Determination of lithium in pharmaceutical formulations used in the treatment of bipolar disorder by flow injection analysis with spectrophotometric detection

In this work, a flow injection system with spectrophotometric detection was developed for the determination of lithium in pharmaceutical formulations used in the treatment of bipolar disorder. Reaction between Quinizarine (1,4-dihydroxyanthraquinone) and Li(I) ion in alkaline medium containing dimethylsulfoxide (DMSO) was explored for this purpose. The flow system was optimized regarding to its chemical (DMSO, Quinizarine and NaOH concentrations and sample pH) and physical parameters (sample loop volume, carrier flow rate and reactor length) in order to establish better conditions in terms of sensitivity and sampling frequency. The results obtained showed that the concentration of DMSO in the reagent solution presents remarkable influence on the magnitude of analytical signal. Chemical species that could be found in the formulations such as Na(I), K(I), Mg(II), Ca(II), Ti(IV), Cl⁻, CO₃²⁻ e sodium dodecylsulfate were tested as possible interfering ions. Among them, only non-monovalent cations presented noticeable interference on lithium signal. However, they were not found in concentrations high enough to cause interference in the determination of lithium in the samples. Sample preparation was performed by sonicating a slurry prepared by dispersing 100 mg of powdered sample in 15 mL of 0.10 mol L⁻¹ HCl solution. Results obtained by developed methodology were not statistically different from those obtained by flame emission spectrometry. In the optimized conditions the method presented a linear range of 5-40 mg L⁻¹ and a relative standard deviation of 3.6% at 5 mg L⁻¹ Li concentration. Detection and quantification limits were 0.54 and 1.8 mg L⁻¹, respectively. Sampling frequency, calculated as the time interval passed between two consecutive injections, was 60 samples per hour. The methodology was successfully applied in the determination of lithium in three commercial samples.     

Characterization of cyclodextrin-modified infrared chemical sensors: Part I. Modeling the mechanisms of interaction

To explore the properties of cyclodextrins (CDs) as an optical sensing phase, the behavior of immobilized CD in interaction with analytes was studied in this work. CDs having different cavity sizes were immobilized onto the surface of infrared (IR) internal reflection-sensing element (IRE) to kinetically monitor the behavior of CD in interaction with analytes. Several aromatic compounds having various molecular sizes and functional groups were used to characterize the interaction mechanism. A two-layer modification method was proposed in this work, which utilized a thin hydrophobic film (polyvinyl benzyl chloride) to stick on the IRE and to covalently bond to the CDs through an ethylene diamine linker. The synthesized CD phases exhibited high stability in aqueous solution. To analyze the behavior during the formation of complexes between the guest molecules and the CD phases, we modeled the interaction behavior and treated the kinetic data with the theoretical equations developed in this work. The results indicate that the behavior of the interaction between guest molecules and CDs was explained by considering the formation of two types of complexes: adsorbed complexes and inclusion complexes. The formation of the inclusion complexes was relatively fast, the time required to reach equilibrium could be shorter than a few minutes. The adsorbed complexes were also observed, but their rate of formation was relatively slow; equilibrium could be reached at times greater than 60 min. Based on the signals observed under equilibrium conditions, the concentration of inclusion complexes was approximately three times than that of the adsorbed complexes.     

动力学电位法测定硼

本文根据硼酸，苯乙醇酸，孔雀绿形成三元离子缔合型配合物的反应，用孔雀绿离子选择性电极监测反应速率，在最佳实验条件下，用固定时间法，电位变化与硼量在０．２－５．０μｇ／ｍＬ范围呈线性关系，用於测定标准钢样和玻璃标样中的硼，结果与标准值十分接近。     

Characteristic features of intra- and intermolecular interactions in crystals of pyrrole-2-carbaldehyde isonicotinoylhydrazone and its hydrate

Pyrrole-2-carbaldehyde isonicotinoylhydrazone (1) and its hydrate [1·H₂O] (2) were studied by single-crystal X-ray diffraction analysis. The introduction of the pyrrole substituent into N"-substituted isonicotinic hydrazide (INH) causes the intramolecular redistribution of the electron density compared to those in INHs studied earlier, which increases the basicity of the hydrazone nitrogen atom (N") involved in intermolecular hydrogen bonding. This effect has not been observed in the structures of N"-substituted INHs and benzhydrazides studied previously. Intermolecular hydrogen bonds play a decisive role in the formation of the crystal structures of 1 and 2.     

Ion-selective electrode for gallium determination in nickel alloy, fly-ash and biological samples

A poly(vinyl chloride)-based membrane of 2,9-dimethyl-4,11-diphenyl-1,5,8,12-tetraazacyclotetradeca-1,4,8,11-tetraene (DDTCT) with sodium tetraphenyl borate (STB) as an anion excluder and dibutyl phthalate (DBP), dibutyl butylphosphonate (DBBP), tris(2-ethylhexyl) phosphate (TEP) and tributyl phosphate (TBP) as plasticizing solvent mediators was prepared and investigated as a Ga(III)-selective electrode. The best performance was observed with the membrane having the ligand-PVC-DBP-STB composition 1:4:1:1, which worked well over a wide concentration range (1.45 × 10⁻⁶ to 0.1 mol L⁻¹) with a Nernstian slope of 28.7 mV per decade of activity between pH 4.0 and 10.0. This electrode showed a fast response time of 12 s and was used over a period of 100 days with good reproducibility (s = 0.3 mV). The selectivity coefficients for monovalent, divalent and trivalent cations indicate excellent selectivity for Ga(III) ions over a large number of cations. Anions such as Cl⁻ and SO₄²⁻ do not interfere and the electrode also works satisfactorily in partially water-alcohol medium. The practical utility of the membrane sensor has also been observed in solutions contaminated with detergents, i.e., cetyltrimethylammonium bromide and sodium dodecyl sulfate and used for the determination of gallium in nickel alloy, fly-ash and biological samples.     

Sesquiterpene Lactones from <Emphasis Type="Italic">Stizolophus balsamita</Emphasis> and Their Biological Activity

Four sesquiterpene lactones with the germacrane structure were isolated from the aerial part of Stizolophus balsamita. X-ray structure analyses showed that two of them were previously known balsamin derivatives. A third was a crystalline isomorphous mixture of the known lactone stizolin and 11,13-dihydrostizolin in a 53:47 ratio. The biological activities of the balsamin derivatives were investigated. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 454–457, September–October, 2005.     

Electronic structure and conformational flexibility of 1,2-dihydropyridine, 1,2- and 1,6-dihydropyrimidines,and their ylide derivatives

Molecular and electronic structures of 1,2-dihydropyridine, 1,2- and 1,6-dihydropyrimidine, and their oxo, imino, and methylene derivatives were studied by the semiempirical quantum-chemical AM1 method. In all compounds, the heterocycle exhibits a high conformational flexibility. The transition from a planar equilibrium conformation to a distorted sofa conformation with the =C-NH-C-C(N)= torsion angle of ±20° causes an increase in the energy by less than 1.7 kcal mol^–1. All molecules have similar -electronic structures, which, apparently, determines the similarity in their conformational behavior. The bending strain and the nonaromatic character of the cyclic -system are the factors that stabilize the nonplanar conformation of the ring in unsubstituted dihydroazines and ylide derivatives, respectively.Translated fromIzvestiva Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1934–1937, August, 1996.     

HPLC determination of urinary 2,4- and 2,6-toluendiamines as potential degradation products of polyurethane breast implants

Summary A reversed-phase HPLC method has been developed for the urinary determination of mutagenic 2,4- and 2,6-toluendiamines. These amines are degradation products of polyurethane, a material used to cover textured silicone breast implants. FMOC-Cl was used as fluorescent derivatising agent in order to obtain a limit of detection of 15 ng/ml in urine. Pre-treatment of urine samples was by liquid/liquid extraction and urine specimens of patients after surgury were analysed.     

Error Levels of Different Methods of Evaluation of TG Measurements

It follows from an analysis of the error levels of TG evaluation methods that it is a conceptual error to disregard the analogies of mass, energy and momentum streams of subordinate partial processes. This error is bypassed by means of the introduced method of dimensionless analysis and by determining the characteristic, constants-like data of thermal processes by using the measured data directly. These methods are very suitable for increasing the consistency of the calculated results by seeking for similarity, even in comparisons of measurements made under very different conditions and for emphasizing the differences too, quantitatively. With this new interpretation of TG processes, the idea of the kinetic compensation effect becomes only a consequence of the discussed conceptual error. This revised version was published online in August 2006 with corrections to the Cover Date.     

Diffusion-based calibration for solid-phase microextraction of benzene, toluene, ethylbenzene, p-xylene and chlorobenzenes from aqueous samples

Short-term solid-phase microextraction (SPME) was performed to test a recently proposed semi-empirical model for the prediction of concentrations of analyte in water samples from the fibre-extracted mass without further calibration. The mass uptake rates obtained for benzene, toluene, ethylbenzene and p-xylene (BTEX) differ considerably from the before published, showing that interfibre comparability is a serious issue. The relative prediction errors are between -55% for benzene and +82% for p-dichlorobenzene under optimal conditions, i.e. they are by an order of magnitude higher than originally published. A sensitivity analysis shows the dominant influence of the estimated thickness of the diffusional boundary layer around the fibre on the concentration predicted. Empirical modification of the model equation for this parameter yields satisfactory results under the conditions tested for both BTEX and the selected chlorobenzenes.