Absolute detector calibration using twin beams

A method for the determination of absolute quantum detection efficiency is suggested based on the measurement of photocount statistics of twin beams. The measured histograms of joint signal-idler photocount statistics allow us to eliminate an additional noise superimposed on an ideal calibration field composed of only photon pairs. This makes the method superior above other approaches presently used. Twin beams are described using a paired variant of quantum superposition of signal and noise.     

One-pot Crabbé homologation-radical cascade cyclisation with memory of chirality

The tandem Crabbé homologation-radical rearrangement of terminal enediynes leads, in a one-pot procedure, to the enantioselective synthesis of six- and seven-membered ring α-aminoesters bearing a quaternary stereocenter based on the phenomenon of memory of chirality.     

Truth-telling and Nash equilibria in minimum cost spanning tree models

In this paper we consider the minimum cost spanning tree model. We assume that a central planner aims at implementing a minimum cost spanning tree not knowing the true link costs. The central planner sets up a game where agents announce link costs, a tree is chosen and costs are allocated according to the rules of the game. We characterize ways of allocating costs such that true announcements constitute Nash equilibria both in case of full and incomplete information. In particular, we find that the Shapley rule based on the irreducible cost matrix is consistent with truthful announcements while a series of other well-known rules (such as the Bird-rule, Serial Equal Split, and the Proportional rule) are not.     

Short range order at the amorphous TiO(2)-water interface probed by silicic acid adsorption and interfacial oligomerization: an ATR-IR and 29Si MAS-NMR study

Adsorption and oligomerization of H(4)SiO(4) at the amorphous TiO(2)-aqueous interface were studied using in situ Attenuated Total Reflectance Infrared (ATR-IR) and ex situ solid state (29)Si nuclear magnetic resonance (NMR). The ATR-IR spectra indicate that a monomeric silicate species is present at low silicate surface concentration (Γ(Si)). Above a threshold Γ(Si) linear silicate oligomers are formed and these oligomers dominate the surface at high Γ(Si). Interestingly the ATR-IR spectra of H(4)SiO(4) on the TiO(2) surface are very similar to those previously observed on the poorly ordered iron oxide phase ferrihydrite. The (29)Si NMR spectrum of silicate on the TiO(2) surface shows the presence of Si in three states with chemical shifts corresponding to isolated monomers (Q(0)), the ends of linear oligomers (Q(1)) and the middle of linear oligomers (Q(2)). The ratio of the area of the Q(1) and Q(2) peaks was ≈2:1 which is consistent with the proposed formation of linear silicate trimers by insertion of a solution H(4)SiO(4) between adjacent suitably orientated adsorbed silicate monomers. A structural interpretation indicates that the observed interfacial silicate oligomerization behavior is a general phenomenon whereby bidentate silicate monomers on oxide surfaces are disposed towards forming linear oligomers by condensation reactions involving their two terminal Si-OH groups. The high surface curvature of nanometer sized spheres inhibits the formation of interfacial silicates with a higher degree of polymerization.     

Silver thiolato complexes grafted on silica and dissolved in organic solution

The formation of a covalent, stable, silver-thiolato bond was used to compare the coordination of the silver cation with mercaptopropylsilane molecules grafted on silica and dissolved in organic solvents. The characterization of the homemade ≡SiLH trap, performed by DRIFT, ²⁹Si- and ¹³C-CP-MAS-n.m.r., showed the presence of a ligand monolayer on the silica surface. This ligand was characterized by its free S—H function. The coordination of Ag⁺ ions was illustrated by the color change of the surface from white to yellow, the disappearance of the S—H vibration and the downfield shift of the carbon atoms located near the S atom. All these changes were also observed for the silver thiolates synthesized in homogeneous medium. Three molecular complexes were isolated as yellow solids and characterized using physicochemical techniques. Monomeric [HNEt₃][Ag(NO₃)L²] (1), tetrameric (AgL²)₄ (2) and trimeric (AgL³)₃ (3) species, each with a linearly coordinated silver cation, were proposed. L²H, (MeO)₃Si(CH₂)₃SH, and L³H, N(C₂H₄O)₃Si(CH₂)₃SH, are respectively trimethoxysilyl- and silatranyl- propanethiols. The silver salt and the steric hindrance of the ligand influenced the nuclearity of the molecular silver complexes. Optimization of the ≡SiLH trapping conditions with pH and time indicated that the best trapping of the Ag⁺ cation was performed for pH values 5–7 and 30 min in batch experiments. Safety discharged waters were obtained after percolation through an ≡SiLH filled column. The mercaptopropyl-modified silica gel was regenerated with a 1 M thiourea solution at pH 1.     

Pupils learning algebra with DERIVE

This article deals with the use of computer algebra systems in mathematics secondary education. First, we present the global framework of a research project carried out in France with pupils of grades 9 to 12, from 1993 through 1995. Then we focus on a specific part of this project concerning two grade 9 classes of different mathematical ability taught by the same teacher. We briefly present the aims and organisation of DERIVE's use in the two classes, before embarking with more details on a specific topic: systems of linear equations. Finally, we present the data provided by the pupils' answers to a questionnaire taken at the end of the academic year; we use them for investigating pupils' assumptions about DERIVE's potential for mathematics learning, and compare these representations with those emerging from the entire population.     

Polyoxomolybdate‐Stabilized Ru0 Nanoparticles Deposited on Mesoporous Silica as Catalysts for Aromatic Hydrogenation

We use polyoxometalates as precursors for the preparation of heterogeneous catalysts. In the starting molecular precursor [{Ru(C₆Me₆)}₂Mo₅O₁₈{Ru(C₆Me₆)(H₂O)}], three ruthenium arene fragments are supported on a formally lacunary Lindqvist‐type polyoxomolybdate. This species was introduced by incipient wetness impregnation into the porosity of a SBA‐15‐type mesoporous silica. The evolution of the system under reducing atmosphere is followed by several methods, such as temperature‐programmed reduction (TPR), Raman, and X‐ray absorption spectroscopy (XAS). The results indicate that the polyoxometalate structure is retained after grafting on silica and allows the stabilization of Ru⁰ nanoparticles after reduction. The resulting system exhibits interesting catalytic activity in benzene hydrogenation.     

A numerical strategy to defectuous knowledge using

Knowledge-Based Systems are based on an often defectuous knowledge, be this knowledge acquired from experts or learned from examples.This paper presents a strategy designed to cope with defectuous knowledge: given a set of rules, it builds a similarity function over the work space of the problem. This similarity function together with a set of examples then enables case-based reasoning, through aK-nearest-neighbour-like process.Compared to other case-based reasoning techniques, the advantage of this approach is the following: the topology of the space is automatically induced from the given rules, instead of being explicitly provided (and tuned) by the expert.     

Catalytic oxidation with air of cyclohexanone to dicarboxylic acids on synthetic carbons. Effect of supported metals and solvents

The oxidation with air of cyclohexanone was conducted in the presence of synthetic carbons catalysts. The effect of carbon activation treatment (CO2 or air burnoff), phosphorus additive, platinum loading, and nature of the solvent (water or water/acetic acid mixture) were studied. Cyclohexanone oxidation at 140 degrees C yielded a mixture of C6, C5, and C4 dicarboxylic acids. Air activated carbons, including those containing phosphorus or those supporting platinum, resulted in a higher yield of adipic acid. The activity and selectivity was associated with the oxygenated functional groups, essentially carbonyl/quinone groups, created during air activation of the carbon. The incorporation of phosphorus into the carbon increased slightly the selectivity to 34.3%, probably because this additive increased the density of oxygenated functional groups. The deposition of platinum by impregnation and liquid-phase reduction with formaldehyde increased the reaction rate and improved the selectivity to adipic acid, where the highest figure was 38.8%. It was suggested that platinum contributed to molecular oxygen activation. In contrast platinum deposition by cationic exchange followed by reduction under H2 resulted often in a detrimental effect probably because the density of the oxygenated groups on carbon is decreased upon H2 reduction in the presence of platinum. When the oxidation of cyclohexanone was carried out in mixtures of water/acetic acid, the selectivity given by the different samples were quite close and generally smaller than those obtained in water which indicates that acetic acid interacts with the oxygenated surface functional groups responsible for the activity and selectivity. Oxidation experiments with methyl-labeled 4-methylcyclohexanone indicated that glutaric acid was produced by oxidative decarbonylation of both the C1 and C2 carbon atoms of the molecule.