Gas-Phase Stability of Negatively Charged Organophosphate Metabolites Produced by Electrospray Ionization and Matrix-Assisted Laser Desorption/Ionization

The formation mechanisms of singly and multiply charged organophosphate metabolites by electrospray ionization (ESI) and their gas phase stabilities were investigated. Metabolites containing multiple phosphate groups, such as adenosine 5'-diphosphate (ADP), adenosine 5'-triphosphate (ATP), and D-myo-inositol-1,4,5-triphosphate (IP₃) were observed as doubly deprotonated ions by negative-ion ESI mass spectrometry. Organophosphates with multiple negative charges were found to be unstable and often underwent loss of PO₃ ^–, although singly deprotonated analytes were stable. The presence of fragments due to the loss of PO₃ ^– in the negative-ion ESI mass spectra could result in the misinterpretation of analytical results. In contrast to ESI, matrix-assisted laser desorption ionization (MALDI) produced singly charged organophosphate metabolites with no associated fragmentation, since the singly charged anions are stable. The stability of an organophosphate metabolite in the gas phase strongly depends on its charge state. The fragmentations of multiply charged organophosphates were also investigated in detail through density functional theory calculations.

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Any algebraic variety in positive characteristic admits a projective model with an inseparable Gauss map

We determine the values attained by the rank of the Gauss map of a projective model for a fixed algebraic variety in positive characteristic p. In particular, it is shown that any variety in p>0 has a projective model such that the differential of the Gauss map is identically zero. On the other hand, we prove that there exists a product of two or more projective spaces admitting an embedding into a projective space such that the differential of the Gauss map is identically zero if and only if p=2.     

Biharmonic Submanifolds in a Riemannian Manifold with Non-Positive Curvature

In this paper, we show that, for every biharmonic submanifold (M, g) of a Riemannian manifold (N, h) with non-positive sectional curvature, if ${\int_M\vert \eta \vert^2 v_g < \infty}$ , then (M, g) is minimal in (N, h), i.e., ${\eta\equiv0}$ , where η is the mean curvature tensor field of (M, g) in (N, h). This result gives an affirmative answer under the condition ${\int_M\vert \eta \vert^2 v_g < \infty}$ to the following generalized Chen’s conjecture: every biharmonic submanifold of a Riemannian manifold with non-positive sectional curvature must be minimal. The conjecture turned out false in case of an incomplete Riemannian manifold (M, g) by a counter example of Ou and Tang (in The generalized Chen’s conjecture on biharmonic sub-manifolds is false, a preprint, 2010).     

Zirconia-based amperometric sensor using La–Sr-based perovskite-type oxide sensing electrode for detection of NO2

An amperometric zirconia-based sensor attached with perovskite-type oxide sensing electrode was examined for monitoring NO₂ in automobile exhaust. The sensor using La_0.6Sr_0.4Co_0.98Mn_0.02O₃ showed high response to NO₂. The response was almost linear to NO₂ concentration in the range between 50 and 800 ppm, and a 90% reaction time to 400 ppm NO₂ was less than 20 s. Though the NO₂ response of the sensor was slightly affected by the changes in O₂ concentrations, it showed still high response in the examined range of 5–21 vol%.     

Growth and characterization of Fe nanostructures on GaN

We have investigated the growth of Fe nanostructures on GaN(0 0 0 1) substrates at room temperature using reflection high-energy electron diffraction (RHEED), scanning tunneling microscopy (STM), and superconducting quantum interference device magnetometer. Initially, a ring RHEED pattern appears, indicating the growth of polycrystalline α-Fe. At around 0.5 nm deposition, the surface displays a transmission pattern from α-Fe films with the epitaxial relationship of Fe(1 1 0)//GaN(0 0 0 1) and Fe[1 −1 1]//GaN[1 1 −2 0] (Kurdjumov-Sachs (KS) orientational relationship). Further deposition to 1 nm results in the appearance of a new spot pattern together with the pattern from domains with the KS orientation relationship. The newly observed pattern shows that Fe layers are formed with the epitaxial relationship of Fe(1 1 0)//GaN(0 0 0 1) and Fe[0 0 1]//GaN[1 1 −2 0] (Nishiyama-Wasserman (NW) orientational relationship). From STM images for Fe layers with the KS and NW orientational relationships, it can be seen that Fe layers with the KS relationship consist of round-shaped Fe nanodots with below 7 nm in average diameter. These nanodots coalesce to form nanodots elongating along the Fe[1 0 0] direction, and they have the KS orientational relationship. Elongated Fe nanodots with the NW relationship show ferromagnetism while round-shaped Fe nanodots with the KS relationship show super-paramagnetic behavior. We will discuss their magnetic properties in connection with the change in crystalline configurations of nanodots.     

Strong continuity implies uniform sequential continuity

Uniform sequential continuity, a property classically equivalent to sequential continuity on compact sets, is shown, constructively, to be a consequence of strong continuity on a metric space. It is then shown that in the case of a separable metric space, uniform sequential continuity implies strong continuity if and only if one adopts a certain boundedness principle that, although valid in the classical, recursive and intuitionistic setting, is independent of Heyting arithmetic.     

Equivalents of the finitary non-deterministic inductive definitions

We present statements equivalent to some fragments of the principle of non-deterministic inductive definitions (NID) by van den Berg (2013), working in a weak subsystem of constructive set theory CZF. We show that several statements in constructive topology which were initially proved using NID are equivalent to the elementary and finitary NIDs. We also show that the finitary NID is equivalent to its binary fragment and that the elementary NID is equivalent to a variant of NID based on the notion of biclosed subset. Our result suggests that proving these statements in constructive topology requires genuine extensions of CZF with the elementary or finitary NID.     

New Combinatorial Bounds for Authentication Codes and Key Predistribution Schemes

This paper provides new combinatorial bounds and characterizations of authentication codes (A-codes) and key predistribution schemes (KPS). We first prove a new lower bound on the number of keys in an A-code without secrecy, which can be thought of as a generalization of the classical Rao bound for orthogonal arrays. We also prove a new lower bound on the number of keys in a general A-code, which is based on the Petrenjuk, Ray-Chaudhuri and Wilson bound for t-designs. We also present new lower bounds on the size of keys and the amount of users' secret information in KPS, the latter of which is accomplished by showing that a certain A-code is hiding inside any KPS.     

New approach to block copolymerization of ethylene with polar monomers by the unique catalytic function of organolanthanide complexes

This paper describes the first examples of ABA‐ and AB‐type block copolymerizations of a nonpolar monomer, in this case ethylene, with polar monomers, such as methyl methacrylate (MMA), ϵ‐caprolactone (CL), and 2,2‐dimethyltrimethylene carbonate (DTC), initiated by the unique catalytic function of rare earth metal complexes [Sm(II) and Ln(III) (Ln = Y, Sm)] as initiators. The Sm(II) species conducts the ABA‐type triblock copolymerization, leading to poly(MMA‐co‐ethylene‐co‐MMA), poly(CL‐co‐ethylene‐co‐CL), or poly(DTC‐co‐ethylene‐co‐DTC) by the efficient catalysis of racemic Me₂Si(C₅H₂‐2‐Me₃Si‐4‐tBu)₂Sm(THF)₂ ( 1 ) or meso Me₂Si(Me₂SiOSiMe₂)(C₅H₂‐3‐tBu)Sm(THF) ( 2b ). The resulting block copolymers are completely insoluble in THF and CHCl₃, but the homopolymers of MMA, CL, and DTC are freely soluble in these solvents. TEM profiles provide direct evidence for the block copolymerizations, where the spheric morphology of homogeneously dispersed polar polymers was observed. Ln(III) species, such as racemic Me₂Si(C₅H₂‐2‐Me₃Si‐4‐tBuMe₂Si)YH ( 5 ) and Me₂Si(C₅H₂‐2‐Me₃Si‐4‐tBu)SmH ( 6 ), afford AB‐type block copolymers between ethylene and MMA or CL, whose TEM images reveal the homogeneous dispersion of poly(MMA) or poly(CL) units in the polyethylene region. The ABA‐ and AB‐type block copolymers demonstrate high break stress and high tensile modulus as compared with their corresponding blended polymers. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 4095–4109, 2000