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.     

Structural and electronic effects in metallocene catalysts studied by x‐ray techniques

A series of metallocenes, namely, [Cp₂ZrCl₂], [(MeCp)₂ZrCl₂], [(nBuCp)₂ZrCl₂], [(iBuCp)₂ZrCl₂], [(tBuCp)₂ZrCl₂], [Et(Ind)₂ZrCl₂], [Et(IndH₄)₂ZrCl₂], and [MeSi₂(Ind)₂ZrCl₂)] were analyzed by extended x‐ray absorption fine structure (EXAFS) and x‐ray photoelectron spectroscopy (XPS). Complementary techniques, UV–vis spectroscopy and cyclic and differential pulse voltammetry, were employed to characterize the organometallic complexes. The catalysts were evaluated in ethylene polymerization, having methylaluminoxane (MAO) as the cocatalyst, and the resulting polymers were characterized by gel permeation chromatography. The structural and electronic effects caused by the coordination sphere around the metal center and their effects on the catalytic activity and polymer characteristics are discussed. Copyright © 2008 John Wiley & Sons, Ltd.     

Mixed 2D molecular systems: Mechanic, thermodynamic and dielectric properties

Study of Langmuir monolayers consisting of stearic acid (SA) and dipalmitoylphosphatidylcholine (DPPC) molecules was done by surface pressure-area isotherms (π-A), the Maxwell displacement current (MDC) measurement, X-ray reflectivity (XRR) and atomic force microscopy (AFM) to investigate the selected mechanic, thermodynamic and dielectric properties based on orientational structure of monolayers. On the base of π-A isotherms analysis we explain the creation of stable structures and found optimal monolayer composition. The dielectric properties represented by MDC generated monolayers were analyzed in terms of excess dipole moment, proposing the effect of dipole-dipole interaction. XRR and AFM results illustrate deposited film structure and molecular ordering.     

The influence of shear bands on final structure and magnetic properties of 3% Si non-oriented silicon steel

The presence of shear bands in the deformed material before final annealing is very important for Goss and Cube textures formation in silicon steel [S.C. Paolinelli, M.A. Cunha, J. Magn. Magn. Mater. 255 (2003) pp. 379. [1]; J.T. Park, J.A. Szpunar, Acta Mater., 51 (2003) 3037. [2]]. The increase of the hot-band grain size can increase the number of shear bands, which favor the nucleation of these orientations. In this work, the effect of the hot band grain size variation, promoted by varying the hot rolling finishing temperature, on final structure and magnetic properties was investigated for 3% Si alloy. It was found that the increase of the hot-band grain size increases the occurrence of shear bands and promotes an increase of η fiber fraction and a reduction of γ fiber fraction, improving the magnetic induction. On the other hand, the final grain size is reduced when the hot-band grain size is larger than 190 μm, deteriorating the core loss values in spite of the texture benefits. The reduction of final grain size was explained by the increase of the number of nuclei at the beginning of the recrystallization caused by the increase of shear bands in the deformed material.     

Elastic scattering from a sapphire microsphere placed on a silica optical fiber coupler: Possible applications to biosensing

Elastic light scattering is performed in the original band of optical fiber communication at 1300 nm for a 500 μm sapphire microsphere placed on a silica optical fiber half coupler. The morphology dependent resonances (MDRs) are observed in the transverse magnetically (TM) polarized and transverse electrically (TE) polarized 0^° transmission and 90^° elastic scattering obtained from the sapphire microsphere. The TE and TM MDRs can be detected selectively with the use of a Glan polarizer. The TE and TM polarization selectivity provides the ability to select relative MDR to BG levels. The TM polarization provides higher MDR signal to background ratio (SBR) and is suitable for optical monitoring, biological sensing or any other optoelectronic application that requires a high resolution optical filter. The polar angular mode spacing of 0.36 nm of the resonances correlates well with the optical size of the sapphire microsphere. The autocorrelation of the 90^° elastic scattering spectra also shows peaks at 0.36 nm. The spectral linewidths of the resonances are on the order of 0.1 nm, which corresponds to quality factors on the order of 10⁴. A sapphire sphere with a radius of 500 μm and relative refractive index of 1.31, resonances will red-shift by 1.01 nm (0.077%). This shift is on the order of 10 linewidths, making sapphire biophotonic sensors an interesting alternative to silica biophotonic sensors.     

Nonlinear dynamics of a spinor Bose-Einstein condensate in a double-well potential

We examine the nonlinear dynamical behavior of a spinor Bose-Einstein condensate in a double-well potential. Considering a condensate with large number of atoms, such that it can be described using the mean field theory, we separate the spinor dynamics from the spatial dynamics under the single-mode approximation. We limit ourselves to certain initial conditions under which the spatial mode is frozen so that we can focus on the spinor dynamics only. Identifying collective spin variables of our system, we derive the corresponding nonlinear equations of motion for them. Employing standard stability analysis, we find and characterize fixed points of the system. For a wide range of physical parameters such as tunneling strength and non-linear interactions, as well as for various initial preparations of the system, we identify qualitatively different dynamical regimes possible in the system. In particular, complete and incomplete oscillations of spin variables between quantum wells are found. We also show that by bringing some fixed points close to each other in the phase space of the system, it is possible to induce amplitude modulation to those otherwise regular tunneling oscillations.     

Thermal stability of corrugated epitaxial graphene grown on Re(0001)

We report on a novel approach to determine the relationship between the corrugation and the thermal stability of epitaxial graphene grown on a strongly interacting substrate. According to our density functional theory calculations, the C single layer grown on Re(0001) is strongly corrugated, with a buckling of 1.6 ?, yielding a simulated C 1s core level spectrum which is in excellent agreement with the experimental one. We found that corrugation is closely knit with the thermal stability of the C network: C-C bond breaking is favored in the strongly buckled regions of the moiré cell, though it requires the presence of diffusing graphene layer vacancies.     

Accurate intensity calibration for low wavenumber (−150 to 150 cm−1) Raman spectroscopy using the pure rotational spectrum of N2

We report on an accurate intensity calibration method for low wavenumber Raman spectroscopy. It uses the rotational Raman spectrum of N₂. The intensity distributions in the rotational Raman spectra of diatomic molecules are theoretically well established. They can be used as primary intensity standards for intensity calibration. The intensity ratios of the Stokes and anti‐Stokes transitions originating from the same rotational levels are not affected by thermal population. Taking the effect of rotation–vibration interactions appropriately into account, we are able to calculate these intensity ratios theoretically. The comparison between the observed and calculated ratios of the N₂ pure rotational spectrum provides an accurate relative sensitivity curve (error ~5 × 10⁻⁴) in the wavenumber region of −150 to 150 cm⁻¹. We determine the temperature of water solely from the low wavenumber Raman spectra, using a thus calibrated spectrometer. The Raman temperature shows an excellent agreement with the thermocouple temperature, with only 0.5 K difference. The present calibration technique will be highly useful in many applications of low wavenumber quantitative Raman spectroscopy. Copyright © 2015 John Wiley & Sons, Ltd.