Solid phase extraction conditioning

Because of the widespread use of LC/MS/MS for drug discovery bioanalysis, there is currently less of a necessity for finely tuned solid-phase extractions than there once was in this area. Instead, generic solid-phase extraction conditions that can accommodate many different analyte structures using the same extraction conditions have become more interesting. To make a solid-phase sample preparation useful for LC/MS/MS it must remove as much of the sample salts as possible in order to reduce the effects of ion suppression [47,51—52] and it must remove as many nonvolatile matrix components as possible so that the instrument ion source is not quickly fouled. Because the LC/MS/MS instrument is inherently so selective, added assay selectivity, per se, is no longer an objective of solid-phase extraction. 

Prepai ative isolation of nonvolatile and semivolatile organic compounds fractions (hydrophobic weak acids, hydrophobic weak bases, hydrophobic neutrals, humic and fulvic acids) from natural and drinking waters in optimal conditions was systematically investigated by solid-phase extraction method with porous polymer sorbents followed by isolation from general concentrate of antropogenic and/or toxic semivolatile compounds produced in chlorination and ozonation processes. 

Prepare the solid-phase extraction (SPE) tube (1 ml LC-18 SPE tube) by conditioning with 1 ml of methanol followed by 1 ml of water. 

To determine secondary alkanesulfonates in sewage wastewaters, solid phase extraction (SPE) and a single-step procedure which combines elution and injection port derivatization for analysis with GC-MS were developed [36]. Again a tetrabutylammonium ion pair reagent was employed both to elute the secondary alkanesulfonates as their ion pairs from CI8-bonded silica disks and to derivatize sulfonate ion pairs under GC injection port conditions. Secondary alkanesulfonates were effectively recovered from samples of raw sewage (>92%) and from primary (>98%) and secondary (>85%) effluents. No... 

Milbemectin consists of two active ingredients, M.A3 and M.A4. Milbemectin is extracted from plant materials and soils with methanol-water (7 3, v/v). After centrifugation, the extracts obtained are diluted to volume with the extraction solvent in a volumetric flask. Aliquots of the extracts are transferred on to a previously conditioned Cl8 solid-phase extraction (SPE) column. Milbemectin is eluted with methanol after washing the column with aqueous methanol. The eluate is evaporated to dryness and the residual milbemectin is converted to fluorescent anhydride derivatives after treatment with trifluoroacetic anhydride in 0.5 M triethylamine in benzene solution. The anhydride derivatives of M.A3 and M.A4 possess fluorescent sensitivity. The derivatized samples are dissolved in methanol and injected into a high-performance liquid chromatography (HPLC) system equipped with a fluorescence detector for quantitative determination. 

FIG. 3 Time course of the solid-phase extraction of bovine serum albumin by an AOT-based w/o-Me solution. Conditions 500 mg of solid-phase protein 20 mL of iso-octane containing 25 mM AOT and 1000 mM water (w = 40). (Reprinted with permission from Ref. 58.)... 

There are basically three methods of liquid sampling in GC direct sampling, solid-phase extraction and liquid extraction. The traditional method of treating liquid samples prior to GC injection is liquid-liquid extraction (LLE), but several alternative methods, which reduce or eliminate the use of solvents, are preferred nowadays, such as static and dynamic headspace (DHS) for volatile compounds and supercritical fluid extraction (SFE) and solid-phase extraction (SPE) for semivolatiles. The method chosen depends on concentration and nature of the substances of interest that are present in the liquid. Direct sampling is used when the substances to be assayed are major components of the liquid. The other two extraction procedures are used when the pertinent solutes are present in very low concentration. Modem automated on-line SPE-GC-MS is configured either for at-column conditions or rapid large-volume injection (RLVI). 

Combalbert S, Pype ML, Bemet N, Hemandez-Raquet G (2010) Enhanced methods for conditioning, storage, and extraction of liquid and solid samples of manure for determination of steroid hormones by solid-phase extraction and gas chromatography-mass spectrometry. Anal Bioanal Chem 398 973-984... 

Furthermore, multicomponent reactions can also be performed under fluorous-phase conditions, as shown for the Ugi four-component reaction [96], To improve the efficiency of a recently reported Ugi/de-Boc/cyclization strategy, Zhang and Tempest introduced a fluorous Boc group for amine protection and carried out the Ugi multicomponent condensation under microwave irradiation (Scheme 7.84). The desired fluorous condensation products were easily separated by fluorous solid-phase extraction (F-SPE) and deprotected by treatment with trifluoroacetic acid/tet-rahydrofuran under microwave irradiation. The resulting quinoxalinones were purified by a second F-SPE to furnish the products in excellent purity. This methodology was also applied in a benzimidazole synthesis, employing benzoic acid as a substrate. 

The assembly of tetrapeptide 19 that contains all possible 0-dipeptide bonds, (03-03)-, (03-02)-, and (02-03), and also a turn inducing 03-(R)-Ala-02-(R)-Val element was achieved employing a Boc-strategy (Scheme 5). A fluorous benzyl group was incorporated in the first amino acid to streamline the purification procedure by fluorous solid phase extraction (LSPE) (Lilippov et al. 2002 de Visser et al. 2003). Thus, the assembly of the fully protected tetrapeptide commenced with the construction of the first 03-03-peptide bond by applying the previously established conditions. A residence time of 3 min at 90°C provided the Boc-protected dipeptide 15 in 91% isolated yield after LSPE. Notably, the product precipitated in the collection flask, which was kept at ambient temperature, indicating the poor solubility of this class of compounds (Hessel et al. 2005). 

Application of SPE to sample clean-up started in 1977 with the introduction of disposable cartridges packed with silica-based bonded phase sorbents. The solid phase extraction term was devised in 1982. The most commonly cited advantages of SPE over liquid-liquid extraction (LLE) as practiced on a macroscale include the reduced time and labor requirements, use of much lower volumes of solvents, minimal risk of emulsion formation, selectivity achievable when desired, wide choices of sorbents, and amenability to automation. The principle of operation consists of four steps (1) conditioning of the sorbent with a solvent and water or buffer, (2) loading of the sample in an aqueous or aqueous low organic medium, (3) washing away unwanted components with a suitable combination of solvents, and (4) elution of the desired compound with an appropriate organic solvent. 

Conditions for Automated Solid Phase Extraction of Vitamin D Metabolite from Plasma after Protein Precipitation... 

Pankey et al.21 described a rapid, reliable, and specific enzyme multiplied immunoassay technique (EMIT ) for amitriptyline, nortriptyline, imipramine, and desipramine in sera. To overcome crossreactivity, solid phase extraction was included in sample pretreatment. Disposable 1 mL columns packed with covalently labeled silica gel were conditioned with HPLC-grade methanol (1 mL) and then with de-ionized or distilled water (1 mL). Serum (calibrator, control, or patient sample, 500 L) was applied onto the column, eluted to waste, washed with 900 /uL of wash solution containing acetonitrile (236.1 g/L) and ion-pairing reagent in acetate buffer, pH 4.2, washed with 500 fiL of mobile phase solution containing acetonitrile (393.5 g/L) in methanolic phosphate buffer, pH 7.0,... 

An example of a solid-phase extraction (SPE) used as a cleanup procedure is given in Procedure 12.7 The column is conditioned by passing water and the... 

In environmental analytical applications where analyte concentrations, e.g. surfactants or their metabolites, are quite low, extraction and concentration steps become essential. Solid phase extraction (SPE) with cartridges, disks or SPME fibres (solid phase micro extraction) because of its good variety of SP materials available has become the method of choice for the analysis of surfactants in water samples in combination with FIA as well as LC—MS analysis. SPE followed by sequential selective elution provides far-reaching pre-separations if eluents with different polarities and their mixtures are applied. The compounds under these conditions are separated in the MS spectrometer by their m/z ratios providing an overview of the ionisable compounds contained in a sample. Identification in the sense it has been mentioned before, however, requires the generation of fragments. 

Product extraction from large volumes of fermentation broth can be complex, requiring large volumes of organic solvent or solid-phase extraction techniques, which can sometimes greatly reduce or even cancel out the benefits of the biotransformation itself, such as shorter route and environmentally benign conditions. 

The crude oil used by Bennett and Barter (1997) was a typical North Sea oil generated from Upper Jurassic, Kimmeridge clay formation source rocks. The alkylphenol distribution in a sample of (Miller) crude oil, determined using solid phase extraction (SPE), is shown in Fig. 16.21. The crude oil is dominated by phenol and cresol and contains appreciable quantities of dimethylphenols. The concentrations of 2,3-, 3,4-, and 3,5-dimethylphenol also include a contribution from 2-, 3-, and 4-ethylphenols, because they coelute under the conditions employed (Bennett et ah, 1996). 

Other sulfonamides. The fact that the extraction of one of these sulfonamides is only optimized at a totally different pH displays the compilations in relying on a single set of extraction conditions as representative for all members within each class of PPCPs. To trap acid components in the sample, the sample has to be acidified to pH < 2, passed through a conditioned column such as an RP C18 solid-phase extraction column, and then eluted with a volatile solvent. Neutral compounds are, on the other hand, extracted by adjusting the sample to pH 7-8 before ranning the sample through the extraction column, which has been conditioned with acetone, methanol, or distilled water. Basic compounds are extracted by initially adjusting the sample to pH > 12 with EDTA and KOH. 

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