Derivatization procedure of estradiol with a combination of MPDNP-F and 4-dimethylaminopyridine to generate product ion containing estradiol-skeleton for reliable determination of its serum/plasma concentrations by LC/ESI-MS/MS
The quantification of serum/plasma estradiol ($ E_{2} $) is useful for the diagnosis, pathological analysis, and monitoring of the therapeutic efficacy of estrogen-dependent diseases. In this study, an improved derivatization method using 1-(2,4-dinitro-5-fluorophenyl)-4,4-dimethylpiperazinium iodide (MPDNP-F) was developed and combined with liquid chromatography/electrospray ionization-tandem mass spectrometry (LC/ESI-MS/MS) for the sensitive and specific quantification of the serum/plasma $ E_{2} $. In the new method, the reaction time was reduced to 15 min from 90 min (two-step reaction in the previous method) by the direct reaction of MPDNP-F with $ E_{2} $ at 60°C in the presence of 4-dimethylaminopyridine (DMAP). DMAP served as the organic catalyst and had a less negative effect on the LC/ESI-MS/MS instrument compared to the non-volatile inorganic salt ($ NaHCO_{3} $), which was used in the previous method. The collision-induced dissociation of the molecular cation ([M]+) of the resulting derivative provided a product ion containing the $ E_{2} $-skeleton ([M–$ NO_{2} $–H]+), which significantly enhanced the assay sensitivity and specificity; compared to the dansyl chloride derivatization, which is the currently most-used derivatization procedure for the LC/ESI-MS/MS assays of $ E_{2} $, the MPDNP-F derivatization had significantly fewer interfering peaks and a clear and flat baseline in the serum sample analysis. The MPDNP-F derivatization–LC/ESI-MS/MS method enabled the precise and accurate quantification of $ E_{2} $ even at a 5.0 pg/mL concentration (lower limit of quantification) with a small sample volume (100 μL of serum/plasma) and had a tolerance for the matrix effect. This method was also proven to serve as a more sensitive and specific alternative to the clinically used chemiluminescence enzyme immunoassay. Graphical Abstract.
| Medienart: |
E-Artikel |
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| Erscheinungsjahr: |
2023 |
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| Erschienen: |
2023 |
| Enthalten in: |
Zur Gesamtaufnahme - volume:416 |
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| Enthalten in: |
Analytical and bioanalytical chemistry - 416(2023), 2 vom: 12. Dez., Seite 597-608 |
| Sprache: |
Englisch |
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| Beteiligte Personen: |
Kaneko, Honoka [VerfasserIn] |
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| Links: |
Volltext [kostenfrei] |
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| Themen: |
Derivatization |
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| Anmerkungen: |
© The Author(s) 2023 |
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| doi: |
10.1007/s00216-023-05069-9 |
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| funding: |
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| Förderinstitution / Projekttitel: |
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| PPN (Katalog-ID): |
SPR054218292 |
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| 245 | 1 | 0 | |a Derivatization procedure of estradiol with a combination of MPDNP-F and 4-dimethylaminopyridine to generate product ion containing estradiol-skeleton for reliable determination of its serum/plasma concentrations by LC/ESI-MS/MS |
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| 520 | |a The quantification of serum/plasma estradiol ($ E_{2} $) is useful for the diagnosis, pathological analysis, and monitoring of the therapeutic efficacy of estrogen-dependent diseases. In this study, an improved derivatization method using 1-(2,4-dinitro-5-fluorophenyl)-4,4-dimethylpiperazinium iodide (MPDNP-F) was developed and combined with liquid chromatography/electrospray ionization-tandem mass spectrometry (LC/ESI-MS/MS) for the sensitive and specific quantification of the serum/plasma $ E_{2} $. In the new method, the reaction time was reduced to 15 min from 90 min (two-step reaction in the previous method) by the direct reaction of MPDNP-F with $ E_{2} $ at 60°C in the presence of 4-dimethylaminopyridine (DMAP). DMAP served as the organic catalyst and had a less negative effect on the LC/ESI-MS/MS instrument compared to the non-volatile inorganic salt ($ NaHCO_{3} $), which was used in the previous method. The collision-induced dissociation of the molecular cation ([M]+) of the resulting derivative provided a product ion containing the $ E_{2} $-skeleton ([M–$ NO_{2} $–H]+), which significantly enhanced the assay sensitivity and specificity; compared to the dansyl chloride derivatization, which is the currently most-used derivatization procedure for the LC/ESI-MS/MS assays of $ E_{2} $, the MPDNP-F derivatization had significantly fewer interfering peaks and a clear and flat baseline in the serum sample analysis. The MPDNP-F derivatization–LC/ESI-MS/MS method enabled the precise and accurate quantification of $ E_{2} $ even at a 5.0 pg/mL concentration (lower limit of quantification) with a small sample volume (100 μL of serum/plasma) and had a tolerance for the matrix effect. This method was also proven to serve as a more sensitive and specific alternative to the clinically used chemiluminescence enzyme immunoassay. Graphical Abstract | ||
| 650 | 4 | |a Derivatization |7 (dpeaa)DE-He213 | |
| 650 | 4 | |a Estradiol |7 (dpeaa)DE-He213 | |
| 650 | 4 | |a Skeleton-containing product ion |7 (dpeaa)DE-He213 | |
| 650 | 4 | |a LC/ESI-MS/MS |7 (dpeaa)DE-He213 | |
| 650 | 4 | |a Serum/plasma |7 (dpeaa)DE-He213 | |
| 700 | 1 | |a Matsuoka, Hiroki |4 aut | |
| 700 | 1 | |a Ishige, Takayuki |4 aut | |
| 700 | 1 | |a Kobayashi, Hironori |4 aut | |
| 700 | 1 | |a Higashi, Tatsuya |4 aut | |
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