Transesterification of an RNA model in buffer solutions in H2O and D2O

Transesterification of a phosphodiester bond of RNA models has been studied in various buffer solutions, under neutral and slightly alkaline conditions in H₂O and D₂O. The results show that imidazole is the only buffer system where a clear buffer catalysis on the cleavage of a phosphodiester bond is observed. The rate enhancement in sulphonic acid buffers is smaller, and a sulphonate base, particularly, is inactive as a catalyst. The rate‐enhancing effect of imidazole is, however, catalytic, and the catalytic inactivity of sulphonate buffers can be attributed to their structure and/or charge. The catalysis by imidazole is a complex system which, in addition to first‐order reactions, involves a process that shows a second‐order dependence in imidazole concentration. The latter reaction becomes significant in acidic imidazole buffers (pH < pK_a), as the buffer concentration increases. The kinetic solvent deuterium isotope effect k_H/k_D, referring to first‐order catalysis by imidazole base, is 2.3 ± 0.3. That referring to second‐order catalysis is most probably much larger, but an accurate value could not be obtained. Copyright © 2007 John Wiley & Sons, Ltd.     

Unambiguous Mono Deuterium Labelling of Alkyl Ethyl Ketones at the α Position of the Ethyl Group by Ruthenium (III) Catalyzed Isomerization of O-Deuterated Allylic Alcohols

Ruthenium (III) tris acetylacetonate is an efficient catalyst for the isomerization of O-deuterated alkylvinyl carbinols allowing thus a facile route to the title compounds.     

Enumerating Perfect Matchings in n-Cubes

The perfect matchings in the n-cube have earlier been enumerated for n?≤?6. A dynamic programming approach is here used to obtain the total number of perfect matchings in the 7-cube, which is 391 689 748 492 473 664 721 077 609 089. The number of equivalence classes of perfect matchings is further shown to be 336 in the 5-cube, 356 788 059 in the 6-cube and 607 158 046 495 120 886 820 621 in the 7-cube. The techniques used can be generalized to arbitrary bipartite and general graphs.     

Amine-Directed Palladium-Catalyzed C−H Halogenation of Phenylalanine Derivatives

An efficient primary-amine-directed, palladium-catalyzed C−H halogenation (X=I, Br, Cl) of phenylalanine derivatives is reported on a range of quaternary amino acid (AA) derivatives thanks to suitable conditions employing trifluoroacetic acid as additive. The extension of this original native functionality-directed ortho-selective halogenation was even demonstrated with the more challenging native phenylalanine as tertiary AA.     

Comparison of entropy and complexity measures for the assessment of depth of sedation

Entropy and complexity of the electroencephalogram (EEG) have recently been proposed as measures of depth of anesthesia and sedation. Using surrogate data of predefined spectrum and probability distribution we show that the various algorithms used for the calculation of entropy and complexity actually measure different properties of the signal. The tested methods, Shannon entropy (ShEn), spectral entropy, approximate entropy (ApEn), Lempel-Ziv complexity (LZC), and Higuchi fractal dimension (HFD) are then applied to the EEG signal recorded during sedation in the intensive care unit (ICU). It is shown that the applied measures behave in a different manner when compared to clinical depth of sedation score--the Ramsay score. ShEn tends to increase while the other tested measures decrease with deepening sedation. ApEn, LZC, and HFD are highly sensitive to the presence of high-frequency components in the EEG signal.     

Wetting effects at a grain boundary

We consider a tier of weakened bonds along the center line of a two-dimensional Ising ferromagnet strip as a model of a grain boundary. When an interface traverses such a strip at an angle, whether or not there is a continuous pinning-depinning transition at subcritical temperature depends on this angle and the degree of bond weakening. We also study the relaxation of such a system to its equilibrium state using continuous time Monte Carlo simulation with Kawasaki dynamics; this reveals a matter transport mechanism confined to the grain boundary.     

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