Anion separations for liquid chromatography using propylpyridinium silica as the stationary phase.

This work describes the characterization and potential applications of a silica-based anion-exchange phase prepared by a two-step modification process that incorporates a propylpyridinium group. The effects of pH and eluent concentration on anion separation were examined using 150 mm × 3.9 mm HPLC columns packed with the new phase. The mobile phase pH values ranged from 3.8 to 6.6 using phthalic acid/Tris solutions. The best separation was achieved using 2.5 mmol L(-1) phthalate/2.4 mmol L(-1) Tris solution at pH 4.2 as mobile phase with non-suppressed conductivity detection. The new stationary phase was used for the separation of some inorganic and organic anions showing good resolution. The stability of the silica-based anion exchange phase was also evaluated. Analytical curves, for concentrations ranging from 0.25 to 10 mg L(-1) for the inorganic anions chloride, nitrite, bromide and nitrate, showed good linear correlations (r>0.998). The method was tested with certified rainwater samples. The measured and certified values were in good agreement, indicating that the new phase holds significant promise for the analysis of these anions in environmental samples.

Development of a polymer-coated stationary phase with improved chemical stability in alkaline mobile phases.

An endcapped stationary phase is prepared by thermal immobilization of poly(methyltetradecylsiloxane) (PMTDS) onto a doubly zirconized silica support followed by endcapping using a mixture of hexamethyldisilazane and trimethylchlorosilane. The preparation of the Si-Zr(PMTDS)ec phase shows good repeatability with RSD <3.0% for carbon loadings and column efficiency. This new stationary phase has a lower density of residual hydroxyl groups, according to spectroscopic methods while basic compounds from the Tanaka and Engelhardt test mixtures are eluted with essentially symmetric peaks. Furthermore, the stability of the Si-Zr(PMTDS)ec stationary phase, measured using an accelerated aging test, is twice as great as the stability of a similar nonendcapped phase. The new phase shows promise for the separation of basic pharmaceuticals.

A new generation of more pH stable reversed phases prepared by silanization of zirconized silica.

To further extend our studies in the search for reversed phases with enhanced durability at high pH, zirconized silica has now been explored as an alternative support. The synthesis of the new stationary phases involves silanization of a zirconium-modified silica support with a C(18) trifunctional silane, followed by endcapping. The chromatographic properties of the C(18) phases based on zirconized silica are similar to their titanized silica counterparts. Accelerated high pH stability tests, using phosphate mobile phases and elevated temperature, have shown that the zirconized silica phases have promising advantages not only over similarly prepared non-metalized phases but also over titanized silica C(18) phases.

Aminopropyl-modified magnesium-phyllosilicates: layered solids with tailored interlayer access and reactivity.

Despite its wide application, the synthesis of aminopropyl-modified magnesium-phyllosilicates was known only in the case where every silicon atom bore an organic pending group. This paper shows the preparation of aminopropyl-modified talc where tailored amounts of silicon atoms are bound to an aminopropyl group. The decrease in the concentration of the organoamino group leaves a proportional concentration of interlayer SiOH groups that can be used to react with other silylation agents. The amino group reacts with CO2, forming a carbamate functionality; it seems that the presence of this group avoids delamination in water as performed for the parent compound. Bearing in mind that the aminopropyl group can be changed by other groups, the present synthesis strategy demonstrates ways to produce solids with controlled surface properties with interlayer amino and SiOH groups in variable concentrations, allowing formation of several other interlayer functionalities.

An overview of the chromatographic properties and stability of C18 titanized phases.

Phases based on titanized silicas are an alternative in the search for HPLC stationary phases with enhanced pH stability. This technology explores the chemical modification of the bare silica surface by grafting a titanium oxide layer with the objective of retarding the dissolution of the support in alkaline mobile phases, followed by C18 silanization. The present manuscript describes recent work on the development of chemically bonded titanized phases, including phases containing embedded urea groups, and phases prepared both in the absence and in the presence of a monolayer of water preadsorbed onto the bare silica. The advantages and disadvantages of these alternative C18 titanized phases are discussed, taking into account their chromatographic properties accessed by some common test procedures. Column lifetimes, measured by accelerated aging tests using aggressive conditions, such as high-pH phosphate mobile phases and elevated temperature, are also discussed.

Spin transition in magnesiowüstite in earth's lower mantle.

Iron in the major lower mantle (LM) minerals undergoes a high spin (HS) to low spin (LS) transition at relevant pressures (23-135 GPa). Previous failures of standard first principles approaches to describe this phenomenon have hindered its investigation and the clarification of important consequences. Using a rotationally invariant formulation of LDA + U we report a successful study of this transition in low solute concentration magnesiowüstite, (Mg(1-x)Fe(x)(O), (x < 0.2) the second most abundant LM phase. We show that the HS-LS transition goes through an insulating (semiconducting) intermediate mixed spins (MS) state without discontinuous changes in properties, as seen experimentally. We show that the HS state crosses over smoothly to the LS state passing through an insulating MS state where properties change continuously, as seen experimentally.

Influence of the TiO2 content on the chromatographic performance and high pH stability of C18 titanized phases.

To extend pH stability, protective metal oxide layers, such as titanium oxide, that are more stable in alkaline medium, can be chemically bonded to the chromatographic silica surface prior to reaction with silanes. In the present work, the influence of the titanium oxide content on the chromatographic performance was investigated by synthesizing a C18 phase onto a doubly-titanized silica support and comparing its chromatographic performance with a C18 phase on singly-titanized silica. The Engelhardt and Tanaka test mixtures were used for chromatographic characterizations using short HPLC columns. The column lifetimes of these titanized phases were also compared by performing accelerated aging tests at 50 degrees C using aggressive phosphate mobile phases at pH 10.

Preparation and characterization of a new C18 urea phase based on titanized silica.

A new stationary phase containing embedded urea groups (-NH-C(O)-NH-) was prepared by a procedure based on the synthesis of a trifunctional C18 urea-alkoxysilane, followed by modification of titanized silica and further endcapping to evaluate if the embedded group would minimize the higher retention and tailing for basic compounds seen with C18 titanized silica phases. Infrared, 13C and 29Si spectroscopies were employed to characterize the C18-urea titanized silica phase. Chromatographic evaluations used hydrophobic, polar and basic compounds to verify the effects of the polar urea groups embedded in the C18 urea phase. The chromatographic parameters, especially for the separation of basic compounds, compare favorably with those obtained on a C18 titanized silica stationary phase, prepared by silanization of titanized silica with octadecyltrimethoxysilane.

New stationary phase for anion-exchange chromatography.

This work describes the preparation of an anion-exchange phase based on silica, using a two-step modification process. First, 10 microm Davisil silica particles were silanized with chloropropyltrimethoxysilane to yield chloropropyl silica. The modified silica was then reacted with pyridine to produce positively charged propylpyridinium groups on the surface, the anion-exchange sites. The phase was characterized by thermogravimetric analysis and infrared and solid state 13C and 29Si NMR spectroscopies. HPLC separations of common inorganic anions, including chloride, nitrite, bromide and nitrate, were performed using 150 x 3.9 HPLC columns packed with the phase, using a phthalate buffer solution as mobile phase with non-suppressed conductivity detection. Efficiency and resolution were calculated and the results show that the new phase has significant promise for the analysis of these anions in environmental samples.

Titanized silicas, modified by C18, as promising stationary phases for high pH separations.

To enhance the high pH stability of silica based reversed phases, chemically bonded octadecyl phases were prepared through silanization of titanized silica particles containing approximately 14% titanium oxide on the surface. The present work describes some spectroscopic characterizations using infrared, solid-state 13C and 29Si nuclear magnetic resonance (NMR) and X-ray absorption spectroscopy (XAS). Chromatographic characterizations for the titanized phase as well as for a conventional C18 phase, based on the same silica support without titanization, are also described using three different test mixtures containing neutral, polar and basic compounds. After an artificial stability test at pH 10, the titanized phase was again characterized by elemental and X-ray fluorescence analyses to determine the remaining carbon and titanium contents. As an application to real world samples, the separation of some herbicides and highly basic drugs using buffered mobile phases are also shown.