Assignment of the 5,6-Double-Bond Configuration in Iloprost and Isoiloprost from 13C-NMR Shifts Determined by 2D Methods

The configurations of the 5,6-double bond in the carbacyclins iloprost ( 3 ; (E)) and isoiloprost ( 4 ; (Z)) are based on a complete assignment of the ¹³C and ¹H resonances determined by 1D and 2D ¹³C-NMR and ¹H-NMR methods.     

Synthesis of substituted 5-aminomethyl tetrahydro-isoquinolines and dihydro-isoindoles

The synthesis of ten substituted aminomethylene tetrahydro-isoquinolines is described, proceeding in eight steps from 5-hydroxyisoquinoline via reductive amination of N-Boc tetrahydro-isoquinoline 5-carboxaldehyde. Likewise, reductive amination was used to prepare four substituted dihydro-isoindoles from the corresponding aldehyde. The dihydro-isoindole ring system was conveniently accessed via a 2+2+2 cycloaddition reaction.     

Natural abundance 13C - 13C coupling constants observed via double quantum coherence. Structural elucidation by the one- and the two-dimensional NMR experiements of velloziolone,a new seco-diterpene.

With the help of Natural Abundance ¹³C - ¹³C Coupling Constants, observed via double quantum coherence, the structural determination of VELLOZIOLONE (1), a new diterpene, has been carried out.     

The effect of dipole-dipole interaction on zero-THz frequency polarisation

The effect of intramolecular dipole-dipole interaction on polarisation at frequencies from 0 – 10¹² Hz in dipolar media is investigated using a numerical solution of the Sturm-Liouville eigenvalue problem to which the governing Smoluchowski equation reduces. The results of Budó for the long-wavelength limit are extended to all frequencies up to the far infrared, where the predominant inertial effects are treated using a preliminary first-order correction. The numerical method of Pryce may be used to investigate much more realistic interaction potentials than the simple harmonic and cosine form considered by Budó. These simple forms are, however, sufficient to indicate that the integrated absorption intensity per molecule in the far infrared is very sensitive to dipole-dipole interaction and relative hydrodynamic drag on both interacting groups. Applications of the theory to the disordered solid and nematic phases are considered.     

A study of the oxidation of vegetable oils by inverse gas chromatography

Summary Inverse gas chromatography is shown to be suitable for the study of the oxidation of vegetable oils. With air as carrier gas characteristic plots of retention index versus time are obtained for hydroxylic test solutes that are consistent with the oxidation behaviour of vegetable oils. Shifts of retention are found to be accompanied by changes of column efficiency due to the oxidative crosslinking of polyunsaturated vegetable oils. The technique also leads to useful information concerning the oxidation of antioxidant inhibited systems. Presented at the 15th International Symposium on Chromatography, Nürnberg, October 1984     

Gas-phase ion/molecule reactions between dimethoxyphosphonium ions and aromatic hydrocarbons

Ion/molecule reactions between O=P(OCH(3))(2)(+) phosphonium ions and six aromatic hydrocarbons (benzene, toluene, 1,2,4-trimethylbenzene, naphthalene, acenaphthylene and fluorene) were performed in a quadrupole ion trap mass spectrometer. The O=P(OCH(3))(2)(+) phosphonium ions, formed by electron impact from neutral trimethyl phosphite, were found to react with aromatic hydrocarbons (ArHs) to give (i) an adduct [ArH, O=P(OCH(3))(2)](+) and (ii) for ArHs which have an ionization energy below or equal to 8.14 eV, a radical cation ArH(+ *) by charge transfer reaction. Collision-induced dissociation experiments, which produce fragment ions other than the O=P(OCH(3))(2)(+) ions, indicate that the adduct ions are covalent species. Isotope-labeled ArHs were used to elucidate fragmentation mechanisms. The charge transfer reactions were investigated using density functional theory at the B3LYP/6-311 + G(3df,2p)//B3LYP/6-31G(d,p) level of theory. The potential energy surface obtained from B3LYP/6-31G(d,p) calculations for the reaction between O=P(OCH(3))(2)(+) and benzene is described.     

Direct quantitative analysis of peptides using matrix assisted laser desorption ionization

The protocol and various matrices were examined for quantification of biomolecules in both the low ca. 1200 amu and mid mass 6000-12000 amu ranges using an internal standard. Comparative studies of different matrices of MALDI quantitative analysis showed that the best accuracy and standard curve linearity were obtained for two matrices: (a) 2,5-dihydroxybenzoic acid (DHB) combined with a comatrix of fucose and 5-methoxysalicylic acid (MSA) and (b) ferulic acid/fucose. In the low mass range, the quantitative limit was in the 30 fmol range and in the mid mass range the quantitative limit was in the 250 fmol range. Linear response was observed over 2-3 decades of analyte concentration. The relative error of the standard curve slope was 1.3-1.8% with correlation coefficients of 0.996-0.998.The main problem for quantitative measurement was suppression of the signal of the less concentrated component (analyte or internal standard) by the more concentrated component. The effect was identified with saturation of the matrix by the analyte. The threshold of matrix saturation was found to be in the range of 1/(3000-5000) analyte/matrix molar ratio. To avoid matrix saturation the (analyte+internal standard) to matrix molar ratio should be below this threshold. Thus the internal standard concentration should be as low as possible.DHB/MSA/fucose and ferulic acid/fucose matrices demonstrated good accuracy and linearity for standard curves even when the internal standard had chemical properties different from the analyte. However, use of an internal standard with different chemical properties requires highly stable instrumental parameters as well as constant (analyte+internal standard)/matrix molar ratio for all samples.