Development of a Sensor Based on Modified Carbon Paste with Com Iron(III) Protoporphyrin Immobilized on SiNbZn Silica Matrix for L‐tryptophan Determination

In this work, SiO₂/Nb₂O₅/ZnO prepared by the sol‐gel processing method was used as substrate base for immobilization of the protoporphyrin‐IX ion. Iron(III) ion was inserted into the porphyrin ring (SiNbZn‐PPFe). A simple square wave voltammetry method based on a composite sensor carbon paste electrode of this material,designed as EPC‐SiNbZn‐PPFe, was developed and validated successfully for the determination of L‐tryptophan (Trp). The optimum conditions were obtained by using sensor modified with 18.00 mg SiNbZn‐PPFe material, 12.00 mg graphite powder and 6.0 μL mineral oil and phosphate buffer 0.3 mol L⁻¹ pH 7.0. The sensitivity of the sensor was found to be 0.523 AL mol ⁻¹, linear range from 10 to 70 μmol L⁻¹ and limit of detection of 3.28 μmol L⁻¹. Therefore, the developed method was successfully applied for the Trp determination in real samples of pharmaceutical formulation and can be used for routine quality control pharmaceutical formulations containing Trp.     

Construction and Validation of New Electrochemical Carbon Nanotubes Sensors for Determination of Acebutolol Hydrochloride in Pharmaceuticals and Biological Fluids

A simple, rapid and a highly selective method for direct electrochemical determination of acebutolol hydrochloride (AC) was developed. The developed method was based on the construction of three types of sensors conventional polymer (I), carbon paste (II) and modified carbon nanotubes (MCNTs) carbon paste (III). The fabricated sensors depend mainly on the incorporation of acebutolol hydrochloride with phosphotungstic acid (PTA) forming ion exchange acebutolol‐phosphotungstate (AC‐PT). The performance characteristics of the proposed sensors were studied. The sensors exhibited Nernstian responses (55.6 ± 0.5, 57.14 ± 0.2 and 58.6 ± 0.4 mV mol L^?1) at 25 °C over drug concentration ranges (1.0 × 10^?6‐1.0 × 10^?2, 1.0 × 10^?7‐1.0 × 10^?2 and 5.0 × 10^?8‐1.0 × 10^?2 mol L^?1 with lower detection limits of (5.0 × 10^?7, 5.0 × 10^?8 and 2.5 × 10^?8 mol L^?1 for sensors (I), (II) and (III), respectively. The influence of common and possible interfering species, pharmaceutical additives and some related pharmacological action drugs was investigated using separate solution method and no interference was found. The stability indicating using forced degradation of acebutolol hydrochloride was studied. The standard addition method was used for determination of the investigated drug in its pharmaceutical dosage forms and biological fluids. The results were validated and statistically analysed and compared with those from previously reported methods.     

A near-infrared spectroscopy method to determine aminoglycosides in pharmaceutical formulations

The analytical determination of aminoglycosides in pharmaceutical formulations is very difficult due to the lack of chromophores or fluorophores. Several analytical methods have been developed along the years mainly based on derivatization reactions. The European Pharmacopeia (EP) and the United States Pharmacopeia (USP) describe a microbiological assay to the quantification of aminoglycosides. Near infrared spectroscopy (NIRS) can be used alternatively to analyse aminoglycosides without the need of derivatization reactions or other type of sample processing. A new NIRS based method was developed for the analysis of the aminoglycoside antibiotic neomycin. The method was developed with samples based on a commercial formulation containing neomycin sulphate and three excipients: lactose, talc and magnesium stearate. Synthetic and doped samples were manufactured for this purpose. Three lots of a commercial solid formulation were also used to assess the validity of the method to quantify neomycin sulphate in the industrial pharmaceutical product. The method proposes measurements in reflectance mode using a Fourier-transform near infrared (FT-NIR) spectrometer. Partial least squares regression was the multivariate method adopted to calibrate the NIR spectra with the neomycin sulphate mass fraction. The concentration of neomycin sulphate present in the commercial samples was confirmed by HPLC with pre-column derivatization with phenylisocyanate. Results show that neomycin sulphate was determined successfully in the commercial samples using the method calibrated with the doped samples (mass fraction error of 6.6%). Moreover, the synthetic samples were found to be unqualified to develop the method, producing a biased calibration.     

Kinetic catalytic determination of trace levels of iodide based on the oxidation of basic dyes with hydrogen peroxide monitored potentiometrically using simple PVC electrodes

Four sensitive catalytic potentiometric methods have been developed for trace levels determination of iodide based on its catalytic effects on the oxidation of four dyes: viz. variamine blue (VB), rhodamine B (RB), methylene blue (MB) and malachite green (MG), with H₂O₂ in H₃PO₄ medium at 25 ± 0.5 °C. The catalyzed reaction rates were estimated potentiometrically by monitoring the potential of the corresponding dye-PVC ion selective electrodes. To select the optimized reaction conditions offering the highest sensitivity of the method, parallel studies were carried out on each dye catalyzed reaction including: the effect of reactant concentration, reaction medium and temperature. The working calibration curves were linear over the concentration range from 0.32 to 2.54 mg L⁻¹ iodide for VB method and from 3.2 to 12.7 mg L⁻¹ for other ones. The tolerance limits of more than 20 interfering species were listed indicating the high selectivity of the method. Trace iodide in edible salt and pharmaceutical samples was determined without the need for separation or preconcentration procedures.     

Ultra-high capacity liquid chromatography chip/quadrupole time-of-flight mass spectrometry for pharmaceutical analysis

Nanoflow liquid chromatography/mass spectrometry (nano-LC/MS) has attracted increasing interest in virtue of high sensitivity, low sample consumption, and minimal matrix effect. In this work a HPLC-Chip/quadrupole time-of-flight (Q-TOF) MS device with a new ultra-high capacity small molecule chip (UHC-Chip) which features a 500 nL enrichment column and a 150 mm × 75 μm analytical column, was evaluated with a drug mixture covering a wide range of polarities. Excellent chromatographic precision with 0.1-0.5% RSD for retention time and 1.7-9.0% RSD for peak area, low limit of detection, good chip-to-chip reproducibility and linearity were obtained by using this UHC-Chip. Compared with the standard HPLC-Chip with 40 nL trapping column, the UHC-Chip showed higher enrichment capability and hence gave a higher response in signal detection. Additionally, 4-30 times increase in sensitivity was obtained compared with conventional LC/MS, which indicated that UHC-Chip/MS was a valuable tool for the quantitative analysis of low level impurities and degradation products in pharmaceuticals. Moreover, satisfactory results obtained from trace drug analysis of serum samples further proved its practicality and potential for use in drug testing and development.     

PMR Spectrometric Analysis of Tolmetin Sodium in Capsules Forms

An analytical method is described for the assay of tolmetin, 1-methyl-5-(4-methylbenzoyl)-1H-pyrrole-2-acetic acid, as sodium salt, (Tolectin[rgrave] - 200 mg) using PMR. The protocol reported in this study is simple, precise and yields accurate results of 99.78±0.84 and 100.67±2.08 for the authentic material and capsules respectively. In addition, the PMR spectrum obtained provides a means for qualitative identification of the drug and checking its purity. The principle of the method involves comparison of the integral of the well-defined singlet (positioned at 2.41 Δ) to that of the sharp singlet due -CH₃ (positioned at 1.91 Δ) of sodium acetate as an internal standard in presence of maleic acid using DMSO-d₆ solvent. The rationale for the use of maleic acid in the assay procedure has been discussed.     

Least-squares finite element formulations for one-dimensional radiative transfer

We present least-squares-based finite element formulations for the numerical solution of the radiative transfer equation in its first-order primitive variable form. The use of least-squares principles leads to a variational unconstrained minimization problem in a setting of residual minimization. In addition, the resulting linear algebraic problem will always have a symmetric positive definite coefficient matrix, allowing the use of robust and fast iterative methods for its solution. We consider space-angle coupled and decoupled formulations. In the coupled formulation, the space-angle dependency is represented by two-dimensional finite element expansions and the least-squares functional minimized in the continuous space-angle domain. In the decoupled formulation the angular domain is represented by discrete ordinates, the spatial dependence represented by one-dimensional finite element expansions, and the least-squares functional minimized continuously in space domain and at discrete locations in the angle domain. Numerical examples are presented to demonstrate the merits of the formulations in slab geometry, for absorbing, emitting, anisotropically scattering mediums, allowing for spatially varying absorption and scattering coefficients. For smooth solutions in space-angle domain, exponentially fast decay of error measures is demonstrated as the p-level of the finite element expansions is increased. The formulations represent attractive alternatives to weak form Galerkin finite element formulations, typically applied to the more complicated second-order even- and odd-parity forms of the radiative transfer equation.     

Infrared-induced conformational isomerization of ethylene glycol in a low-temperature argon matrix

The paramagnetic BrO₂ molecule with lifetime τ > 10 s has been found amoung the products of the O + Br₂ reaction in a discharge flow system. Identification was made by the technique of molecular beam focusing in an inhomogeneous magnetic field with mass-spectrometric detection. Its symmetry appeared to be C₂, like the stable OClO molecule, as was determined by focusing in an inhomogeneous electric field. Approximate rate constants for the reactions O + BrO₂ (k₃ = (2.5–6)×10^?12 cm³/s) and Br + BrO₂ (k₇ = 5 × 10^?11 cm³/s) were obtained.     

Strong duality for a special class of integer programs

A pair of primal-dual integer programs is constructed for a class of problems motivated by a generalization of the concept of greatest common divisor. The primal-dual formulation is based on a number-theoretic, rather than a Lagrangian, duality property; consequently, it avoids the dualitygap common to Lagrangian duals in integer programming.This research was partially supported by the National Science Foundation, Grant No. DCR-74-20584     

Determination of volatile residual solvents in pharmaceutical products by headspace liquid-phase microextraction gas chromatography-flame ionization detector

This paper demonstrates headspace liquid-phase microextraction (HS-LPME) as used for the determination of volatile residual solvents in pharmaceutical products. This method is based on headspace liquid-phase microextraction capillary column gas chromatography. Under optimum conditions, the linerary of the method ranged from 1 to 1,000 mg l⁻¹. The limits of detection are 0.2–2.0 mg l⁻¹ and relative standard deviations (RSD) for most of the volatile solvents were below 10%. This novel method is applied to the analysis of volatile residual solvents in pharmaceutical products with satisfactory results.