Molar volumes and ion pairing of lithium halides in alcohols

The concentration dependence of the apparent molar volumes of lithium halides (and electrolytes in general) in alcohols (and solvents permitting association in general) is, in the first instance, due to changes in the degree of association and to the inherent difference between the apparent molar volumes of the ions and of the ion pairs. Previous publications on the molar volumes of electrolytes in organic solvents, disregarding altogether ion pairing, appear to be incorrect. Data from the literature for lithium chloride and lithium bromide in normal primary alcohols and several branched alcohols from C₁ to C₈ and data from our laboratory for lithium halides in 1-hexanol and 2-ethyl-1-hexanol served for the determination of φ _V and φ _E . Electrical and structural contributions to the values of these functions for the ions and for the ion pairs are discussed.     

NMR studies on the stereospecific polymerization of methyl vinyl ether. Part I. Polymerization by metal halides: Penultimate effect

Methyl vinyl ether (MVE) was polymerized under various conditions by BF₃·O(C₂H₅)₂ and SnCl₄·CCl₃CO₂H catalysts. The effect of polymerization conditions on the steric structure of poly(methyl vinyl ether) (PMVE) was studied by NMR spectra. It was found that the triad isotacticity of PMVE decreased and the syndiotacticity and heterotacticity increased with increasing polarity of the solvent and increasing polymerization temperature. This result coincided with the qualitative conclusion estimated from softening point and infrared spectra. However, the variation of tacticity by the change of the polarity of a solvent was not so large as expected. There was no large difference between the behavior of BF₃·O(C₂H₅)₂ and SnCl₄·CCl₃CO₂H as catalysts. From the relation between the difference of free energy of monomer addition due to the steric structure of the polymer and the polymerization temperature, it was concluded that the penultimate effect really existed and was due to only the difference in enthalpy in the MVE–BF₃. O(C₂H₅)₂ or MVE–SnCl₄·CCl₃CO₂H systems. The penultimate effect was not greatly changed by the polymerization conditions in these systems.     

Systematic optimization of micellar electrokinetic chromatographic separation of flavonoids

Summary A simple and rapid systematic optimization scheme was described for the micellar electrokinetic chromatographic separation of a group of flavonoids. The scheme employed an interpretative optimization approach to predict the optimum conditions for the separation of a group of flavonoids by micellar electrokinetic chromatography. By performing a set of nine pre-planned experiments conducted over the maximum working range for the system, global optimum separation conditions could be determined. To validate the optimization procedure, additional experiments were performed using the optimum experimental conditions derived from the optimization scheme. The results showed that satisfactory separation of all the peaks could be obtained. In addition, the application of the method in micropreparative micellar electrokinetic chromatography of the flavonoids was demonstrated.     

Pharmacokinetics of brain natriuretic peptide in rats.

The pharmacokinetics of rat brain natriuretic peptide (rBNP) was compared with that of alpha-rat atrial natriuretic peptide (alpha-rANP) in rats. After intravenous infusion in rats (600 pmol min-1kg-1 for 2 min), the disappearance of plasma rBNP was 4-fold slower than that of alpha-rANP. The estimated mean plasma clearance rates for rBNP and alpha-rANP were 45.9 ml min-1kg-1 and 74.4 ml min-1kg-1, respectively. The affinity of rBNP for the clearance receptor or degradation enzyme was considered to be lower than that of alpha-rANP.     

Small angle X-ray scattering study of an extremely elongated micelle system of CTAB-p-toluidine solution

Whenp-toluidine is added to an aqueous solution of CTAB, a remarkable increase of viscosity is accompanied by a spectacular elasticity. We detected the existence of extremely elongated rod-like micelles in electron micrographs. SAXS measurements indicate a closely packed array of cylindrical rod-like micelles, brought about when solutions flow through a thin capillary. A scattering maximum ofd=160 Å almost corresponds to the distance between the nearest neighbours of the cylindrical rod-like micelles. This value agrees with the diameter measured on electron micrographs. The second broad peak (d=75 Å) is assigned to a subsidiary maximum of the shape function of the cylinder with infinite length.     

Simultaneous determination of R- and S-prenylamine in plasma and urine by reversed-phase high-performance liquid chromatography

A high-performance liquid chromatographic method for the determination of R- and S-prenylamine in human plasma and urine is described. It involves a two-step liquid-liquid extraction of prenylamine from biological material and preparation of diastereomeric urea derivatives with R-(-)-naphthylethyl isocyanate, a chiral fluorescence marker. Separation and quantitation of the diastereomeric prenylamine derivatives are carried out by a reversed-phase high-performance liquid chromatographic system with fluorimetric detection. The limit of determination is less than 2 ng of enantiomer per ml of urine and less than 1 ng of enantiomer per ml of plasma. A preliminary kinetic study on one healthy volunteer who had received a single oral dose of racemic prenylamine (100-mg film tablet) showed distinctly higher plasma and urine concentrations of the R-enantiomer.     

Fluorometric determination of aromatic aldehydes with 1,2-Diaminonaphthalene

A new fluorometric method for the determination of aldehydes is presented. 1,2-Diaminonaphthalene reacts with aldehyde in dilute sulphuric acid to give a compound which fluoresces intensely in alkaline medium. The fluorescences produced from aromatic aldehydes in this method are fairly characteristic of individual aldehydes and their intensities are generally higher than those of fluorescences from aliphatic aldehydes. The only interference is from 2-oxo acids. The method may be suitable for the determination of aldehyde in complex samples.     

Birefringence induite dans les directions remarquables d'une suspension de particules rigides en ecoulement

A theoretical formula is derived for the flow birefringence exhibited along the streamlines and in the direction of the shear rate (G) by dilute suspensions of rigid spheroid-like macromolecules; numerical values are computed up to σ = G/D = 900 (D = rotary diffusion coefficient). These results provide two tests for identifying prolate and oblate particles; when combined with the data for observation perpendicular to the plane of flow, they confirm the connection between non-Newtonian viscosity and the Maxwell effect for monodisperse samples; for vanishing rate of shear, they allow a mixture of particles to be characterized by means of a mean rotary diffusion constant ($\text{D}$) and a mean shape coefficient ($\text{R}$).     

Evolution of antibodies for environmental monitoring: from mice to plants

Immunoassays are one of the most convenient methods for environmental monitoring, but have been limited so far by low yield and low affinity antibodies (Abs). With the advent of recombinant Ab (rAb) technology and the expression of these Abs in organisms such as yeast, bacteria, insects and plants, widespread monitoring of our food and environment for organic contaminants using immunoassays has become feasible. A multitude of immunoassays have been developed to detect pesticides in soils, ground and river water, foods and biological samples, such as urine and semen. In this paper, we describe advances in Ab production, the move away from using animals, phage-display technologies and the advent of plant-derived Ab expression systems. Finally, we describe future possibilities in Ab technology for environmental monitoring.     

Accurate and rapid estimation on spectral interferences in routine analysis by ICP-AES: use of mutual interference coefficients

A practical method to estimate spectral interferences and to select optimum analytical lines in ICP-AES is suggested. Depending on the matrix composition and the amounts of the analyte, the analytical lines suffering from little interferences and the limit of determination can be determined from calculation using spectral interference coefficients. For this calculation, the spectral interference coefficients, which are defined as apparent mass of the analyte equivalent to the spectral interference from unit mass of the interferent, are obtained experimentally for 639 emission lines of 68 elements. There is a good correlation between the coefficients obtained on two spectrometers having different resolutions.