Negative electrospray, ion trap multistage mass spectrometry of synthetic fragments of the O-PS of Vibrio cholerae O:1

Saccharides (mono through hexasaccharides) that mimic the terminal epitopes of O-antigens of Vibrio cholerae O:1, serotypes Ogawa and Inaba, were studied by electrospray ion trap (ESI IT) mass spectrometry (MS) in the negative mode. Anionized adducts are the characteristic ions formed by the capture of H(3)O(2)(-) under the condition of ESI MS analysis. The reactive species are produced by reaction of hydroxyl anions with the molecule of water. Thus the [M + H(3)O(2)](-) have the highest m/z value in the ESI IT negative mass spectra. After dissociation of adducts by loss of 2H(2)O the [M-H](-) ions are produced. The fragmentation pathways were confirmed by multistage measurements (MS(n)). The predominant pathway of fragmentation of the mono- and oligomers is the elimination of a molecule of alpha- hydroxy--gammabutyrolactone from the 4-(3-deoxy-L-glycero-tetronamido) group. The other characteristic pathway occurs by shortening the length of oligosaccharides. In this way, conversion of the Ogawa to Inaba fragments takes place under the conditions of measurement. Negative ESI MS/MS provided sufficient information about molecular mass, the number of saccharide residues, basic structure of saccharides, about the tetronamide part of the compounds investigated and allowed Ogawa and Inaba serotypes to be distinguished.     

A Liouville-type theorem and the decay of radial solutions of a semilinear heat equation

We consider the semilinear parabolic equation _ut=Δu+u^p$u_t=\mathrm{\Delta }u+u^p$ on R^N${\mathbb{R}}^N$, where the power nonlinearity is subcritical. We first address the question of existence of entire solutions, that is, solutions defined for all x∈R^N$x\in {\mathbb{R}}^N$ and t∈R$t\in \mathbb{R}$. Our main result asserts that there are no positive radially symmetric bounded entire solutions. Then we consider radial solutions of the Cauchy problem. We show that if such a solution is global, that is, defined for all t?0$t?0$, then it necessarily converges to 0, as t→∞$t\to \infty$, uniformly with respect to x∈R^N$x\in {\mathbb{R}}^N$.     

A Singular Differential Equation Stemming from an Optimal Control Problem in Financial Economics

We consider the ordinary differential equation $$x^2 u''=axu'+bu-c \bigl(u'-1\bigr)^2, \quad x\in(0,x_0), $$ with $a\in\mathbb{R}, b\in\mathbb{R}$ , c>0 and the singular initial condition u(0)=0, which in financial economics describes optimal disposal of an asset in a market with liquidity effects. It is shown in the paper that if a+b<0 then no continuous solutions exist, whereas if a+b>0 then there are infinitely many continuous solutions with indistinguishable asymptotics near 0. Moreover, it is proved that in the latter case there is precisely one solution u corresponding to the choice x ₀=∞ which is such that 0≤u(x)≤x for all x>0, and that this solution is strictly increasing and concave.     

Spectral Properties of Probes Containing Benzothioxanthene Chromophore Linked with Hindered Amine in Solution and in Polymer Matrices

Absorption and emission spectroscopy as well as laser flash photolysis was employed in order to characterize the spectral properties of novel probes based on benzothioxantheneimide chromophore covalently linked with different types of sterically hindered amines. These were chosen as 2-(2,2,6,6-tetramethyl-4-piperidyl)-thioxantheno[2,1,9-dej]isoquinoline-1,3-dione (BTXINH), the equivalent stable nitroxyl radical, i.e. 2-(1-oxo-2,2,6,6-tetramethyl-4-piperidyl)thioxantheno[2,1,9dej]isoquinoline 1,3-dione (BTXINO) and the alkoxy derivative 2-(1-(1′-phenylethoxy)-2,2,6,6-tetramethyl-4-piperidyl)-thioxantheno[2,1,9-dej]isoquinoline-1,3-dione (BTXINOR). Spectral properties, in solutions and in various polymer matrices such as polystyrene, polymethyl methacrylate, polyvinyl chloride and polypropylene, were compared with the compound 2-(1-dodecyl)-thioxantheno[2,1,9-dej]isoquinoline-1,3-dione (BTXID) taken in the present study as a reference compound. By means of the fluorescence decay and in the contrary to three other probes, BTXINO probe clearly showed a biexponential decay while the three other probes led to monoexponential decay. Two different singlet excited states with lifetimes of about 0.4 and 5 ns were proposed. They correspond to two dispositions of the nitroxyl radical chain above and along the fluorescent moiety of the molecule. Such behaviour depends on the surrounding media. Moreover, an efficient intramolecular quenching of the fluorescence emission was only observed with the short lived singlet excited state. The ratio BTXID/BTXINO was found equal to about 4 and 9 in solutions and polymer matrices respectively. Laser flash photolysis indicated that the novel probes as well as the model compound yielded transient absorption with maximum at 530 nm, corresponding to the triplet states. The intermolecular quenching of such species by molecular oxygen and by free N-oxyl, such as 1-oxy-2,2,6,6-teramethylpiperidine (TEMPO) and 1-oxy-2,2,6,6-teramethyl-4-hydroxypiperidine (TEMPOL), and the intramolecular quenching was not efficient.     

Magnetic properties and macroscopic heterogeneity of FeCoNbB Hitperms

Nanocrystalline ribbons of Fe_81−xCo_xNb₇B₁₂ (where x ranges from 0 to 40.5 at%) Hitperm alloys have been investigated as to their basic magnetic properties and the influence of the macroscopic heterogeneity. Different crystalline share at surfaces compared with the volume average is observed by conversion electron Mössbauer spectroscopy (CEMS) and Mössbauer spectroscopy (MS), respectively. This marks the presence of macroscopic heterogeneity in these Hitperms. The heterogeneity is generally more significant in Ar-annealed samples than in the vacuum-annealed ones. The characteristic slant hysteresis loops (hard-ribbon-axis) are seen as a rule with few exceptions. An inspection of hysteresis loop response of resin potted samples shows that the surfaces bi-axially squeeze the ribbon interior in heterogeneous Hitperms when the ribbons cool down after annealing. Certain compositions show macroscopic viscous flow prior to crystallization so the heterogeneity gets another chance to induce anisotropy during annealing. The induction attains 1.5 T but saturates poorly due to the heterogeneity and the ensuing anisotropy. Moreover the heterogeneity appears to hamper the crystallization within the ribbon interior. Unlike Finemets, the density of these Hitperms show no pronounced trend with annealing.     

Study of radon exhalation from the soil

The influence of meteorological parameters on radon exhalation rate was analyzed. The analyses show a significant influence of precipitation on radon exhalation rate. The highest exhalation rate was found during dry periods and the lowest during the periods of strong precipitation. We also tested two different types of detectors for the measurement of radon exhalation rate—the ionization chamber (AlphaGUARD) and the scintillation chamber of Lucas type. The exhalation rates measured by these detectors were in a good agreement. Likewise, there was an agreement in radon exhalation rates determined from short term and long term increases in radon activity concentration.     

Bifunctional iminophosphorane superbases: Potent organocatalysts for enantio- and diastereoselective Michael addition reactions

Bifunctional iminophosphorane (BIMP) organocatalysts catalyze the enantio- and diastereoselective Michael additions of high pK_a cyclic malonamate ester pro-nucleophiles to nitroalkenes with reactivity profiles of up to 3 orders of magnitude greater than tertiary amine bifunctional Brønsted base/(thio)urea organocatalysts. The unrivalled performance of the BIMPs allows reaction times of challenging reactions to be slashed from weeks to minutes and has enabled new flow chemistry applications using polystyrene-supported versions contained within a flow reactor.     

A nonafluoro nucleoside as a sensitive 19f NMR probe of nucleic acid conformation

A nucleoside carrying a perfluorinated tert-butyl group ( 4) was prepared by a Sonogashira coupling of 5-iodo-2'-deoxyuridine with 4,4,4-trifluoro-3,3-bis(trifluoromethyl)-1-butyne in nearly quantitative yield and subsequently incorporated into DNA oligomers. Thermal denaturation studies showed that 4 had a negligible effect on duplex stability when compared to thymidine. Transition from single strand to duplex was monitored by (19)F NMR spectroscopy at micromolar concentrations of oligomers, demonstrating the sensitivity of 4 as an NMR reporter nucleoside.     

DNA fragment separations by on‐line combination of capillary isotachophoresis–capillary zone electrophoresis with UV detection

A high‐speed DNA fragment separation system based on an on‐line combination of capillary ITP with CZE (CITP‐CZE) and using UV detection at 260 nm was developed. A novel CITP‐CZE buffer system of pH 6.1 was designed for the separation of ten DNA fragments with sizes ranging from 100 to 1000 bp. An effect of underivatized α‐, β‐ and γ‐cyclodextrins on the resolution of DNA fragments in the CZE step of the CITP‐CZE combination was systematically investigated. Methylhydroxyethylcellulose present in the BGE was used to eliminate the EOF. DNA ladder fragments were separated within 10 min with LODs in the range of 1–5 ng/μL (S/N = 3). The RSDs of the migration time and peak area of individual DNA fragments were in the range of 1–3 and 3–9%, respectively. The developed CITP‐CZE system was further applied to the analysis of digest plasmid DNA samples.