Catalytic Adventures in Space and Time Using High Energy X-rays

Very high energy X-rays (ca. >40 keV) have long offered great promise in providing great insight into the inner workings of catalysts; insights that may complement the battery of techniques available to researchers in catalysis either in the laboratory or at more conventional X-ray wavelengths. This contribution aims to critically assess the diverse possibilities now available in the high energy domain as a result of the maturation of third generation synchrotron facilities and to look forward to the potential that forthcoming developments in synchrotron source technology may offer the world of catalysis in the near future.     

Repository-Scale Modeling of the Long-Term Hydraulic Perturbation Induced by Gas and Heat Generation in a Geological Repository for High-and Intermediate-Level Radioactive Waste: Methodology and Example of Application

The current design of a deep geological repository for high- and intermediate-level radioactive waste in France consists of a complex system of different underground structures (ANDRA, Dossier 2005 Argile, les recherches de l’Andra sur le stockage géologique des déchets radioactifs à haute activité et à vie longue, collection les Rapports. Chatenay-Malabry, France, 2005). For a comprehensive understanding of the long-term hydraulic evolution of the entire repository, numerical non-isothermal two-phase flow and transport simulation, taking into consideration the generation, accumulation, and release of hydrogen gas and decay heat, are compulsory. However, a detailed numerical model of the entire repository system would require a tremendous computational effort and pose a laborious task with respect to the operation of the model. To handle these difficulties, we have developed an efficient method for the numerical modeling of a complete repository system and its geologic environment. The method consists of the following steps: (i) subdivision of the repository plane into a large number of “sectors” based on the position of hydraulic seals and on other geometrical considerations, (ii) exploitation of existing symmetries (inside or between sectors), (iii) adoption of the “multiplying concept”, and (iv) connection of the individual sectors at the drift interfaces to form the entire repository model. Each sector is modeled as a three-dimensional (3D) block, and the entire model is computed with TOUGH2-MP. The method allows for a massive reduction in overall finite-volume elements and, at the same time, provides an adequate representation of the small-sized structures in the repository. The main characteristics of the method and its application to an entire deep geological repository system in a clay host rock are presented.     

Specific molecular and cellular events induced by irradiated X‐ray photoactivatable drugs raise the problem of co‐toxicities: particular consequences for anti‐cancer synchrotron therapy

Synchrotrons are capable of producing intense low‐energy X‐rays that enable the photoactivation of high‐Z elements. Photoactivation therapy (PAT) consists of loading tumors with photoactivatable drugs and thereafter irradiating them at an energy, generally close to the K‐edge of the element, that enhances the photoelectric effect. To date, three major photoactivatable elements are used in PAT: platinum (cisplatin and carboplatin), iodine (iodinated contrast agents and iododeoxyuridine) and gadolinium (motexafin gadolinium). However, the molecular and cellular events specific to PAT and the radiobiological properties of these photoactivatable drugs are still misknown. Here, it is examined how standard and synchrotron X‐rays combined with photoactivatable drugs impact on the cellular response of human endothelial cells. These findings suggest that the radiolysis products of the photoactivatable drugs may participate in the synergetic effects of PAT by increasing the severity of radiation‐induced DNA double‐strand breaks. Interestingly, subpopulation of highly damaged cells was found to be a cellular pattern specific to PAT. The data show that the efficiency of emerging anti‐cancer modalities involving synchrotron photoactivation strongly depends on the choice of photoactivatable drugs, and important series of experiments are required to secure their clinical transfer before applying to humans.     

Stereospecific Synthesis and Acylation of cis 1-Halo 2-Trimethylsilyl Ethylenes

Several routes to 1-halo 2-trimethylsilyl ethylenes have been previously proposed ^1-6: from ethyn7yltrimethylilane (addition of HBr^1,2), ethyltrichlorosilane (addition H by C1, followed by dehydrohalogenation and further methylation of th Si-C1 bonds)³ or by other ways ^4,5, especially by reaction of (2-trimethylsilyl) vinyl lithium with dibromoethane⁶.     

Sodium calcium orthovanadate,NaCa4(VO4)3

Single crystals of sodium tetra­calcium trivanadium dodeca­oxide were prepared by melting a powder sample of NaCa₄(VO₄)₃ at 1673 K, followed by slow cooling to room temperature. The compound crystallizes in the Pnma space group and is isostructural with the mineral silicocarnotite, Ca₅(PO₄)₂SiO₄. The structure is composed of isolated VO₄ tetra­hedra linked by sodium and calcium cations disordered over eight‐ and seven‐coordinated sites.     

Generators of the product of two Schoenflies motion groups

Schoenflies motion is often termed X-motion for conciseness. A set of X-motions with a given direction of its axes of rotations has the algebraic properties of a Lie group for the composition product of rigid-body motions or displacements. The product of two X-subgroups, which is the mathematical model of a serial concatenation of two kinematic chains generating two distinct X-motions, characterizes a noteworthy type of 5-dimensional (5D) displacement set called double Schoenflies motion or X–X motion for brevity. This X–X motion set is a 5D submanifold of the displacement 6D Lie group. Such a motion type includes any spatial translation (3T) and any two sequential rotations (2R) provided that the axes of rotation are parallel to two fixed independent vectors. This motion set also contains the rotations that are products of the foregoing two rotations. In the paper, some preliminary fundamentals on the 4D X-motion are recalled; the 5D set of X–X motions is emphasized. Then implementing serial arrays of one-dof Reuleaux pairs and hinged parallelograms, we enumerate all serial mechanical generators of X–X motion, which have no redundant internal mobility. Based on the group-theoretic concepts, one can differentiate two families of irreducible representations of an X–X motion. One family is realized by twenty-one open chains including the doubly planar motion generators as special cases. The other is generally classified into eight major categories in which one hundred and six distinct open chains generating X–X motion are revealed and nineteen more ones having at least one parallelogram are derived from them. Meanwhile, these kinematic chains are graphically displayed for a possible use in the structural synthesis of parallel manipulators.     

An equilibrium-conserving taxation scheme for income from capital

Under conditions of market equilibrium, the distribution of capital income follows a Pareto power law, with an exponent that characterizes the given equilibrium. Here, a simple taxation scheme is proposed such that the post-tax capital income distribution remains an equilibrium distribution, albeit with a different exponent. This taxation scheme is shown to be progressive, and its parameters can be simply derived from (i) the total amount of tax that will be levied, (ii) the threshold selected above which capital income will be taxed and (iii) the total amount of capital income. The latter can be obtained either by using Piketty’s estimates of the capital/labor income ratio or by fitting the initial Pareto exponent. Both ways moreover provide a check on the amount of declared income from capital.