Synthesis of methyl 2-oxo-5-vinyl-2,5-tetrahydrofuran-3-carboxylate

A synthesis of methyl 2-oxo-5-vinyl-tetrahydrofuran-3-carboxylate involving five synthetic steps from commercially available 3,4-dihydroxybutene is reported.     

Regio- and Stereochemical Aspects of the Palladium-Catalyzed Desilylation-Arylation of Substituted Vinylsilanes

The palladium-catalyzed desilylation-arylation of substituted vinylsilanes by p-iodoanisole in the presence of bidentate phosphine ligands is described. Apart from enhancing the rate of the reaction considerably, heteroatom-based functional groups in the vinylsilane moiety have a profound influence on the regiochemistry. A catalytic cycle for the chelation-controlled desilylation-arylation reaction involving five- and six-membered chelate rings is proposed.     

Electrochemical oxidation of substituted pyrroles. III. Anodic oxidation of 2,5-diphenyl-3-acetylpyrrole

The electrochemical oxidation of 2,5-diphenyl-3-acetylpyrrole (I) is described. The cyclic derivative 1,6a-dihydro-2,5,6a-triphenyl-3,4-diacetylbenzo[g]pyrrolo[3,2-e]indole (II) was obtained in very good yield. However, when water was present in the reaction medium, a different derivative, 4-acetyl-2-hydroxy-2,5-diphenyl-3-(4′-acetyl-2′,5′-diphenyl-3′-yl)-2H-pyrrole (III) , was obtained as the main product. 2,2′,5,5′-Tetraphenyl-4,4′-diacetyl-3,3′-dipyrryl (IV) , a potentially useful intermediate for the synthesis of condensed pyrroles, was synthesized by zinc reduction of III.     

Radon Measure-Valued Solutions for a Class of Quasilinear Parabolic Equations

Initial value problems for quasilinear parabolic equations having Radon measures as initial data have been widely investigated, looking for solutions which for positive times take values in some function space. In contrast, it is the purpose of this paper to define and investigate solutions that for positive times take values in the space of the Radon measures of the initial data. We call such solutions measure-valued, in contrast to function-valued solutionspreviously considered in the literature. We first show that there is a natural notion of measure-valued solution of problem (P) below, in spite of its nonlinear character. A major consequence of our definition is that, if the space dimension is greater than one, the concentrated part of the solution with respect to the Newtonian capacity is constant in time. Subsequently, we prove that there exists exactly one solution of the problem, such that the diffuse part with respect to the Newtonian capacity of the singular part of the solution (with respect to the Lebesgue measure) is concentrated for almost every positive time on the set where “the regular part (with respect to the Lebesgue measure) is large”. Moreover, using a family of entropy inequalities we demonstrate that the singular part of the solution is nonincreasing in time. Finally, the regularity problem is addressed, as we give conditions (depending on the space dimension, the initial data and the rate of convergence at infinity of the nonlinearity ψ) to ensure that the measure-valued solution of problem (P) is, in fact, function-valued.     

Analytical performance of glucometers in a tertiary care hospital

Point-of-care (POC) testing of glucose (glucometers) represents a convenient alternative to monitor glycemia since the measurement procedure is performed without delay after sampling of the capillary blood, thereby avoiding the metabolism by the blood cells of glucose present in plasma. Likely because of sample instability, there is no proficiency test provider in Brazil for this type of POC sample. In this context, this study aimed to evaluate the analytical performance of glucometers used in a tertiary care hospital. The glucometers used were the Accu-Chek Performa^® model from Roche Diagnostics, which use the principle of amperometry. The reference method was the reaction with modified hexokinase/glucose-6-phosphate in a Dimension^® device. The stability evaluation of the control samples showed that it can be performed up to 90 min after the collection of whole blood samples. In the two rounds performed, only one result of the 17 glucometers evaluated was out of the threshold of two standard deviation. Thus, this method for control of glucometers met the expectations and enabled comparing the glucometers in a hospital. Given the current quality guidelines, daily internal quality control of glucometers is recommended, besides at least two annual comparisons between the results of the glucometers and the reference method and one EQA every 3 months.     

Synthesis and Chemistry of New Central and Planar Chiral Sulfur-Containing Ferrocenyl Compounds

Abstract

Enantiomerically pure 2-hydroxyalkyl, 2-aminoalkyl and 2-iminoalkyl ferrocenyl p-tolylsulfides are easily prepared in good yields and with complete diastereocontrol from (S)-(2-p-tolylthio)ferrocencarboxyaldehyde. 2-Iminoalkyl ferrocenyl derivatives can be used as ligands in asymmetric catalysis and as starting materials for asymmetric Staudinger reaction.     

Synthesis of Some Selectively N-Protected (1S,2S)-p-Nitrophenylserinol–Based Diamino-1,3-dioxanes and Tripodands

The unconventional methodology for the non-epimerizable cycloacetalization of optically active (1S,2S)-2-amino-1-(4-nitrophenyl)propane-1,3-diol (p-nitrophenylserinol) (condensed H₂SO₄ 96% as solvent and catalyst, i.e., sulfuric transacetalization) producing (2R,4S,5S) diamino-1,3-dioxanes was enlarged by the use of N-protected forms of 2,2-dimethoxyethylamine (DMEA, aminoacetaldehyde dimethylacetal). Conversely, N-protected derivatives of p-nitrophenylserinol were successfully cyclocondensed with DMEA in the same sulfuric conditions. N-Functionalization of DMEA upon treatment with trimesic acid trichloride and cyanuric chloride yielded the corresponding triple amide and melamine, respectively. Their adapted sulfuric transacetalization in triplicate in reaction with arylserinols (aryl: phenyl, p-nitrophenyl) afforded a new series of optically active tripodands.     

Multiplicity studies and effective energy in ALICE at the LHC

In this work we explore the possibility to perform “effective energy” studies in very high energy collisions at the CERN large hadron collider (LHC). In particular, we focus on the possibility to measure in pp collisions the average charged multiplicity as a function of the effective energy with the ALICE experiment, using its capability to measure the energy of the leading baryons with the zero degree calorimeters. Analyses of this kind have been done at lower centre-of-mass energies and have shown that, once the appropriate kinematic variables are chosen, particle production is characterized by universal properties: no matter the nature of the interacting particles, the final states have identical features. Assuming that this universality picture can be extended to ion–ion collisions, as suggested by recent results from RHIC experiments, a novel approach based on the scaling hypothesis for limiting fragmentation has been used to derive the expected charged event multiplicity in AA interactions at LHC. This leads to scenarios where the multiplicity is significantly lower compared to most of the predictions from the models currently used to describe high energy AA collisions. A mean charged multiplicity of about 1000–2000 per rapidity unit (at η∼0) is expected for the most central Pb–Pb collisions at . In memory of A. Smirnitskiy