Determination of the pH of binary mobile phases for reversed-phase liquid chromatography

The measurement of pH in chromatographic mobile phases has been a constant subject of discussion during many years. The pH of the mobile phase is an important parameter that determines the chromatographic retention of many analytes with acid-base properties. In many instances a proper pH measurement is needed to assure the accuracy of retention-pH relationships or the reproducibility of chromatographic procedures. Three different methods are common in pH measurement of mobile phases: measurement of pH in the aqueous buffer before addition of the organic modifier, measurement of pH in the mobile phase prepared by mixing aqueous buffer and organic modifier after pH calibration with standard solutions prepared in the same mobile phase solvent, and measurement of pH in the mobile phase prepared by mixing aqueous buffer and organic modifier after pH calibration with aqueous standard solutions. This review discusses the different pH measurement and calibration procedures in terms of the theoretical and operational definitions of the different pH scales that can be applied to water-organic solvent mixtures. The advantages and disadvantages of each procedure are also presented through chromatographic examples. Finally, practical recommendations to select the most appropriate pH measurement procedure for particular chromatographic problems are given.     

On distribution of molecular weight in anionic polymerizates of caprolactam

Measurement has been made of the dependence of the molecular weight distribution on the ratio of the catalytic system components and on the polymerization time for polycaprolactam obtained by anionic polymerization. A bimodal character of the curves was observed for products made using molar ratios of activator (N-benzoylcaprolactam) to initiator (sodium dihydro-bis(methoxyethoxy)aluminate) of 1:1 and 1:3, when the polymerization times were less than 1 hr. This course is explained by the influence of fast side-reactions, mainly condensations. For a ratio of 3:1 of the components of the catalytic system, smooth integral distribution curves are obtained, accounting for a very fast decrease in the strong base concentration in the initial stages of the polymerization.     

Geometrical structure of yttrium and metal-bromine complexes in solution: limitations of extended X-ray absorption fine structure analysis (EXAFS)

An extensive study on the appearance of multi-electron features in the X-ray absorption spectra of several yttrium(III)-based compounds has been performed. The existence of a multi-electron transition of non-negligible intensity within the extended X-ray absorption fine structure (EXAFS) region of the Y K-edge spectra has been proven. The impact of such features in the EXAFS analysis is made evident for aqueous solutions of YBr3 x 6H2O in liquid and glassy states in the concentration range 0.005-2.0 M, in which this transition induces an overestimation in the coordination numbers derived from EXAFS. We have performed theoretical computation of cross-sections for the double-electron processes at the K-edge of both Y and Br. These computations have been applied to the experimental EXAFS K-edge spectra of both Y and Br in several solids and in aqueous solutions. While in the case of Y K-edge spectra the presence of such multi-electron transitions was seen to seriously affect the standard EXAFS analysis, its influence in the case of Br K-edge spectra was determined to be negligible.     

Reactions of pyrrolidine enamines of cyclic and acyclic 3,4-dioxobutanoic acid Derivatives with dimethyl acetylenedicarboxylate. A new case of atropoisomerism.

Reaction conditions and structure of the starting enamines (cyclic or open-chain) determine greatly the final products of the title reactions. Whereas in benzene and acetonitrile, DMAD and 1 give a mixture of the diastereoisomeric dienamines 5, in methanol they afford pirrolizine 3. Enaminofuranones 2 and 10 furnish the corresponding “Michael adducts” 7a,b,c and 11a,b,c but fail to yield pirrolizines. It has been demonstrated that above b and c adducts differ exclusively on the arrangement of groups around a chiral axis.     

Etude de la chloration du polychlorure de vinyle en fonction de sa tacticite

Polyvinyl chloride samples of various tacticity have been prepared and photochlorinated in CCl₄ for 4 hr. The chlorination degree correlates directly with the degree of syndiotacticity. Initial PVC with syndiotacticity about 56 per cent, which can be regarded as alternate sequences of syndiotactic and isotactic diads, is quickly chlorinated. The mechanism of chlorine attack on the macromolecula is directly connected with the stereoregularity.     

Thermodynamic parameters for the molecular inclusion reaction of dulcin with beta-cyclodextrin. spectrofluorimetric determination of dulcin

The inclusion of dulcin in alpha- and beta-cyclodextrin has been studied by fluorescence spectroscopy. To quantitatively describe complex formation between the beta-cyclodextrin and dulcin, an association constant of 290 M(-1) at 21 degrees was obtained. The thermodynamics associated with the complex formation between dulcin and beta-cyclodextrin in aqueous solution has been studied. The obtained value of DeltaG(0) = -13.7 kJ/mole at 21 degrees , together with DeltaH(0) = -33.6 +/- 2.3 kJ/mole and DeltaS(0) = -67.2 +/-8.3 Jmole(-1) K(-1) indicate that dulcin has a very marked tendency to associate with beta-cyclodextrin in water. The inclusion complex of dulcin in beta-cyclodextrin has been used to determine dulein in the range 0.13-5 mug/ml the method has been applied to determine dulcin in soft drinks.     

Analysis of primary aliphatic short-chain monoamines by LC in water samples

Several derivatization procedures with o-phthaldialdehyde-N-acetylcysteine (OPA-NAC) were compared for a rapid analysis of primary aliphatic short-chain monoamines in water samples by HPLC using a LiChorospher analytical separation column (100RP₁₈ mm i.d., 5 μm). Both the solution and the solid-support assisted off-line derivatization on C₁₈ SPE cartridges were inadequate options because of beginning degradation processes of the instable isoindol derivatives during their transfer to the analytical column. This problem was precluded with the on-column or solid-support assisted on-line derivatization. In the last mentioned procedure, the derivatization took place in a Hypersil C₁₈ precolumn ( mm i.d., 30 μm) connected with an additional preconcentration step resulting in better detection limits (0.002-0.040 μg ml⁻¹ requiring only 150 μl of water sample) than in the on-column procedure (0.08-0.16 μg ml⁻¹). The improved sample handling, the better control of parameters affecting reaction rates, the fully automation of this method with only 10 min analysis time for each sample are further advantageous. The potential of the solid-support assisted on-line derivatization was outlined and applied to water samples from several sources. Recovery values near 100% were obtained.     

Rapid determination of aliphatic amines in water samples by pressure-assisted monolithic octadecylsilica capillary electrochromatography-mass spectrometry

A pressure-assisted capillary chromatography-mass spectrometry method based on the use of a monolithic octadecylsilica (ODS) capillary is proposed for the determination of aliphatic amines. A 25 mM citric acid buffer containing 10% methanol is used as running electrolyte. Separation is achieved by simultaneously applying a capillary electrophoresis (CE) voltage of 13 kV and an overimposed pressure of 8 bar. The use of pressure is required to ensure stable electrospray conditions. Analysis times are reduced by using a capillary column consisting of a 30 cm long monolithic silica capillary column bound with ODS and a fused-silica capillary column also 30 cm long. The proposed method was successfully applied to the determination of low-molecular-weight aliphatic amines in tap and river water. The analysis of real samples requires cleanup and preconcentration, which can be performed automatically by inserting a minicolumn in the replenishment system of the commercial instrument.     

On-line sorbent extraction, preconcentration and determination of lead by atomic absorption spectrometry

A method for the quantitative preconcentration of lead based on an existing batch process was developed for implementation in a flow system including a flame AAS detector. Lead can be quantitatively preconcentrated as pyrrolidinedithiocarbamate or dithizonate on an activated carbon minicolumn. The chelates are eluted in methyl isobutyl ketone and introduced directly into the nebuliser-burner. An enrichment factor of 50 is typically obtained for a preconcentration time of 2 min (lead can be determined at concentrations between 15 and 400 ng/ml), which results in a throughput of ca. 25 samples per hr. The sensitivity achieved with the two reagents is similar, but the selectivity provided by APDC exceeds that of dithizone. Based on the results obtained in the determination of lead in reference materials (minerals and skim milk), the proposed APDC method is applicable to real samples.     

Reconocimiento de nicotina en una hebrita de tabaco

Summary Adaption of theLuís method for the detection of nicotine to microscale, usingEmich's capillary technic proved successful, attaining identification limit of 0,03g.Applying a sub-micro steam distillation effect, the nicotine in a speck of tobacco (1 mm² and less) could still be detected by using the above reaction.Extension of the above procedure to mixtures of nicotine with substances not volatile with steam, inorganic (halides) as well as organic compounds (other alkaloids, acids, etc.) proved to be successful, even when the nicotine is present in proportions of only 1 part in 1000.

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Zusammenfassung Die Anwendung der Kapillartechnik vonEmich zum Nachweis von Nikotin nachLuís war erfolgreich und zeigte eine Erfassungsgrenze von 0,03g.Bei Anwendung einer Ultramikrodampfdestillation kann das Nikotin nach obiger Methode noch in Spuren von Tabak (1 mm² und weniger) nachgewiesen werden.Die Reaktion ist auch positiv bei Gemischen von Nikotin mit anderen, mit Wasserdampf nicht flüchtigen sowohl anorganischen (Halogenide) als auch organischen Substanzen (andere Alkaloide, Säuren etc.), selbst dann noch, wenn das Nikotin bloß im Verhältnis von 11000 vorhanden ist.

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Résumé La technique capillaire d'Emich a été utilisée avec succès pour identifier la nicotine suivant le procédé deLuís; la limite de sensibilité est alors de 0,03g. La mise en oeuvre d'un ultramicroentraînement à la vapeur permet en outre, par application de la précédente méthode, d'identifier la nicotine dans des traces de tabac (moins de 1 mm²). La réaction est également positive en présence d'autres substances non entraînables par la vapeur d'eau, qu'elles soient minérales (halogénures) ou organiques (autres alcaloïdes, acides, etc. ...) même si la proportion de nicotine n'est que de l'ordre de grandeur de 1/1000.