Dielectric relaxation analysis of starch oligomers and polymers with respect to their chain length

Starch belongs to the polyglucan group. This type of polysaccharide shows a broad β-relaxation process in dielectric spectra at low temperatures, which has its molecular origin in orientational motions of sugar rings via glucosidic linkages. This chain dynamic was investigated for α(1,4)-linked starch oligomers with well-defined chain lengths of 2, 3, 4, 6, and 7 anhydroglucose units (AGUs) and for α(1,4)-polyglucans with average degrees of polymerization of 5, 10, 56, 70, and so forth (up to 3000; calculated from the mean molecular weight). The activation energy (E_a) of the segmental chain motion was lowest for dimeric maltose (E_a = 49.4 ± 1.3 kJ/mol), and this was followed by passage through a maximum at a degree of polymerization of 6 (E_a = 60.8 ± 1.8 kJ/mol). Subsequently, E_a leveled off at a value of about 52 ± 1.5 kJ/mol for chains containing more than 100 repeating units. The results were compared with the values of cellulose-like oligomers and polymers bearing a β(1,4)-linkage. Interestingly, the shape of the E_a dependency on the chain length of the molecules was qualitatively the same for both systems, whereas quantitatively the starch-like substances generally showed higher E_a values. Additionally, and for comparison, three cyclodextrins were measured by dielectric relaxation spectroscopy. The ringlike molecules, with 6, 7, and 8 α(1,4)-linked AGUs, showed moderately different types of dielectric spectra. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 188–197, 2004     

Electrochemical reduction of 1-([(4-halophenyl)imino]methyl)-2-naphthols in aprotic media.

The electrochemical reduction of 1-([(4-halophenyl)imino]methyl)-2-naphthols on graphite electrodes was studied using cyclic voltammetry, chronoamperometry, constant-potential coulometry and preparative constant-potential electrolysis techniques. The data revealed that the reduction on graphite was irreversible and followed an EC mechanism. The diffusion coefficients and the number of electrons transferred were determined using the chronoamperometric Cottrell slope and the ultramicro disc Pt-electrode steady-state current. The number of electrons was also determined by bulk electrolysis. The compounds were subjected to constant-potential preparative electrolysis and the electrolysis products were purified and identified by spectroscopic methods. Based on these findings, a mechanism for the electro-reduction process is proposed.     

A nucleophilic substitution reaction in microemulsions based on either an alcohol ethoxylate or a sugar surfactant

A nucleophilic substitution reaction between 4-tert-butylbenzyl bromide and a series of iodide salts has been performed in oil-in-water microemulsions based on either a fatty alcohol ethoxylate or a sugar surfactant. The reaction kinetics was compared with the kinetics of the same reaction performed in a microhomogeneous reaction medium, d-MeOH. Previous results showing a particularly high reactivity in the microemulsion based on the fatty alcohol ethoxylate was confirmed. It was shown that in both microemulsions the reaction rate was almost independent of the choice of counterion to iodide. This indicates that complexation of the cation with the surfactant headgroup, which, in particular, could have taken place with surfactants containing oligooxyethylene chains (a “crown ether effect”), seems not to be of importance.

¹²⁷I NMR studies, as well as quadrupole splitting experiments performed by ²H NMR, indicate that there is a certain accumulation of iodide at the oil–water interface of the microemulsions. It is difficult to draw any quantitative conclusions in this respect, however.

The results obtained in this study, combined with results from previous investigations of the same reaction, indicate that the unexpectedly high reactivity obtained in the microemulsion based on a surfactant containing an oligooxyethylene headgroup is most probably due to the nucleophile being poorly solvated when present in the headgroup layer of such a microemulsion. Poorly solvated anions are known to be highly reactive nucleophiles.     

Appropriate problems for learning and for performing—an issue for teacher training

Selecting, modifying or creating appropriate problems for mathematics class has become an activity of increaing importance in the professional development of German mathematics teachers. But rather than asking in general: “What is a good problem?” there should be a stronger emphasis on considering the specific goal of a problem, e.g.: “What are the ingredients that make a problem appropriate for initiating a learning process” or “What are the characteristics that make a problem appropriate for its use in a central test?” We propose a guiding scheme for teachers that turns out to be especially helpful, since the newly introduced orientation on outcome standards a) leads to a critical predominance of test items and b) expects teachers to design adequate problems for specific learning processes (e.g. problem solving, reasoning and modelling activities).     

Recombination of Au25+ with free electrons at low energies

The origin of the widely observed enhancement of rates for electron-ion recombination at very low energies is still unknown. We investigated the recombination of Au²⁵⁺ with free electrons in a merged-beams experiment at the UNILAC accelerator of the GSI in Darmstadt. At E _rel= 0 eV we found an enormous enhancement factor of 365 compared to the theory of radiative recombination. An increase of the electron density by a factor of 10 had not much influence on the measured rate coefficient. This revised version was published online in July 2006 with corrections to the Cover Date.     

The Witt ring of a Brauer–Severi variety

For a Brauer–Severi variety X over a field k of characteristic not two, every symmetric bilinear space over X up to Witt equivalence is defined over k. Received: 2 February 1998     

Anisotropic transport of charge and complexified duality

Charge transport in two dimensions provides an ideal laboratory for investigating parameter space geometries. The Onsager relations for anisotropic transport in a parity-violating external field endow these spaces with a highly nontrivial complex (and Kähler) structure, which can be given a simple geometrical interpretation. A large class of Coulomb gases exhibiting this structure have a generalized Kramers-Wannier symmetry (complexfield duality) which is contained in the modular group. Knowledge of this symmetry and the degrees of freedom encoded in the Coulomb gas appear to be sufficient to determine the global phase diagram and the renormalization group fixed-point structure, including the critical exponents. This accounts for all the scaling behavior observed so far in the quantum Hall system.     

A Bicriterial Optimization Problem of Antenna Design

In this paper we consider a special optimization problem withtwo objectives which arises in antenna theory. It is shown that thisabstract bicriterial optimization problem has at least one solution.Discretized versions of this problem are also discussed, and therelationships between these finite dimensional problems and the infinitedimensional problem are investigated. Moreover, we presentnumerical results for special parameters using a multiobjectiveoptimization method.