Analysis of nucleotides by pressure-assisted capillary electrophoresis-mass spectrometry using silanol mask technique

A method for the determination of nucleotides based on pressure-assisted capillary electrophoresis-electrospray ionization mass spectrometry (PACE-MS) is described. To prevent multi-phosphorylated species from adsorbing onto the fused-silica capillary, silanol groups were masked with phosphate ions by preconditioning the capillary with the background electrolyte containing phosphate. During preconditioning, nebulizer gas was turned off to avoid contamination of MS detector with phosphate ions. To detect nucleotides using the CE positive mode at a pH 7.5, it was necessary to apply air pressure to the inlet capillary during electrophoresis to supplement the electroosmotic flow (EOF) toward the cathode. Moreover, we exchanged the running electrolyte every analysis using the buffer replenishment system to obtain the required reproducibility. Under the optimized conditions, 14 phosphorylated species such as nucleotides, nicotinamide-adenine dinucleotides and coenzyme A (CoA) compounds were well determined in less than 20 min. The relative standard deviations (n=6) of the method were better than 0.9% for migration times and between 1.7% and 8.1% for peak areas. The detection limits for these species were between 0.5 and 1.7 micromol/L with pressure injection of 50 mbar for 30 s (30 nL) at a signal-to-noise ratio of 3. This approach is robust and quantitative compared to the previous method, and its utility is demonstrated by the analysis of intracellular nucleotides and CoA compounds extracted from Escherichia coli wild type, pfkA and pfkB knockout mutants. The methodology was used to suggest that pfkA is the main functional enzyme.     

Multiple nuclear Bragg scattering

Multiple nuclear resonant scattering from an ⁵⁷FeBO₃ single crystal has been observed in the three-beam case. A change of the lifetime and a modulation of the quantum beat were observed in our study. The high brilliance of synchrotron radiation and the high perfection of the synthetic ⁵⁷FeBO₃ single crystal enabled us to observe such an effect. This revised version was published online in August 2006 with corrections to the Cover Date.     

Synthesis and Surface Chemical Properties of Adhesive Protein of the Asian Freshwater Mussel,Limnoperna fortunei

The adhesive polydecapeptide poly(Lys‐Pro‐Thr‐Gln‐Tyr‐Ser‐Asp‐Glu‐Tyr‐Lys) (average repeating number, n = 5), which is the consensus sequence of the Asian freshwater mussel Limnoperna fortunei adhesive protein (Lffp), has been synthesized by the polycondensation of the active esters. The surface chemical experiments revealed the following characteristics of the freshwater adhesive protein: (i) wettability of the Lffp solution is affected by the polar component value (γ_s^p) of the surface free energy of the substrate, and a substrate having a γ_s^p less than 10 mJ·m^–2 exhibits a reduced wettability of the Lffp solution; (ii) the comparison of wettability of native Lffp with synthetic Lffp suggests that the decapeptide sequence, ‐Lys‐Pro‐Thr‐Gln‐Tyr‐Ser‐Asp‐Glu‐Tyr‐Lys‐, contributes to the interaction with the underwater surface; (iii) the Lffp tends to adsorb on nonpolar surfaces that have a low γ_s^p value; and (iv) the adsorption ability of the freshwater adhesive protein is less than that of the marine adhesive protein because of the higher hydrophilicity of the freshwater adhesive protein. An antifouling examination indicated that a γ_s^p value of the substrate surface of less than 10 mJ·m^–2 should achieve a higher antifouling effect towards the L. fortunei attachment. These results are the first findings for the development of a freshwater antifouling strategy based on the molecular mechanism underlying the attachment of L. fortunei.     

Near-Infrared Imaging Using a High-Speed Monitoring Near Infrared Hyperspectral Camera(Compovision)

This review paper reports near-infrared (NIR) imaging studies using a newly-developed NIR camera, Compovision. Compovision can measure a significantly wide area of 150 mm×250 mm at high speed of between 2 and 5 s. It enables a wide spectral region measurement in the 1 000～2 350 nm range at 6 nm intervals. We investigated the potential of Compovision in the applications to industrial problems such as the evaluation of pharmaceutical tablets and polymers. Our studies have demonstrated that NIR imaging based on Compovision can solve several issues such as long acquisition times and relatively low sensitivity of detection. NIR imaging with Compovision is strongly expected to be applied not only to pharmaceutical tablet monitoring and polymer characterization but also to various applications such as those to food products, biomedical substances and organic and inorganic materials.     

Direct conversion of a metal organic compound to epitaxial Sb-doped SnO2 film on a (0 0 1) TiO2 substrate using a KrF laser, and its resulting electrical properties

Epitaxial Sb-doped SnO₂ (0 0 1) thin film on a TiO₂ (0 0 1) substrate was successfully prepared by laser-assisted metal organic deposition at room temperature. The effects of the precursor thin film and laser fluence on the resistivity, carrier concentration, and mobility of the Sb-doped SnO₂ film were investigated. The resistivity of the Sb-doped SnO₂ film prepared by direct irradiation to metal organic film is one order of magnitude lower than that of film prepared by irradiation to amorphous Sb-doped SnO₂ film. From an analysis of Hall measurements, the difference between the resistivity of the Sb-doped SnO₂ film prepared using the metal organic precursor film and that of amorphous precursor film appears to be caused by the mobility. Direct conversion of the metal organic compound by excimer laser irradiation was found to be effective for preparing epitaxial Sb-doped SnO₂ film with low resistivity.     

Application of the Perimeter Model to the Assignment of the Electronic Absorption Spectra of Gold(III) Hexaphyrins with [4n+2] and [4n] π‐Electron Systems

Expanded porphyrins : The electronic excited states of two forms of meso‐hexakis(pentafluorophenyl)‐substituted gold(III) hexaphyrin(1.1.1.1.1.1), such as that depicted, have been investigated by density functional calculations and magnetic circular dichroism spectroscopy to assign their low‐energy excited singlet states.

     

Improved prediction for a multivariate normal distribution with unknown mean and variance

The prediction problem for a multivariate normal distribution is considered where both mean and variance are unknown. When the Kullback–Leibler loss is used, the Bayesian predictive density based on the right invariant prior, which turns out to be a density of a multivariate t-distribution, is the best invariant and minimax predictive density. In this paper, we introduce an improper shrinkage prior and show that the Bayesian predictive density against the shrinkage prior improves upon the best invariant predictive density when the dimension is greater than or equal to three.     

Comparison of bifurcation and imperfection analyses of localized necking in rate-independent polycrystalline sheets

Plastic flow localization into a narrow band is investigated for a rate-independent polycrystalline sheet. Strain localization is considered to initiate at a point of bifurcation from the homogeneous deformation state or to result from the growth of a preexisting imperfection. Bifurcation analysis based on the rate-independent crystal plasticity model is found to give limit strains at a realistic strain level in the biaxial-stretching range. Limit strains predicted by the imperfection analysis are lower than those for bifurcation analysis and tend to approach those strain levels with decreasing amount of initial imperfection. Then, the bifurcation analysis is applied to the simulation of the forming limit for strongly textured sheets. The bifurcation analysis reveals the same trend of a texture dependence of limit strains as that for the imperfection analysis employing a rate-dependent model reported in the literature.