ALL-trans β-CAROTENE-5,6-EPOXIDE IN THYLAKOID MEMBRANES

All- trans β-carotene-5,6-epoxide has been found in the thylakoid membranes of spinach and of the cyanobacterium Synechococcus vulcanus Copeland. The epoxide was extracted from the thylakoid membranes with acetone, and was isolated by high-performance liquid chromatography (HPLC). The structure of the epoxide was identified by means of mass, Raman, and electronic absorption spectroscopy. Changes in the amount of the epoxide, as a result of epoxidation and (apparent) de-epoxidation reactions in the membranes, were traced by analysis of extracts on HPLC. In isolated thylakoid membranes, only the epoxidation reaction took place. The reaction was caused by irradiation or by the addition of ferricyanide, suggesting that electron transport reactions in the membranes are involved in the epoxidation. In intact spinach leaves, however, both epoxidation and de-epoxidation took place; the extent of epoxidation correlated with the intensity of light incident on the leaves. The epoxidation and de-epoxidation of all- trans β-carotene are contrasted with those of xanthophylls (in the violaxanthin cycle).     

A Compound I Mimic Reveals the Transient Active Species of a Cytochrome P450 Enzyme: Insight into the Stereoselectivity of P450-Catalysed Oxidations

Catching the structure of cytochrome P450 enzymes in flagrante is crucial for the development of P450 biocatalysts, as most structures collected are found trapped in a precatalytic conformation. At the heart of P450 catalysis lies Cpd I, a short-lived, highly reactive intermediate, whose recalcitrant nature has thwarted most attempts at capturing catalytically relevant poses of P450s. We report the crystal structure of P450BM3 mimicking the state in the precise moment preceding epoxidation, which is in perfect agreement with the experimentally observed stereoselectivity. This structure was attained by incorporation of the stable Cpd I mimic oxomolybdenum mesoporphyrin IX into P450BM3 in the presence of styrene. The orientation of styrene to the Mo-oxo species in the crystal structures sheds light onto the dynamics involved in the rotation of styrene to present its vinyl group to Cpd I. This method serves as a powerful tool for predicting and modelling the stereoselectivity of P450 reactions.     

X-ray structural study of a zinc(II) inclusion complex of a phenolate-pendant cyclam

The molecular structure of phenol-pendant cyclam-zinc(II) complex,4a, has been determined by X-ray structure analysis. Crystals of4a · ClO₄ · CH₃OH (C₁₆H₂₇N₄OZn · ClO₄ · CH₃OH) are monoclinic, space groupP2₁/nn, with four molecules in the unit cell of dimensionsa=31.198(2) Å,b=8.426(1) Å,c=8.214(1) Å, and=93.96(1)°. The structure was solved by the heavy atom method and refined anisotropically toR=0.044,R _w=0.062 for 1551 independent reflections. The complex assumes a five-coordinate, square pyramidal geometry, where zinc(II) is surrounded by the cyclam moiety in a planar fashion with the pendant phenolate anion occupying an axial position. An extremely short Zn-O(phenolate) bond distance of 1.983(5) Å, in conjunction with the 0.288 Å displacement of Zn(II) above the cyclam N₄ plane toward the phenolate, accounts for the extremely low pK _a value of 5.8 for the pendant phenol. These facts about4a, in comparison with the previous findings for the Ni(II) (4b) and Cu(II) complexes (4c) with the same ligand, illustrate well the characteristics of zinc(II) ion coordination properties.This paper is dedicated to the memory of the late Dr C. J. Pedersen.     

Limit theorems for the pre-averaged Hayashi–Yoshida estimator with random sampling

We will focus on estimating the integrated covariance of two diffusion processes observed in a nonsynchronous manner. The observation data is contaminated by some noise, which possibly depends on the time and the latent diffusion processes, while the sampling times also possibly depend on the observed processes. In a high-frequency setting, we consider a modified version of the pre-averaged Hayashi–Yoshida estimator, and we show that such a kind of estimator has the consistency and the asymptotic mixed normality, and attains the optimal rate of convergence.     

Pseudo-hyperbolic Gauss maps of Lorentzian surfaces in anti-de Sitter space

In this paper, we determine the type numbers of the pseudo-hyperbolic Gauss maps of all oriented Lorentzian surfaces of constant mean and Gaussian curvatures and non-diagonalizable shape operator in the 3-dimensional anti-de Sitter space. Also, we investigate the behavior of type numbers of the pseudo-hyperbolic Gauss map along the parallel family of such oriented Lorentzian surfaces in the 3-dimensional anti-de Sitter space. Furthermore, we investigate the type number of the pseudo-hyperbolic Gauss map of one of Lorentzian hypersurfaces of B-scroll type in a general dimensional anti-de Sitter space.     

Construction of CM Picard curves

In this article we generalize the CM method for elliptic and hyperelliptic curves to Picard curves. We describe the algorithm in detail and discuss the results of our implementation.

     

Gauss maps of the Ricci-mean curvature flow

In this paper, we investigate the Gauss maps of a Ricci-mean curvature flow. A Ricci-mean curvature flow is a coupled equation of a mean curvature flow and a Ricci flow on the ambient manifold. Ruh and Vilms (Trans Am Math Soc 149: 569–573, 1970) proved that the Gauss map of a minimal submanifold in a Euclidean space is a harmonic map, and Wang (Math Res Lett 10(2–3):287–299, 2003) extended this result to a mean curvature flow in a Euclidean space by proving its Gauss maps satisfy the harmonic map heat flow equation. In this paper, we deduce the evolution equation for the Gauss maps of a Ricci-mean curvature flow, and as a direct corollary we prove that the Gauss maps of a Ricci-mean curvature flow satisfy the vertically harmonic map heat flow equation when the codimension of submanifolds is 1.     

On the rate of convergence of solutions in free boundary problems via penalization

The rate of convergence of approximate solutions via penalization for free boundary problems are concerned. A key observation is to obtain global bounds of penalized terms which give necessary estimates on integrations by the nonlinear adjoint method by L.C. Evans.     

Several contributions to soil compactibility induced by cyclic loading test

To investigate the soil compactibility during the cyclic loading, three different kinds of paddy field soils were prepared so as to clarify interrelationships among stress amplitude ratio, bulk density, soil water content and pore water pressure. The presetting values of specimen include the soil water content(percent dry basis) and bulk density of 25% d.b. and 1.1 Mg/m³ respectively. The relation between the number of cyclic loading and axial strain exhibited an asymptotically increasing trend, converging toward a specific value for each experimental condition. Possible effect caused by elastic–plastic characteristics could be recognized, when axial strain for 0.5 Hz excitation becomes greater than the one of 1.0 Hz under same stress amplitude ratio. When the stress amplitude ratio took 0.1, the absolute value of axial strain of 0.5 Hz was greater than the one of 1.0 Hz, whereas its decreasing trend was recognized in the sequence of silt, clay and silty sand. The qualitative relations between pore water pressure and number of cyclic loading were also examined to scrutinize the effect of effective water pressure to the soil compactibility.