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     

A mixed‐FEM formulation for nonlinear incompressible elasticity in the plane

This article deals with an expanded mixed finite element formulation, based on the Hu‐Washizu principle, for a nonlinear incompressible material in the plane. We follow our related previous works and introduce both the stress and the strain tensors as further unknowns, which yields a two‐fold saddle point operator equation as the corresponding variational formulation. A slight generalization of the classical Babu?ka‐Brezzi's theory is applied to prove unique solvability of the continuous and discrete formulations, and to derive the corresponding a priori error analysis. An extension of the well‐known PEERS space is used to define an stable associated Galerkin scheme. Finally, we provide an a posteriori error analysis based on the classical Bank‐Weiser approach. © 2002 John Wiley & Sons, Inc. Numer Methods Partial Differential Eq 18: 105–128, 2002     

Raman spectroscopic investigations of the structure and phase transitions of liquid crystalline lead(II) alkanoates

Lead(II) alkanoates with even chain lengths from octanoate to octadecanoate have been investigated by Raman spectroscopy. In the low frequency region, transverse and longitudinal acoustical modes (TAM, LAM) have been assigned. It was shown that LAM-1 is the vibration of the double chain with the node of the vibration in the Pb²⁺ layer. A fully extended conformation of the chains in the low temperature phase was confirmed. The frequencies and intensities of the LAMs as compared with those of the alkanes and the fatty acids led to an estimate of the force constant and polarizability of the Pb²⁺ -COO^- bond relative to the C-C bond. The defects at the chain ends were investigated in the ρ(CH₃) and v(CC) region. For the intermediate (CM) phase, both the Pb²⁺ layer distance reduction and the chain length independent enthalpy contributions can be attributed mainly to defects at the chain ends.     

Characterisation of adsorbed layers on sulphide minerals by photoelectron spectroscopy

The systems galena/2-mercaptobenzothiazole (MBT) and pyrite/MBT have been studied using synchrotron radiation excited photoelectron spectroscopy (SRXPS). The chemisorption of MBT and the multilayer formation of 2,2′-dithiobis(benzothiazole) (BBTD) are evidenced by additional structures, observed beside the substrate signals, in the S2p-spectra of cleaved mineral surfaces after adsorption of MBT. The amount of the complex remains constant at concentrations as high as 10^–5 mol/L whereas the amount of BBTD increases. From the dependence of the adsorbate intensities on the excitation energy the conclusion can be drawn that an overlayer of BBTD on a chemisorbed layer of MBT is formed. The very weak adsorption of MBT on pyrite in alkaline solutions may explain the selective flotation of galena from pyrite in alkaline media.     

Semi-insulating electrical properties of undoped inp after heat treatment in a phosphorus atmosphere

Nominally undoped InP wafers have been annealed in a phosphorus atmosphere under a pressure of about 5 bar at temperatures of 900 °C for about 80 h. It was found that the electrical properties of the samples changed considerably after this treatment. A room temperature resistivity of up to 2×10⁷cm (semi-insulating behaviour) was obtained in the bulk of the samples. The resistivity finally obtained depends on the starting carrier concentration of the untreated samples. The Hall coefficient and Hall mobility have been measured up to 600 °C. The results can be interpreted in terms of a deep electronic level (E _A=0.63 ... 0.65 eV below the conduction band). The Hall coefficient was always found to be negative resulting in a Hall mobility of 1.4 to 4.9×10³ cm²/Vs. The highest resistivity in nominally undoped bulk InP so far reported in the literature [1] was =3.6 × 10⁵cm. Therefore, this paper demonstrates for the first time that a really semi-insulating behaviour of >10⁷ cm can be achieved for bulk InP with the purity of nominally undoped material (10¹⁵ to 10¹⁶cm^–3).     

Wavelength independence of Eu quantum yields

A quantitative comparison between the excitation and absorption spectra of Eu³⁺ in aqueous solution is given which leads to the conclusion that fluorescence quantum yields are independent of the excitation wavelength. Use is made therefore of the series of homologous lines ⁵D₃, ⁵D₂, ⁵D₁, ⁵D₀ → ⁷F₁.     

Umsetzung von hydrobromiertem 1,4-Polybutadien mit lithiumorganischen Verbindungen

Ohne ZusammenfassungMit 1 Abbildung und 1 Tabelle     

Quantitative analysis of small pharmaceutical drugs using a high repetition rate laser matrix-assisted laser/desorption ionization source

In this work, a high repetition rate laser matrix-assisted laser desorption/ionization (MALDI) source is studied on a quadrupole-time-of-flight (QqTOF) and a triple quadrupole (QqQ) mass spectrometer for rapid quantification of small pharmaceutical drugs. The high repetition rate laser allows an up to 100-fold higher pulse frequency as compared with regular MALDI lasers, resulting in much larger sample throughput and number of accumulated spectra. This increases the reproducibility of signal intensities considerably, with average values being around 5% relative standard deviation after taking into account the area ratio of the analyte to an internal standard. Experiments were conducted in MS/MS mode to circumvent the large chemical background due to MALDI matrix ions in the low mass range. The dynamic range of calibration curves on the QqTOF mass spectrometer extended over at least two orders of magnitude, whereas on the QqQ it extended over at least three orders of magnitude. Detection limits ranged from 60-400 pg/microL on the QqTOF and from 6-70 pg/microL on the QqQ for a series of benzodiazepines. The benzodiazepine content of commercial pill formulations was quantified, and less than 5% error was obtained between the present method and the manufacturer's certified values. Furthermore, a high sample throughput was achieved with this method, so that a single MALDI spot could be quantitatively scanned in as little as 15 s, and an entire 96-well MALDI plate in 24 min.     

Eine Tüpfelreaktion für den Nitritnachweis

Zusammenfassung Durch Tüpfeln auf Chromatographiepapier, das mit Brucin, Benzidin und Phosphorsäure imprägniert wurde, läßt sich Nitrit empfindlieh und spezifisch nachweisen. 20 ng Nitrit können neben Nitrat und anderen Anionen festgestellt werden.

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Summary Nitrite can be detected sensitively and specifically by spotting on Chromatograph paper impregnated with brucine, benzidine and phosphoric acid. It is possible to detect 20g nitrite in the presence of nitrate and other anions.

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Résumé On peut rechercher les nitrites d'une manière sensible et spécifique sur les taches du papier chromatographique et qui a été imprégné de brucine, de benzidine et d'acide phosphorique. On peut déceler 20g de nitrite en présence de nitrates et d'autres ions A-.