Liquid chromatography/mass spectrometry matrix effects

The method for chloroacetanilide soil metabolites in water determines concentrations of ethanesulfonic acid (ESA) and oxanilic acid (OXA) metabolites of alachlor, acetochlor, and metolachlor in surface water and groundwater samples by direct aqueous injection LC/MS/MS. After injection, compounds are separated by reversed-phase HPLC and introduced into the mass spectrometer with a TurboIonSpray atmospheric pressure ionization (API) interface. Using direct aqueous injection without prior SPE and/or concentration minimizes losses and greatly simplifies the analytical procedure. Standard addition experiments can be used to check for matrix effects. With multiple-reaction monitoring in the negative electrospray ionization mode, LC/MS/MS provides superior specificity and sensitivity compared with conventional liquid chromatography/mass spectrometry (LC/MS) or liquid chromatography/ultraviolet detection (LC/UV), and the need for a confirmatory method is eliminated. In summary,... 

Kruve, A., A. Kunnapas, K. Herodes, et al. 2008. Matrix effects in pesticide multi-residue analysis by liquid chromatography-mass spectrometry. J. Chromatogr. A 1187 58-66. 

Xia YQ, Jemal M (2009) Phospholipids in liquid chromatography/mass spectrometry bio-analysis comparison of three tandem mass spectrometric techniques for monitoring plasma phospholipids, the effect of mobile phase composition on phospholipids elution and the association of phospholipids with matrix effects. Rapid Commun Mass Spectrom 23 2125-2138... 

Little JL, Wempe MF, Buchanan CM (2006) Liquid chromatography-mass spectrometry/mass spectrometry method development for drug metabolism studies examining lipid matrix ionization effects in plasma. J Chromatogr B 833 219-230... 

Ismaiel OA et al (2010) Investigation of endogenous blood plasma phospholipids, cholesterol and glycerides that contribute to matrix effects in bioanalysis by liquid chromatography/mass spectrometry. J Chromatogr B Analyt Technol Biomed Life Sci 878 3303-3316... 

High-performance liquid chromatography-mass spectrometry (HPLC-MS) is a powerful analytical technique widely used in recent years for the analysis of biomarkers and metabolites. Biomarker determination and quantification, whether metabolic or adducted biomolecules, are commonly used to evaluate exposure and support biomonitoring research, especially in the area of occupational exposure and health. Some of the common problems and strategies of HPLC-MS biomarker analysis involve matrix effects, the use of isotope-labeled internal standard compounds, and sample cleanup usually all of these factors must be evaluated within the development phase of an analysis procedure. Specific examples of biomarker analysis using HPLC-MS include acrylamide, aromatic compounds, and 1-bromopropane, and these examples are discussed in detail. 

Niessen, W.M.A., Manini, R, Andreoli, R. (2006) Matrix Effects in Quantitative Pesticide Analysis Using Liquid Chromatography-Mass Spectrometry. Mass Spectrom. Rev. 25 881-899. 

Trufelli, H Palma, P., Famiglini, G. and Cappiello, A. (2011) An overview of matrix effects in liquid chromatography-mass spectrometry. Mass Spectrom. Rev., 30,491-509. 

Niessen WMA, Manini P, Andreoli R. Matrix effects in quantitative pesticide analysis using liquid chromatography-mass spectrometry. Mass Spec Rev 2006 25 881-99. 

Table 5.15 Relative signal responses from various injection volumes for the LC-MS-MS analysis of a wheat forage matrix sample. Reprinted from J. Chromatogr., A, 907, Choi, B. K., Hercules, D. M. and Gusev, A. L, Effect of liquid chromatography separation of complex matrices on liquid chromatography-tandem mass spectrometry signal suppression , 337-342, Copyright (2001), with permission from Elsevier Science...

Hsieh Y. et al., 2001. Quantitative screening and matrix effect studies of drug discovery compounds in monkey plasma using fast-gradient liquid chromatography/tandem mass spectrometry. Rapid Commun Mass Spectrom 15 2481. 

Jemal, M., Schuster, A., and Whigan, D. B. (2003). Liquid chromatography/tandem mass spectrometry methods for quantitation of mevalonic acid in human plasma and urine method validation, demonstration of using a surrogate analyte, and demonstration of unacceptable matrix effect in spite of use of a stable isotope analog internal standard. Rapid Commun. Mass Spectrom. 17, 1723-1734. 

Tiller, P. R. Romanyshyn, L. A. Implications of matrix effects in ultrafast gradient or fast isocratic liquid chromatography with mass spectrometry in drug discovery. Rapid Commun Mass Spectrom 2002, 16, 92-98. 

Taylor, P. J. Matrix effects the Achilles heel of quantitative high-performance liquid chromatography-electrospray-tandem mass spectrometry. Clin Biochem 2005, 38, 328-334. 

Ylinen et al. [53] developed an ion-pair extraction procedure employing tetrabutylamonium (TBA) counter ions for determination of PFOA in plasma and urine in combination with gas chromatography (GC) and flame ionisation detection (FID). Later on, Hansen et al. [35] improved the sensitivity of the ion-pair extraction approach using methyl tertiary butyl ether (MTBE) and by the inclusion of a filtration step to remove solids from the extract making it amenable to liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) determination. Ion-pair extraction procedure has been the basis of several procedures for biota [49,54-58] and food samples [50,59,60]. However, this method has shown to have some limitations, such as (1) co-extraction of lipids and other matrix constituents and the absence of a clean-up step to overcome the effects of matrix compounds and (2) the wide variety of recoveries observed, typically ranging. 

Marin JM, Gracia-Lor E, Sancho JV et al (2009) Application of ultra-high-pressure liquid chromatography-tandem mass spectrometry to the determination of multi-class pesticides in environmental and wastewater samples Study of matrix effects. J Chromatogr A 1216 1410-1420... 

Hsieh, Y., Chintala, M., Mei, H., Agans, J., Brisson, J. M., Ng, K., and Korfmacher, W. A. (2001). Quantitative screening and matrix effect studies of drug discovery compounds in monkey plasma [by] using fast-gradient liquid chromatography/tandem mass spectrometry. Rapid Commun. Mass Spectrom. 15 2481-2487. 

A selective, sensitive, and rapid hydrophilic interaction liquid chromatography with electrospray ionization tandem mass spectrometry was developed for the determination of donepezil in human plasma [32], Donepezil was twice extracted from human plasma using methyl-ferf-butyl ether at basic pH. The analytes were separated on an Atlantis HILIC Silica column with the mobile phase of acetonitrile ammonium formate (50 mM, pH 4.0) (85 15, v/v) and detected by tandem mass spectrometry in the selective reaction monitoring mode. The calibration curve was linear (r = 0.9994) over the concentration range of 0.10-50.0 ng/ ml and the lower limit of quantification was 0.1 ng/ml using 200 /d plasma sample. The CV and relative error for intra- and inter-assay at four quality control levels were 2.7% to 10.5% and —10.0% to 0.0%, respectively. There was no matrix effect for donepezil and cisapride. The present method was successfully applied to the pharmacokinetic study of donepezil after oral dose of donepezil hydrochloride (10 mg tablet) to male healthy volunteers. 

Kloepfer, A., J.B. Quintana, and T. Reemtsma. 2005. Operational options to reduce matrix effects in liquid chromatography-electrospray ionization-mass spectrometry analysis of aqueous environmental samples. 7. Chromatogr. A 1067 153-160. 

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