Zur Photochemie von Allylaryläthern. 55. Mitteilung über Photoreaktionen

The photochemical reactions of different allyl aryl ethers (Scheme 3) were investigated in hydrocarbons (Chap. 3.1) and in alcoholic solvents (Chap. 3.2). The composition of the photoproducts depended very much on the nature of the solvent. Irradiation (3–95 h) of different methyl substituted allyl aryl ethers ( 1, 3, 5, 7 and 11 ) with a low pressure mercury lamp (λ_Emiss. = 254 nm; 6 or 15 Watt) under argon (quartz vessel) resulted in the formation of 2-, 3– and 4-substituted phenols, dienones and products of consecutive reactions (Tables 1–4 and 6). The results suggested that all products were formed by homolytic cleavage of the C? O bond in the singlet state of the ethers to intermediate radical-geminates (Scheme 5) followed by radical recombination of the two fragments. No products were formed by concerted processes (Table 5, Schemes 5 and 6). Upon irradiation of allyl aryl ethers lacking alkyl substituents at position 4 ( 1 and 5 ) in protic solvents, mainly 2- and 4-allylated phenols were obtained (Tables 1 and 4); 3-allylated phenols were formed only in small amounts (0.02%). However, in aromatic hydrocarbons or cyclohexane 3-allylated phenols were obtained from 1 , 5 and 11 in significant amounts (3–11%; Tables 1, 4 and 6). E.g., upon irradiation of allyl-2,6-dimethyl-2,4-cyclohexadien-1-one ( 6 ) besides 3- and 4-allyl-2, 6-dimethyl-phenol ( 23 and 24 ). Irradiation of 5 in methanol afforded 23 and 6 only in traces, whereas 24 was the main product.     

Magnetostriction measurement by means of strain modulated ferromagnetic resonance (SMFMR)

A novel method for measuring magnetostriction constants is presented. A strain, periodic in time, applied to the sample, causes a modulation of the ferromagnetic resonance line position. The height of the signal obtained after phase-sensitive detection is proportional to the strain modulation depth. The appropriate magnetostriction constant λ is obtained by comparing the height of the SMFMR signal with that of the FMR line, as recorded by means of magnetic field modulation. Features of the new technique are:

1. high sensitivity: λ_min? 10_?9 forM=100 Oe and linewidth ΔH _d=1 Oe;
2. λ's belonging to distinct precession modes are separately determined;
3. applicable to thin layers for which strain gauge techniques cannot be used;
4. wide temperature range: 1.2 K<T<300 K;
5. uniform stress.

An illustrative example (YIG layer on GGG substrate) is given.     

Stabilitätsungleichungen für Diskretisierungen von Randwertaufgaben gewöhnlicher Differentialgleichungen

Summary We consider two-point boundary value problems for linear differential equations (of ordern). The main part consists in proving stronger apriori estimates for (mn–1) using discreteL ₁-norms of the involved right-hand sides; thus extending known results for discreteL _p -norms with 2p. These estimates are the main tool in proving sharp estimates for the error \y–y _h \ _h, as well asfor \P _y –P _h y _h \ _h, , whereP _h denotes a consistent approximation of the differential operatorP of ordermn–1, in terms of the discretL ₁-norm of the truncation error. By means of an interpolation technique these estimates yield a correct estimate of the order of convergence, also in case that the solution satisfies locally some Lipschitz-conditions.     

Anion radicals and dianions as electron transfer reagents

The catalytic regeneration of depolarizers by certain substrates has been demonstrated by means of cyclic voltammetry. As depolarizers we have employed anion radicals of aromatic hydrocarbons, heteroaromatic compounds, ketones, esters, nitriles, and olefins, and dianions of aromatic hydrocarbons, heteroaromatic compounds, ketones, and esters. As substrates we have investigated simple aromatic and aliphatic halides, 1,2- and 1,3-dihalides, carbon dioxide, and activated olefins. A requirement for the observation of a catalytic wave is that the reduced substrate undergoes a practically irreversible reaction after the reaction with the reduced depolarizer; for simple halides it is a cleavage reaction, for 1,2- and 1,3-dihalides an elimination, for carbon dioxide an addition, and for activated olefins a coupling. Electrochemical investigations of these kinds of reactions may be of interest in connection with the mechanism of several types of reactions in organic chemistry.     

Trennung von Strontium-90-Yttrium-90 und Calcium-45-Scandium-46

Ohne Zusammenfassung     

Rheology of gelling polymers in the Zimm model

In order to study rheological properties of gelling systems in dilute solution, we investigate the viscosity and the normal stresses in the Zimm model [B. H. Zimm, J. Chem. Phys. 24, 269 (1956)]. for randomly cross-linked monomers. The distribution of cluster topologies and sizes is assumed to be given either by Erdos-Renyi random graphs or three-dimensional bond percolation. Within this model the critical behavior of the viscosity and of the first normal stress coefficient is determined by the power-law scaling of their averages over clusters of a given size n with n. We investigate these scaling relations numerically and conclude that the scaling exponents are independent of the hydrodynamic interaction strength. The numerically determined exponents agree well with experimental data for branched polymers. However, we show that this traditional model of polymer physics is not able to yield a critical divergence at the gel point of the viscosity for a polydisperse dilute solution of gelation clusters. A generally accepted scaling relation for the Zimm exponent of the viscosity is thereby disproved.