Sample enrichment

Coupled liquid chromatography-gas chromatography is an excellent on-line method for sample enrichment and sample clean-up. Recently, many authors have reviewed in some detail the various LC-GC transfer methods that are now available (1, 43-52). For the analysis of normal phase eluents, the main transfer technique used is, without doubt, concurrent eluent evaporation employing a loop-type interface. The main disadvantage of this technique is co-evaporation of the solute with the solvent. 

H. G. J. Mol, H.-G. Janssen, C. A. Cramers and U. A. Th Brinkman, On-line sample enrichment-capillary gas clir omatography of aqueous samples using geometr ically deformed open-tubular extraction columns , 7. Microcolumn Sep. 7 247-257 (1995). 

Homomodal LC-LC. In this type of development, the chromatographic improvement occurs by switching columns of analogous selectivity. Mainly the goal is to optimize an already satisfactory separation, that is, to concentrate a dilute sample (sample enrichment) or to shorten an analysis time. 

Water solubility, dissociation constant(s) and n-octanol/water partition coefficients allow one to predict how an analyte may behave on normal-phase (NP), reversed-phase (RP), or ion-exchange solid-phase extraction (SPE) for sample enrichment and cleanup. 

NMR/MS has also been hyphenated to LC-SPE and LC-DAD modules. Sample enrichment and exchange of the HPLC mobile phase with an NMR suitable solvent is advantageous. LC-SPH-NMR/MS gains up to a factor of four in LC-NMR S/N for a single injection. No deuterated solvents are needed for separation and trapping. Optimisation of the separation procedure is less critical than for HPLC-UV. 

Mass spectrometry can be specific in certain cases, and would even allow on-line QA in the isotope dilution mode. MS of molecular ions is seldom used in speciation analysis. API-MS allows compound-specific information to be obtained. APCI-MS offers the unique possibility of having an element- and compound-specific detector. A drawback is the limited sensitivity of APCI-MS in the element-specific detection mode. This can be overcome by use of on-line sample enrichment, e.g. SPE-HPLC-MS. The capabilities of ESI-MS for metal speciation have been critically assessed [546], Use of ESI-MS in metal speciation is growing. Houk [547] has emphasised that neither ICP-MS (elemental information) nor ESI-MS (molecular information) alone are adequate for identification of unknown elemental species at trace levels in complex mixtures. Consequently, a plea was made for simultaneous use of these two types of ion source on the same liquid chromatographic effluent. 

In this design, on-column sample enrichment is incorporated into the sheathless interface (Janini et al., 2003). A miniaturized solid-phase extraction (mSPE) cartridge, made of reversed-phase material, was attached to the CE capillary near the injection end as shown in Fig. 16.1. 

Janini, G.M., Zhou, M., Yu, L.-R., Blonder, J., Gignac, M., Comads, T.P., Issaq, H.J., Veenstra, T.D. (2003). On-column sample enrichment for capillary electrophoresis sheathless electrospray ionization mass spectrometry evaluation for peptide analysis and protein identification. Anal. Chem. 75, 5984—5993. 

Finally, Podoplelov and coworkers41 have prepared trimethyltin hydride and benzyltrimethyltin labelled with tin-117 from a tin sample enriched to 92% in 117Sn. The photochemical reaction between dibenzyl ketone and trimethyltin-117 hydride was used to investigate the chemically induced dynamic nuclear polarization of tin-containing radicals. 

Seidel V, Lindner W. 1993. Universal sample enrichment technique for organochlorine pesticides in environmental and biological samples using a redesigned simultaneous steam distillation-solvent extraction apparatus. Anal Cem 65 3677-3683. 

J.A. Jonsson and L. Mathiasson, Membrane-based techniques for sample enrichment. J. ChromatogrA 902 (2000) 205-225. 

Various sample enrichment techniques are used to isolate volatile organic compounds from mammalian secretions and excretions. The dynamic headspace stripping of volatiles from collected material with purified inert gas and trapping of the volatile compounds on a porous polymer as described by Novotny [3], have been adapted by other workers to concentrate volatiles from various mammalian secretions [4-6]. It is risky to use activated charcoal as an adsorbent in the traps that are used in these methods because of the selective adsorption of compounds with different polarities and molecular sizes on different types of activated charcoal. Due to the high catalytic activity of activated charcoal, thermal conversion can occur if thermal desorption is used to recover the trapped material from such a trap. 

An excellent review of modern sorptive sampling techniques that could be considered for the enrichment of volatiles from mammalian secretions appeared recently [10]. To be on the safe side, more than one sample preparation and sample enrichment method should be used to analyze mammalian secretions. If GC and GC-MS analyses are employed, the results obtained with split/split-less, on-column, SPME and solventless (solid) sample introduction methods [11,12] should be compared. 

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