Photooxidations of 2-(γ,ε-dihydroxyalkyl) furans in water: synthesis of DE-bicycles of the pectenotoxins

Photooxygenations of 2-(γ,ε-dihydroxyalkyl) furans in H(2)O followed by in situ reduction and ketalization affords, in one synthetic operation, DE-bicyclic ketals of the pectenotoxins.     

Removing ruthenium residues from olefin metathesis reaction products

Olefin metathesis has revolutionized the way chemists design and synthesize molecules, mostly due to the development of well-defined ruthenium catalysts with high oxygen-, moisture-, and functional-group tolerance. However, the complete removal of residual ruthenium after the end of a metathesis reaction often imposes significant challenges. This Minireview summarizes the strategies for the sequestration of ruthenium impurities from olefin metathesis post-reaction mixtures, thus comprising a practical guide for synthetic chemists employing ruthenium-catalyzed metathesis reactions in the synthesis of organic or polymeric materials.     

An optimal Hardy–Morrey inequality

In this work we improve the sharp Hardy inequality in the case p?>?n by adding an optimal weighted H?lder seminorm. To achieve this we first obtain a local improvement. We also obtain a refinement of both the Sobolev inequality for p?>?n and the Hardy inequality, the latter having the best constant.     

Liquid chromatography–mass spectrometry based global metabolite profiling: A review

Untargeted, global metabolite profiling (often described as metabonomics or metabolomics) represents an expanding research topic and is, potentially, a major pillar for systems biology studies. To obtain holistic metabolic profiles from complex samples, such as biological fluids or tissue extracts, requires powerful, high resolution and information-rich analytical methods and for this spectroscopic technologies are generally used. Mass spectrometry, coupled to liquid chromatography (LC–MS), is increasingly being used for such investigations as a result of the significant advances in both technologies over the past decade. Here we try to critically review the topic of LC–MS-based global metabolic profiling and describe and compare the results offered by different analytical strategies and technologies. This review highlights the current challenges, limitations and opportunities of the current methodology.     

The integrability criterion in SU(2) Chern-Simons gauge theory

We prove that the multiplicity spaces appearing in Chern-Simons theory, as defioned by Segal, vanish unless they are associated to integrable representations. This and other links with conformal field theory are examined.Supported in part by NSF Mathematics Postdoctoral Fellowship DMS-9007255     

A singular function boundary integral method for elliptic problems with singularities

In this work we present a singular function boundary integral method for elliptic problems with boundary singularities. In this method, the approximation is constructed from the truncated asymptotic expansion for the solution near the singular point and the Dirichlet boundary conditions are weakly enforced by means of Lagrange multiplier functions. The resulting discrete problem is posed and solved on the boundary of the domain, away from the point of singularity. We are able to show that the method approximates the generalized stress intensity factors, i.e. the coe cients in the asymptotic expansion, at an exponential rate. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

A variational principle for adaptive approximation of ordinary differential equations

Summary A variational principle, inspired by optimal control, yields a simple derivation of an error representation, global error=local errorweight, for general approximation of functions of solutions to ordinary differential equations. This error representation is then approximated by a sum of computable error indicators, to obtain a useful global error indicator for adaptive mesh refinements. A uniqueness formulation is provided for desirable error representations of adaptive algorithms. Mathematics Subject Classification (2000):65L70, 65G50This work has been supported by the EU–TMR project HCL # ERBFMRXCT960033, the EU–TMR grant # ERBFMRX-CT98-0234 (Viscosity Solutions and their Applications), the Swedish Science Foundation, UdelaR and UdeM in Uruguay, the Swedish Network for Applied Mathematics, the Parallel and Scientific Computing Institute (PSCI) and the Swedish National Board for Industrial and Technical Development (NUTEK).     

磁性纳米结构中由激光引起的超快自旋动力学研究

以单个磁性中心的NiO以及由Co和Ni等元素构成的双磁性中心的纳米结构为例,总结了近年所做的主要工作.为了在理论上实现磁性纳米结构中的超快自旋翻转和转移,提出了一种称为Λ进程(Λ process)的超快自旋转换机理.在实际计算中,首先采用量子化学第一性原理计算得到磁性纳米结构中精确的隙间d电子态,然后考虑外加磁场和自旋轨道耦合分析磁性原子中的自旋局域化程度,最后引入激光脉冲项,研究在其作用下材料的自旋态经由Λ进程实现转换的时间历程.研究结果表明自旋翻转和转移可以在线偏振光的作用下在亚皮秒的时间尺度内完成. 关键词： 超快自旋动力学 第一性原理计算 Λ进程 磁性纳米结构     

Intramolecular and intermolecular kinetic isotope effects (KIE) in the nitrosoarene ene reaction: experimental evidence for reversible intermediate formation

The intramolecular and intermolecular kinetic isotope effects (KIE) have been determined for the nitrosoarene ene reaction with deuterium-stereolabeled 2,3-dimethyl-2-butenes (TME). trans-TME-d(6) (k(H)/k(D) = 3.0) and gem-TME-d(6) (k(H)/k(D) = 4.0) show large intramolecular primary isotope effects. In contrast, the intramolecular competition in cis-TME-d(6) (k(H)/k(D) = 1.5) and the intermolecular competition for the TME-d(0)/TME-d(12) pair (k(H)/k(D) = 1.98) show considerably smaller, but mechanistically significant kinetic isotope effects. The latter fact is rationalized in terms of reversible formation of a three-membered-ring intermediate, namely the aziridine N-oxide, or a similar unsymmetrical, polarized diradical in the first step of the reaction. Such reversibility has also been implied earlier for triazolinedione (TAD) and singlet oxygen ((1)O(2)) with deuterium-stereolabeled 2-butenes, but of the three enophiles, ArNO is the most sensitive toward reversibility, which is due to its moderate reactivity and its high steric demand.     

Novel Monte Carlo scheme for systems with short-ranged interactions

We propose a Monte Carlo (MC) sampling algorithm to simulate systems of particles interacting via very short-ranged discontinuous potentials. Such models are often used to describe protein solutions or colloidal suspensions. Most normal MC algorithms fail for such systems because, at low temperatures, they tend to get trapped in local potential-energy local minima due to the short range of the pair potential. To circumvent this problem, we have devised a scheme that changes the construction of trial moves in such a way that the potential-energy difference between initial and final states drops out of the acceptance rule for the Monte Carlo trial moves. This approach allows us to simulate systems with short-ranged attraction under conditions that were unreachable up to now.