Diels–Alder derivatization for sensitive detection and characterization of conjugated linoleic acids using LC/ESI-MS/MS

The utility of Diels–Alder derivatization with 4-phenyl-1,2,4-triazoline-3,5-dione (PTAD) for liquid chromatography/electrospray ionization tandem mass spectrometry of conjugated linoleic acids (CLAs) was examined. PTAD rapidly reacted with the CLAs, and the resulting derivatives were highly responsive in electrospray ionization mass spectrometry operating in the positive-ion mode. The derivatives produced characteristic product ions during tandem mass spectrometry, which enabled the sensitive detection [limit of detection 18 fmol (signal-to-noise ratio of 5)] and the identification of the conjugated diene position. The PTAD derivatization also significantly increased the reversed-phase liquid chromatography separation selectivity for the most biologically active CLA isomers: cis-9,trans-11-CLA and trans-10,cis-12-CLA. The PTAD derivatization was applied to analyses of food and biological samples; the major CLAs in milk and beef fat samples were successfully identified, and trace amounts of CLAs in human saliva were detected with a simple pretreatment and short analysis time.     

CH bond functionalization: emerging synthetic tools for natural products and pharmaceuticals

The direct functionalization of C? H bonds in organic compounds has recently emerged as a powerful and ideal method for the formation of carbon–carbon and carbon–heteroatom bonds. This Review provides an overview of C? H bond functionalization strategies for the rapid synthesis of biologically active compounds such as natural products and pharmaceutical targets.     

Nickel-catalyzed C-H/C-O coupling of azoles with phenol derivatives

The first nickel-catalyzed C-H bond arylation of azoles with phenol derivatives is described. The new Ni(cod)(2)/dcype catalytic system is active for the coupling of various phenol derivatives such as esters, carbamates, carbonates, sulfamates, triflates, tosylates, and mesylates. With this C-H/C-O biaryl coupling, we synthesized a series of privileged 2-arylazoles, including biologically active alkaloids. Moreover, we demonstrated the utility of the present reaction for functionalizing estrone and quinine.     

Bifurcation approach to a logistic elliptic equation with a homogeneous incoming flux boundary condition

In this paper, we consider a semilinear elliptic boundary value problem in a smooth bounded domain, having the so-called logistic nonlinearity that originates from population dynamics, with a nonlinear boundary condition. Although the logistic nonlinearity has an absorption effect in the problem, the nonlinear boundary condition is induced by the homogeneous incoming flux on the boundary. The objective of our study is to analyze the existence of a bifurcation component of positive solutions from trivial solutions and its asymptotic behavior and stability. We perform this analysis using the method developed by Lyapunov and Schmidt, based on a scaling argument.     

Second order optimality for estimators in time series regression models

We consider the second order asymptotic properties of an efficient frequency domain regression coefficient estimator proposed by Hannan [Regression for time series, Proc. Sympos. Time Series Analysis (Brown Univ., 1962), Wiley, New York, 1963, pp. 17-37]. This estimator is a semiparametric estimator based on nonparametric spectral estimators. We derive the second order Edgeworth expansion of the distribution of . Then it is shown that the second order asymptotic properties are independent of the bandwidth choice for residual spectral estimator, which implies that has the same rate of convergence as in regular parametric estimation. This is a sharp contrast with the general semiparametric estimation theory. We also examine the second order Gaussian efficiency of . Numerical studies are given to confirm the theoretical results.     

Analysis of red phosphorus in resins using pyrolysis-gas chromatography/mass spectrometry.

Although red phosphorus is used as a flame retardant for polymer materials, no analysis methods for it in resins has been established. Analysis methods for red phosphorus in resins were investigated using pyrolysis-gas chromatograpy/mass spectrometry (Py-GC/MS) by paying attention to the fact that it has a sublimation property. We found that the mass spectrum of red phosphorus shows a series of ions at m/z=62, 93 and 124, and a fragment pattern indicating that red phosphorus (P4=124, P=31) was pyrolytically decomposed. The coefficient of the correlation between the content of red phosphorus in the resin and the peak intensity in Py-GC/MS was 0.9781. The relative standard deviations of this analysis method was 6.29% (n=5). Py-GC/MS was applicable not only to qualitative analysis but also to the quantitative analysis of red phosphorus.     

An indefinite concave-convex equation under a Neumann boundary condition I

We investigate the problem (P _λ) ?Δu = λb(x)|u| ^q?2 u + a(x)|u| ^p?2 u in Ω, ?u/?n = 0 on ?Ω, where Ω is a bounded smooth domain in R ^N (N ≥ 2), 1 < q < 2 < p, λ ∈ R, and a, b ∈ \({C^\alpha }\left( {\overline \Omega } \right)\) with 0 < α < 1. Under certain indefinite type conditions on a and b, we prove the existence of two nontrivial nonnegative solutions for small |λ|. We then characterize the asymptotic profiles of these solutions as λ → 0, which in some cases implies the positivity and ordering of these solutions. In addition, this asymptotic analysis suggests the existence of a loop type component in the non-negative solutions set. We prove the existence of such a component in certain cases, via a bifurcation and a topological analysis of a regularized version of (P _λ).     

Zero-cycles on self-product of modular curves

We use the elements in K-cohomology groups which are constructed by Flach and Mildenhall to obtain a finiteness result for the torsion part of the Chow group of a self-product of a modular curve.