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     

Resonance-stabilized phenoxy-like radicals formed by NO-mediated mono-nitration of coumarins containing a hydroxy group

Stable aminoxyls and an iminoxyl were observed by spin trapping and EPR techniques during the nitration of coumarins containing a hydroxy group by nitric oxide. The trapped free radicals are deduced to be the resonance stabilized phenoxy-like radicals. The mechanisms for the nitrations are suggested.     

Baker＇s Yeast Mediated Reduction of Optically Active Diketone

Baker‘s yeast mediated reduction of optically active diketone is described. The two keto groups are efficiently differentiated and the ee value of the recovered material is considerably raised. It affords highly optically active key intermediates efficiently for the synthesis of natural polyhydroxylated agarofuran products.     

Long-wavelength GaInAsSb/AlGaAsSb DFB lasers emitting near 2.6 μm

We have successfully fabricated and characterized room temperature continuous wave (cw) GaInAsSb/AlGaAsSb distributed feedback lasers emitting in the wavelength region between 2.499 and 2.573 μm. To the best of our knowledge, this is the longest emission wavelength realized with a GaSb-based DFB laser diode. The laser structure used for DFB processing was grown by solid source molecular beam epitaxy. A DFB concept requiring no subsequent overgrowth step was used by defining first-order Cr-Bragg gratings laterally patterned to a ridge waveguide. Threshold currents smaller than 60 mA and room temperature cw output powers up to 6.5 mW were obtained. The laser diodes show single mode emission with side mode suppression ratios (SMSR) of up to 32 dB.     

Investigation on nonradiative decay of I13/2→I15/2 transition of Er-doped oxide glasses

Nonradiative decay of ⁴I_13/2→⁴I_15/2 transition of Er³⁺ has been investigated in a series of oxide glasses. For Er³⁺-doped glass samples, the Judd-Ofelt analysis on absorption spectra was performed and the fluorescence lifetime was determined by extrapolating to zero Er³⁺ concentration limit. Infrared spectra were measured in order to investigate the influence of OH⁻ groups in different glasses. The effects of glass matrix on the decay rate were discussed from the viewpoint of phonon energy, variations of effective fields, and OH⁻ groups. Compared to other glasses, phosphate glass presents low quantum efficiency and large nonradiative decay rate due to its high phonon energy and hygroscopic behavior.     

Chip-calorimeter for small samples

A method for measuring heat capacities of small samples using a chip-calorimeter and a heat pulse technique is described. The theoretical background to calculate the heat transport properties and the heat capacity of the sample from the pulse response function is given. Problems and potentials of the method are discussed. An example is given.     

Molecular addressing? Studies on light-induced reorientation in liquid-crystalline side chain polymers

Polarized light leads to an effective reorientation of the optic axis in the glassy state of liquid-crystalline side chain polymers containing azobenzene mesogenic groups, via a trans-cis and cis-trans isomerization. Using a combination of U V and IR dichroitic studies it is shown for copolymers consisting of chromophores (azobenzene) and non-chromophores (phenylbenzoate) that only the chromophores are reoriented by light as far as the glassy state is concerned. Individual chromophores are thus addressed by photoselection. Photoselection in the fluid nematic state, on the other hand, leads also to a reorientation of the non-chromophores.