Stereospecific synthesis of enamines from α,β-epoxysilanes

Isomerically pure cis and trans enamines were prepared from α,β-epoxysilanes by alumina-assisted ring opening with pyrrolidine and morpholine followed by β-elimination.     

Comparative analysis by gas chromatography-mass spectrometry of the essential oils from bark and leaves of Cedrelopsis grevei Baill, an aromatic and medicinal plant from Madagascar

The essential oils from bark and leaves of Cedrelopsis grevei Baill (Ptaeroxylaceae), an aromatic and medicinal plant from Madagascar, are widely used in folk medicine. These two commercially available oils have been examined separately by means of GC-MS. The oil constituents were identified according to their mass spectra and their relative retention indices determined on both polar and non-polar stationary phase capillary columns. A total of 55 compounds have been identified constituting 76.7% (bark) and 91.6% (leaves) of the volatile constituents. Both oils were found to have a similar composition; however the relative percentages of some compounds notably differed. The bark essential oil contained beta-pinene (17.1%), cis-sesquisabinene hydrate (12.8%) and caryophyllene oxide (7.0%) as the main components whereas the leaf essential oil was largely dominated by trans-beta-farnesene (35.6%); beta-pinene (12.8%), cis-sesquisabinene hydrate (9.8%) and ar-curcumene (8.6%) were also present as major components. As far as we know, this is the first report on the Cedrelopsis grevei bark and leaf essential oils which therapeutic properties may be attractive for aromatherapy.     

Additives for the stabilization of double-stranded DNA in UV-MALDI MS

Molecular complexes such as double-stranded oligonucleotides contain non-covalent bonds that are difficult to maintain in the MALDI experiment. Quantifiers are introduced in order to evaluate, summarize, and compare spectra from experiments in which additives are used to stabilize duplex oligonucleotides. Compounds known to complex with and stabilize duplex molecules can be useful as additives in MALDI. Spermine and methylene blue, present at concentrations similar to the matrix, are detected, bound to the duplex. When peptides are used as additives, the duplex is stabilized when the peptide is present at an amount less than that of the duplex.     

Ozonation of pyrene and benzo[a]pyrene in silica and soil –14C-mass balances and chemical analysis of oxidation products as a first step to ecotoxicological evaluation

Ozonation of polycyclic aromatic hydrocarbons (PAHs) in soil is a process that can be used for in-situ soil remediation or in combination with bioremediation techniques. First steps to a comprehensive ecotoxicological evaluation of this method is done by ozonation of radioactively labeled (¹⁴C) pyrene and benzo[a]pyrene in a silty soil (LUFA 2.2) under mass-balancing conditions and GC-MS analysis of aromatic ozonation products. ¹⁴C-Mass-balances for pyrene and benzo[a]pyrene (b[a]p) in soil showed that, apart from ¹⁴CO₂ formation, considerable percentages of both PAHs are oxidized to water soluble substances (20–30%) or to non-extractable or bound residues (10% for pyrene, 30% for b[a]p). TLC and GC-MS analysis of ozonation products extractable from artificially contaminated silica and soil by organic solvents revealed a large number of aromatic substances. PAH-quinones and ten ring fission products with formyl- and carboxy-groups of both pyrene and b[a]p could be identified.     

Solid-Phase Synthesis of a Sialyl-Tn-Glycoundecapeptide of the MUC1 Repeating Unit

The synthesis of glycopeptides carrying tumour-associated antigens is of interest for cancer diagnosis and treatment. Here, a very efficient route lo disaccharide threonine building block 8 is presented which allows the introduction of the sialyl-Tn antigen into a peptide. The syntheses of the undecapeptide and the sialyl-Tn-containing glycoundecapeptide, which are a part of the repeating unit of MUC1, were performed by solid-phase synthesis with an allylic anchor cleavable under neutral conditions. After detachment from the resin, the peptide and the glycopeptide arc completely deprotected giving the target compounds 13 and 15 , respectively.     

Characterisation and proposed origin of mass spectrometric ions observed 30 Th above the ionised molecules of per-O-methylated carbohydrates

Derivatisation of carbohydrates by permethylation significantly improves the mass spectrometric intensity of carbohydrate-derived ions and allows more readily interpretable fragmentation; in addition, samples are conveniently separated from salts, and larger oligosaccharides are more readily ionised. It has previously been recognised that, in the mass spectra of permethylated carbohydrates, a series of ions indicating species 30 Da larger than the fully methylated carbohydrate molecules are also observed. These species have not been characterised in the literature despite their apparently ubiquitous occurrence in the mass spectra of permethylated carbohydrates. Tandem mass spectrometry (MS/MS) experiments were performed on permethylated carbohydrates and reduced permethylated carbohydrates that exhibit the artefact, demonstrating that the artefact is not reducing terminal specific, and that the artefact can be introduced at any hydroxyl residue. It was further demonstrated through the use of different alkylation reagents that the origin of this artefact group is the alkylating reagent itself. It is proposed that side reactions that occur between the permethylation reagents allow the production of small amounts of iodomethyl methyl ether. This reagent can then compete with methyl iodide for reaction with the carbohydrate -OH groups. The result is partial incorporation of a methoxymethyl moiety instead of a methyl group, detected as '+30' artefact ions.     

Insight into the reactivity of olefins in the Pauson-Khand reaction

The reactivity of different Co(2)(CO)(6)-acetylene complexes in the Pauson-Khand reaction is strongly dependent on the nature of the olefin. Theoretical calculations at both the DFT and ONIOM levels are concordant with experimental observations and suggest how the olefin-cobalt interactions in the complex could have a major effect on the relative reactivity of the olefins. This study rationalizes for the first time the experimentally observed reactivity differences of cyclohexene, cyclopentene, and norbornene.     

A multitechnique surface analytical study of a segmented block copolymer poly(ether-urethane) modified through an H2O radio frequency glow discharge

Recent work in our laboratories has fully characterized the surface region of a segmented poly(ether-urethane) (PEU) extending from the air/polymer interfacial region through bulk depths in the micron range. This characterization utilized energy and angle dependent Electron Spectroscopy for Chemical Analysis (ESCA), Attenuated Total Reflectance–Fourier Transform Infrared Spectroscopy (ATR–FTIR), and Comprehensive Wettability Profiling (contact angle using a homologous series of liquids) as defined by Zisman. In this study this same multi-analytical-technique approach is used to elucidate changes in these PEU surfaces induced through an H₂O Radio Frequency Glow Discharge (RFGD) plasma. This investigation reports both qualitative and quantitative changes due to the modification treatments as well as the permanency of the changes effected on these surfaces through the plasma treatment. From our analyses, the amount of surface residing polyurethane (hard segment) is observed to increase due to a proposed plasma etching mechanism. Further, the addition of oxygen containing functionality is detected at the modified surfaces unique with respect to the unmodified PEU. These surface modifications which show large increases in wettability, are finally observed to be semi-permanent over a time period of 6 months.     

On the determination of crystallinity and cellulose content in plant fibres

A comparative study of cellulose crystallinity based on the sample crystallinity and the cellulose content in plant fibres was performed for samples of different origin. Strong acid hydrolysis was found superior to agricultural fibre analysis and comprehensive plant fibre analysis for a consistent determination of the cellulose content. Crystallinity determinations were based on X-ray powder diffraction methods using side-loaded samples in reflection (Bragg-Brentano) mode. Rietveld refinements based on the recently published crystal structure of cellulose Iβ followed by integration of the crystalline and amorphous (background) parts were performed. This was shown to be straightforward to use and in many ways advantageous to traditional crystallinity determinations using the Segal or the Ruland–Vonk methods. The determined cellulose crystallinities were 90–100 g/100 g cellulose in plant-based fibres and 60–70 g/100 g cellulose in wood based fibres. These findings are significant in relation to strong fibre composites and bio-ethanol production.     

Simultaneous determinations of a monofluorinated imidazo[1, 5-a] [1, 4] benzodiazepine and the corresponding benzophenone as a function of pH and in aqueous formulations by 19F nuclear magnetic resonance spectrometry

8-Chloro-6-(2-fluorophenyl)-1-methyl-4H-imidazo[1, 5-a] [1, 4 ]benzodiazepine (called “midazolam”) exists in equilibrium with the corresponding benzophenone (the“open-Mng form”). The two compounds were determined simultaneously as a function of pH with ¹⁹F-n.m.r. spectrometry. In a unique application of ¹⁹F-n.m.r. spectrometry, the compounds are determined simultaneously in aqueous dosage forms without the need for sample preparation. The optimum signal-to-noise ratio for the major compound for the lowest concentration of sample used (≈ 1 mg ml^-1) was 200:1 for 3000 scans. This was obtained by partial proton decoupling and exponential multiplication of the free induction decay with a line-broadening parameter of 12 Hz. Quantitative results are presented with a standard deviation of < 2.0% in the mean ratio of the two compounds. The results are also compared with those obtained by the spectrophotometric fluorescamine method. Advantages of the ¹⁹F-n.m.r. technique in this determination are discussed.