Struktur und Mechanismus bei Fragmentierungsreaktionen 1. Teil. Die stereoisomeren 10-Chlor-decahydro-isochinoline. Fragmentierungsreaktionen, 23. Mitteilung

cis-10-Chloro-N-methyl-decahydro-isoquinoline ( 5 ) and its trans-isomer 6 undergo heterolytic fragmentation in 80% ethanol by different mechanisms. As predictable on stereo-chemical grounds the cis-isomer 5 reacts by the accelerated synchronous mechanism, the trans-isomer 6 , however, by the two-step carbonium ion mechanism. Synchronous fragmentation therefore dominates over the two-step process even when the latter would lead to a relatively stable tertiary carbonium ion. In both cases the more highly substituted and thermochemically more stable olefinic fragment 8 is formed.     

The Compressibility of pH‐Sensitive Microgels at the Oil–Water Interface: Higher Charge Leads to Less Repulsion

pH‐responsive microgels are unique stabilizers for stimuli‐sensitive emulsions that can be broken on demand by changing the pH value. However, recent experiments have indicated that electrostatic interactions play a different role to that in conventional Pickering emulsions. The influence of charges on the interactions between microgels at the oil–water interface is now described. Compression isotherms of microgels with different charge density and architecture were determined in a Langmuir trough, and counter‐intuitive results were obtained: Charged microgels can be compressed more easily than uncharged microgels. The compressibility of microgels is thus not determined by direct Coulomb repulsion. Instead, the different swelling of the microgels in the charged and the uncharged states is proposed to be the key parameter.     

Prevalence of unstable attractors in networks of pulse-coupled oscillators

We present and analyze the first example of a dynamical system that naturally exhibits attracting periodic orbits that are unstable. These unstable attractors occur in networks of pulse-coupled oscillators, and become prevalent with increasing network size for a wide range of parameters. They are enclosed by basins of attraction of other attractors but are remote from their own basin volume such that arbitrarily small noise leads to a switching among attractors.     

Modulation and incommensurability in a superionic conductor

The structure factor S(q) is calculated for the Frenkel-Kontorova model at high temperatures. Application to the 1-d ionic conductor K-Hollandite gives an explanation of diffuse X-ray scattering in terms of a modulation phenomenon. The positions of the diffuse sheets are predicted precisely from the stoichiometric composition. It is confirmed thereby that the mobile K⁺ ions behave like a chain with spacing b = 1/n where n is the concentration. The disorder is characterized as short-range crystalline order of wavelength b, competing with and modulated by the framework potential with a different period a.     

Linear and nonlinear response of discrete dynamical systems

We carry out a linear response theory for discrete dynanmical systems with periodic attractors. The symmetry properties of the susceptibility matrix are studied and its eigenvalues and eigenvectors are determined. Close to a period-doubling bifurcation where the susceptibility diverges, its half-width is related to the Lyapunov exponent. At the transition to chaos the susceptibility has some universal behaviour which is described by a critical exponent κ=1?(ln2/lnδ)=0.550193... At the bifurcation points where linear response theory becomes insufficient we also determine the nonlinear response.     

Particle dispersion on rapidly folding random heteropolymers

We investigate the dynamics of a particle moving randomly along a disordered heteropolymer subjected to rapid conformational changes which induce superdiffusive motion in chemical coordinates. We study the antagonistic interplay between the enhanced diffusion and the quenched disorder. The dispersion speed exhibits universal behavior independent of the folding statistics. On the other hand it is strongly affected by the structure of the disordered potential. The results may serve as a reference point for a number of translocation phenomena observed in biological cells, such as protein dynamics on DNA strands.     

Unstable attractors induce perpetual synchronization and desynchronization

Common experience suggests that attracting invariant sets in nonlinear dynamical systems are generally stable. Contrary to this intuition, we present a dynamical system, a network of pulse-coupled oscillators, in which unstable attractors arise naturally. From random initial conditions, groups of synchronized oscillators (clusters) are formed that send pulses alternately, resulting in a periodic dynamics of the network. Under the influence of arbitrarily weak noise, this synchronization is followed by a desynchronization of clusters, a phenomenon induced by attractors that are unstable. Perpetual synchronization and desynchronization lead to a switching among attractors. This is explained by the geometrical fact, that these unstable attractors are surrounded by basins of attraction of other attractors, whereas the full measure of their own basin is located remote from the attractor. Unstable attractors do not only exist in these systems, but moreover dominate the dynamics for large networks and a wide range of parameters.     

Scattering of light and neutrons in a model for superionic conductors

We discuss the cross sections for neutron scattering and light scattering from a superionic conductor. The motion of the mobile ions is treated as an independent continuous diffusion process through a periodic potential. While this determines the neutron scattering intensity completely, the light scattering is, in addition, strongly influenced by the spatial variation of the polarizability. This leads to selection rules and to differences between the two kinds of spectra. We present a rather complete study of a one-dimensional model which displays the general features of the problem. The results are based on a numerically accurate solution of the corresponding Fokker-Planck equation.     

Conversion of N-arylglycolohydroxamic acids to 1,2,3-oxathiazolidin-4-one 2,2-dioxides

N-Arylglycolohydroxamic acids 1A are converted by in situ prepared 2,2′-dipyridyl sulfite to 1,2,3-oxathiazolidin-4-one 2,2-dioxides 5 , the formation of which can be rationalized via a radical pair mechanism. The alkylating potential of the heterocyclic system 5 is demonstrated by the alkaline ethanolysis giving rise to the open chained 2-ethoxypropionanilide 6 .     

Assay of whole blood (6S)-5-CH3-H4folate using ultra performance liquid chromatography tandem mass spectrometry

Folates act as essential coenzymes in many biological pathways, including the synthesis and methylation of DNA. Low folate concentration in serum and whole blood (WB) is associated with several disease conditions. We describe a stable-isotope-dilution ultra performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS) method for the quantification of (6S)-5-CH(3)-H(4)folate (where H(4)folate is tetrahydrofolate) and non-CH(3)-H(4)folate [sum of HCO-H(4)folate, (6R)-5,10-CH(+)-H(4)folate, (6R)-5,10-CH(2)-H(4)folate, (6S)-H(4)folate, dihydrofolate, and folic acid] in WB. The assay includes a solid-phase extraction procedure after the hemolysis and deconjugation. The method was linear over the concentration range from 0.2 to 200 nmol/L. The limits of detection were 0.40 nmol/L or lower for the folate forms. The interassay coefficients of variation were 7.4% for (6S)-5-CH(3)-H(4)folate and 15.4% for non-CH(3)-H(4)folate. For the folate forms, the recoveries were between 97.1% and 102.7%. Sample preparation caused the generation of artificial folic acid in WB and serum in a dose-dependent manner, which can lead to misinterpretation of the results. The use of antioxidants could not prevent the formation of folic acid. The median fasting WB folate concentrations from 42 nonsupplemented and nonfortified adults were 576 nmol/L (6S)-5-CH(3)-H(4)folate and 73.6 nmol/L non-CH(3)-H(4)folate, and 1,206 nmol/L (6S)-5-CH(3)-H(4)folate and 155 nmol/L non-CH(3)-H(4)folate for 35 adults who had taken 500 μg of folic acid, 50 mg of vitamin B(6), and 500 μg of vitamin B(12) per day orally for 6 months. In conclusion, the UPLC-MS/MS method is fast and has a good sensitivity and selectivity for WB folates. We observed a dose-dependent oxidation of (6S)-H(4)folate, which resulted in the formation of artificial folic acid in serum and WB. To minimize this effect, we recommend a fast sample preparation.