Mass spectroscopy of natural products. XXIII,Comparative positive and negative ion mass spectral studies of scapanin-type diterpenoidst

The mass spectral behaviour of 15 scapanin-type diterpenoids (8α,12-epoxylabdanes) was elucidated using accurate mass measurements and deuterium-labelled derivatives. The results obtained allow a localization of the functional groups in the diterpenoid system. Furthermore, the negative ion mass spectra of the scapanin-type diterpenoids are discussed and compared with the positive ion spectra.     

The absolute configurations of (+)-usnic and (+)-isousnic acid. X-ray analyses of the (−)-α-phenylethylamine derivative of (+)-usnic acid and of (−)-pseudoplacodiolic acid,a new dibenzofuran,from the lichen Rhizoplaca chrysoleuca.

The absolute configuration of (+)-usnic acid has been shown to be (4aR) as in (1) by X-ray analysis of the (?)-α-phenylethylamine derivative (2). The structure and absolute stereochemistry of (?)-pseudoplacodiolic acid (4) have been established.     

Fast separation of UV absorbing anions using ion-interaction chromatography

Ion-interaction chromatography on a short (30 x 4.6 mm) 3 microm ODS column has been investigated with the aim of developing fast chromatographic separations of selected inorganic anions. Tetrabutylammonium chloride (TBA-Cl) was used as the ion-interaction reagent in mobile phases that also contained up to 20% methanol. Separations of simple test mixtures of up to eight UV absorbing anions illustrated how excellent efficiencies (>50,000 plates/m) could be obtained under optimized conditions. The use of an optimised mobile phase containing 20 mM TBA-Cl and 20% methanol resulted in the baseline separation of five important anions (iodate, bromate, nitrite, bromide and nitrate) in a separation window of just 28 s, with a shortest total analysis time of 50 s. The method was briefly applied to the rapid analysis of nitrite and nitrate in both a drinking water and a river water sample with a view to future on-line monitoring.     

Metallocene-DNA: synthesis,molecular and electronic structure and DNA incorporation of C5-ferrocenylthymidine derivatives

Ferrocenylthymidine derivatives have been prepared by Pd-catalysed cross-coupling between ethynylferrocene or vinylferrocene and 5-iodo-2'-deoxyuridine. In the latter case a mixture of trans (2a) and gem (2b) isomers was obtained. The cis-vinylferrocenyl (2c), and ethylferrocenyl (3) derivatives were obtained by catalytic hydrogenation of ethynylferrocenyl-dT (1a), and 2c respectively. Single-crystal X-ray data for 1a, the ferrocenyl-2'furano-pyrimidone 1b, and 2a show that the nucleobase is essentially co-planar with the substituted Cp ring of the metallocene. The selective reduction of the linkage between the ferrocenyl and thymidine moieties, from -C identical to C- to -CH2CH2-, causes a shift in the reduction potential of -124 mV. DFT calculations for the one-electron oxidised species indicate that the diminished conjugation reduces the spin transfer onto the bridging C2 group, but has less effect on the extent transferred to the nucleobase from the ferrocenyl group. Compound 1a was incorporated site-specifically into DNA oligonucleotides by using automated solid-phase methods. However, some interconversion of 1a-->1b occurs, even under rapid mild conditions of deprotection.     

Design and commissioning of a timestamp-based data acquisition system for the DRAGON recoil mass separator

The fission fragment mass distribution followed by neutron emission is studied for the ²³⁸U(¹⁸O,f) reaction using the asymmetric two-center shell model. Within the thermodynamic approach, excitation energy carried by the compound nucleus is dissipated in the emission of a pair of neutrons in several consecutive steps. Therefore, we have considered 2–12 (in step of 2) neutron emission channels in our formalism. The mass distribution corresponding to 8-neutron emission channel compares reasonably well with the experimental data. The observed fine structure dips corresponding to shell closure (Z = 50 and N = 82 of individual fission fragment arise mainly due to shell structure in the mass parameters. However, an exact location and magnitude of the dip at A = 124 in the mass distribution depends on how the temperature modifies masses and, also, on the precise information of pre- and post-neutron emission data. This suggests a possible importance of extending these calculations to get new insight into an understanding of the dynamical behaviour of fragment formation in the fission process.     

A Diene Synthesis of Quinone Aldehydes

Cycloaddition of 2-(hydroxymethyl)-1,3-butadiene with representative quinones occurs readily in refluxing toluene. Oxidative dehydrogenation of the resulting cycloadduct with activated manganese dioxide in refluxing benzene affords quinone aldehydes in good to excellent overall yield.     

Iminodiacetic acid functionalised organopolymer monoliths: application to the separation of metal cations by capillary high-performance chelation ion chromatography

Lauryl methacrylate-co-ethylene dimethacrylate monoliths were polymerised within fused silica capillaries and subsequently photo-grafted with varying amounts of glycidyl methacrylate (GMA). The grafted monoliths were then further modified with iminodiacetic acid (IDA), resulting in a range of chelating ion-exchange monoliths of increasing capacity. The IDA functional groups were attached via ring opening of the epoxy group on the poly(GMA) structure. Increasing the amount of attached poly(GMA), via photo-grafting with increasing concentrations of GMA, from 15 to 35 %, resulted in a proportional and controlled increase in the complexation capacity of the chelating monoliths. Scanning capacitively coupled contactless conductivity detection (sC⁴D) was used to characterise and verify homogenous distribution of the chelating ligand along the length of the capillaries non-invasively. Chelation ion chromatographic separations of selected transition and heavy metals were carried out, with retention factor data proportional to the concentration of grafted poly(GMA). Average peak efficiencies of close to 5,000 N/m were achieved, with the isocratic separation of Na, Mg(II), Mn(II), Co(II), Cd(II) and Zn(II) possible on a 250-mm-long monolith. Multiple monolithic columns produced to the same recipes gave RSD data for retention factors of <15 % (averaged for several metal ions). The monolithic chelating ion-exchanger was applied to the separation of alkaline earth and transition metal ions spiked in natural and potable waters.     

Carapolide A,A novel hexanortriterpenoid and carapolides b and c,novel tetranortriterpenoids from the seeds of carapaprocera (meliaceae)

Carapolide A, a novel hexanortriterpenoid, and carapolides B and C, novel tetranortriterpenoids have been isolated from the seeds of $\text{Carapa}$$\text{procera}$ and have been assigned structures (2), (10) and (11) respectively on the basis of chemical and spectroscopic evidence.