Simultaneous determination of N-butylscopolamine and oxazepam in pharmaceutical formulations by first-order digital derivative spectrophotometry

A simple method has been developed for the simultaneous determination of N-butylscopolamine bromide and oxazepam in pharmaceutical formulations using first-order digital derivative spectrophotometry. Acetonitrile was selected as the solvent in which both compounds showed well-defined bands. Both analytes showed good stability in this solvent when solutions of the analytes were exposed to light and temperatures between 20 degrees and 80 degrees C. The simultaneous determination of both drugs was performed by the zero-crossing method at 226.0 and 257.0 nm for N-butylscopolamine and oxazepam, respectively. The linear range of determination was found to be 2.5 x 10(-7) to 8.0 x 10(-5) mol/L for N-butylscopolamine and 7.1 x 10(-8) to 8.0 x 10(-5) mol/L for oxazepam. A very good level of repeatability (relative standard deviation) of 0.2% was observed for N-butylscopolamine and oxazepam. The ingredients commonly found in pharmaceutical formulations do not interfere. The proposed method was applied to the determination of these drugs in pharmaceutical formulations (capsules).     

Chronocoulometric study of the electrochemistry of Prussian blue

During the electrochemical oxidation of Prussian blue (PB) to Prussian yellow (PY), an electrocatalytic oxygen production proceeds at the electrode when aqueous electrolyte solutions are used. The formed oxygen is scavenged by the PY, probably by absorption, and it is consumed during the electrochemical reduction of PY to PB by a heterogeneous chemical reaction of PB with oxygen to PY and hydrogen peroxide. Because of this catalytic regeneration of PY, it is impossible to determine the amount of low-spin iron by chronocoulometry using a potential program in which PB is first oxidized to PY and then the charge is measured to reduce PY to PB. The latter charge is biased by the electrocatalytic PY regeneration.     

New aspects of the electroadsorption of ethyl xanthate on copper electrodes

The interaction of the ethyl xanthate (EX) anion with a copper electrode in a borate buffer solution, pH 9.2, has been investigated by cyclic voltammetry (CV), electrochemical quartz crystal microbalance (EQCM), electrochemical impedance spectroscopy (EIS), and measurements of contact angle (CA) under controlled potential. The results obtained allow establishing that, in the potential range from -0.80 and -0.60 V, two parallel reactions were characterized. These reactions were the ethyl xanthate electroadsorption and the hydrogen evolution reaction (HER). This last reaction has not been described by previous authors. Besides, the EIS measurements show that the mechanism of the HER on copper electrodes is not affected by the presence of a ethyl xanthate species. The EQCM study shows that in the electrodesorption process the departure of each ethyl xanthate species from the copper electrode is accompanied with the simultaneous entry of four to five water molecules. This fact is in accordance with the number of copper atoms involved in the adsorption of one ethyl xanthate species.     

A ruthenium probe for cell viability measurement using flow cytometry, confocal microscopy and time-resolved luminescence

The capability of the new luminescent probe (dibenzo[h,j] dipyrido[3,2-a:2',3'-c]phenazine)bis(2,2'-bipyridine)ruthenium(II) dication, (RB2Z), to discriminate live and dead cells has been tested on rat hepatocytes and mouse lymphocytes. RB2Z-stained cells were analyzed using flow cytometry, fluorescence (confocal) microscopy and time-resolved luminescence measurements. The established viability probes propidium iodide (PI) and SYTOX green (SG) were used as controls. The intense luminescence of RB2Z at 606 nm is localized in the nucleus of nonviable cells. Viability measurements by flow cytometry and fluorescence microscopy using RB2Z as dead-cell marker yield the same results as PI and SG. The luminescence lifetime of RB2Z also displays sensitivity to cell viability (0.45 and 0.82 microsecond in presence of fully viable and dead cells, respectively). This ruthenium complex is photostable under laser sources and its 200 nm Stokes shift facilitates multicolor labeling experiments in flow cytometry and fluorescence microscopy. Unlike the currently available probes, the long-lived excited state of RB2Z also allows assays based on luminescence decay measurements.     

Validation of a confirmatory method for lipophilic marine toxins in shellfish using UHPLC-HR-Orbitrap MS

Lipophilic marine toxins are produced by harmful microalgae and can accumulate in edible filter feeders such as shellfish, leading to an introduction of toxins into the human food chain, causing different poisoning effects. During the last years, analytical methods, based on liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS), have been consolidated by interlaboratory validations. However, the main drawback of LC-MS/MS methods remains the limited number of compounds that can be analyzed in a single run. Due to the targeted nature of these methods, only known toxins, previously considered during method optimization, will be detected. Therefore in this study, a method based on ultra-high-performance liquid chromatography coupled to high-resolution Orbitrap mass spectrometry (UHPLC-HR-Orbitrap MS) was developed. Its quantitative performance was evaluated for confirmatory analysis of regulated lipophilic marine toxins in shellfish flesh according to Commission Decision 2002/657/EC. Okadaic acid (OA), dinophysistoxin-1 (DTX-1), pectenotoxin-2 (PTX-2), azaspiracid-1 (AZA-1), yessotoxin (YTX), and 13-desmethyl spirolide C (SPX-1) were quantified using matrix-matched calibration curves (MMS). For all compounds, the reproducibility ranged from 2.9 to 4.9 %, repeatability from 2.9 to 4.9 %, and recoveries from 82.9 to 113 % at the three different spiked levels. In addition, confirmatory identification of the compounds was effectively performed by the presence of a second diagnostic ion (¹³C). In conclusion, UHPLC-HR-Orbitrap MS permitted more accurate and faster detection of the target toxins than previously described LC-MS/MS methods. Furthermore, HRMS allows to retrospectively screen for many analogues and metabolites using its full-scan capabilities but also untargeted screening through the use of metabolomics software. Figure

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New results on the peak algebra

The peak algebra is a unital subalgebra of the symmetric group algebra, linearly spanned by sums of permutations with a common set of peaks. By exploiting the combinatorics of sparse subsets of [n−1] (and of certain classes of compositions of n called almost-odd and thin), we construct three new linear bases of . We discuss two peak analogs of the first Eulerian idempotent and construct a basis of semi-idempotent elements for the peak algebra. We use these bases to describe the Jacobson radical of and to characterize the elements of in terms of the canonical action of the symmetric groups on the tensor algebra of a vector space. We define a chain of ideals of , j = 0,..., , such that is the linear span of sums of permutations with a common set of interior peaks and is the peak algebra. We extend the above results to , generalizing results of Schocker (the case j = 0). Aguiar supported in part by NSF grant DMS-0302423 Orellana supported in part by the Wilson Foundation     

Structure of neutron stars in R-squared gravity

The effects implied for the structure of compact objects by the modification of General Relativity (GR) produced by the generalization of the Lagrangian density to the form $f(R)=R+\alpha R^2$ , where $R$ is the Ricci curvature scalar, have been recently explored. It seems likely that this squared-gravity may allow heavier Neutron Stars (NSs) than GR. In addition, these objects can be useful to constrain free parameters of modified-gravity theories. The differences between alternative gravity theories are enhanced in the strong gravitational regime. In this regime, because of the complexity of the field equations, perturbative methods become a good choice to treat the problem. Following previous works in the field, we performed a numerical integration of the structure equations that describe NSs in $f(R)$ -gravity, recovering their mass-radius relations, but focusing on particular features that arise from this approach in the profiles of the NS interior. We show that these profiles run in correlation with the second-order derivative of the analytic approximation to the Equation of State (EoS), which leads to regions where the enclosed mass decreases with the radius in a counter-intuitive way. We reproduce all computations with a simple polytropic EoS to separate zeroth-order modified gravity effects.     

Influence of surface hydroxylation on 3-aminopropyltriethoxysilane growth mode during chemical functionalization of GaN Surfaces: an angle-resolved X-ray photoelectron spectroscopy Study

A comparative study of the chemical functionalization of undoped, n- and p-type GaN layers grown on sapphire substrates by metal-organic chemical vapor deposition was carried out. Both types of samples were chemically functionalized with 3-aminopropyltriethoxysilane (APTES) using a well-established silane-based approach for functionalizing hydroxylated surfaces. The untreated surfaces as well as those modified by hydroxylation and APTES deposition were analyzed using angle-resolved X-ray photoelectron spectroscopy. Strong differences were found between the APTES growth modes on n- and p-GaN surfaces that can be associated with the number of available hydroxyl groups on the GaN surface of each sample. Depending on the density of surface hydroxyl groups, different mechanisms of APTES attachment to the GaN surface take place in such a way that the APTES growth mode changes from a monolayer to a multilayer growth mode when the number of surface hydroxyl groups is decreased. Specifically, a monolayer growth mode with a surface coverage of approximately 78% was found on p-GaN, whereas the formation of a dense film, approximately 3 monolayers thick, was observed on n-GaN.