation of the unit normal and curvature, and to prescribe the far‐field conditions. For flow over an obstacle, hemispheres are taken. For flow around an obstacle, circular cylinders are modelled and the contact angle condition on the obstacle/free surface intersection specified using the RBF formulation. Explicit profiles are produced for flow over and around two obstacles placed in various locations relative to one another. Interaction due to two obstacles is given by comparisons made with the profiles for flow over and around individual obstacles. In general, when the obstacles are separated by a sufficiently large distance the flow profiles are identical to a single obstacle analysis. For flow over and around two obstacles in‐line with the incident flow, effects of the governing parameters are examined, with variations in plane inclination angle, Bond number, obstacle size, and in the case of obstacles intersecting the free surface, static contact angle is considered. Finally flows over and around three obstacles are modelled. Copyright © 2009 John Wiley & Sons, Ltd.