Adaptive efficient analysis for big data ergodic diffusion models

Statistical Inference for Stochastic Processes - We consider drift estimation problems for high dimension ergodic diffusion processes in nonparametric setting based on observations at discrete...     

Measurements of Temperatures and Electron Number Density in an Argon–Nitrogen Plasma Jet Generated by a dc Torch-Operation Close to Supersonic Threshold

An investigation of the plasma jet generated by a dc argon–nitrogen plasma torch, operated in association with a controlled-pressure chamber, is presented. The purpose of this article is to describe a study of the properties of a subsonic plasma jet under such operating conditions, when its transition to supersonic flow regime is nearly complete. The goal is that of performing plasma diagnostics not only in the initial region of the jet but also in the downstream region where the plasma emission is weak. For this purpose two different diagnostic methods are used. The first approach is based on non-intrusive optical emission spectroscopy, which yields both excitation and rotational temperatures as well as electron number density fields. The zone investigated by this method extends from the torch exit to about 10 nozzle diameters downstream. The second approach consisted of the use of the intrusive enthalpy probe technique for the measurement of the plasma gas temperature, mainly in the tail region of the plasma jet. In the present work, the effects of axial and radial distances across the jet, on the temperature and electron density profiles are discussed for subsonic flow conditions. Interesting features revealed are the data shown for the various diagnostic methods, which either disagree or overlap with each other. Finally, our results show the need for involving non-equilibrium models for the argon–nitrogen plasma due to the presence of significant differences between the temperatures of light and heavy particles.     

Circular dichroism signatures of features simultaneously present in structured guanine-rich oligonucleotides: a combined spectroscopic and electrophoretic approach

In order to identify possible signatures of the most typical structures adopted by guanine-rich oligonucleotides, we submitted them to the crossed fire of circular dichroism (CD) and electrophoresis. These signatures show up in the circular dichroism spectra even when simultaneously present within the same molecule. Guanine-rich oligonucleotides, when structured, manifest themselves by CD contributions around 260 or 295 nm. For instance, positive bands at 264 nm and 295 nm, respectively, signal the parallel and antiparallel guanine quartets, while a positive band around 261 nm may indicate the presence of a (parallel?) Hoogsteen duplex. A positive band at 264 nm may also reflect the presence of rigidly and unusually oriented GpT and TpG steps within loops. The signatures are additive with those of other structural features of the same molecule, such as hairpins or Watson-Crick duplexes, whose bands are observed at 280 nm.     

Investigation of the formation of poly(ethylene terephthalate) with model molecules. IV. Catalysis of the esterification of ethylene glycol with benzoic acid and of the condensation of ethylene glycol monobenzoate

The esterfication of ethylene glycol (EG) with benzoic acid (BA) is an acid-catalyzed reaction which leads, as a first intermediate, to ethylene glycol monobenzoate (EGMB). This compound has an ? OH group which is more active towards carboxylic groups than the first ? OH group of EG. Moreover, it is a key intermediate in the formation of sideproducts containing diethylene glycol (DEG) moieties. The condensation reaction of EGMB was particularly studied in the presence of carboxylic acids or metal derivatives as catalysts. Titanium is the most active. Sb, which is widely used in the industrial synthesis of PET, needs to be present at a high level of concentration to show an activity. The presence of carboxylic groups in the reaction medium does not affect its activity, but it is necessary to remove the ethylene glycol as soon as it is formed in order to keep it active during the condensation reaction.     

Determination of Pesticide Ethion by Linear Sweep Stripping Voltammetry

IntroductionOrganophosphorus pesticides( OPPs) are widelyused in agriculture as insecticides, but they are foundto contaminate agricultural products such as fruits andvegetables to variable extents. Because of their toxicproperties[1,2]and the potential r…     

Synthesis of a versatile (S)-3-(hydroxymethyl)butane-1,2,4-triol building block and its application for the stereoselective synthesis of N-homoceramides

[structures: see text] A versatile (S)-3-(hydroxymethyl)butane-1,2,4-triol building block has been synthesized starting from D-isoascorbic acid, a common food preservative. The key transformation in this approach was the introduction of branching through a high yield and fully regioselective epoxide opening. This flexible synthon has been elaborated to a new class of (dihydro-)N-homo(phyto)ceramides.     

An efficient reagent for the phosphorylation of deoxyribonucleosides, DNA oligonucleotides, and their thermolytic analogues

[reaction: see text] The phosphoramidite 11 was prepared in three steps from methyl 2-mercaptoacetate and demonstrated efficiency in the synthesis of conventional 5'-/3'-phosphate/thiophosphate monoester derivatives of 2'-deoxyribonucleosides and DNA oligonucleotides. Moreover, the use of 11 has enabled the preparation of the dinucleoside phosphorothioate analogue 26 in high yields (>95%) with minimal cleavage (<2%) of the thermolytic thiophosphate protecting group.     

Study of support effects on the reduction of Ni2+ ions in aqueous hydrazine

We have studied the effect of silica of quartz-type on the reducibility of nickel acetate in aqueous hydrazine (80 degrees C, pH = 10-12) and metal particle formation. The obtained materials were characterized by X-ray diffraction, transmission electron microscopy, and thermodesorption experiments. With nickel acetate alone, the reduction was partial (45%) and a metal film at the liquid-gas interface or a powdered metal precipitate with an average particle size of 120 nm was obtained. In the presence of silica as the surfactant, the reduction of nickel acetate was total and the nickel phase deposited as a film on the support with an average particle size of 25 nm. Supported nickel acetate was also totally reduced. Crystallites of a mean particle size of about 3 nm were obtained. Decreasing the nickel content or increasing the hydrazine/nickel ratio decreased the metal particle size. Whiskers were formed for low nickel loadings. Hydrogen thermal treatment of the reduced phase showed that the organic acetate fragment, belonging to the precursor salt, still remained strongly attached to the nickel phase. The amount of the retained organic matrix depended on the metal particle size. Surface defects are suggested as active sites, which enhanced nickel ion reduction in the presence of silica as the surfactant or support. Metal-support interactions and the nucleation/ growth rate were the main factors determining the size and morphology of the supported metal particles formed. The organic matrix covered the reduced nickel phase.     

Investigation of a stereoselective co-mediated rearrangement reaction

A stereocontrolled approach to alpha-alkyl beta-alkynyl cyclohexanones is reported through a Lewis acid mediated rearrangement reaction of enol ethers bearing an Co-alkyne moiety. The reaction proceeds with high levels of stereoselectivity in the presence of Ti- and B-Lewis acids to provide a range of alpha,beta-disubstituted cyclohexanones in high yield although the products are prone to epimerization at the alpha-position in the presence of the B-promoter system. The potential for an enantioselective variant of this process is outlined, and a rationale for the observed stereochemical trends and detailed structural analyses of the ketone products are described.     

Group-theoretical approach to the investigation of reaction graphs for highly degenerate rearrangements of chemical compounds I. Criterion of the connectivity of a graph

We give a necessary and sufficient condition for a reaction graph of a degenerate rearrangement to be connected. This condition is formulated in terms of vertex stabilizers of the automorphism group of a molecular graph. The condition is illustrated on several examples, including the reaction graph of bullvalene. We consider different mathematical models for the construction of reaction graphs and state the problem: which of the models is more adequate?