Electroactive copper(II) bimetallic self-assembled multilayers on Si(100)

Silicon (100) surfaces were modified by reacting 4-aminopyridine and Si–Cl bond. These surfaces were further used for tethering copper bimetallic complexes and growing monolayers and multilayers by changing the axial position via Lewis acid–base reactions. In this way, coordination chemistry approach can be used as building blocks for controlling the design of functional surfaces. Furthermore, the outcomes of the several characterization techniques indicate that the complex is spatially oriented suggesting that this simple strategy allows the preparation of three dimensional molecular structures exhibiting spatial order. The structures on surface show interesting electroactive behaviors leading two cathodic signals, that can be related to Cu(II)/Cu(I) and Cu(I)/Cu(0) electro-reduction species (signals at ? 0.15 V and ? 0.50 V) and one peak in the anodic region (? 0.15 V) ascribed to the Cu(0)/Cu(II) electro-oxidation reaction, using an Ag/AgCl saturated electrode and platinum wire as reference and counter electrodes, respectively.     

Coibacins A-D, Antileishmanial Marine Cyanobacterial Polyketides with Intriguing Biosynthetic Origins

Four unsaturated polyketide lactone derivatives, coibacins A-D, were isolated from a Panamanian marine cyanobacterium, cf. Oscillatoria sp. The two different types of termini observed in these co-occurring metabolites, either a methyl cyclopropyl ring as seen in curacin A or a methyl vinyl chloride similar to that observed in the jamaicamides, suggest an intriguing flexibility in the "beta branch" forming biosynthetic process. The coibacins possess selective antileishmanial activity as well as potent anti-inflammatory activity.     

Self-trapping of single and paired electrons in Ge2Se3

We report the theoretical prediction of single and paired electron self-trapping in Ge(2)Se(3). In finite atomic cluster, density functional calculations, we show that excess single electrons in Ge(2)Se(3) are strongly localized around single germanium dimers. We also find that two electrons prefer to trap around the same germanium dimer, rupturing a neighboring Ge-Se bond. Localization is less robust in periodic, density functional calculations. While paired electron self-trapping is present, as shown by wavefunction localization around a distorted Ge-Ge dimer, single-electron trapping is not. This discrepancy appears to depend only on the boundary conditions and not on the exchange-correlation potential or basis set. For single- and paired-electron trapping, we report the adiabatic barriers to motion and we estimate hopping rates and freeze-in temperatures. For the single trapped electron, we also predict the (73)Ge and (77)Se hyperfine coupling constants.     

Hexacoordinated spirocyclic germanium(IV) complex: Synthesis and structural characterization

The spiro‐dibenzogermocine [O(o‐C₆H₄S)₂]₂Ge ( 1 ) was prepared in a reaction between O(o‐C₆H₄SH)₂ and Ge(OⁱPr)₄, and its molecular structure was determined by X‐ray diffraction studies. In the solid state, 1 shows the existence of two weak O → Ge transannular interactions, resulting in a hexacoordinated germanium atom that displays the geometry of a distorted bicapped tetrahedron. © 2009 Wiley Periodicals, Inc. Heteroatom Chem 20:45–49, 2009; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20510     

Mössbauer characterization of an amorphous steel with optimal Mo content

Three amorphous steel alloys, Fe_71.2?xC_7.0Si_3.3B_5.5P_8.7Cr_2.3Al_2.0Mo_x (x = 0, 4.5 and 6.5 at.%), have been produced by the melt-spinning technique and characterized by X-ray diffraction and transmission Mössbauer spectrometry (TMS). TMS allows us to study the local environments of the Fe atoms in the glassy state, showing the changes in the amorphous structure due to the addition of Mo. A reduction of the mean hyperfine field is observed as the amount of Mo increases. With intermediate Mo content, this reduction is associated to the substitution of Fe by Mo in a disordered magnetic Fe-rich structure, whereas for high Mo content, this structure is destroyed leading to an increase of paramagnetic environments. Finally, the relationship between the glass forming ability (GFA) of these alloys and their local structure determined by TMS will be discussed.     

Surprising relations between parametric level correlations and fidelity decay

Relations among fidelity, cross-form-factor (i.e., parametric level correlations), and level velocity correlations are found both by deriving a Ward identity in a two-matrix model and by comparing exact results, using supersymmetry techniques, in the framework of random matrix theory. A power law decay near Heisenberg time, as a function of the relevant parameter, is shown to be at the root of revivals recently discovered for fidelity decay. For cross-form-factors the revivals are illustrated by a numerical study of a multiply kicked Ising spin chain.     

The heavy quarkonium spectrum at order mαslnαs

We compute the complete leading-log terms of the next-to-next-to-next-to-leading-order corrections to potential NRQCD. As a by-product we obtain the leading logs at O(mα_s⁵) in the heavy quarkonium spectrum. These leading logs, when Λ_QCDmα_s², give the complete O(mα_s⁵lnα_s) corrections to the heavy quarkonium spectrum.     

Rapid and sensitive determination of levofloxacin in microsamples of human plasma by high‐performance liquid chromatography and its application in a pharmacokinetic study

A rapid, sensitive and simple high‐performance liquid chromatographic assay with ultraviolet detection was developed for the quantification of levofloxacin in microsamples (100 μL) of human plasma. The extraction procedure included a protein precipitation technique and a short chromatographic running time (4.5 min). Analyses were carried out on a Symmetry C₁₈ column using a mixture of acetonitrile and 0.01 m potassium dihydrogen aqueous solution (pH 3.4; 14:86 v/v) as mobile phase. The method provided specificity and was linear (r ≥ 0.9992) over the concentration range 0.1–12 µg/mL. The average absolute recovery was 93.59%. The intra‐ and inter‐day coefficients of variation were <6%. Additionally, levofloxacin was stable in all evaluations. The usefulness of this method was demonstrated in a pharmacokinetic study of levofloxacin in healthy adult volunteers. The present method offers two main advantages: (a) the use of microsamples reduces the total volume of blood to be collected from patients; and (b) it provides a good cost–effectiveness ratio. It is concluded that the method is rapid, simple, sensitive, economical and suitable for the determination of levofloxacin in human plasma using a small volume of sample. Copyright © 2014 John Wiley & Sons, Ltd.     

Pungency evaluation of onion cultivars from the Venezuelan West-Center region by flow injection analysis-UV-visible spectroscopy pyruvate determination

A flow injection analysis (FIA) method was developed for the determination of pyruvate in onion cultivars (Allium cepa L.) from the West-Center region of Venezuela. The reference Schwimmer and Weston (1961) (J. Agric. Food Chem. 9 (1961) 301) Batch method was modified and adapted to FIA conditions. The formation kinetic of the 2,4-dinitrophenylhydrazine (DNPH)–pyruvate complex was evaluated at room temperature and at 37 °C. It was demonstrated the suitability of the chromopher formation at room temperature. The optimal values for the FIA parameters were: sample injection volume 3 mL, flow rate 6 mL min⁻¹, reactor length 1.5 m, sodium hydroxide concentration 1.0 mol L⁻¹ and hydrochloric acid concentration 0.5 mol L⁻¹. The working calibration range was extended from 80 mg L⁻¹ (Batch method) to 700 mg L⁻¹ with the FIA set up. The sample dilution step is thus avoided, simplifying the whole analysis process. The pungency in representative samples of the cultivars Yellow granex 438, Ultra Hybrid and Red onion “Sangre de Toro” was evaluated by the flow injection analysis (FIA)–pyruvate method and the results were compared to the reference Batch pyruvate method and to the taste panel test. Non-significant differences were found at the 95% of confidence level between the FIA method and the Batch reference method. Correlation coefficient when comparing the FIA results to the taste panel test was r² = 0.8353. Significant differences (P < 0.05) were found in the pungency of the cultivars, the Ultra Hybrid having the highest pungency. The pungency order from minor to major was: Red onion, Texas Grano 438 and Ultra Hybrid.