Solid-phase extraction on silica cartridges as an aid to platelet-activating factor enrichment and analysis

Solid-phase extraction methods using pre-packed silica cartridges and various elution solvents have been developed and evaluated as chromatographic means to enrich biological lipid extracts for platelet-activating factor (PAF). The optimized procedure advanced selectively removed the major tissue/blood neutral lipids and non-choline-containing phospholipids from complex lipid mixtures and yielded thereby a choline phospholipid fraction markedly enriched in bioactive PAF. Some tested solid-phase extraction procedures, while capable of resolving choline phospholipids from other polar and non-polar species, were detrimental to PAF's bioactivity and evidenced considerable loss or degradation of this analyte. It is concluded that, with solvents of appropriate composition, strength and polarity, solid-phase extraction on silica cartridges has several unique advantages over conventional thin-layer and column chromatographic methods presently in use for PAF enrichment from biological sources.     

Synthesis of inorganic gels in a lyotropic liquid crystal medium. I. Synthesis of silica gels in lamellar phases obtained from non-ionic surfactants

Some lamellar phases made with aqueous lyotropic liquid crystals were used as templates for the gelation of a silica inorganic network from tetramethylorthosilicate (TMOS). The aim was to synthesize materials with an anisotropic texture.Lamellar phases were obtained by using non-ionic surfacants. At first, structural, textural and rheological properties of the lamellar phases were studied. Then, the evolution of the system after introduction of the alkoxide, i.e., during the sol-gel transition, was followed by low angle X ray diffraction and rheological measurements. Finally, a textural study of dried gels was carried out.The formation of gels with a lamellar structure was analysed by compressing the total phase diagram (quaternary system) to a ternary system. The hydrolysis and condensation reactions of the TMOS are strongly influenced by the presence of the structured lamellar phase. Gelation seems to happen around the liquid crystal microdomains. A schematic model of gelation is proposed based on experimental observations.     

Solid-phase extraction preconcentration of 2,4-dichlorophenoxyacetic acid on silica with immobilized polyethoxylated isooctylphenol groups

Silica with immobilized polyethoxylated isooctylphenol groups (SiO ₂ -TX) is studied as an adsorbent for the solid-phase extraction preconcentration of pesticides based on chlorophenoxyalkanecarboxylic acids from aqueous solutions. It is demonstrated that 2,4-dichlorophenoxyacetic acid (2,4-D) is efficiently (up to 96%) extracted as an ion associate with cetyltrimethylammonium bromide (CTMAB) with SiO₂-TX in the pH range 8–10. The optimum CTMAB-to-2,4-D molar ratio is 200: 1. The capacity of SiO₂-TX to 2,4-D in the Henry region is 0.42 mg/g of adsorbent, and the distribution coefficients reach 9 × 10² mL/g. It is shown that 2,4-D is quantitatively eluted with 1–2 mL of acetonitrile, which allowed us to use the adsorbent in a preconcentration cartridge before determining pesticides by HPLC. The procedure allowed pesticides to be recovered from aqueous solutions in concentrations beginning from 0.025 mg/L.     

Direct analysis of pharmaceutical compounds in human plasma with chromatographic resolution using an alkyl-bonded silica rod column

Monolithic columns have been successfully used with steep gradient and high flow rates for the direct analysis of a candidate pharmaceutical compound in human plasma. The monolithic columns showed excellent robustness with nearly 300 20-microL injections of plasma (diluted 1:1 with water) being made onto one column without significant deterioration in performance. The system gave excellent sensitivity with a limit of quantification of 5 ng/mL being achieved. Unlike previous methods of direct analysis the monolithic columns showed excellent resolution even after nearly 300 plasma injections. The column performance was measured before and after the analysis of the plasma samples.     

Solid-phase extraction using C(18) bonded silica disks: interferences and analysis of chlorotriazines in seawater samples

The interferences in C(18) Empore extraction disks were obtained by processing 5 1. of HPLC water with average blanks of 1 ng/l. A C(19) alkane, plasticizers and the antioxidant Nonox A were identified in the blanks as possible interferences. The extraction of the components of the disks was carried out with methanol, acetonitrile and/or ethyl acetate with subsequent analysis by gas chromatography-mass spectrometry (GCMS). The identification of interferences was a requirement for the determination of the chlorotriazine herbicides atrazine and simazine, and of a transformation product, de-ethylatrazine, at concentration levels varying between 2 and 140 ng/l. Seawater samples of 3-28 parts-per-thousand were pre-filtered through a 47-mm diameter of 0.7 mum and subsequently with 0.45 mum glass-fibre filters to trap particulate matter, followed by Empore extraction disks of 500 mg C(18) bonded silica. Water volumes of 5 1. could be processed within 150 min. The disks were extracted with methanol, the extract was blown down under nitrogen, and the analytes were quantified by GC with nitrogen-phosphorus detection (NPD) with further confirmation using GCMS in the selected ion monitoring (SIM) mode. The proposed method has been applied to the determination of the environmental levels of atrazine and simazine in seawater samples of varying salinity. The recovery of de-ethylatrazine was 10%, so the method was not appropriate for this compound. The concentration of the herbicides has been plotted against the salinity values, showing a decrease in the levels as the salinity increases, with two inflexion points that indicate a non-conservative mixing with loss of the herbicides in the mixing zone of the estuary.     

Solid-phase extraction for multiresidue analysis of organic contaminants in water

To overcome the limitations of the detection systems associated with gas or liquid chromatography, a sample pretreatment is required with the objective to provide a sample fraction enriched with all the target analytes and as free as possible from other matrix components. There is now no doubt that solid-phase extraction (SPE) has now become the method of choice for carrying out simultaneously the extraction and concentration of many compounds in aqueous samples. Many recent applications of SPE to multiresidue analysis are reviewed with an emphasis on the importance of the choice of the sorbent and of the sample volume. SPE is particularly well adapted to multiresidue analysis including compounds from a wide range of polarity or characterized by various physico-chemical properties. However, SPE is not completely free from practical problems inherent to the nature of the compounds or to the coupling to the chromatographic systems. Many examples are reported to illustrate these problems which can in most cases be circumvented. New developments in SPE are also reviewed.     

Weibull analysis of the mechanical strength of silica gels

Since gels are typically brittle materials, reliable analyses are essential to determine the strength distribution. The mechanical strength of silica gels has been measured by the three point bending technique. Based on the Weibull function, the statistical analysis allows determination of the Weibull modulus (m), which characterizes the strength distribution and the flaw size effect.Two kinds of gels, alcogels and aerogels, have been investigated with respect to their different mechanical behaviour owing to the transformations occurring during the supercritical drying (SD). The toughness of the two materials has been also measured by the SENB technique. It appears that the strength increases by a factor greater than two during SD, the K_IC increases slightly. However, m is not greatly affected which would suggest that SD does not induce significant flaws or defects change in the network.     

Solid-phase extraction coupling to capillary electrophoresis with emphasis on environmental analysis

This article reviews the status of solid-phase extraction (SPE) coupled with capillary electrophoresis (CE). It focuses on some of the organic pollutants which have captured the interest of analytical chemists--phenols, surfactants, dyes, polynuclear aromatic hydrocarbons (PAHs), aromatic and aliphatic amines, aromatic acids and aromatic sulfonic acids--and, in particular, on monitoring pesticides from different sources. It shows that the coupling of SPE to CE has considerable potential in the analysis of environmental pollutants.     

Solid-phase extraction with C30 bonded silica for analysis of polycyclic aromatic hydrocarbons in airborne particulate matters by gas chromatography-mass spectrometry

A solid-phase extraction (SPE) method using triacontyl bonded silica (C30) as sorbent was developed for the determination of 16 US Environmental Protection Agency polycyclic aromatic hydrocarbons (PAHs) in airborne particulate matters quantitatively by gas chromatography-mass spectrometry (GC-MS). Optimization experiments were conducted using spiked standard aqueous solution of PAHs and real airborne particulates samples aiming to obtain highest SPE recoveries and extraction efficiency. Factors were studied in SPE procedures including the concentration of organic modifier, flow rate of sample loading and elution solvents. The ultrasonication time and solvents were also investigated. Recoveries were in the range of 68-107% for standard PAHs aqueous solution and 61-116% for real spiked sample. Limits of detection (LODs) and limits of quantification (LOQs) with standard solution were in the range of 0.0070-0.21 microgL(-1) and 0.022-0.67 microgL(-1), respectively. The optimized method was successfully applied to the determination of 16 PAHs in real airborne particulate matters.     

A chromatographic analysis of hindered diffusion of saccharides in silica gels

Summary The chromatographic technique as a means for experimental studies of diffusion in porous solids has been demonstrated. In this paper we report the effective diffusion coefficients which we have chromatographically obtained for two dextran samples and three low molecular weight solutes. The chromatographic method of measuring diffusional resistances in porous solids has the advantages of rapidity and simplicity. This method also provides information on the axial dispersion and distribution of a solute between the moving phase and the solvent held stationary in the pore. The elution curves of a packed column in pulse response experiments were analyzed by the method of moments to give the parameters of interest. The results indicate that pore diffusion of the solutes was appreciably restricted in comparison with diffusion in bulk solution. The degree of hindrance depended on the size of the diffusing substances.     

Encapsulation of bacteria in silica gels

Escherichia coli cells have been encapsulated within sol-gel silica matrices. The cellular organization of these bacteria appears to be well preserved. Their β-galactosidase activity was measured via the hydrolysis of p-NPG. The formation of p-nitrophenol was followed by optical absorption. These experiments show that the enzymatic activity of entrapped cells still exhibit a Michaelis behaviour. Their affinity toward the p-NPG substrate seems even better when the cells are trapped. They can be kept for days in wet gels but their activity decreases drastically upon drying.     

Solid-phase extraction clean-up procedure for the analysis of PAHs in lichens

A clean-up procedure based on a solid-phase extraction column was optimized for determination of polycyclic aromatic hydrocarbons (PAHs) in lichen extracts to remove co-extracted compounds from the matrix in the final extract. Several kinds of solid phases were evaluated: normal phase (-NH₂ and alumina), strong anion exchange and reversed phase. The -NH₂ columns were the most effective by using a packed solid bed of 500?mg. The lichen raw extract was loaded on the column previously conditioned with dichloromethane and hexane. Hexane (0.5?mL) was used as rinsing solvent, and PAHs were quantitatively eluted (80–97%) using 2?mL of hexane–dichloromethane (65–35) as eluting solvent. In these conditions, even the heaviest PAHs were quantitatively eluted. The optimized SPE method provides a short time and low-solvent-consumption sample clean-up compared with other conventional methods based on column chromatography. The analytical procedure, dynamic sonication-assisted extraction, followed by the optimized solid-phase extraction clean-up, was used to determine the 16 EPA priority PAHs from native lichens collected from the Aragon valley in central Pyrenees. The PAH concentrations in lichen samples ranged from 352 to 1654?ng?g^?1, and the minimum concentration value was established as the regional reference PAH levels in the area.     

Solid-phase extraction of acidic herbicides

A discussion of solid-phase extraction method development for acidic herbicides is presented that reviews sample matrix modification, extraction sorbent selection, derivatization procedures for gas chromatographic analysis, and clean-up procedures for high-performance liquid chromatographic analysis. Acidic herbicides are families of compounds that include derivatives of phenol (dinoseb, dinoterb and pentachlorophenol), benzoic acid (acifluorfen, chloramben, dicamba, 3,5-dichlorobenzoic acid and dacthal--a dibenzoic acid derivative), acetic acid [2,4-dichlorophenoxyacetic acid (2,4-D), 4-chloro-2-methylphenoxyacetic acid (MCPA) and 2,4,5-trichlorophenoxyacetic acid (2,4,5-T)], propanoic acid [dichlorprop, fluazifop, haloxyfop, 2-(4-chloro-2-methylphenoxy)propanoic acid (MCPP) and silvex], butanoic acid [4-(2,4-dichlorophenoxy)butanoic acid (2,4-DB) and 4-(4-chloro-2-methylphenoxy)butanoic acid (MCPB)], and other miscellaneous acids such as pyridinecarboxylic acid (picloram) and thiadiazine dioxide (bentazon).     

Electrochromatography in packed tubes using 1.5 to 50 μm silica gels and ODS bonded silica gels

Summary Electrochromatography (that is HPLC where the eluent is driven along the column by electro-osmosis using fields of up to 100 kV m⁻¹) promises plate efficiencies for HPLC which are comparable to those attained in capillary gas chromatography, but this requires that narrow-bore columns can be successfully packed with submicron particles. This paper demonstrates that we have now moved a considerable distance towards this goal. We show (1) that, following theory, there is no evidence of any reduction in electroosmotic velocity in columns packed with particles down to 1.5 μm diameter, (2) that reduced plate heights as low as unity are attainable for unretained solutes using both slurrypacked and drawn-packed columns 30 to 200 μm bore and up to 1 m long when packed with conventional 3 and 5 μm silica gels or with 1.5 μm impermeable silica spheres, (3) that columns driven electrically show higher plate efficiencies than identical columns driven by pressure, and (4) that 100,000 plate HPLC separations can be achieved in relatively short times of 30 minutes using in situ derivatised drawn packed capillaries containing 3 and 5 μm ODS-silica gels.     

Some aspects of estimation of extraction selectivity under the conditions of competitive sorption on modified silica gels

Systematic studies of silica gels with covalently immobilized thiosemicarbazide and formazan groups under the conditions of competitive sorption from multicomponent systems were conducted. A methodological approach to determine the selectivity of the modified sorption material with regard to Cu(II), Ni(II), Co(II), Cd(II), and Zn(II) was proposed. Solid-phase extraction in equilibrium conditions of Cu(II), Zn(II), Co(II), Cd(II), and Ni(II) on a silica gel with covalently immobilized thiosemicarbazide and formazan groups in the conditions of competitive sorption was studied. The possibility to use the pseudo-second-order kinetic equation for assessment of mutual influence at competitive sorption has been shown. We found that sorption from multicomponent solutions proceeds as a non-additive process under the conditions of an excess of functional groups.

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Growth and aging phenomena in silica gels

Growth and aging of silica aggregates are influenced both by temperature and by catalyzing fluorine ions as shown by SAXS and BET. It was found that both fluorine and increased temperature slightly increased the fractal dimension Df during aging, but the fluorine catalyzed system showed a lower BET surface area.To understand the effect of fluorine and increased temperature on the aggregates, 2D aggregations and SAXS simulations were carried out using two new programs GRASP and DALAI. In agreement with experiments it was found that binary RLCCA aggregates have a slightly higher Df value compared to DLCCA aggregates and that branch-flexibility during aging increases Df even further.     

Organic-inorganic gels based on silica and multifunctional acrylates

Rigid, microporous silica rods, prepared previously by the sol-gel process, were infiltrated with three triacrylate monomers to give sequential interpenetrating networks (IPNs). The three commercially available triacrylate monomers are glycerol propoxy triacrylate (GPTA), trimethylolpropane triacrylate (TMPTA) and pentaerythritol triacrylate (PETA). Each solution containing a photoinitiator was allowed to infiltrate the silica rod, after which the sample was UV irradiated to polymerize the triacrylate monomer. Emphasis was placed on establishing the infiltration and polymerization conditions leading to optically transparent composites. For comparison, one of the triacrylates (GPTA) was introduced into a hydrolyzing sol-gel formulation containing TEOS, ethanol, water and acid catalyst, to effect a simultaneous IPN. The sequential IPN and the simultaneous IPN samples gave similar transmission curves, despite differences in skeletal density.1992 Fulbright Visiting Scholar, on leave from Marie Curie Sklodowska University, Lublin, Poland.     

Liquid-liquid extraction in inorganic analysis: current status and prospects

This review surveys the progress in inorganic liquid-liquid extraction in the last 25 years. Achievements are emphasized in the theoretical foundations of the method, and in the synthesis, characterization and application of new extractants. Special attention is paid to the implementation of extraction methods and to the automation of extractive separation. The combination of liquid-liquid extraction as a method of preconcentration with the methods of subsequent determination of trace concentrations of elements is described in detail.     

Solid-phase extraction for multi-residue analysis of some triazole and pyrimidine pesticides in water

Summary A multi-residue analytical method based on solid-phase extraction (C₁₈) has been developed for the analysis of 12 compounds in groundwater. These compounds are triazoles, e.g. diclobutrazol, flutriafol, hexaconazole, paclobutrazol and its ketone analogue and pyrimidines, e.g. bupirimate, pirimicarb, pirimiphos-methyl, ethirimol, and other pesticides: fluazifop-P-butyl, fluazifop and fomesafen. In summary, one litre of water modified with 1% methanol was extracted using a C₁₈ solid-phase extraction column, containing 1 g of adsorbent. The retained compounds were eluted from the column with successive elutions of acetonitrile and methanol. No further clean-up was necessary. Residues were determined either by capillary gas-liquid chromatography (GLC) using a nitrogen-phosphorus selective detector, or high performance liquid chromatography (HPLC) using a UV detector. Recovery data on these compounds were obtained by fortifying water at 0.05–100 g/l levels. Depending on the compound, mean recoveries were within the range of 80–107% with a coefficient of variation of 9–15%. The limit of determination, defined as four times the baseline noise, varied between 0.003–0.1 g/l also depending on the compound and detection sensitivity of the instrument. These recovery data have also been compared to values generated by conventional liquid-liquid partition. Various techniques were used to confirm the identity of these compounds. Gas Chromatography-Mass Spectrometry (GC-MS) using selective ion monitoring (SIM) was used to confirm the compounds which were amenable to gas-liquid chromatography. These were all the triazoles and bupirimate, pirimicarb, pirimiphos-methyl and fluazifop-P-butyl. HPLC methods were developed using different mobile phase and adsorbent combinations for the confirmation of ethirimol, fluazifop and fomesafen residues in water.