Physico-chemical modelling of solute retention in reversed-phase HPLC with methanol-water mobile phase

Chromatographia - A relationship is derived for the retention parameter (i. e. the retardation coefficient, RF of a solute chromatographed in reversed-phase HPLC using methanol-water mixtures as...     

Physico-chemical measurements of CL-20 for environmental applications. Comparison with RDX and HMX

CL-20 is a polycyclic energetic nitramine, which may soon replace the monocyclic nitramines RDX and HMX, because of its superior explosive performance. Therefore, to predict its environmental fate, analytical and physico-chemical data must be made available. An HPLC technique was thus developed to measure CL-20 in soil samples based on the US Environmental Protection Agency method 8330. We found that the soil water content and aging (21 days) had no effect on the recoveries (>92%) of CL-20, provided that the extracts were kept acidic (pH 3). The aqueous solubility of CL-20 was poor (3.6 mg l(-1) at 25 degrees C) and increased with temperature to reach 18.5 mg l(-1) at 60 degrees C. The octanol-water partition coefficient of CL-20 (log KOW = 1.92) was higher than that of RDX (log KOW = 0.90) and HMX (log KOW = 0.16), indicating its higher affinity to organic matter. Finally, CL-20 was found to decompose in non-acidified water upon contact with glass containers to give NO2- (2 equiv.), N2O (2 equiv.), and HCOO- (2 equiv.). The experimental findings suggest that CL-20 should be less persistent in the environment than RDX and HMX.     

Industrial applications of SAW-sensors: on-line control of preparative HPLC

Results of on-line process control with an SAW-sensor based gas-sensor microsystem (SAGAS PC) are presented for industrial applications. The control of the solvent mixer of an HPLC-system was chosen as a typical example. All applications dealt with the detection and subsequent qualification as well as quantification of volatile organic compounds (VOC’s), e.g. organic solvents or even water by investigating their vapor. Mass-sensitive transducers, especially surface acoustic wave (SAW)-devices, have become a feasible tool for VOC-analytics. The measurement principle is based on frequency changes which are directly correlated with mass changes on the sensor surface and thus provide a particularly suitable signal transduction. The data analysis of all applications is based on pattern recognition methods, and focused on artificial neural networks for quantitative determination of these solvents and solvent-mixtures. The results obtained clearly showed the suitability of such a sensor system for on-line process-control purposes. Received: 25 September 1998 / Revised: 18 November 1998 / Accepted: 26 November 1998     

Industrial applications of SAW-sensors: on-line control of preparative HPLC

Results of on-line process control with an SAW-sensor based gas-sensor microsystem (SAGAS PC) are presented for industrial applications. The control of the solvent mixer of an HPLC-system was chosen as a typical example. All applications dealt with the detection and subsequent qualification as well as quantification of volatile organic compounds (VOC’s), e.g. organic solvents or even water by investigating their vapor. Mass-sensitive transducers, especially surface acoustic wave (SAW)-devices, have become a feasible tool for VOC-analytics. The measurement principle is based on frequency changes which are directly correlated with mass changes on the sensor surface and thus provide a particularly suitable signal transduction. The data analysis of all applications is based on pattern recognition methods, and focused on artificial neural networks for quantitative determination of these solvents and solvent-mixtures. The results obtained clearly showed the suitability of such a sensor system for on-line process-control purposes. Received: 25 September 1998 / Revised: 18 November 1998 / Accepted: 26 November 1998     

Recent analytical applications of fluorinated hydrocarbon-based stationary phases in HPLC

Fluorocarbon stationary phases have taken great advances in recent years in liquid chromatography. Numerous studies to elucidate the retention mechanism have been undertaken that concluded the retention is driven by a multitude of factors, due to the presence of fluorine atoms in the molecule. Many applications in this domain have been described in the literature so far. Applications for other fields have also been published in various original papers for fluorocarbon silica.     

Preparation and HPLC applications of rigid macroporous organic polymer monoliths

Rigid porous polymer monoliths are a new class of materials that emerged in the early 1990s. These monolithic materials are typically prepared using a simple molding process carried out within the confines of a closed mold. For example, polymerization of a mixture comprising monomers, free-radical initiator, and porogenic solvent affords macroporous materials with large through-pores that enable applications in a rapid flow-through mode. The versatility of the preparation technique is demonstrated by its use with hydrophobic, hydrophilic, ionizable, and zwitterionic monomers. Several system variables can be used to control the porous properties of the monolith over a broad range and to mediate the hydrodynamic properties of the monolithic devices. A variety of methods such as direct copolymerization of functional monomers, chemical modification of reactive groups, and grafting of pore surface with selected polymer chains is available for the control of surface chemistry. Since all the mobile phase must flow through the monolith, the convection considerably accelerates mass transport within the molded material, and the monolithic devices perform well, even at very high flow rates. The applications of polymeric monolithic materials are demonstrated mostly on the separations in the HPLC mode, although CEC, gas chromatography, enzyme immobilization, molecular recognition, advanced detection systems, and microfluidic devices are also mentioned.     

HPLC in clinical chemistry: Selected topics and clinical applications

Nowadays, HPLC is a very valuable tool in the clinical laboratory. In the future more and more HPLC methods will replace old photometric assays and also immunoassays, since these methods fulfill the claims in clinical chemistry: high precision, accuracy, sensitivity and specificity.     

Physico-chemical investigation of slag occurrences

Results of physico-chemical investigations of slag occurrences from site Rgotski Kamen (Timok region, Serbia), obtained by using chemical analysis, XRD analysis, EDXRF spectroscopy, thermal analysis, mass spectrometry and optical microscopy, are presented in this paper. This revised version was published online in August 2006 with corrections to the Cover Date.     

Physico-chemical investigation of asymmetrical peptidolipidyl-cyclodextrins

A new class of amphiphilic peptidolipidyl-cyclodextrins is reported. The derivatives are chiral due to the presence of an L-leucine in the spacer arm that links a saccharide moiety and a grafted, saturated hydrocarbon chain. Self-assembly properties of the peptidolipidyl-cyclodextrins are characterized by quasi-elastic light scattering, turbidity and UV-visible absorption measurements. NMR experiments give insight into the intermolecular dipolar interactions as a function of temperature and concentration. N-dodecyl-N alpha-(6 I-amidosuccinyl-6 1-deoxy-cyclomaltoheptaose)-L-leucine (1) is poorly soluble in aqueous media. N-dodecyl-N(alpha)-(6 I-amidosuccinyl-6 I-deoxy-2 I,3 I-di-O-methyl-hexakis-(2 II-VII,3 II-VII,6 II-VII-tri-O-methyl)-cyclomaltoheptaose)-L-leucine (2) is found to be more soluble and self-assembles into stable supramolecular colloidal aggregates with nanometric dimensions above a critical aggregation concentration (CAC). It has a propensity for solubilization of hydrophobic species revealing a micellar-like behavior, which is compared to that of the non-ionic detergent octyl glucoside. On the contrary, compound 1 precipitates in a crystalline phase beyond its water solubility limit, and it does not display any solubilizing capacity. The observed behavior corroborates at the molecular level with the NMR results.     

Physico-chemical behavior of bile salts

Roles and potential roles of bile salts in the human body and in health have been reviewed. The nomenclature of these biological amphiphiles, the mechanism of their formation in the liver and subsequent structural modifications in the enterohepatic cycle have been summarized. Emphasis has been placed on the controversies surrounding their physico-chemical properties, especially the patterns of their aggregation, and their ability to catalyze hydrolysis pathways in aqueous solution and to stimulate the activity of human milk lipase. The role of bile salts as biological surfactants and their participation in the dissolution of cholesterol gallstones, lipid solubilizatlon and absorption, and their ability to cause lysis of membrane surfaces has been discussed. Where possible, emphasis has been placed on the importance of the presence of monomers or small oligomers on the physico-chemical properties of these steroidal molecules.     

Physico-chemical properties of Chitosan films

Chitosan films obtained by dry phase inversion were prepared from an aqueous solution of chitosan in acetic acid. The films, of thickness less than 20 μm, were transparent, very flexible and had smooth surfaces. Increasing the film thickness induced an increase of the internal tensions and the consequent formation of a rough surface. Structural investigations by X-ray diffraction and Fourier transform IR analysis, showed that the chitosan films, as prepared, are amorphous. Further annealing to evaporate acetic acid and water traces, changed the amorphous phase into a more ordered phase, characterized by diffraction peaks at 2θ values of 9, 17, 20 and 23 degrees. Thermal investigations by TG, DTG, and DTA revealed that the decomposition of the chitosan films as prepared proceeds in two stages, starting from 180°C and 540°C.     

Physico-chemical applications of liquid chromatography I. Investigation of the adsorption of cardiac glycosides from water-ethanol solutions on silanized silica

Summary Using the cardiac glycoside cymarin as the example the application of liquid chromatography for the study of adsorption from solutions and the determination of the corresponding thermodynamic characteristics was investigated. The adsorption isotherm of cymarin at small concentrations from a water-ethanol solvent on silica gel modified by dimethyldichlorosilane was measured under static conditions using analytical LC to determine the concentrations of solutions after adsorption. The values of the Henry constants were obtained by extrapolating the slope of the adsorption isotherm down to zero concentration. The specific retention volumes for different but small sample sizes of cymarin in the chromatographic column were measured, the adsorbent and the water-ethanol eluent being the same as in the static conditions. The specific retention volume for a small (zero) sample size determined by liquid chromatography experiment coincides with the Henry constant of cymarin adsorption determined in static conditions. In favourable cases liquid chromatography can be used to determine the equilibrium constants for adsorption from solution. The dependence of the Henry constants on temperature was investigated for several cardiac glycosides. The influence of the modification of the adsorbent surface on the separation of the cardiac glycosides was also studied.     

Hydride-based silica stationary phases for HPLC: fundamental properties and applications

Silica hydride is a recent development in chromatographic support materials for HPLC where hydride groups replace 95% of the silanols on the surface. This conversion changes many of the fundamental properties of the material as well as the bonded stationary phases that are the result of further chemical modification of the hydride surface. The general approach for fabricating the silica hydride and subsequent bonded phases is reviewed. Properties of the silica hydride surface are compared to those of the standard material obtained in the preparation of most commercial HPLC stationary phases. Some unique chromatographic properties of hydride-based phases are described as well as some general application areas where these bonded materials may be used in preference to or have advantages not available from typical stationary phases.     

Physico-chemical properties of alginate gel beads

Alginate gel beads are used in many applications as matrices for release or immobilisation. Until now, the parameters (such as type and concentration of cation, ionic strength and pH) of the beads formation solution in which the Na-alginate solution was dropped were not deeply studied. Therefore, in this paper, the gel formation of alginate beads and their behavior in demineralized water has been investigated carefully. The results obtained in the present study about the gel formation showed that (1) the type and the concentration of the cation play a determinant role in the gel formation phenomenon giving beads of different volumes and characteristics; (2) the weight and volume losses occurring in the ‘syneresis’ are essentially by water elimination; (3) NaCl, which gives the ionic strength of the beads formation solution, plays two roles: a competitor with calcium and a screen in the electrostatic repulsion; and (4) finally, the pH controls the gel formation process as regulator in the dissociation of the alginate and in the complexation of the calcium cations. A study by weight change dynamic analysis was also carried out. The results showed that the transfer of a bead from its formation solution into demineralized water provokes a modification of its volume, weight and stability. These results are important to understand the behavior of beads in their utilization medium.     

Physico-chemical characterization of nanofiltration membranes.

This study presents a methodology for an in-depth characterization of six representative commercial nanofiltration membranes. Laboratory-made polyethersulfone membranes are included for reference. Besides the physical characterization [molecular weight cut-off (MWCO), surface charge, roughness and hydrophobicity], the membranes are also studied for their chemical composition [attenuated total reflectance Fourier spectroscopy (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS)] and porosity [positron annihilation spectroscopy (PAS)]. The chemical characterization indicates that all membranes are composed of at least two different layers. The presence of an additional third layer is proved and studied for membranes with a polyamide top layer. PAS experiments, in combination with FIB (focused ion beam) images, show that these membranes also have a thinner and a less porous skin layer (upper part of the top layer). In the skin layer, two different pore sizes are observed for all commercial membranes: a pore size of 1.25-1.55 angstroms as well as a pore size of 3.20-3.95 angstroms (both depending on the membrane type). Thus, the pore size distribution in nanofiltration membranes is bimodal, in contrast to the generally accepted log-normal distribution. Although the pore sizes are rather similar for all commercial membranes, their pore volume fraction and hence their porosity differ significantly.