An Unusual Terpene Cyclization Mechanism Involving a Carbon–Carbon Bond Rearrangement

Terpene cyclization reactions are fascinating owing to the precise control of connectivity and stereochemistry during the catalytic process. Cyclooctat‐9‐en‐7‐ol synthase (CotB2) synthesizes an unusual 5‐8‐5 fused‐ring structure with six chiral centers from the universal diterpene precursor, the achiral C₂₀ geranylgeranyl diphosphate substrate. An unusual new mechanism for the exquisite CotB2‐catalyzed cyclization that involves a carbon–carbon backbone rearrangement and three long‐range hydride shifts is proposed, based on a powerful combination of in vivo studies using uniformly ¹³C‐labeled glucose and in vitro reactions of regiospecifically deuterium‐substituted geranylgeranyl diphosphate substrates. This study shows that CotB2 elegantly demonstrates the synthetic virtuosity and stereochemical control that evolution has conferred on terpene synthases.     

Unidirectional evolution equations of diffusion type

This paper is concerned with the uniqueness, existence, partial smoothing effect, comparison principle and long-time behavior of solutions to the initial-boundary value problem for a unidirectional diffusion equation. The unidirectional evolution often appears in Damage Mechanics due to the strong irreversibility of crack propagation or damage evolution. The existence of solutions is proved in an $L^2$-framework by employing a backward Euler scheme and by introducing a new method of a priori estimates based on a reduction of discretized equations to variational inequalities of obstacle type and by developing a regularity theory for such obstacle problems. The novel discretization argument will be also applied to prove the comparison principle as well as to investigate the long-time behavior of solutions.     

On fluorescence imaging: The diffusion equation model and recovery of the absorption coefficient of fluorophores

Science China Mathematics - To quantify fluorescence imaging of biological tissues, we need to solve an inverse problem for the coupled radiative transfer equations which describe the excitation...     

Stability analysis of asymptotic profiles for sign-changing solutions to fast diffusion equations

Every solution u = u(x, t) of the Cauchy–Dirichlet problem for the fast diffusion equation, ? _t (|u| ^m-2 u) = Δu in Ω × (0, ∞) with a smooth bounded domain Ω of ${\mathbb{R}^N}$ and 2 < m < 2* : = 2N/(N ? 2)₊, vanishes in finite time at a power rate. This paper is concerned with asymptotic profiles of sign-changing solutions and a stability analysis of the profiles. Our method of proof relies on a detailed analysis of a dynamical system on some surface in the usual energy space as well as energy method and variational method.     

Meeting Reports: 2005 Annual Meeting of JSSRR (Japanese Society for Synchrotron Radiation Research)

The 18th Annual Meeting and General Assembly of the Japanese Society for Synchrotron Radiation Research (JSSRR) and the joint symposium of synchrotron radiation facility user's society groups were held at Sun-Messe Tosu Conference Hall in Tosu City, Japan, from January 7 to 9, 2005. The meeting was attended by 607 people and included 6 symposiums, 96 oral presentations, and 356 poster presentations covering all aspects of synchrotron radiation research and technology. The meeting also included 49 industrial exhibitions.

The six symposiums were on “Recent progress on soft X-ray optical elements,” “Now and the future on SR-XRF analysis for biological and environmental sciences,” “Recent development of THz Coherent Synchrotron Radiation,” “Super high-resolution protein structure analysis,” “Frontlines of Bio-Nano-microspectroscopy by UV-SX high brilliance SR,” and “The role of synchrotron radiation in the future of science: groundbreaking SR utilization for research on excited states”.     

Non-acoustical and acoustical properties of reticulated and partially reticulated polyurethane foams

A series of measurements on four polyurethane foam samples with pore membranes and a polyurethane foam sample without pore membranes have been made. Tortuosity has been deduced using the ultrasonic slope method. It has been found that the deduced value of tortuosity depends on the measurement temperature and for two of the polyurethane foam samples with many pore membranes physically meaningful values of tortuosity cannot be obtained at a temperature of around 25 °C. However more realistic values of tortuosity have been obtained by from measurements at or around the glass transition temperature of polyurethane foam (i.e. at ?20 °C) when using the ultrasonic slope method.Flow resistivity, Young’s moduli and loss factors have been measured also.Vibration of the pore membranes has been observed to influence the effective density and characteristic impedance derived from the surface impedance measured in an impedance tube. This paper discusses relationships between membrane vibration and the slow and fast compressional waves. The relative merits of predictions based on rigid-porous models and the Biot–Johnson–Champoux–Allard model are discussed also.     

Periodic solutions for doubly nonlinear evolution equations

We discuss the existence of periodic solution for the doubly nonlinear evolution equation A(u^′(t))+∂?(u(t))∋f(t) governed by a maximal monotone operator A and a subdifferential operator ∂? in a Hilbert space H. As the corresponding Cauchy problem cannot be expected to be uniquely solvable, the standard approach based on the Poincaré map may genuinely fail. In order to overcome this difficulty, we firstly address some approximate problems relying on a specific approximate periodicity condition. Then, periodic solutions for the original problem are obtained by establishing energy estimates and by performing a limiting procedure. As a by-product, a structural stability analysis is presented for the periodic problem and an application to nonlinear PDEs is provided.     

Structural analyses of mannose pentasaccharide of high mannose type oligosaccharides by 1D and 2D NMR spectroscopy

NMR spectroscopy is a very important and useful method for the structural analysis of oligosaccharides, despite its low sensitivity. We first applied conventional measuring methods, 2D DQF COSY, ¹H–¹³C HSQC, and ¹H–¹³C HMBC, and also the Double Pulsed Field Gradient Spin Echo (DPFGSE)‐TOCSY and DPFGSE‐NOESY/ROESY techniques to analyze a branched mannose pentasaccharide as a model of high mannose type N‐glycans in natural abundance. The NMR spectra of the model compound are very complex and difficult to analyze owing to overlapping signals. The superior selective irradiation capability of the DPFGSE technique is useful for fine structural and conformational analyses of such complex oligosaccharides. We here introduce a novel technique called DPFGSE‐Double‐Selective Population Transfer (SPT)‐Difference and DPFGSE‐NOE/ROE‐SPT‐Difference spectroscopy. The DPFGSE‐Double‐SPT‐Difference method involves irradiation of two peaks from one proton and the subtraction of higher and lower peaks from each spectrum. The DPFGSE‐NOE/ROE‐SPT‐Difference method involves the transfer of the magnetization polarized by NOE/ROE from the nuclei to the spin‐coupled nuclei through scalar spin–spin interaction using the SPT method. Even if the signals in the NMR spectra overlap, each signal can be accurately assigned. In particular, DPFGSE‐NOE/ROE‐SPT‐Difference is very useful for identifying sugar connectivity. Copyright © 2012 John Wiley & Sons, Ltd.