Determination of the relative configuration of vic-amino alcohols

A large set of syn- and anti-1,2-amino alcohols has been synthesized. Upon comparison of the CH?O and CH?N ¹H NMR shifts a general trend has been observed, making it possible to determine the relative configuration of 1,2-amino alcohols without derivatization or shift reagents.     

Investigation of the metabolic fate of 2-, 3- and 4-bromobenzoic acids in bile-duct-cannulated rats by inductively coupled plasma mass spectrometry and high-performance liquid chromatography/inductively coupled plasma mass spectrometry/electrospray mass spectrometry

Inductively coupled plasma mass spectrometry (ICPMS) has been used to determine the rate and routes of excretion of bromine following the intraperitoneal administration (50 mg kg(-1)) of 2-, 3- and 4-bromobenzoic acids to male bile-duct-cannulated rats. Analysis of urine and bile for (79/81)Br using ICPMS showed that all three bromobenzoic acids were rapidly excreted (82-98%) within 48 h of dosing, primarily via the urine. High-performance liquid chromatography/inductively coupled plasma mass spectrometry (HPLC/ICPMS) was then used to obtain metabolite profiles for bile and urine. These profiles revealed that extensive metabolism had taken place, with the unchanged bromobenzoic acids forming a minor part of the total of compound-related material detected. Concomitant MS studies, supplemented by alkaline hydrolysis, enabled the identification of the major metabolite of all three of the bromobenzoic acids as a glycine conjugate. Ester glucuronide conjugates were also identified, but formed only a small proportion of total.     

Determination of average degree of polymerisation and distribution of oligosaccharides in a partially acid-hydrolysed homopolysaccharide: a comparison of four experimental methods applied to mannuronan

The average degree of polymerisation (DP) and distribution of oligosaccharides in partially acid hydrolysed mannuronans were quantitatively evaluated by 1H NMR, electrospray ionisation mass spectrometry (ESI-MS), micellar electrokinetic capillary chromatography with UV detection (MEKC-UV), and high-pressure anion-exchange chromatography with pulsed amperometric detection (HPAEC-PAD). Our investigation shows that 1H NMR, MEKC-UV and, in particular, HPAEC-PAD can be used as quantitative tools to aid the investigation of polysaccharide structure, function and synthesis. For the latter two techniques, especially, this represents a significant new development as it enables calculation of the quantity of individual oligomers of nominal DP by direct analysis of a defined oligomer mixture. Appropriate statistical averages of number and weight distributions were also calculated and found to fit very well to predicted Kuhn distributions that assume random depolymerisation.     

DIFFERENT PHOTOINACTIVATION MECHANISMS IN Propionibacterium acnes FOR NEAR-ULTRAVIOLET and VISIBLE LIGHT

The light sensitivity of Propionibacterium acnes was investigated when the cells were exposed to anoxia, sodium azide, D₂O or superoxide dismutase in combination with visible light (broad band red light and 415 nm) and near-ultraviolet irradiation (360 and 320 nm). During anoxia the cells became less sensitive when the irradiation wavelength increased. Oxygen increased the photodamage to a greater extent in the case of visible light than of near-UV light. The photosensitization effects were, however, more or less oxygen dependent at all wavelengths used. An effect of azide and D₂O on the light sensitivity was observed for visible light, while superoxide dismutase was effective only at 320 nm.
The results support the hypothesis that inactivation of P. acnes with near-UV and visible light is based on different mechanisms. Porphyrin photosensitization, accomplished by singlet oxygen, is the most important mechanism when visible light is used. At shorter wavelengths (320 and 360 nm) singlet oxygen is not involved and for 320 nm the destruction might occur via superoxide anion formation.     

Mediated action in teachers’ discussions about mathematics tasks

This paper presents analyses of teachers?? discussions within mathematics teaching developmental research projects, taking mediation as the central construct. The relations in the so-called ??didactic triangle?? form the basic framework for the analysis of two episodes in which upper secondary school teachers discuss and prepare tasks for classroom use. The analysis leads to the suggestion that the focus on tasks places an emphasis on the task as object and its resolution as goal; mathematics has the role of a mediating artefact. Subject content in the didactic triangle is thus displaced by the task and learning mathematics may be relegated to a subordinate position.     

Fluorinated and Trifluoromethylated Corannulenes

The syntheses and properties of corannulenes carrying electron‐withdrawing groups (F, CF₃, C₆F₅) are reported. Direct fluorination of corannulene (C₂₀H₁₀) was carried out with xenon difluoride, and the crystal structure of the product was confirmed by the X‐ray analysis. Novel trifluoromethylated corannulenes, including the versatile 4,9‐dibromo‐1,2‐bis(trifluoromethyl)corannulene, were obtained by various established ring‐closing reactions. Besides the use of hexafluorobutyne for the construction of fluoranthenes by Diels–Alder reaction as precursor molecules to form 1,2‐disubstituted corannulenes, bis(pentafluorophenyl)acetylene was employed as dienophile. The molecular structure and crystal packing of a trifluoromethylated corannulene was determined by single‐crystal X‐ray analysis and compared with those known brominated and trifluoromethylated corannulenes. The general electron‐acceptor properties of corannulenes bearing substituents introduced in particular positions by liquid‐phase synthesis are discussed together with published computational results.     

Arylation with Unsymmetrical Diaryliodonium Salts: A Chemoselectivity Study

Phenols, anilines, and malonates have been arylated under metal‐free conditions with twelve aryl(phenyl)iodonium salts in a systematic chemoselectivity study. A new “anti‐ortho effect” has been identified in the arylation of malonates. Several “dummy groups” have been found that give complete chemoselectivity in the transfer of the phenyl moiety, irrespective of the nucleophile. An aryl exchange in the diaryliodonium salts has been observed under certain arylation conditions. DFT calculations have been performed to investigate the reaction mechanism and to elucidate the origins of the observed selectivities. These results are expected to facilitate the design of chiral diaryliodonium salts and the development of catalytic arylation reactions that are based on these sustainable and metal‐free reagents.     

One-Pot Synthesis and Applications of N-Heteroaryl Iodonium Salts

An efficient one-pot synthesis of N-heteroaryl iodonium triflates from the corresponding N-heteroaryl iodide and arene has been developed. The reaction conditions resemble our previous one-pot syntheses, with suitable modifications to allow N-heteroaryl groups. The reaction time is only 30 min, and no anion exchange is required. The obtained iodonium salts were isolated in a protonated form, these salts can either be employed directly in applications or be deprotonated prior to use. The aryl groups were chosen to induce chemoselective transfer of the heteroaryl moiety to various nucleophiles. The reactivity and chemoselectivity of these iodonium salts were demonstrated by selectively introducing a pyridyl moiety onto both oxygen and carbon nucleophiles in good yields.     

Synthesis and Biological Studies of O3-Aryl Galactosides as Galectin Inhibitors

β-Galactose derivatives have recently been reported to selectively inhibit galectin-3, and a library of O3-arylated galactosides with varying substitution patterns was designed to study such inhibitions further. The O3-arylated galactosides were synthesized using diaryliodonium salts under mild and transition metal free conditions, providing the target products in moderate to good yields. An O3-trifluoroethylated galactoside was also synthesized using iodonium salt chemistry. Azido-substituted products were subsequently transformed into the corresponding triazoles. After deprotection, a selection of galactoside derivatives were evaluated for inhibitory potencies against galectins-1, 3, 4 N (N-terminal domain), 4 C (C-terminal domain), 7, 8 N, 8 C, 9 N, and 9 C and one compound with promising affinity and selectivity for both the N- and C-terminal domain of galectin-9 was discovered.     

Influence of higher harmonics of the undulator in X‐ray polarimetry and crystal monochromator design

The spectrum of the undulator radiation of beamline P01 at Petra III has been measured after passing a multiple reflection channel‐cut polarimeter. Odd and even harmonics up to the 15th order, as well as Compton peaks which were produced by the high harmonics in the spectrum, could been measured. These additional contributions can have a tremendous influence on the performance of the polarimeter and have to be taken into account for further polarimeter designs.