Ultrahigh Loading Copper Single Atom Catalyst for Palladium-free Wacker Oxidation

Wacker oxidation is an industry-adopted process to transform olefins into value-added epoxides and carbonyls. However, traditional Wacker oxidation involves the use of homogeneous palladium and copper catalysts for the olefin addition and reductive elimination. Here, we demonstrated an ultrahigh loading Cu single atom catalyst(14% Cu, mass fraction) for the palladium-free Wacker oxidation of 4-vinylanisole into the corresponding ketone with N-methylhydroxylamine hydrochloride as an additive under mild conditions. Mechanistic studies by ¹⁸O and deuterium isotope labelling revealed a hydrogen shift mechanism in this palladium-free process using N-methylhydroxylamine hydrochloride as the oxygen source. The reaction scope can be further extended to Kucherov oxidation. Our study paves the way to replace noble metal catalysts in the traditional homogeneous processes with single atom catalysts.     

电子自旋假说的提出及其历史经验

电子自旋是原子物理学和量子力学的重要概念，电子自旋假说的产生在物理学史上具有一定的特殊性，该文系统论述了电子自旋假说提出了与被物理学界接受的历史，并从荷兰莱顿理论物理研究的学术环境、乌仑贝克和哥德斯密“理论型”与实验型”的互补、艾仑费斯行的教育艺术等方面分析了其历史经验。     

Fractional Brownian Heavy Traffic Approximations of Multiclass Feedforward Queueing Networks

We consider multiclass feedforward queueing networks under first in first out and priority service disciplines driven by long-range dependent arrival and service time processes. We show that in critical loading the normalized workload, queue length and sojourn time processes can converge to a multi-dimensional reflected fractional Brownian motion. This weak heavy traffic approximation is deduced from a deterministic pathwise approximation of the network behavior close to constant critical load in terms of the solution of a Skorokhod problem. Since we model the doubly infinite time interval, our results directly cover the stationary case.AMS subject classification: primary 90B15, secondary 60K25, 68M20     

A novel specimen for investigating the mechanical behavior of elastomers under multiaxial loading conditions

In this paper we describe the design and manufacture of an axial-torsion test specimen, and provide relationships needed when conducting stress-strain characterization experiments with the specimen. The specimen is a short hollow cylinder of rubber bonded between two steel mounting rings, in which simultaneous axial and shear strains are produced via independently controlled axial and twist displacements. We present calculations for the strain-displacement and stress-load relationships, and strain energy density. These relationships have been established and validated via a combination of analytical and experimental techniques, and finite element analysis. We have investigated the extent and effects of strain and stress field non-uniformity in the test specimen. The specimen design is sufficiently simple that a closed-form expression for the strain-displacement relationship has been successfully developed.     

Crystal dissolution kinetics and Gibbs free energy

The dependence of dissolution rates on the difference of Gibbs free energy is of critical importance for our understanding of crystal dissolution, reactive flow models and their applications to a variety of environmentally related problems. Here, we review experimental data generated with mineral powders and single crystals to develop a better understanding of apparent inconsistencies between otherwise internally consistent data sets. Additional information from direct surface observations and measurements with vertical scanning interferometry (VSI) and atomic force microscopy (AFM) of albite dissolution at 25, 150 and 185 °C may shed new light on this old but unsolved question. Our discussion is based on the importance of etch pit development, its ΔG dependence, and the pits’ role as a source for steps and step movement in the dissolution process. Results indicate that reaction history may be of critical importance in determining the overall reaction mechanism and its rate. Different rates are observed for systems having otherwise identical ΔG_r acquired from increasing versus decreasing disequilibrium positions.

In this context, we finally discuss the validity of the common application of transition state theory (TST) to elementary and overall reactions governing the dissolution process. In this discussion of crystal dissolution, we contrast TST applications with a stochastic, many-body treatment that has led to the development of a stepwave model. This discussion also focuses on the controversy caused by the rivalry between surface adsorption models and a probabilistic model that seeks to incorporate the full three-dimensional crystal structure.     

不同温度均匀二半空间接触后产生的辐射场

 应用电磁线路中涨落耗散理论，推导了不同温度均匀二半空间接触后产生辐射场密度的公式。将此公式近似展开后，即得Grover和Urtiew所获得的表示式，不过多了一松弛项，该项如用非富里叶热传导理论推导，也是存在的。该结果和实验结果一致，不过这里的松驰时间可以应用介质性质进行计算。     

The many facets of linear programming

We examine the history of linear programming from computational, geometric, and complexity points of view, looking at simplex, ellipsoid, interior-point, and other methods. Received: June 22, 2000 / Accepted: April 4, 2001?Published online October 2, 2001     

Constructing Space for Science at the Royal Institution of Great Britain

Those who have worked in the Royal Institution of Great Britain have, since its foundation in 1799, made significant contributions to scientific knowledge, to its practical application, and to its communication to a wide variety of audiences. Such work cannot be carried out in an architectural vacuum, and in this paper we examine how the buildings of the Royal Institution, 20 and 21 Albemarle Street in central London, have shaped the work undertaken within its walls and how, on a number of occasions, the buildings have been reconfigured to take account of the evolving needs of scientific research and communication. This paper is based on the Conservation Plan of the Royal Institution that we wrote during 2003. The Conservation Plan did not examine the land owned by the Royal Institution to the north (i.e., 22 and 23 Albemarle Street; for this area see Richard Garnier, “Grafton Street, Mayfair,” Georgian Group Journal 13 (2003), 210–272), but it did discuss 18 and 19 Albemarle Street. In this paper we concentrate on the core Royal Institution buildings at 20 and 21 Albemarle Street. Other studies of the relationship of architecture,space, and science include Crosbie Smith and Jon Agar, ed., Making Space for Science: Territorial Themes in the Shaping of Knowledge (Basingstoke: Macmillan, 1997); Peter Galison and Emily Thompson, ed., The Architecture of Science (Cambridge, Mass.: MIT Press, 1999); and Sophie Forgan,“The architecture of science and the idea of a university,” Studies in History and Philosophy of Science 20 (1989), 405–434. Frank A.J.L. James is Professor of the History of Science at the Royal Institution; he has written widely on the history of nineteenth-century science in its social and cultural contexts and is editor of the Correspondence of Michael Faraday. He is President of the British Society for the History of Science. Anthony Peers is an Associate of Rodney Melville and Partners where he works in the field of building conservation as an architectural historian. He is a Council member of the Ancient Monument Society.     

Creep of composites with a porous fibre/matrix interface under variable loading

A micromechanical model of island-type fibre/matrix interface is described and experimental data are represented and analysed. Changes in the interface strength during a cycle loadings and, correspondingly, changes in the creep resistance of a composite due the island-like scheme of the fibre/matrix interface are described.     

甲基百里(香)酚蓝新负载树脂的特 性及应用

本文以金属指示剂甲基百里(香)酚蓝作为鳌合剂制得具有相应鳌合基团的负载树脂.研究了该树脂的某些分析特性及其在富集天然水中微量铜、钻、镍、锌中的应用.