Elution behavior of styrene oligomer fractions in supercritical fluid chromatography

Summary In supercritical fluid chromatography (SFC), the elution behavior of styrene oligomers in pentane depends greatly on the degree of oligomerization, n. The influence of capacity ratio, k, on the lower oligomers up to about n=11 resembles the behavior of other substrates of low molecular weight, like aromatic hydrocarbons. Thus, with pentane of 100 bar and below, minima are found in plots of k versus temperature. In contrast, the k of oligomers of higher molecular weight (n>11) increase monotonously with increasing temperature. The studies were performed using oligostyrene fractions obtained by semipreparative SFC fractionation.     

Gas-Phase cationization and protonation of neutrals generated by matrix-assisted laser desorption

The ionization mechanisms involved in matrix-assisted ultraviolet laser desorption/ionization (MALDI) were studied with a time-of-flight mass spectrometer. When protonated or cationized quasimolecular ions generated by MALDI are not extracted promptly, their abundance is a function of the delay time between laser irradiation and ion extraction, maximizing at an optimum delay time (DTM) of a few hundred nanoseconds. The ion abundance at DTM exceeds that of prompt extraction by a factor of 2 or more. Increasing the cation density near the sample surface reduces the DTM, whereas increasing the desorption laser irradiance has the opposite effect. The enhancement suggests extensive gas-phase ion-molecule reactions after irradiation by the desorption laser has ceased.     

Three Saponins, a Steroid, and a Flavanol Glycoside from Achyrantes aspera

Summary.  Three bisdesmosidic saponins, 20-hydroxyecdysone, and quercetin-3-O-β-D-galactoside were isolated from the methanol extract of the aerial parts of Achyranthes aspera L. (Amaranthaceae). Their structures were established on the basis of NMR spectroscopic analysis; the complete ¹H and ¹³C assignments of the compounds were achieved by means of 2D NMR studies. Received July 21, 1999. Accepted August 26, 1999     

Mass transfer limitation in thermogravimetry of biomass gasification

In order to determine the intrinsic reactivity behavior from thermogravimetry studies, the experimental conditions should be such that the reactions are not mass transfer limited. Biomass char usually has a higher reactivity than coal chars. Therefore, mass transfer limitations may be more problematic when studying biomass char reactivity. Chemical reaction kinetics and mass transfer processes present in thermogravimetry are used for modeling the overall reaction rate for spruce bark CO₂ gasification. Thermogravimetric experiments are carried out between 700 and 900 °C, and the CO₂ concentration is varied between 10 and 90 vol%. The intrinsic activation energy is found to be 120 kJ mol^?1. The transition temperature between regimes I and II is here defined when the fraction apparent to true activation energy equals 0.75. Higher external mass transfer (e.g., by decreasing the diffusion path through the crucible’s freeboard), decreasing the sample amounts, and higher CO₂ partial pressures for the Langmuir–Hinshelwood reaction type increase the transition temperature. The results show that the transition temperature between regimes I and II conditions is approx. 1,030 °C for 90 vol% CO₂.     

Structural studies of transition metal complexes with 4,5-bis(2-pyridylmethylsulfanyl)-4',5'-ethylenedithiotetrathiafulvalene: probing their potential for the construction of multifunctional molecular assemblies

Three divalent transition metal complexes of 4,5-bis(2-pyridylmethylsulfanyl)-4',5'-ethylenedithiotetrathiafulvalene have been prepared and crystallographically characterized. The isostructural Co(II) and the Ni(II) complexes show octahedral geometries around the metal ions with the coordination sites occupied by the pyridyl nitrogen atoms and the thioether sulfur atoms of the ligand and cis coordination of the halide ions. Cyclic voltammetry reveals that the complexation leads to a small anodic shift in the first oxidation potential of the TTF system.