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.     

Book Review

Structural Chemistry -     

Synthesis of paramagnetic BODIPY dyes as new double (spin and fluorescence) sensors

Paramagnetic pyrroline and 1,2,3,6-tetrahydropyridine derivatives of BODIPY and their diamagnetic analogs have been synthesized and characterized as novel redox double sensor and cation sensitive reagents.     

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.     

Laser systems specialized for laser spectroscopy at storage rings

Laser spectroscopy at storage rings often suffers from a limited resolution due to Doppler-broadened resonances. Broadening is caused by the velocity spread of the ions stored in the beam. In the following, the present status of our work on laser systems specialized on the specific needs of laser spectroscopy at storage rings is reported. Two pulsed laser systems were developed. One is a dye laser whose spectral bandwidth can be switched by inserting different Littrow-prisms into the resonator. An increase in bandwidth up to a factor of 45 was achieved. This laser was used for fast qualitative scans and high resolution measurements. The other laser system is a Nd : YAG laser pumped optical parametric oscillator. It is a tunable laser system covering the spectral range from 410 to 4000 nm. Furthermore, a continuous wave laser with a frequency shifted feedback cavity is described. It shows broadband emission with an adjustable bandwidth of up to 4.5 GHz. This laser can be advantageous for laser cooling of ion beams. This revised version was published online in August 2006 with corrections to the Cover Date.     

Luttinger liquid with asymmetric dispersion

We present an extension of the Tomonaga-Luttinger model in which left and right-moving particles have different Fermi velocities. We derive expressions for one-particle Green's functions, momentum-distributions, density of states, charge compressibility and conductivity as functions of both the velocity difference ε and the strength of the interaction β. This allows us to identify a novel restricted region in the parameter space in which the system keeps the main features of a Luttinger liquid but with an unusual behavior of the density of states and the static charge compressibility κ. In particular κ diverges on the boundary of the restricted region, indicating the occurrence of a phase transition. Received 20 May 2002 / Received in final form 23 August 2002 Published online 19 November 2002