Reversal of stereoselectivity in [5 + 2] pyrone--alkene cycloadditons using a sulfoxide-to-sulfoximine switch. Enantiodivergent synthesis of 8-oxabicyclo[3.2.1]octane systems

[reaction: see text] Switching from a sulfinyl to a sulfonimidoyl group allows the reversal of the sense of asymmetric induction in thermal [5C + 2C] intramolecular pyrone-alkene cycloadditions. Removal of the sulfoximine unit from the resulting cycloadducts yields optically active oxabicyclic systems that are enantiomeric to those obtained using the sulfinyl chiral auxiliary.     

Qualitative and quantitative sensitivity in flame photometry

Concepts of sensitivity in flame photometry are discussed. A distinction is made between sensitivity itself, concentration limits and dilution limits applied to qualitative and quantitative analysis by flame photometry. Sensitivity values, as well as the concentration limits, are considered from two different aspects: as a function of the slope of calibration curves-percentual values-and as a function of fluctutions-fluctuational values. The concepts are applied to the two main branches of flame photometry, emission and absorption.     

Molecular emission cavity analysis: Part 21. Effect of Phosphoric Acid on the Determination of Sulphate

Phosphoric acid at levels above 10^-3 M depresses the S₂ emission from sulphate, but concentrations up to 0.1 M may be necessary to eliminate cationic interferences.     

Ag(I) complexes with alkylidene-bis(2-aminopyrimidines) as building units for discrete metallomacrocyclic frames. A structural and solution study

Alkylidene-bis(2-aminopyrimidines) (pyr2Cx, x = 2-5) are useful ligands to interact with Ag(I) yielding discrete metallocycles. Crystal structures of the [(pyr2C2)Ag(NO3)]2 and [(H-pyr2C4)Ag(NO3)2]2 have been isolated where each macrocyclic moiety interacts with their surroundings through weak interactions, yielding 3D discrete structures, On the other hand, the solution study shows that the equilibrium constants for the formation of Ag(pyr2Cx)+ complexes are higher than the literature values for Ag(I) complexes with single pyrimidines, although the differences could be explained by invoking the solid-state structures of the Ag(I)-pyr2Cx complexes.     

Analytical applications of the o-dianisidine-persulfate reaction: Kinetic determination of silver and cobalt

A kinetic method for the silver determination based on the catalytic effect of Ag(I) on the oxidation of o-dianisidine by persulfate at pH = 4.5 in the presence of 1,10-phenanthroline is proposed. Ag(I) can be determined by measuring the absorbance of the reaction product at 450 nm, using the fixed time method. Co(II) does not have a catalytic effect in the reaction, but in the simultaneous presence of silver and cobalt the reaction shows an induction period the length of which is related to the Ag/Co molar ratio. As a consequence, two new methods for the determination of cobalt and silver using the induction period method are proposed. The two methods for silver are applied to the determination of silver in lead.     

Simple and rapid determination of the drug naproxen in pharmaceutical preparations by heavy atom-induced room temperature phosphorescence

A simple, selective and sensitive heavy atom-induced room temperature phosphorimetric method (HAI-RTP) is described for the determination of naproxen (NAP) in pharmaceutical preparations. The phosphorescence signals are a consequence of intermolecular protection when analytes are, exclusively, in presence of a heavy atom salt and sodium sulfite as an oxygen scavenger to minimize RTP quenching. These variables selection constitute the basis of a HAI-RTP method for the determination of naproxen (detection limit 17.6 ng ml(-1); 1.71% relative standard deviation at 250 ng ml(-1)). The method has been applied satisfactorily to the analysis of pharmaceutical preparations.     

Highly enantioselective Cu-catalysed asymmetric 1,4-addition of diphenylzinc to cyclohexenone

Highly enantioselective Cu-catalysed 1,4-addition of diphenylzinc to cyclohexenone has been achieved for the first time using a monodentate phosphoramidite ligand.     

Stabilization of cobalt(II) chloro-complexes with the butanediammonium cation

Summary Cobalt(II) chlorocomplexes with empirical formulae (bnH₂)₂CoCl₆·2H₂O (1) and (bnH₂)₂CoCl₆ (2), where bnH ₂ ²⁺ represents the diprotonated species of putrescine (1,4-butanediamine), were prepared.The visible spectra in the solid state and measurement of the magnetic moments permit the assignation of an octahedral geometry for cobalt in (1) and a tetrahedral geometry for (2).     

Determination of molybdenum, chromium and aluminium in human urine by electrothermal atomic absorption spectrometry using fast-programme methodology

Rapid and direct procedures for the determination of molybdenum, chromium and aluminium in human urine samples are developed. Fast-programme methodology is used to simplify the heating cycles. Hydrogen peroxide, nitric acid and Triton X-100 are added to the urine samples which are directly introduced into the furnace. For molybdenum, two successive injection steps are required due to the low level of this element in the samples analyzed. Calibration is carried out using aqueous standards for aluminium and the standard additions method for both molybdenum and chromium. The reliability of the procedures is checked by analyzing two certified reference materials.     

Characterization of three agave species by gas chromatography and solid-phase microextraction-gas chromatography-mass spectrometry

Steam distillation (SD) extraction-solid-phase microextraction coupled to GC-MS was developed for the determination of terpenes and Bligh-Dyer extraction-derivatization coupled with GC for the determination of fatty acids such as ethyl esters were used. It was found that the three different Agave species have the same profile of fatty acids; the quantity of these compounds is different in each Agave variety. On the other hand, different terpenes were identified in the three Agave plants studied: nine in A. salmiana, eight in A. angustifolia and 32 in A. tequilana Weber var. azul.