Cover Picture

The cover picture shows in the background the whole cell of a methanotrophic bacterium on which are superimposed components of methane monooxygenase (the structure of the hydroxylase component (top), one of the two four-helix bundles that house the catalytic diiron centers (left)) and a schematic diagram of the catalytic cycle by which the enzyme converts dioxygen and methane into methanol and water. More about this unusual enzyme system is reported by Lippard et al. on p. 2782 ff.     

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.     

The vibrational spectra of some 1,3-dimethyl-1,3-diaza-2-boracyclopentanes

A detailed vibrational assignment is proposed for 1,3-dimethyl-1,3-diaza-2-boracyclopentanes:

where X = Cl, Br or NMe₂. The assignments are generally in accord with C_2v symmetry, but there is some evidence for a slight breakdown, as some A₂ modes appear in the IR. The BN₂ stretches are near 1500 cm^?1, (antisymmetric) and 1300 cm^?1 (symmetric), consistent with a large degree of π-bonding.     

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     

Dendritic molecular capsules for hydrophobic compounds

Reichardt's dye, a highly solvatochromic dye, was encapsulated within poly (glycerol succinic acid) ([Gn]-PGLSA-OH) dendrimers to investigate the interior environment of these dendritic macromolecules. The absorption maximum for the encapsulated Reichardt's dye in water was indicative of a relatively high dielectric constant present within the dye/dendrimer complex. (1)H NMR of the encapsulated complex showed the presence of aromatic protons from Reichardt's dye along with the aliphatic protons of the dendrimer. Additionally, there were substantial changes in T(1) and T(2) times of the encapsulated dye when compared with the free dye, and (1)H NOESY spectra for the complex showed a significant number of intermolecular NOE cross-peaks. These data reveal the close through-space proximity of the dye to the dendrimer and the restricted motion of the encapsulated dye. To demonstrate the potential use of these macromolecules as drug delivery vehicles, the poorly water-soluble anticancer drug 10-hydroxycamptothecin (10HCPT) was encapsulated within a carboxylated PGLSA dendrimer ([G4]-PGLSA-COONa). Cytotoxicity assays with human breast cancer cells showed a significant reduction of cell viability, demonstrating that 10HCPT retains activity upon encapsulation.     

Simultaneous analysis of oxidized and reduced glutathione in cell extracts by capillary zone electrophoresis

Glutathione (GSH) and glutathione disulfide (GSSG) levels in cells constitute a thiol redox system. They can be used as an indicator of oxidative stress of the cell. In this study, a capillary zone electrophoresis (CZE) method is described that enables quantitation of GSH and GSSG from cellular extracts. The CZE buffer used was 20 mM ammonium acetate containing 5% (v/v) acetic acid at pH 3.1 in conjunction with a polybrene coated capillary operated in reverse polarity mode. Effects of different acids used to prepare cell samples were investigated on CZE performance. The acids include meta phosphoric acid (MPA), trichloroacetic acid (TCA), phosphoric acid (PA) and sulfosalicylic acid (SSA) and are used to stabilize GSH and GSSG before performing CZE analysis. The method features a limit of detection of 4 microM and a limit of quantitation of 12 microM for both GSSG and GSH and recoveries of 94% for GSH and 100% for GSSG. Quantitative analysis of GSSG and GSH in HaCaT cell extracts (5% SSA, w/v) was performed with this method and changes in the ratio of GSH to GSSG in N-ethylmaleimide treated cell sample was observed by comparing with control cell samples.