Sample solid phase extraction

Figure 13.11 Electropherogram of a solid-phase extraction sample in acetonitrile/ methanol [87.5/12.5 (v/v)] containing 2.5 mM NaOH and 1.0 mM SDS, derived from a seawater sample spiked with 0.5 [tg/L of TNT, TNB, and tetryl. Applied separation field strength, —506 V/cm, using a 10-s floating load. (Reprinted from [38] with permission from Elsevier.)...

The Zymark and Gilson ASPEC workstations process solid-phase extraction samples sequentially without the intervention of a human analyst. These workstations are programmed to activate extraction cartridges with solvent to prepare them to receive a specimen. After the sample application, cartridges are washed to remove impurities. The analytes of interest are then eluted into collection tubes or injected onto a liquid chromatograph for sequential analysis. 

Samples rarely come in a form that can be injected directly into the instrument some form of sample preparation usually is required. Sample preparation includes any manipulation of the sample prior to analysis, including techniques such as weighing, dilution, concentration, filtration, centrifugation, and liquid- or solid-phase extraction. Sample preparation can be performed either on-line or off-line, but it is usually performed offline. Off-line preparation can be time-consuming and tedious, and the more steps that are required, the more susceptible the analytical method is to operator error and irreproducibility. 

Tong, X.S. et al., High-throughput pharmacokinetics screen of VLA-4 antagonists by LC/MS/MS coupled with automated solid-phase extraction sample preparation, J. Pharm. Biomed. Anal., 35(4), 867, 2004. 

In Chapter 18, we described solvent extraction and solid-phase extraction sample preparation methods, which are applicable to GC analyses as well as others. A convenient way of sampling volatile samples for GC analysis is the technique of head-space analysis. A sample in a sealed vial is equilibrated at a fixed temperature, for example, for 10 min, and the vapor in equilibrium above the sample is sampled and injected into the gas chromatograph. A typical 20-mL glass vial is capped with a silicone rubber septum lined with polytetrafluoroethylene (PTFE). A syringe needle can be inserted to withdraw a 1-mL portion. Or the pressurized vapor is allowed to expand into a 1-mL sample loop at atmospheric pressure, and then an auxiliary carrier gas carries the loop contents to the GC loop injector. Volatile compounds in solid or liquid samples can be determined at parts per million or less. Pharmaceutical tablets can be dissolved in a water-sodium sulfate solution... 

If the sample contains very polar constituents, it is advisaUe to remove them through sample preparation techniques like solid-phase extraction. Samples dissolved in water should not be injected directly onto a normal-phase column. When an aminopropyl column is used, additional precautions are necessary, which were outlined above when we discussed this stationary ffiase. 

Application of Solid-Phase Extraction Sample Preparation Before MALDI-MS 1355... 

Fig. 3 Schematic workflow of porous silicon-ISET iMALDI top (I), antibody-immobilized porous silicon was used to capture the antigen angiotensin I bottom (II), RP solid-phase extraction sample preparation protocol on the ISET chip was used to purify and reconcentrate the elution followed by MALDI MS deteetion (Yan et al. 2011) (Reprinted with permission from Analytical Chemistry, 83, Yan, Ahmad-Tajudin, Bengtsson, Xiao, Laurell, Ekstrom, Noncovalent antibody immobilization on porous silieon eombined with miniaturized solid-phase extraction SPE) for array based immunoMALDI assays, 4942-4948. Copyright 2011 Ameriean Chemieal Society)...

Solid-Phase Extractions In a solid-phase extraction the sample is passed through a cartridge containing solid particulates that serve as the adsorbent material. For liquid samples the solid adsorbent is isolated in either a disk cartridge or a column (Figure 7.17). The choice of adsorbent is determined by the properties of the species being retained and the matrix in which it is found. Representative solid adsorbents... 

Selected Adsorbents for Solid-Phase Extraction of Liquid Samples... 

Two examples from the analysis of water samples illustrate how a separation and preconcentration can be accomplished simultaneously. In the gas chromatographic analysis for organophosphorous pesticides in environmental waters, the analytes in a 1000-mL sample may be separated from their aqueous matrix by a solid-phase extraction using 15 mb of ethyl acetate. After the extraction, the analytes are present in the ethyl acetate at a concentration that is 67 times greater than that in... 

Extraction Eiltering limits particulate gravimetry to solid particulate analytes that are easily separated from their matrix. Particulate gravimetry can be extended to the analysis of gas-phase analytes, solutes, and poorly filterable solids if the analyte can be extracted from its matrix with a suitable solvent. After extraction, the solvent can be evaporated and the mass of the extracted analyte determined. Alternatively, the analyte can be determined indirectly by measuring the change in a sample s mass after extracting the analyte. Solid-phase extractions, such as those described in Ghapter 7, also may be used. 

Description of Method. Fluoxetine, whose structure is shown in Figure 12.31a, is another name for the antidepressant drug Prozac. The determination of fluoxetine and its metabolite norfluoxetine. Figure 12.31 b, in serum is an important part of monitoring its therapeutic use. The analysis is complicated by the complex matrix of serum samples. A solid-phase extraction followed by an HPLC analysis using a fluorescence detector provides the necessary selectivity and detection limits. 

Table 1. Samples Analyzed by Solid-Phase Extraction...

The liquid chromatography - tandem mass spectrometry (LC/MS/MS) technique was proposed for the determination of corticosteroids in plasma and cerebrospinal fluid (CSF, liquor) of children with leucosis. Preliminai y sample prepai ation included the sedimentation of proteins, spinning and solid-phase extraction. MS detection was performed by scanning selected ions, with three chai acteristic ions for every corticosteroids. The limit of detection was found 80 pg/ml of plasma. 

Figure 2.12 Schematic representation of an on-line SPE-GC system consisting of three switching valves (VI-V3), two pumps (a solvent-delivery unit (SDU) pump and a syringe pump) and a GC system equipped with a solvent-vapour exit (SVE), an MS instrument detector, a retention gap, a retaining precolumn and an analytical column. Reprinted from Journal of Chromatography, AIIS, A. J. H. Eouter et al, Analysis of microcontaminants in aqueous samples hy fully automated on-line solid-phase extraction-gas chromatography-mass selective detection , pp. 67-83, copyright 1996, with permission from Elsevier Science.

Supercritical fluid extraction (SFE) and Solid Phase Extraction (SPE) are excellent alternatives to traditional extraction methods, with both being used independently for clean-up and/or analyte concentration prior to chromatographic analysis. While SFE has been demonstrated to be an excellent method for extracting organic compounds from solid matrices such as soil and food (36, 37), SPE has been mainly used for diluted liquid samples such as water, biological fluids and samples obtained after-liquid-liquid extraction on solid matrices (38, 39). The coupling of these two techniques (SPE-SFE) turns out to be an interesting method for the quantitative transfer... 

A method which uses supercritical fluid/solid phase extraction/supercritical fluid chromatography (SE/SPE/SEC) has been developed for the analysis of trace constituents in complex matrices (67). By using this technique, extraction and clean-up are accomplished in one step using unmodified SC CO2. This step is monitored by a photodiode-array detector which allows fractionation. Eigure 10.14 shows a schematic representation of the SE/SPE/SEC set-up. This system allowed selective retention of the sample matrices while eluting and depositing the analytes of interest in the cryogenic trap. Application to the analysis of pesticides from lipid sample matrices have been reported. In this case, the lipids were completely separated from the pesticides. 

The first bioanalytical application of LC-GC was presented by Grob et al. (119). These authors proposed this coupled system for the determination of diethylstilbe-strol in urine as a replacement for GC-MS. After hydrolysis, clean-up by solid-phase extraction and derivatization by pentafluorobenzyl bromide, the extract was separated with normal-phase LC by using cyclohexane/1 % tetrahydrofuran (THE) at a flow-rate of 260 p.l/min as the mobile phase. The result of LC-UV analysis of a urine sample and GC with electron-capture detection (ECD) of the LC fraction are shown in Ligures 11.8(a) and (b), respectively. The practical detection limits varied between about 0.1 and 0.3 ppb, depending on the urine being analysed. By use of... 

When a first column of a very short length (and therefore a low selectivity) is used (this is especially suitable for multiresidue methods), we talk about an on-line precolumn (PC) switching technique coupled to LC (PC-LC or solid-phase extraction (SPE)-LC). This is particulary useful for the enrichment of analytes, and enables a higher sample volume to be injected into the analytical column and a higher sensitivity to be reached. The sample is passed through the precolumn and analytes are retained, while water is eliminated then, by switching the valve, the analytes retained in the precolumn are transferred to the analytical column by the mobile phase, and with not just a fraction, as in the previous cases. 

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