Liquid Chromatography–Tandem Mass Spectrometry Assay for Simultaneous Measurement of Estradiol and Estrone in Human Plasma

Nelson, Robert E.; Grebe, Stefan K.; O’Kane, Dennis J.; Singh, Ravinder J.

doi:10.1373/clinchem.2003.025478

Cited by 333 publications

(243 citation statements)

References 39 publications

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“…The product ion spectrum of the dansyl derivative of E2 showed the dominant ion of m/z 171 (Fig. 2D), as has been previously observed and assigned to an ion representing the 5-(dimethylamino)naphthyl moiety, formed by homolytic cleavage of the C-S bond between the naphthalene and sulfonyl groups [14,23].…”

Section: Lc-esi-ms/ms Analysis Of Four Aryl-sulfonyl Derivatives Of E2supporting

confidence: 75%

“…For the analysis of steroidal estrogens by LC-ESI-MS/MS, pre-column derivatization by reaction with dansyl chloride at the C-3 hydroxyl groups of these compounds is by far the most popular technique, and is now widely used in both biomedical [14,[23][24][25][26][27][28][29] and environmental [30][31][32] applications. There are, however, aspects of the analysis of estrogens as dansyl derivatives that are not desirable.…”

Section: Introductionmentioning

confidence: 99%

“…There are, however, aspects of the analysis of estrogens as dansyl derivatives that are not desirable. With dansyl derivatization and LC-ESI-MS/MS of steroidal estrogens, the vast majority of the ion current after collision-induced dissociation (CID) of the [M+H] + ion is carried by a single ion derived from the protonated 5-(dimethylamino)-naphthyl moiety [14,[23][24][25][26], and very little of it by estrogen-derived ions, thereby making MS/MS and third stage MS (MS 3 ) analyses structurally uninformative. The identification of unknown estrogens and their metabolites is therefore not significantly aided by the formation and analysis of dansyl derivatives.…”

Section: Introductionmentioning

confidence: 99%

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Analysis of steroidal estrogens as pyridine-3-sulfonyl derivatives by liquid chromatography electrospray tandem mass spectrometry

Spink

2008

Analytical Biochemistry

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Sulfonyl chlorides substituted with functional groups having high proton affinity can serve as derivatization reagents to enhance the sensitivity for steroidal estrogens in liquid chromatography electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS). The most commonly used reagent for derivatization of estrogens for LC-ESI-MS/MS is dansyl chloride. In this study, we compared dansyl chloride, 1,2-dimethylimidazole-4-sulfonyl (DMIS) chloride, pyridine-3-sulfonyl (PS) chloride, and 4-(1H-pyrazol-1-yl)benzenesulfonyl (PBS) chloride for derivatization of 17β-estradiol (E2) prior to LC-ESI-MS/MS. The product ion spectra of the dansyl and DMIS derivatives were dominated by ions representing derivatization reagent moieties. In contrast, the product ion spectrum of the PS derivative of E2 and, to a lesser extent, the PBS derivative, showed analytespecific fragment ions. Derivatization with PS chloride was therefore chosen for further investigation. The product ion spectrum of the PS derivative of E2 showed intense ions at m/z 272, assigned to the radical E2 cation, and at m/z 350, attributed to the loss of SO 2 from the [M+H] + ion. Third-stage mass spectrometry of the PS derivative of E2 with isolation and collisional activation of the m/z 272 ion resulted in steroid C and D ring cleavages analogous to those observed in electron ionization mass spectrometry. The product ion spectra of the PS derivatives of estrone, 17α-ethinylestradiol, equilin, and equilenin showed similar estrogen-specific ions. Using derivatization with PS chloride, we developed an LC-ESI-MS/MS method with multiple reaction monitoring of primary and confirmatory precursor-to-product ion transitions for the determination of E2 in serum.

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Section: Lc-esi-ms/ms Analysis Of Four Aryl-sulfonyl Derivatives Of E2supporting

confidence: 75%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Analysis of steroidal estrogens as pyridine-3-sulfonyl derivatives by liquid chromatography electrospray tandem mass spectrometry

Spink

2008

Analytical Biochemistry

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“…Reaction with hydroxylamine and its derivatives, and Diels-Alder reagents were shown to improve the sensitivity for keto-steroids (Kushnir et al, 2006a,b); dansyl derivatives allow to significantly improve the sensitivity for steroids containing within the structure hydroxyl or phenol groups (Anari et al, 2002;Nelson et al, 2004;Kushnir et al, 2008). Derivatization with mono (dimethylaminoethyl)succinyl imidazolide was shown to significantly improve the sensitivity for cholesterol and dehydrocholesterol (Johnson, ten Brink, & Jakobs, 2001).…”

Section: Lc-ms/ms In Clinical Diagnosticsmentioning

confidence: 99%

“…Recently, it was shown that commercial IAs for E2 are inaccurate to measure low endogenous concentrations . Earlier published LC-MS/MS methods for estrogens (Anari et al, 2002;Nelson et al, 2004) also lack the sensitivity and the specificity needed to measure low concentrations of estrogens. One of the approaches for enhancing the sensitivity was through the use of negative ion mode ESI on a more sensitive instrument API5000 (Applied Biosystems/ Sciex) (Guo et al, 2008).…”

Section: Lc-ms/ms In Clinical Diagnosticsmentioning

confidence: 99%

Liquid chromatography-tandem mass spectrometry applications in endocrinology

Kushnir

Rockwood

Bergquist

2009

Mass Spectrom. Rev.

138

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Liquid chromatography-tandem mass spectrometry (LC-MS/ MS) has been recognized as a primary methodology for the accurate analysis of endogenous steroid hormones in biological samples. This review focuses on the use of LC-MS/MS in clinical laboratories to assist with the diagnosis of diverse groups of endocrine and metabolic diseases. Described analytical methods use on-line and off-line sample preparation and analytical derivatization to enhance analytical sensitivity, specificity, and clinical utility. Advantages of LC-MS/MS as an analytical technique include high specificity, possibility to simultaneously measure multiple analytes, and the ability to assess the specificity of the analysis in every sample. All described analytical methods were extensively validated, utilized in routine diagnostic practice, and were applied in a number of clinical and epidemiological studies, including a study of the steroidogenesis in ovarian follicles. #

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Current Strategies and Future Trends

Zhou

2010

Regulated Bioanalytical Laboratories

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Liquid Chromatography–Tandem Mass Spectrometry Assay for Simultaneous Measurement of Estradiol and Estrone in Human Plasma

Cited by 333 publications

References 39 publications

Analysis of steroidal estrogens as pyridine-3-sulfonyl derivatives by liquid chromatography electrospray tandem mass spectrometry

Analysis of steroidal estrogens as pyridine-3-sulfonyl derivatives by liquid chromatography electrospray tandem mass spectrometry

Liquid chromatography-tandem mass spectrometry applications in endocrinology

Current Strategies and Future Trends

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