Miniaturized Analysis of Methylhexanamine in Urine by Gas Chromatography Applying In Situ Derivatization

Chromatographia - The use of stimulants by professional and amateur athletes, as well as in the general population, to enhance their athletic performance represents a human health hazard....     

The value of the stochastic solution in multistage problems

We generalize the definition of the bounds for the optimal value of the objective function for various deterministic equivalent models in multistage stochastic programs. The parameters EVPI and VSS were introduced for two-stage models. The parameter EVPI, the expected value of perfect information, measures how much it is reasonable to pay to obtain perfect information about the future. The parameter VSS, the value of the stochastic solution, allows us to obtain the goodness of the expected solution value when the expected values are replaced by the random values for the input variables. We extend the definition of these parameters to the multistage stochastic model and prove a similar chain of inequalities with the lower and upper bounds depending substantially on the structure of the problem. This research has been partially supported by the grants, 1/BBVA 00038.16421/2004 from Fundación BBVA, SEJ2005-05549/ECON from Ministerio de Educación y Ciencia and the grant GRUPOS79/04 from the Generalitat Valenciana, Spain.     

Synthesis of carbo- and heterobiaryls by intermolecular radical addition of aryl bromides onto aromatic solvents

Tris(trimethylsilyl)silane (TTMSS) and azabisisobutyronitrile (AIBN) promoted the intermolecular arylation of aryl and heteroaryl bromides onto aromatic solvents under thermal conditions via a radical pathway.     

Bioelectrochemical evaluation of the total phenols content in olive oil mill wastewaters using a tyrosinase–colloidal gold–graphite–Teflon biosensor

The use of a robust tyrosinase biosensor, fabricated from graphite–Teflon rigid electrode matrices modified with gold nanoparticles, for the estimation of the total phenols content in olive oil mill wastewaters (OMW), is proposed. The performance of this bioelectrode using both continuous stirring and flow-injection amperometry was studied. A potential value of ?0.10?V was selected for the sensitive and stable detection of various phenolic compounds present in OMW samples: catechol, 3,4-dihydroxycinnamic acid (caffeic acid), 3,4-dihydroxyphenylacetic acid (DOPAC), 4-hydroxyphenylacetic acid, 4-hydroxyphenylethanol (tyrosol), and 4-hydroxyphenylpropionic acid. Using catechol as the target phenol, linear calibration graphs were obtained in the 1.0?×?10^?8???8.0?×?10^?6?mol?L^?1 (batch) and 1.0?×?10^?7???1.0?×?10^?5?mol?L^?1 (FI) concentration ranges, with slope values of 750?mA?L?mol^?1 and 103?mA?L?mol^?1, respectively. Batch amperometry was chosen for the analysis of real samples because of its higher sensitivity. For example, the limit of detection for caffeic acid was 80?nM. The ‘pool’ of phenolic compounds was estimated in OMW obtained from different extraction systems and containing phenols at diverse levels of concentration. A comparison of these results with those obtained by applying the Folin–Ciocalteau spectrophotometric reference method was carried out.     

7-endo radical cyclizations catalyzed by titanocene(III). Straightforward synthesis of terpenoids with seven-membered carbocycles

We describe a novel procedure for the straightforward synthesis of seven-membered carbocycles via free-radical chemistry, based on titanocene(III)-catalyzed 7-endo-dig and 7-endo-trig cyclizations. This procedure has proved to be useful for the chemical preparation of terpenoids with different skeletons containing cycloheptane rings, including the first total syntheses of dauca-4(11),8-diene (2), barekoxide (3), authentic laukarlaol (81), and a valparane diterpenoid (72), as well as a substantially improved synthesis of karahanaenone (1). We also provide theoretical and experimental evidence in support of a plausible mechanism, which may rationalize the preference for the unusual 7-endo cyclization mode shown by radicals with substitution patterns characteristic of the linalyl, nerolidyl, and geranyl linalyl systems. In light of these chemical findings, we discuss the potential involvement of radical cyclizations in the biosynthesis of some terpenoids containing seven-membered carbocycles.