Synthesis and Ruthenium-Catalyzed Enantioselective Hydrogenation of 3-O-Substituted 1,3-Dihydroxypropan-2-ones. Part 2

A number of 3-O-substituted 1,3-dihydroxypropan-2-ones have been synthesized in view of their potential use as prochiral precursors of optically active glycerols. Indeed, the oxo-ethers have been reduced to the corresponding 3-O-substituted glycerols via chiral Ru complexes derived from (S)-binap, ( =(?)-(S)-2,2′-bis(diphenylphosphino)-1,1′-binaphthalene) with enantiomeric excesses up to 93%. The steric course of the catalytic reduction appears to be essentially dependent on the steric encumbrance of the substituents; indeed, a dramatic increase of the enantiomeric excess is observed when the bulky trityl group is substituted by the less encumbering benzyl or octadecyl groups.     

High-performance liquid chromatography-electrospray ionization mass spectrometry and multiple mass spectrometry studies of hyperforin degradation products

The alcoholic extract of the aerial parts of Hypericum perforatum L. finds wide application because of its antidepressant activity. The extract contains a number of constituents with documented biological activity including chlorogenic acid, a broad range of flavonoids, naphthodianthrones and phloroglucinols. Hyperforin and adhyperforin are the major phloroglucinol constituents found in the lipophilic fraction of the extracts. Since the stability of hyperforin has been shown to be limited, an investigation of the hyperforin degradation products using HPLC-electrospray ionization mass spectrometry and multiple mass spectrometry was undertaken.     

Incorporating the effect of ionic strength in free energy calculations using explicit ions

The incorporation of explicit ions to mimic the effect of ionic strength or to neutralize the overall charge on a system in free energy calculations using molecular dynamics simulations is investigated. The difference in the free energy of hydration between two triosephosphate isomerase inhibitors calculated at five different ion concentrations is used as an example. We show that the free energy difference can be highly sensitive to the presence of explicit ions even in cases where the mutation itself does not involve a change in the overall charge. The effect is most significant if the molecule carries a net charge close to the site mutated. Furthermore, it is shown that the introduction of a small number of ions can lead to very severe sampling problems suggesting that in practical calculations convergence can best be achieved by incorporating either no counterions or by simulating at high ionic strength to ensure sufficient sampling of the ion distribution.     

Colour quenching corrections on the measurement of 90Sr through Cerenkov counting

The determination of ⁹⁰Sr through the Cerenkov radiation emitted by its descendant ⁹⁰Y is a well-known method and firmly established in literature. Nevertheless, in order to obtain an accurate result based on a Cerenkov measurement, the experimental work must be extremely rigorous because the efficiency of Cerenkov counting is especially sensitive to the presence of colour. Any traces of colour in the sample produce a decrease in the number of photons detected in the photomultipliers and, therefore, this might cause a diminution in Cerenkov counting efficiency. It is essential not only to detect the effect of colour quenching in the sample but also to correct the decrease in counting efficiency. For this reason, colour quenching correction curves versus counting efficiency are usually done when measuring through Cerenkov counting. One of the most widely used techniques to evaluate colour quenching in these measurements is the channel ratio method, which consists of the measurement of the shift of the spectrum measuring the ratio of counts in two different windows. The selection of the windows for the application of the corrections might have an influence on the quality of the fitting parameters of the correction curves efficiency versus colour quenching degree and hence on the final ⁹⁰Sr result. This work is focused on the calculation of the counting efficiency decrease using the channel ratio method and on obtaining the best fitting correction curve. For this purpose, empirical curves obtained through artificial quenchers have been studied and the results have been tested in real samples. Additionally, given that the Packard Tri-Carb 3170 TR/SL liquid scintillation counter is a novel detector for use in Cerenkov counting, the previous calibration of the Tri-Carb 3170 TR/SL detector, necessary for the measurement of ⁹⁰Sr, is included.     

Model Development in Thermal Styrene Polymerization

Summary: The thermal polymerization of styrene is usually modeled by relying on a reaction scheme and a set of equations that were developed more than three decades ago by Hui and Hamielec. Many detailed models of styrene polymerization are available in the open literature and they are mostly based on the work of Hui and Hamielec, which nearly makes this the standard to follow in explaining the behavior of polystyrene reactors. The model of Hui and Hamielec does a very nice job of describing monomer conversion data but discrepancies are seen between observed and predicted values of number and weight average molecular weights, M_n and M_w. Discrepancies in number average molecular weight seem to be the result of random noise. Discrepancies in weight average molecular weight grow as the polymerization temperature decreases and some of the trends observed in the residuals over the entire temperature range cannot be attributed to random noise. Hui and Hamielec attributed the observed deficiencies to a standard deviation of ±10% in their GPC measurements. A new data set with an experimental error of 2% for average molecular weights is presented. The set contains measured values of M_n, M_w and M_z, so the polymerization scheme has been extended to include third order moments. The data set also includes the effect of ethylbenzene as a chain transfer agent. We present the results of comparing model predictions to our measurements and the adjustments made in the original set of kinetic parameters published by Hui and Hamielec.     

Inkjet-printed electrochemical sensors

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DEA with non-monotonic variables. Application to EU governments’ macroeconomic efficiency

Conventional Data Envelopment Analysis (DEA) considers monotonic variables, ie the lower the inputs and the larger the outputs, the better. There are, however, occasions when the monotonicity of a variable with respect to efficiency depends on the value of the variable, that is in a certain range of values an increase in the variable is desirable, while in another range it is a decrease of the variable that is desirable. In this paper, a DEA model that solves problems considering non-monotonic variables is proposed. An application to assess the macroeconomic efficiency of European Union Member States, as regards taxation, gross debt, GDP growth and employment is presented.     

Gradual technical and scale efficiency improvement in DEA

In data envelopment analysis (DEA) an inefficient unit can be projected onto an efficient target that is far away, i.e. reaching the target may demand large reductions in inputs and increases in outputs. When the inputs and outputs modifications planned are large, it may be troublesome to carry them out all at once. In order to help an inefficient unit reach a distant target, a strategy of gradual improvements with successive, intermediate targets has been proposed. This paper extends such approach to the variable returns to scale (VRS) case. In the VRS scenario we distinguish between units that are technical efficient and those that are not. On the one hand, for those units that are not technical efficient the proposed approach determines successive intermediate targets leading to the technical efficiency frontier, i.e. the priority for those units is to attain technical efficiency. On the other hand, for those units that are technical efficient but not scale efficient the proposed approach computes a sequence of targets ending in the global efficiency frontier, i.e. when technical efficiency is guaranteed the goal is then to attain global efficiency. In both cases, the successive targets are obtained by iteratively solving specific DEA models that take into account given bounds on the rates of change in inputs and outputs that the unit can implement in each step.     

Study of the electron transfer reaction between [Co(EDTA)]− and [Ru(NH3)5py]2+ in methanol–water mixtures

The title reaction was studied in different water–cosolvent (methanol) mixtures. The results have been rationalized employing the Marcus–Hush treatment. To apply this treatment, the true, unimolecular, electron‐transfer rate constants (k_et) were obtained from the experimentally measured rate constants after calculation of the equilibrium constant for the processes of formation of the encounter complex. This calculation was carried out using Eigen–Fuoss (EF) and exponential mean spherical (EMSA) approaches employing effective values of the solvent dielectric constant. These effective values were obtained from the measured association constants corresponding to other ion pairs. The results reveal that in these media there is an additional component of reorganization energy, absent in neat solvents. An explanation of the origin of this component is given. © 2009 Wiley Periodicals, Inc. Int J Chem Kinet 41: 658–666, 2009