Porous graphitic carbon as stationary phase for LC-ICPMS separation of arsenic compounds in water

A new liquid chromatographic separation method was developed for the speciation of the four main arsenic compounds present in water. Arsenite (As(III)), dimethylarsinic acid (DMA), monomethylarsonic acid (MMA) and arsenate (As(V)) were separated on a recently introduced stationary phase: porous graphitic carbon (PGC). The separation was first obtained under formic acid gradient conditions, but an adsorption phenomenon of As(V) on PGC was observed. To overcome this problem, As(V) was backflushed, and an efficient separation of the four solutes was achieved within 10 min. Extremely low detection limits (ranging from 10 to 70 ng x L(-1)) were obtained by coupling LC with an ICPMS. The method was successfully applied to different spiked mineral waters and a naturally arsenic-containing freshwater.     

Simultaneous enhancement of separation selectivity and solvent strength in reversed-phase liquid chromatography using micelles in hydro-organic solvents

The role of micelles and organic solvents as the modifiers of the aqueous mobile phase in reversed-phase liquid chromatography (RPLC) in controlling retention and selectivity is discussed. Elution strength increases in RPLC with an increase in organic solvent or micelle concentration. Simultaneous enhancement of separation selectivity with elution strength in the hybrid eluents of water-organic solvent-micelles was observed. This selectivity enhancement occurs systematically, i.e. peak separation increases monotonically with volume fraction of organic solvent added to micellar eluent, and is observed for a large number of ionic and nonionic compounds with different functional groups and for two surfactants (anionic and cationic). For two test mixtures, 13 amino acids/peptides and 15 phenols, it is shown that a better separation and shorter analysis time are observed at stronger hybrid eluents. This selectivity enhancement can be attributed to the competing partitioning equilibria in micellar LC systems and/or to the unique characteristics of micelles to compartmentalize solutes and organic solvents.     

Factor analysis and experiment design in high-performance liquid chromatography: IV. Influence of mobile phase modifications on the selectivity of chalcones on an ODS stationary phase

Walczak, B., Chrétien, J.R., Dreux, M., Morin-Allory, L. and Lafosse, M., 1987. Factor analysis and experiment design in high-performance liquid chromatography. IV. Influence of mobile phase modifications on the selectivity of chalcones on an ODS stationary pase. Chemometrics and Intelligent Laboratory Systems, 1: 177–189.Chromatographic data were determined for a series of 45 chalcones (E-s-cis and Z-s-cis), separated in systems with Zorbax ODS and heptane + 0.5% of a modifier (tetrahydrofuran, dioxane, ethanol, propanol, octanol or dimethylformamide). To discuss changes in chalcone selectivity arising from mobile phase modifications data processing is carried out with the help of hierarchical ascending classification and correspondence factor analysis. The same methods of analysis are used to compare chalcone selectivity in systems with stationary phases of different polarity (Zorbax ODS and LiChrospher 100 DIOL), and with the same mobile phases. A better understanding of retention mechanism is obtained.     

Retention and separation of adenosine and analogues by affinity chromatography with an aptamer stationary phase

A biotinylated-DNA aptamer (molecular weight 16,600) that binds adenosine and related compounds in solution was immobilized by reaction with streptavidin, which had been covalently attached to porous chromatographic supports. The aptamer medium was packed into fused-silica capillaries (50-150-microm i.d.) to form affinity chromatography columns. Frontal chromatography analysis indicated that the dissociation constants (Kd) of cyclic-AMP, AMP, ATP, ADP, and adenosine were 138 +/- 18, 58 +/- 2, 38 +/- 2, 28 +/- 6 and 3 +/- 1 microM, respectively, for aptamer immobilized on a controlled pore glass support. Similar values were obtained for aptamer immobilized on a polystyrene support except for a slightly higher Kd for adenosine. The Kd for adenosine is similar to the previously reported value of 6 +/- 3 microM for adenosine-aptamer in solution indicating that immobilized aptamers can have affinity similar to that of the solution forms. Columns had 20 nmol of binding sites/100 microL of support media, which is 3.3-fold higher than that previously reported for immobilization of IgG on similar media, indicating that the aptamer can be immobilized with higher density than antibodies. Variation of mobile-phase conditions revealed that ionic strength and Mg2+ level had strong effects on retention of analytes while pH and buffer composition had less of an effect. It was demonstrated that the column could selectively retain and separate cyclic-AMP, NAD+, AMP, ADP, ATP, and adenosine, even in complex mixtures such as tissue extracts.     

Factor analysis and experiment design in high-performance liquid chromatography: III. Influence of mobile phase modifications on the selectivity of chalcones on a diol stationary phase

Walczak, B., Morin-Allory, L., Chrétien, J.R., Lafosse, M. and Dreux, M., 1986. Factor analysis and experiment design in high-performance liquid chromatography. III. Influence of mobile phase modifications on the selectivity of chalcones on a diol stationary phase. Chemometrics and Intelligent Laboratory Systems, 1: 79–90.Chromatographic data for a series of 45 chalcones were determined for eight chromatographic systems with LiChrospher 100 DIOL as the stationary phase and with heptane + 0.5% of a modifier (dichloromethane, tetrahydrofuran, ethanol, propanol, octanol, dimethylsulphoxide or dimethylformamide) as the mobile phase. Analysis of the data was carried out with the help of hierarchical ascending classification (HAC) and correspondence factor analysis (CFA). Such a strategy of data processing allows normal-phase high-performance liquid chromatography data to be treated as a source of information on the electronic and steric properties of compounds. CFA also helps to give a better insight into the chromatographic process.     

All-hydrocarbon liquid crystalline polysiloxane polymer as stationary phase in gas chromatography capillary column for separation of isomeric compounds of polynuclear aromatic hydrocarbons

Two new and high-purity all-hydrocarbon side-chain liquid crystalline polysiloxane polymers were synthesized by grafting all-hydrocarbon liquid crystal monomers onto a polymethylhydrosiloxane backbone. The two polysiloxane polymers show both smectic B and E mesophases which were characterized by (differential scanning calorimetry and X-ray analysis. As stationary phases, these liquid crystalline polysiloxane polymers were coated on the inner surface of a capillary column (i.d. = 0.32 mm, film thickness d(f) ≈ 0.25 μm) using the static coating method. The capillary column was installed on a GC/MS instrument. We used a standard commercial mixture of 21 species of polynuclear aromatic hydrocarbons (purchased from Supelco Co. and Merck Co.) to test the chromatographic behavior of the coated stationary phase. Test results of the isomeric pair compounds show a better separation resolution than identical tests using the commercial HP-5 capillary column, which is a standard and state-of-the-art analytical tool for the chromatographic resolution of PAHs.     

Elution-extrusion countercurrent chromatography. Use of the liquid nature of the stationary phase to extend the hydrophobicity window

Countercurrent chromatography (CCC) is a liquid chromatography technique with a liquid stationary phase. Taking advantage of the liquid nature of the stationary phase, it is possible to perform unique operations not possible in classical liquid chromatography with a solid stationary phase. It is easy to avoid any solute-irreversible absorption in the CCC column. If the retention volumes of solutes become too high, the dual mode will be used. The roles of the phases are reversed. The stationary phase becomes the mobile phase, and the CCC column is started again. The solutes elute rapidly in what was previously the stationary phase. The theoretical basis of the dual-mode method is recalled. The dual-mode method is a discontinuous method. The separation should be stopped when the phase switch is performed. The elution-extrusion procedure is another way to avoid any irreversible adsorption of solutes in the column. The method uses the fact that the liquid volumes occupied by the solutes highly retained inside the column can be orders of magnitude lower than the mobile-phase volume that would be needed to elute them. The elution-extrusion method also has two steps: the first step is a regular CCC chromatogram. Next, the stationary phase containing the partially separated hydrophobic solutes is extruded out of the column in a continuous way using the liquid stationary phase. The theory of the process is developed and compared to the dual-mode theory. Alkylbenzene homologues are experimentally used as model compounds with the heptane/methanol/water biphasic liquid system to establish the theoretical treatment and compare the performance of two types, hydrodynamic and hydrostatic, of CCC columns. It is shown that the method can dramatically boost the separation power of the CCC technique. An apparent efficiency higher than 20 000 plates was obtained for extruded octylbenzene and a 160-mL hydrodynamic CCC column with less than 500 plates when conventionally used.     

Analysis of the liquid phase during the course of crystallization of zeolite Y using an isothermal centrifugal separation technique

During the course of crystallization of zeolite Y, the liquid phase was separated centrifugally and isothermally. Excess Na⁺ ions were detected on the surface of the solid portion and decreased with increasing crystallinity. About 21 Na⁺ ions/192 T sites for amorphous precursor and 1–3 Na⁺ ions/192 T sites for well-crystallized Y were detected.     

Direct chromatographic determination of dissociation rate constants of ligand-receptor complexes: assessment of the interaction of noncompetitive inhibitors with an immobilized nicotinic acetylcholine receptor-based liquid chromatography stationary phase

A liquid chromatographic stationary phase containing immobilized membranes from a cell line expressing the alpha3beta4 subtype of the neuronal nicotinic acetylcholine receptor (nAChR) has been used to assess dissociation rate constants (kd) of 12 noncompetitive inhibitor-nAChR complexes. The pharmacological effects of the noncompetitive inhibitors, expressed as percent recovery of activity at 7 min and 4 h postexposure to the inhibitor, were also determined. The results demonstrate that the kd values correlated with the pharmacological effect and that this approach can be used to identify molecular structures associated with differences in kd values. The method can be adapted for use with membrane-bound receptors, ion channels, and transporters and represents a direct and facile technique for the assessment of dissociation rate constants (kd) of ligand-receptor complexes.     

Column precipitation chromatography: an approach to quantitative analysis of eigencolloids

A new column precipitation chromatography (CPC) technique, capable of quantitatively measuring technetium eigencolloids in aqueous solutions, is presented. The CPC technique is based on the destabilization and precipitation of eigencolloids by polycations in a confined matrix. Tc(IV) colloids can be quantitatively determined from their precipitation onto the CPC column (separation step) and their subsequent elution upon oxidation to pertechnetate by peroxide (elution step). A clean-bed particle removal model was used to explain the experimental results.     

Highly cross-linked self-assembled monolayer stationary phases: an approach to greatly enhancing the low pH stability of silica-based stationary phases

A new type of silica-based stationary phase with dramatically improved acid stability compared to any currently available silica-based stationary phase has been developed. Superior low pH stability is achieved by first self-assembling a densely bonded monolayer of (chloromethyl)-phenylethyltrichlorosilane (CMPES). The self-assembly step is followed by a Friedel-Crafts cross-linking of the reactive moieties with their neighbors, by addition of secondary, cross-linkable aromatic reagents, or by both. This phase is not endcapped. Elemental analysis data shows that an aluminum chloride catalyst is very effective at bonding aromatic cross-linking reagents, such as styrene heptamer and triphenylmethane, to the reactive CMPES monolayer. The stability of the retention factor of decylbenzene on the cross-linked self-assembled CMPES phases is compared to a sterically protected C18 phase to illustrate its superior resistance to acid-catalyzed-phase loss. Inverse size exclusion chromatography and flow-curve comparisons of the cross-linked self-assembled CMPES and the sterically protected C18 stationary phases illustrate their similar chromatographic efficiency.     

Identification and quantification of 77 pesticides in groundwater using solid phase coupled to liquid-liquid microextraction and reversed-phase liquid chromatography

This paper describes a method for the extraction, separation, identification, and quantification of 77 pesticides (neutral, acidic, and basic) including some s-triazine metabolites. The method is appropriate for organically (e.g. with humic acids) highly loaded groundwater samples. A comparative study of a pH-controlled mixed solid phase (LiChroprep RP18/LiChrolut EN) extraction with different desorption solvents (acetonitrile or acetonitrile and dichloromethane/methanol) is elaborated. A subsequent liquid-liquid microextraction reduces matrix effects. The pesticides in the sample are separated using RP-HPLC, detected, and identified by diode array. The efficiency is illustrated on a natural groundwater sample from a phreatic aquifer.     

Transient liquid phase bonding of steel using an Fe–B interlayer: microstructural analysis

Transient liquid phase bonding processes have been performed to join two carbon steel tubes using Fe_96.2B_3.8 wt% amorphous ribbons as interlayer. Welding experiments were performed at the temperature T ≈ 1,250 °C for different durations and under pressures of 0.8, 2, 3, and 4 MPa. From metallographic inspection, it is concluded that the bonding process ends in 7.0 min if a pressure of 4 MPa is applied, whereas the process results incomplete if less pressure is applied. The metallurgical aspects of these joints are analyzed. Plastic deformation at the joint is observed. Micrographs show that if pressure increases, the amount of pro-eutectoid ferrite decreases, therefore, an increase in the hardenability of the steel occurs. This fact could be due to the effect of the compression plastic deformation that prevails at the joint zone.     

Monolithic column HPLC separation of intact proteins analyzed by LC-MALDI using on-plate digestion: An approach to integrate protein separation and identification

A method is developed to integrate a protein separation by monolithic capillary reversed-phase high-performance liquid chromatography to on-probe tryptic digestion for subsequent analyses by MALDI-TOF MS and MALDI-TOF/TOF MS. The method provides a means of directly interfacing separations to MALDI-MS, reducing the amount of time required for traditional procedures involving in-solution enzymatic digestion and sample cleanup prior to MALDI-MS analysis. When used with pI-based fractionation as a first dimension, it provides a means of analyzing complex mixtures of proteins with minimal sample handling and cleanup. The use of monolithic capillary columns sufficiently resolved intact proteins so that peptide mass fingerprinting analysis by MALDI-TOF MS resulted in the identification of close to 40 unique proteins from 120 ng of sample obtained from a prefractionated MCF10 cell line at pH 6.34, where the identifications of several of these proteins were also confirmed by intact MW and tandem mass spectrometric analysis. The reproducibility of this method has been demonstrated to be sufficient for the purpose of protein identifications. Experimental values of protein intact MW are obtained and compared to that expected for each protein identified.     

Guaranteed error bounds in homogenisation: an optimum stochastic approach to preserve the numerical separation of scales

This paper proposes a new methodology to guarantee the accuracy of the homogenisation schemes that are traditionally employed to approximate the solution of PDEs with random, fast evolving diffusion coefficients. More precisely, in the context of linear elliptic diffusion problems in randomly packed particulate composites, we develop an approach to strictly bound the error in the expectation and second moment of quantities of interest, without ever solving the fine‐scale, intractable stochastic problem. The most attractive feature of our approach is that the error bounds are computed without any integration of the fine‐scale features. Our computations are purely macroscopic, deterministic and remain tractable even for small scale ratios. The second contribution of the paper is an alternative derivation of modelling error bounds through the Prager–Synge hypercircle theorem. We show that this approach allows us to fully characterise and optimally tighten the interval in which predicted quantities of interest are guaranteed to lie. We interpret our optimum result as an extension of Reuss–Voigt approaches, which are classically used to estimate the homogenised diffusion coefficients of composites, to the estimation of macroscopic engineering quantities of interest. Finally, we make use of these derivations to obtain an efficient procedure for multiscale model verification and adaptation. Copyright © 2016 John Wiley & Sons, Ltd.     

Mixed convection of non-Newtonian nanofluid in an H-shaped cavity with cooler and heater cylinders filled by a porous material: Two phase approach

In the present problem, two-phase mixed convection of a non-Newtonian nanofluid in a porous H-shaped cavity is studied. Inside the enclosure there are four rotating cylinders, using the Boussinesq approximation, mixed convection is created. Nanofluid includes H₂O + 0.5% CMC and copper oxide nanoparticles. The mixture model was used to model physical phenomena. Different aspect ratios were used in order to achieve the best heat transfer rate. The Darcy and Richardson numbers ranges are 10⁻⁴ ≤ Da ≤ 10⁻² and 1 ≤ Ri ≤ 100 respectively. Also, the aspect ratio and dimensionless angular velocities of cylinders ranges are 1.4 ≤ AR ≤ 1.6 and −10 ≤ Ω ≤ 10 respectively. Streamlines and isotherm-lines contours have been obtained for the variation of Darcy and Richardson numbers, aspect ratio and angular velocity. The heat transfer rates have been obtained for various aspect ratios, Darcy and Richardson numbers, and the direction of the cylinder's rotation, and are compared with each other. The results show that the direction of cylinders rotation influences the strength and extent of the generation vortices. Also, the use of porous material in high permeability can be a good alternative to lowering the angular velocity of the cylinders and ultimately reducing the need for less energy.     

Chiral polymeric reagents for off-line and on-line derivatizations of enantiomers in high-performance liquid chromatography with ultraviolet and fluorescence detection: an enantiomer recognition approach

Optically active and detector-sensitive polymeric reagents have been synthesized, loadings determined, derivatizations/separations/detection optimized, and applications to simple amines and amino alcohols described. Such reagents have been designed to contain different chiral centers, usually amino acids, leashed via an activated ester attachment to an insoluble, structurally rigid, organic polymer backbone. 9-Fluorenylmethyl (FMOC) moieties chemically bonded to the amino acids were used as ultraviolet (UV) and fluorescence (FL) sensitive detector probes to the final diastereomers of enantiomer substrates. Such diastereomers can be readily separated by isocratic or gradient elution normal-phase methods. The kinetics for diastereomer formation have been determined, and final UV/FL responses for known mixtures of enantiomers have been compared to demonstrate overall validity of the method. Minimum detection limits, linearity of calibration plots, dual detector responses, and linear diode array spectra and absorbance ratios have also been demonstrated. In some cases, authentic standards have been prepared to calculate absolute percent derivatizations for specific enantiomer pairs. The overall approach permits, for the very first time, off-line or on-line precolumn derivatization for the formation of diastereomers having unique detector properties. It has been proven that the rates and rate constants for such formations are identical for at least those pairs of enantiomers studied. Separations are base-line or near-base-line, permitting accurate and precise quantitative determinations, by both UV and FL, of enantiomer/optical purity and chemical purity.     

Fluorine speciation analysis using reverse phase liquid chromatography coupled off-line to continuum source molecular absorption spectrometry (CS-MAS): identification and quantification of novel fluorinated organic compounds in environmental and biological samples

Driven by increasing demand for the monitoring of industrial perfluorinated compounds (PFCs), the identification of novel fluorine containing compounds (FOCs) and the tracking of organofluorine drugs and their degradation products, there is a clear need for sensitive, fluorine-specific detection of unknown FOCs. Here we report the first ever direct fluorine-specific (speciation) method; capable of individually detecting untargeted FOCs in environmental and biological samples through the application of continuum source molecular absorption spectrometry (CS-MAS) using a commercial CS-AAS. Two model FOCs (2,4,6, trifluorobenzoic acid (TFBA) and 5-fluoroindol-5-carboxylic acid (FICA)) were used, achieving fluorine-specific detection across a range of 0.1 to 300 ng/mL fluorine, corresponding to a limit of detection of 4 pg F and 5.26 nM for both compounds. Both TFBA and FICA showed a similar response to CS-MAS detection, potentially enabling the quantification of fluorine content in novel FOCs without having molecular standards available. This paper also reports the use of reverse-phase high performance liquid chromatography (RP-HPLC) coupled off-line with CS-MAS for the identification of single organofluorines in a mixture of FOCs via fraction collection. The linear range of both FOCs was determined to be from 1 to 500 ng/mL. The limits of detection of those species were just above 1 ng/mL (100 pg) and can therefore compete with targeted analytical methods such as ESI-MS. Finally, as a proof of principle the analysis of a fluoride-containing groundwater sample from Ghana demonstrated that this method can be used in the detection of novel FOCs, with identification achieved through parallel ESI-MS. Coupled HPLC-CS-MAS/ESI-MS is the first analytical methodology capable of selectively detecting and identifying novel FOCs, making possible the quantification of all fluorine containing compounds in one sample. This is the necessary analytical requirement to perform fluoronomics.