Simple and rapid micellar electrokinetic capillary chromatographic method for simultaneous determination of four antiepileptics in human serum

A very rapid and simple MEKC method was developed for the simultaneous determination of four antiepileptic drugs, ethosuximide (Etho), primidone (Pri), phenytoin (Pht) and carbamazepine (Cbz) in human serum. Sample analysis required only 100 microL of human serum which only needed to be centrifuged, decanted and combined with the running buffer [5.3 mM Na(2)HPO(4)/3.2 mM borax buffer (pH 9.5) containing 55 mM SDS and 3.5% (v/v) acetone]. The analysis was performed in only 10 min into fused-silica capillaries (57 cm total length with 50 microm i.d. and 50 cm to the detector) using the MEKC methodology with diode-array detection at 220 nm. The calibration graphs were established for ethoximide, primidone, phenytoin and carbamazepine between 0 and 20 mg/L. Recoveries were between 85 and 87%. The simplicity of the proposed methodology makes it suitable for routine clinical use, especially for epileptic patients on polytherapy.     

Synthesis of 3-hexahelicenol and its transformation to 3-hexahelicenylamines,diphenylphosphine, methyl carboxylate,and dimethylthiocarbamate

A nonphotochemical synthetic route to 3-hexahelicenol is reported. It involves a key [2+2+2] cycloisomerization of CH(3)O-substituted triyne that is readily available from 1-methoxy-3-methylbenzene and 1-bromo-2-(bromomethyl)naphthalene. Further functional group transformations led to 3-CO(2)CH(3), 3-NH(2), 3-PPh(2), and 3-SC(O)N(CH(3))(2) substituted hexahelicenes.     

Molecular structure of di-aryl-aldimines by multinuclear magnetic resonance and X-ray diffraction

The complete ¹H, ¹³C and ¹⁵N NMR analyses for a series of 25 diaryl-aldimines containing phenyl, pyridyl, pyrazolone and furanyl moieties are described herein. Detailed evaluation of substituent chemical shift and coupling constant effects showed that interaction between the lone pair of the pyrazolone carbonyl group or the nitrogen of 2-substitued pyridines with the aldimine hydrogen increases the value and shifts the resonance signal for this hydrogen to high frequency, in the ¹H NMR spectra. The X-ray crystal structure analysis of pyrazolone substituted aldimines evidenced the planarity of the aryl groups which are conjugated with the CN double bond. In the case of the N-(2-pyridinemethylene)-1,5-dimethyl-2-phenyl-1,2-dihydro-pyrazol-3-one, two rotamers were observed in the same unit cell.     

Study of perrhenate reduction by capillary electrophoresis

The influence of perrhenate concentration, the concentration of the reducing agent and pH of the reaction mixture on the yield of perrhenate reduction were studied to find a possibility to decrease the stannous chloride concentration in the reaction mixture without negative changes on the yield of perrhenate reduction. Britton-Robinson buffer solutions were selected as the background electrolytes because of their buffering capacity in a wide pH interval. The highest degree of perrhenate reduction was obtained at pH 2 at perrhenate concentrations ranging from 10(-4) to 10(-3) mol/L. The stability of reduced rhenium against pH change from 2 to 5.5 and against dilution of rhenium in the reaction mixture to the concentration suitable for the application in radiotherapy were studied as well. The results obtained by capillary electrophoresis and by thin-layer chromatography with radiometric detection were compared.     

Synthesis and kinetics of polymerization of unsaturated monomers with OH groups in their structure: I.3-hydroxyneopentyl acrylate

The synthesis of new unsaturated monomers containing functional groups has been theoretically analyzed by considering a simple kinetic scheme. In the reactions between acetyl and acryloyl chloride with neopentylglycol, it was shown that the comparison between theoretical and experimental results, does not allow us to conclude that the two rate constants controlling the reactions are equivalent. Kinetic experiments of the polymerization of 3-hydroxyneopentyl acrylate were carried out in benzene and 1,4-dioxane solution at different temperatures. Dilatometric techniques and nonlinear least-squares methods were used to obtain kinetic data and to determine the kinetic constants, respectively. The values of $k_p /k_t^{1/2}$ for this monomer were found higher in dioxane than in benzene due, probably, to the fact that in the last solvent the polymerization is heterogeneous. The activation energy, determined by using different values of $k_p /k_t^{1/2}$ was found 7.6 kcal/mol. The stereostructure of the polymers derived from 3-hydroxyneopentyl acrylate and 3-acetoxyneopentyl acrylate was determined by ¹³C-NMR spectroscopy from the analysis of the resonance signals belonging to the carbonyl groups, obtaining values for the fraction of isotactic dyads in the range 0.36 ± 0.03 for both polymers. Finally, the glass transition temperatures of both polymers, determined calorimetrically, were found 281 and 255 K, respectively. © 1994 John Wiley & Sons, Inc.     

On the accuracy of correlation energy calculated by the correlation factor method: first- and second-row atoms

Summary The correlation energy of two- and four-isoelectronic series, a representative example for which the existing spin-density functionals fails, is calculated using the Colle and Salvetti method, considering mono- and multideterminantal wave functions. The results are in agreement with experimental data, and show the potentiality of this method when it is applied to wave functions including the most relevant configurational features. Also, results for the ionization energies and electron affinities of first- and second-row atoms are reported.     

Information content of data and variables and types of weighting in least-squares regression methods

Algorithms are given for evaluating the relative amount of useful information related to a particular parameter which is carried by individual data points and intervals of the variables. The algorithms provide an efficient means of using the information contained in a set of data. Applications to the optimization of weighting in regression methods are described. Several informational and combined informational-statistical types of weighting are studied as a means of improving the accuracy and precision of the parameters obtained by non-linear regression.     

Flow-injection determination of creatine in animal tissues

After deproteination of samples with trichloroacetic acid, creatine is determined by reaction with 1-naphthol and biacetyl, based on a stopped-flow method. The calibration graph is linear over the range 0–250 mg l^?1, and recoveries from muscle samples are quantitative.     

Fast determination of lead and copper in dairy products by graphite furnace atomic absorption spectrometry

A rapid and direct procedure for determining lead and copper in dairy products by electrothermal atomic absorption spectrometry (ETAAS) is described. Samples are slurried in a medium containing 50% v/v hydrogen peroxide, 1% v/v nitric acid, 0.5% w/v dihydrogen phosphate, and 20% v/v ethanol and directly injected into the furnace with no previous mineralization. Calibration is performed with aqueous standards. Limits of determination were 0.4 and 2.4 ng/mL for copper and lead, respectively. The reliability of the procedure was checked by comparison with the acid mineralization procedure and by analyzing 3 certified reference milk samples.     

Nitrogen bridgehead compounds part 21. Preparation of new quaternary 2,3a,6a-triazaphenalenium salts

The first representatives of a new ring system, the 2,3a,6a-triazaphenalenium quaternary salts are prepared by the cycloaddition of tetrahydro-4H-pyrido[1,2-a] pyrimidin-4-ones containing an α-chloroenamine moiety with azomethines.