Optimization of Verapamil Drug Analysis by Excitation-Emission Fluorescence in Combination with Second-order Multivariate Calibration

Excitation emission fluorescence matrices (EEMs) of Verapamil drug were obtained by direct and by derivatization fluorescence spectroscopy. The fluorescence excitation and emission wavelengths were displaced to longer wavelengths and the fluorescence intensity was enhanced upon derivation with respect to the native fluorescence of the drug. The complete EEM of the native fluorescence of the drug and of the derivatization product were rapidly acquired by using a charged-coupled device detector (CCD), which is advantageous in terms of speed in the analysis, with respect to the use of a conventional photomultiplier detector. The EEMs were analyzed by several second-order multivariate calibration methods exploiting the second order advantage. The three-dimensional decomposition methods used, based in different assumptions about the trilinearity of the three way data structure under analysis, were parallel factor analysis (PARAFAC), bilinear least squares (BLLS), parallel factor analysis 2 (PARAFAC2) and multivariate curve resolution—alternating least squares (MCR-ALS). The determination was performed by using the standard addition approach. The figures of merit of the PARAFAC and BLLS methods were calculated, obtaining a lower limit of detection with the derivatization procedure, when compared with the direct measurement of the fluorescence of the drug. In Verapamil drug the best estimations were found with the BLLS and the MCR-ALS models. In the quantification of Verapamil in a pharmaceutical formulation the best estimation, when compared with the result obtained by the US Pharmacopeia high performance liquid chromatography approach, was obtained by direct fluorescence spectroscopy with MCR-ALS and by derivatization fluorescence spectroscopy with the PARAFAC2 model.     

Synthesis and antibacterial activity of silver nanoparticles with different sizes

Silver nanoparticles with different sizes (7, 29, and 89 nm mean values) were synthesized using gallic acid in an aqueous chemical reduction method. The nanoparticles were characterized using transmission electron microscopy (TEM), dynamic light scattering (DLS), X-ray diffraction (XRD), and ultraviolet–visible (UV–Vis) absorption spectroscopy; the antibacterial activity was assessed using the standard microdilution method, determining the minimum inhibitory concentration (MIC) according to the National Committee for Clinical Laboratory Standards. From the microscopies studies (TEM) we observed that silver nanoparticles have spherical (7 and 29 nm) and pseudospherical shape (89 nm) with a narrow size distribution. The sizes of the silver nanoparticles were controlled by varying some experimental conditions. It was found that the antibacterial activity of the nanoparticles varies when their size diminishes.     

Double pion photoproduction from3He at low energies

A generalization of the “Gauge-invariant OPE model” to double pion photoproduction on³He is presented. Results for the total and differential cross-sections are shown. The relevance of double pion photoproduction in the nuclear shadowing of photons is remarked.     

Preparation and basic physical properties of BiTeI single crystals

A modified Bridgman method is described, which makes it possible to prepare homogeneous BiTeI crystals using excess iodine. At room temperature the values of the electrical conductivity of the crystals range around 2000 ^–1 cm^–1, the Hall constant value about 0·09 cm^–3 coul^–1, the Seebeck coefficient about 50 V K^–1. In connection with the assumption of super-stoichiometric iodine content we expect there exist point defects in the crystals, where Te atoms are replaced with I atoms, which gives rise to electric conductivity. On the basis of the temperature dependence of the electron mobility one can suppose a mixed mechanism of the scattering of the free carriers by the acoustic branch of lattice vibrations and by ionized impurities.     

A moment problem associated to rational Szegő functions

Leta ₁,...,a _p be distinct points in the finite complex plane ?, such that |a _j|>1,j=1,..., p and let \(b_j = 1/\bar \alpha _j ,\) j=1,..., p. Let μ₀, μ _π ^(j) , ν _π ^(j) j=1,..., p;n=1, 2,... be given complex numbers. We consider the following moment problem. Find a distribution ψ on [?π, π], with infinitely many points of increase, such that $$\begin{array}{l} \int_{ - \pi }^\pi {d\psi (\theta ) = \mu _0 ,} \\ \int_{ - \pi }^\pi {\frac{{d\psi (\theta )}}{{(e^{i\theta } - a_j )^n }} = \mu _n^{(j)} ,} \int_{ - \pi }^\pi {\frac{{d\psi (\theta )}}{{(e^{i\theta } - b_j )^n }} = v_n^{(j)} ,} j = 1,...,p;n = 1,2,.... \\ \end{array}$$ It will be shown that this problem has a unique solution if the moments generate a positive-definite Hermitian inner product on the linear space of rational functions with no poles in the extended complex plane ?^* outside {a ₁,...,a _p,b ₁,...,b _p}.     

Energy functional depending on elastic strain and chemical composition

In this paper we deal with energy functionals depending on elastic strain and chemical composition and we obtain lower semicontinuity results, existence theorems and relaxation in the spacesH ^1,p(; ⁿ)×L ^q (; ^d) with respect to weak convergence. Our proofs use parametrized measures associated with weakly converging sequences.The research was partially supported by the National Science Foundation under Grants No. DMS-9000133 and DMS-9201215 and also by the Army Research Office and the National Science Foundation through the Center for Nonlinear Analysis.The research was partially supported by the National Science Foundation uncer Grants No. DMs 911572, the AFOSR 91 0301, the ARO DAAL03 92 G 003 and also by the ARO and the NSF through the Center for Nonlinear Analysis.The research was supported by DGICYT (Spain) through Programa de Perfeccionamiento y Movilidad del Personal Investigador and through grant PB90-0245, by the Army Research Office and the National Science Foundation through the Center for Nonlinear Analysis and also by the project EurHomogenization SC1-CT91-0732 of the European Comunity.     

Thermal expansion of cadmium fluoride crystals at high temperatures

The thermal expansion coefficient of cadmium fluoride crystals has been measured over the temperature range of 300 to 1070 K. The data fit well to measurements done by other authors in the range 80–300 K. At temperatures above 1070 K the thermal expansion coefficient shows an anomalous behaviour which has been attributed to the formation of cadmium oxide on the surface of the sample.     

Identification of phototransformation products of sildenafil (Viagra) and its N-demethylated human metabolite under simulated sunlight

Recent publications on pharmaceutical monitoring are increasingly covering the field of illicit drugs and lately the forensic evaluation of designing illegal analogs of lifestyle drugs like the phosphodiesterase type 5 (PDE-5) inhibitors Viagra (sildenafil), Levitra (vardenafil) and Cialis (tadalafil). Recently, the presence of all three erectile dysfunction treatment drugs has been reported in wastewaters at very low concentrations. In the environment, contaminants undergo various physical or chemical processes classified into abiotic (photolysis, hydrolysis) and biotic (biodegradation) reactions. Thus, changes in the chemical structure lead to the formation of new transformation products, which may persist in the environment or be further degraded. This study describes the photolysis of sildenafil (SDF) and its human metabolite N-demethylsildenafil (DM-SDF) under simulated solar radiation (Xenon lamp). Following chromatographic separation of the irradiated samples, eight photoproducts in the SDF samples and six photoproducts for DM-SDF were detected and characterized. The combination of ultra performance liquid chromatography-electrospray ionization-quadrupole time-of-flight-mass spectrometry (UPLC-ESI-QToF-MS), liquid chromatography-atmospheric pressure chemical ionization-triple quadrupole mass spectrometry (LC-APCI-QqQ-MS) and hydrogen/deuterium-exchange experiments allowed to propose plausible chemical structures for the photoproducts, taking into account the characteristic fragmentation patterns and the accurate mass measurements. These mass spectral data provided sound evidence for the susceptibility of the piperazine ring toward photodegradation. A gradual breakdown of this heterocyclic structure gave rise to a series of products, which in part were identical for SDF and DM-SDF. The sulfonic acid, as the formal product of sulfonamide hydrolysis, was identified as key intermediate in the photolysis pathway. In both drug/metabolite molecules, phototransformation processes taking place beyond the sulfonamide group were deemed to be of minor relevance.     

Magnetocaloric effect and magnetic properties in NdMnO3 perovskite: A Monte Carlo approach

The magnetic properties and magnetocaloric effect in $\text{NdMn}{\text{O}}_3$ have been investigated, as well as the effect of magnetic anisotropy in the magnetocaloric properties of the perovskite-type compound. A classical Heisenberg Hamiltonian with nearest and next-nearest neighbors interactions was implemented. Hamiltonian parameters were fitted in order to reproduce experimental results. Magnetic field dependence on the magnetization, for isothermal processes, was performed. In this way, the magnetic entropy change $\left(\mathrm{\Delta }{S}_m\right)$ was computed as well as the relative cooling power (RCP). Results show that as the magnetic anisotropy constant increases, there was not only a sharpening, but also an increase in peak height of $?\mathrm{\Delta }{S}_m$. Finally, the magnetic field and anisotropy dependences on the RCP were obtained, showing that the highest values of the RCP were found for low anisotropy values.