Determination of Rosuvastatin in Urine by Spectrofluorimetry After Liquid–Liquid Extraction and Derivatization in Acidic Medium

Statins are a class of drugs mostly used for treating hyperlipidemia, and rosuvastatin is the newest drug in the market belonging to this class. In this present work, a method was developed based on the molecular fluorescence technique, with the objective to quantify rosuvastatin in urine samples. For this purpose, the study of several parameters was made to achieve the maximum analytical signal (under reaction with sulfuric acid during 40 min). Also, a previous step to avoid matrix interference was carried out (liquid–liquid extraction). The limit of detection (LOD) and the limit of quantification (LOQ) were 0.38 and 1.28 mg L^?1, respectively. Linear relationship between rosuvastatin concentration and it’s fluorescence intensity was found until 5.0 mg L^?1. The proposed method was tested in several samples spiked with rosuvastatin and recovery was found in the range of 90?±?10 %.     

Novel nanostructured electrochemical sensor for voltammetric determination of N-acetylcysteine in the presence of high concentrations of tryptophan

A carbon paste electrode chemically modified with multiwall nanotubes and ethynylferrocene (ETFc) was used as a selective and sensitive electrochemical sensor for the determination of minor amounts of N-acetylcysteine (N-AC) in the presence of a high concentration of tryptophan (Trp). Square wave voltammetry (SWV) of N-AC at the modified electrode exhibited linear dynamic range with a detection limit (3 s) of 0.08 μmol?L^?1. The separations of anodic peak potentials of N-AC and Trp reached 400 mV using SWV. With good selectivity and sensitivity, the present method provides a simple method for selective detection of N-AC in real samples such as drug and urine.     

Efficient multi-dimensional solution of PDEs using Chebyshev spectral methods

A robust methodology is presented for efficiently solving partial differential equations using Chebyshev spectral techniques. It is well known that differential equations in one dimension can be solved efficiently with Chebyshev discretizations, O(N) operations for N unknowns, however this efficiency is lost in higher dimensions due to the coupling between modes. This paper presents the “quasi-inverse“ technique (QIT), which combines optimizations of one-dimensional spectral differentiation matrices with Kronecker matrix products to build efficient multi-dimensional operators. This strategy results in O(N^2D?1) operations for N^D unknowns, independent of the form of the differential operators. QIT is compared to the matrix diagonalization technique (MDT) of Haidvogel and Zang [D.B. Haidvogel, T. Zang, The accurate solution of Poisson’s equation by expansion in Chebyshev polynomials, J. Comput. Phys. 30 (1979) 167–180] and Shen [J. Shen, Efficient spectral-Galerkin method. II. Direct solvers of second- and fourth-order equations using Chebyshev polynomials, SIAM J. Sci. Comp. 16 (1) (1995) 74–87]. While the cost for MDT and QIT are the same in two dimensions, there are significant differences. MDT utilizes an eigenvalue/eigenvector decomposition and can only be used for relatively simple differential equations. QIT is based upon intrinsic properties of the Chebyshev polynomials and is adaptable to linear PDEs with constant coefficients in simple domains. We present results for a standard suite of test problems, and discuss of the adaptability of QIT to more complicated problems.     

An efficient high-order boundary element method for nonlinear wave–wave and wave-body interactions

A highly efficient high-order boundary element method is developed for the numerical simulation of nonlinear wave–wave and wave-body interactions in the context of potential flow. The method is based on the framework of the quadratic boundary element method (QBEM) for the boundary integral equation and uses the pre-corrected fast Fourier transform (PFFT) algorithm to accelerate the evaluation of far-field influences of source and/or normal dipole distributions on boundary elements. The resulting PFFT–QBEM reduces the computational effort of solving the associated boundary-value problem from O(N^2～3) (with the traditional QBEM) to O(N ln N) where N represents the total number of boundary unknowns. Significantly, it allows for reliable computations of nonlinear hydrodynamics useful in ship design and marine applications, which are forbidden with the traditional methods on the presently available computing platforms. The formulation and numerical issues in the development and implementation of the PFFT–QBEM are described in detail. The characteristics of accuracy and efficiency of the PFFT–QBEM for various boundary-value problems are studied and compared to those of the existing accelerated (lower- and higher-order) boundary element methods. To illustrate the usefulness of the PFFT–QBEM, it is applied to solve the initial boundary-value problem in the generation of three-dimensional nonlinear waves by a moving ship hull. The predicted wave profile and resistance on the ship are compared to available experimental measurements with satisfactory agreements.     

N identical particles under quantum confinement: a many-body dimensional perturbation theory approach

Systems that involve N identical interacting particles under quantum confinement appear throughout many areas of physics, including chemical, condensed matter, and atomic physics. In this paper, we present the methods of dimensional perturbation theory, a powerful set of tools that uses symmetry to yield simple results for studying such many-body systems. We present a detailed discussion of the dimensional continuation of the N-particle Schrödinger equation, the spatial dimension D→∞ equilibrium (D⁰) structure, and the normal-mode (D⁻¹) structure. We use the FG matrix method to derive general, analytical expressions for the many-body normal-mode vibrational frequencies, and we give specific analytical results for three confined N-body quantum systems: the N-electron atom, N-electron quantum dot, and N-atom inhomogeneous Bose-Einstein condensate with a repulsive hard-core potential.     

Rapid and Sensitive Online Determination of Some Selective α1-Blockers by Flow Injection Analysis with Micelle-Enhanced Fluorescence Detection

A rapid, sensitive and selective flow injection analysis (FIA) method was developed for the determination of some selective α₁-blockers including; terazosin (TER), doxazosin (DOX), prazosin (PRZ), and alfuzosin (ALF). The method was based on enhancement of the native fluorescence of the studied drugs in the presence of sodium dodecyl sulfate (SDS). The method was optimized for the buffer type, concentration and pH, surfactant type and concentration, flow rate and detection wavelengths in order to achieve the maximum sensitivity. The results showed that the best sensitivity was obtained by using SDS (10 mM) in phosphate buffer (20 mM, pH?=?3), flow rate was 0.5 ml/min and the detector was set at λ_ex?=?250 and λ_em?=?389. Under these optimum conditions there was a linear relationship between the concentration and the fluorescence intensity in the range from 5–400 ng ml^? with correlation coefficient of more than 0.998. The detection and quantitation limits for the studied drugs by the proposed method were 3.2–11.9 ng ml^?1 and 10.8–39.7 ng ml^?1, respectively. The method was validated in accordance with the requirements of ICH guidelines and shown to be suitable for intended applications. Moreover, the binding constants for α₁–blockers –SDS system were determined using the adduct model. The proposed method has been applied successfully for the analysis of the pure forms for studied drugs and also their pharmaceutical formulations and the results were compared with official methods.     

19F-NMR Analysis of Primary and Secondary Amines Following Chemical Derivatization with Trifluoroacetic Anhydride

Five amines were reacted with trifluoroacetic anhydride (TFAA) as derivatization reagent and subsequently analyzed via ¹⁹F nuclear magnetic resonance (NMR) spectroscopy. The ¹⁹F-NMR spectra of derivatives of aniline, 2,4-dimethyl aniline, and 2-methoxy aniline produce a signal that are very close to TFAA. The peaks resulting from the reaction of TFAA with N-ethyl aniline and N-methyl aniline are shifted much farther downfield than any of the other signals. Optimal ¹⁹F-NMR sensitivity based upon T ₁ relaxation time was investigated for derivatization compound and flurbiprofen as internal standard in toluene. The calibration curve was linear for amines over the range of 9.0–100.0?mg?L^?1, with detection limit (S/N?=?3) of 2.6–2.9?mg?L^?1. Solid-phase extraction cartridges were investigated for preconcentration of water samples. The method was validated through spike and recovery for secondary amines from tap water sample.     

The EPS method: A new method for constructing pseudospectral derivative operators

We develop a new type of derivative matrix for pseudospectral methods. The norm of these matrices grows at the optimal rate O(N²) for N-by-N matrices, in contrast to standard pseudospectral constructions that result in O(N⁴) growth of the norm. The smaller norm has a big advantage when using the derivative matrix for solving time dependent problems such as wave propagation. The construction is based on representing the derivative operator as an integral kernel, and does not rely on the interpolating polynomials. In particular, we construct second derivative matrices that incorporate Dirichlet or Neumann boundary conditions on an interval and on the disk, but the method can be used to construct a wide variety of commonly used operators for solving PDEs and integral equations. The construction can be used with any quadrature, including traditional Gauss–Legendre quadratures, but we have found that by using quadratures based on prolate spheroidal wave functions, we can achieve a near optimal sampling rate close to two points per wavelength, even for non-periodic problems. We provide numerical results for the new construction and demonstrate that the construction achieves similar or better accuracy than traditional pseudospectral derivative matrices, while resulting in a norm that is orders of magnitude smaller than the standard construction. To demonstrate the advantage of the new construction, we apply the method for solving the wave equation in constant and discontinuous media and for solving PDEs on the unit disk. We also present two compression algorithms for applying the derivative matrices in O(N log N) operations.     

Optically Detected ESR (OD ESR) of ion-radical Pairs in coloured solutions. Observation of transienttrans-azobenzene radical cation

Trans-azobenzene dissolved in different liquid hydrocarbons absorbs fluorescence arising from all acceptors previously used in Fluorescence Detected Magnetic Resonance (FDMR) and Optically Detected ESR (OD ESR) spectroscopy making optical detection impossible. In this report a new acceptor,rubrene, having sufficient quantum yield of fluorescence in the red band 550–620 nm, has been proven successful. OD ESR spectra of the radical-ion pairtrans-azobenzene⁺/rubrene^? were detected in liquid squalane (2,6,10,15,19,23-hexamethyl-tetracosane) solution in the temperature range 294–243 K. The experimental isotropic hyperfine splittings of the radical cation oftrans-azobenzene (a _N=1.4 mT) have been compared with those from MNDO/INDO calculations and with those of earlier work using freon matrix studies.     

Die Analyse monomolekularer FestkörperoberflÄchenschichten mit Hilfe der SekundÄrionenemission

The use of extremely low primary ion current densities (10^?9 A cm^?2) increases the sputtering time of the original first monolayer of a solid to such a degree (>10⁴ s), that the analysis of this layer by secondary ion spectroscopy can be realized. Changes in its composition (caused by surface reactions, particle bombardment etc.) can be observed for a long period before a considerable fraction of the surface has interacted with the weak ion beam. The capacity of the method is demonstrated by analysis results of Ag and Mo surfaces. Many kinds of ions follow exactly the time dependenceN(t)=N(0)e ^?t/T, characteristic exclusively for ions originating from components present only in the first monolayer. The detection limit for several complex anions is below 1 ppm of a monolayer (<10^?15 g). This method of monolayer analysis shows some advantages compared with electron probe x-ray analysis or Auger electron spectroscopy: Isotope separation, detection of changes of concentration within the first few monolayers, and especially the detection of chemical compounds.     

Validated HPLC-Fl Method for the Analysis of S-Adenosylmethionine and S-Adenosylhomocysteine Biomarkers in Human Blood

The natural methyl donor group, S-adenosylmethionine and its product, S-adenosylhomocysteine play an important role in many biochemical reactions involving transmethylation reactions. These compounds can be used as biomarkers in incipient diagnosis of various pathological disorders therefore the validation of a suitable method to routinely analysis of these compounds is very important. In this paper, a high performance liquid chromatrography method for S-adenosylmethionine and S-adenosylhomocysteine measurement as fluorescent 1,N ⁶-ethanoderivatives from biological samples was validated in terms of selectivity, linearity range of the response (R?>?0.9993), detection limit (9?×?10^?9 and 4.4?×?10^?9 molL^?1), the limit of quantitation (9.7?×?10^?9 and 5.7?×?10^?9?mol?L^?1), precision, trueness and robustness. The method for quantification simultaneous of these compounds is rapid, sensitive and precise and appropriate for clinical analysis.     

Approximation techniques for the quenched master field equations

We present two different approximation schemes for determining non-perturbatively the quenched master field of large-N field theories. The first method is variational and involves minimizing the trace of the squared master-field equation. The second method is based on solving the master-field equation exactly in a truncated basis of stochastic matrices. Either method, when applied to matrix γθ⁴ theory in D = 0 and 1 dimensions, gives results of n-point functions and the mass-gap which are in extremely close agreement with the known exact values.     

Ultrasound assisted the preparation of 1-butoxy-4-nitrobenzene under a new multi-site phase-transfer catalyst – Kinetic study

In the present research work deals with the preparation of 1-butoxy-4-nitrobenzene was successfully carried out by 4-nitrophenol with n-butyl bromide using aqueous potassium carbonate and catalyzed by a new multi-site phase-transfer catalyst (MPTC) viz., N¹,N⁴-diethyl-N¹,N¹,N⁴,N⁴-tetraisopropylbutane-1,4-diammonium dibromide, under ultrasonic (40 kHz, 300 W) assisted organic solvent condition. The pseudo first-order kinetic equation was applied to describe the overall reaction. Under ultrasound irradiation (40 kHz, 300 W) in a batch reactor, it shows that the overall reaction greatly enhanced with ultrasound irradiation than without ultrasound. The present study provides a method to synthesize nitro aromatic ethers by ultrasound assisted liquid–liquid multi-site phase-transfer catalysis condition.     

Synthesis,characterization and luminescence study of dimethyl[N-arylmethylenethiobenzahydrazonato]indium

Five dimethylindium complexes of type Me₂InL [L = N-(4-methoxy)benzylidenethiobenzahydrazonato (1), N-(3,4-dimethoxy)benzylidenethiobenzahydrazonato (2), N-(4-N,N-dimethylamino)benzylidenethiobenzahydrazonato (3), N-(2-naphthyl)methylene thiobenzahydrazonato (4) and N-(9-anthryl)methylenethiobenzahydrazonato (5)] have been synthesized by reaction of trimethylindium with appropriate N-arylmethylenethiobenzahydrozones. The complexes obtained have been characterized by elemental analysis, ¹H NMR, IR and mass spectroscopy. Compounds 1–5 emit blue colors at λ_max = 432–479 nm when irradiated by UV light. The electroluminescent (EL) properties of 1–5 were examined by fabricating EL devices using 1–5 as emitter, respectively. The EL bands are located in the green region (513–578 nm).     

Nuclear Quadrupole Interactions in Nuclear Quadrupole Resonance Detection of Energetic and Controlled Materials: Theoretical Study

There has been a growing interest in nuclear quadrupole resonance (NQR) techniques useful for the detection of explosives and drugs in solid state systems. This paper uses the first-principles one-electron Hartree?CFock theoretical method to study the nuclear quadrupole interaction parameters e ² qQ and ?? for the ¹⁴N nuclei in the explosives RDX and ??-HMX as well as the drugs cocaine and heroin. It has been found in our earlier published investigations reviewed here that there is very good agreement for our calculated e ² qQ and ?? for ¹⁴N, for all these four systems, and experiment. We also present our unpublished theoretical results for cocaine with an HCl molecule attached. We successfully explain quantitatively the drastic decrease in e ² qQ in going to cocaine-HCl from cocaine-free base as well as the observed substantial increase in ?? and discuss the implications of these dramatic changes for NQR detection in general.     

Dynamics of collective decoherence and thermalization

We analyze the dynamics of N interacting spins (quantum register) collectively coupled to a thermal environment. Each spin experiences the same environment interaction, consisting of an energy conserving and an energy exchange part.We find the decay rates of the reduced density matrix elements in the energy basis. We show that if the spins do not interact among each other, then the fastest decay rates of off-diagonal matrix elements induced by the energy conserving interaction is of order N², while that one induced by the energy exchange interaction is of the order N only. Moreover, the diagonal matrix elements approach their limiting values at a rate independent of N. For a general spin system the decay rates depend in a rather complicated (but explicit) way on the size N and the interaction between the spins.Our method is based on a dynamical quantum resonance theory valid for small, fixed values of the couplings. We do not make Markov-, Born- or weak coupling (van Hove) approximations.     

EPR Spectroscopy of Mercury-Organic Compounds with Nitroxide Radicals

Intramolecular electron spin exchange as a function of temperature, solvent viscosity and polarity has been studied by X-band electron paramagnetic resonance (EPR) spectroscopy for two nitroxide biradicals containing mercury-organic groups in the bridge connecting two 1-oxyl-2,2,6,6-tetramethylpiperidine-3,4-ene-nitroxide rings, R. The temperature dependence of the isotropic hyperfine splitting (hfs) constant a ^N and the exchange integral value |J/a| of the biradicals were measured from EPR spectra and subsequently analyzed comparing to a ^N and a ^Hg hfs constants of ClHgR radical dissolved in the same solvents. In all cases, the interaction of solvent molecules (SM) with >N–O fragments of nitroxide rings led to a slight decrease in a values with increasing temperature. The |J/a| value varied slightly with temperature T changes. The changes of |J/a| are much less comparing to those with variation of the solvent polarity. The interaction between SM and Hg atoms inside the bridge is observed and discussed.     

ΛN and ΣN Interactions from Lattice QCD

We present our recent study on ΛN and ΣN (isospin I = 3/2) interactions by measuring Nambu–Bethe–Salpeter wave functions on the Lattice QCD. The lattice QCD calculation is performed by using the N _f  = 2 + 1 gauge configurations generated by PACS-CS collaboration together with employing an improved method to obtain potentials in lattice QCD simulations. For the ¹ S ₀ channel, the central ΣN (I = 3/2) potential and the central ΛN (¹ S ₀) potential are found to be very similar. For the spin triplet (³ S ₁?³ D ₁) channels, the central ΛN(³ S ₁?³ D ₁) potential is attractive while the central ΣN(I = 3/2, ³ S ₁?³ D ₁) potentials is repulsive. Tensor potentials, on the other hand, are rather weak in both ΛN and ΣN(I = 3/2) systems.     

Fourier transform spectrometer remote sensing of O2 A-band electric quadrupole transitions

We observed electric quadrupole transitions in the O₂ A-band, b¹Σ_g⁺←X³Σ_g^?(0,0), in high solar zenith angle atmospheric spectra recorded with the high-resolution solar-viewing Fourier transform spectrometer at Park Falls, WI. We identified 12 ΔN=±3 transitions for the first time, including the first detection of ^NO-branch transitions and extended the ^TS-branch observations of Brault [J Mol Spectrosc 1980;80:384–8] up to N″=23. Additionally, we observed six electric quadrupole transitions of the ΔN=?1 ^PO-branch. These observations demonstrate the excellent sensitivity and long-term stability of the new generation of solar-viewing Fourier transform spectrometers.     

A new tyrosinase biosensor based on covalent immobilization of enzyme on N-(3-aminopropyl) pyrrole polymer film

A conducting polymer film of N-amino substituted pyrrole monomer has been prepared for covalent immobilization of enzyme for biosensing applications, illustrated by tyrosinase (PPO). The tyrosinase enzyme retains its bioactivity when being immobilized on N-substituted pyrrole polymer film by covalent bonding. The enzyme electrode was characterized by UV–Vis and infrared spectroscopy. Phenolic compounds were quantitatively estimated by the direct electrochemical reduction of enzymatically liberated quinone species at −0.2 V vs. Ag/AgCl. The results of amperometric response measurements conducted on enzyme electrode show sensitivity of 57.6, 71.4 and 45.8 mA M⁻¹ cm⁻² and a linear response range of 1.8–170.2, 1.3–110.1 and 2.1–168 μM for phenol, catechol and p-cresol, respectively. The biosensor exhibits a lowest detection limit of 0.9, 0.7 and 1.1 μM, for phenol, catechol and p-cresol, respectively and a period of stable sensitivity of 3 months at 4–5 °C.