Cyanoacetohydrazide As a Novel Derivatization Agent for the Determination of UHPLC-HRMS Steroids in Urine

Overview

Journal Molecules

Publisher MDPI

Specialty Biology

Date 2024 Jun 19

PMID 38893309

Authors

Azamat Temerdashev

Maria Zorina

Yu-Qi Feng

Elina Gashimova

Victor V Dotsenko

Vitalij Ioutsi

Sanka N Atapattu

Affiliations

Soon will be listed here.

Abstract

The possibility of cyanoacetohydrazide usage as a novel derivatizing agent is demonstrated in the presented article, and a comparison with hydroxylamine as the most commonly used reagent is provided. Optimal conditions for steroid derivatization with cyanoacetohydrazide are provided. According to the collected data, the maximum yield of derivatives was observed at pH 2.8 within 70 min at 40 °C with 5 ng/mL limit of detection for all investigated analytes. It was shown that cyanoacetohydrazide derivatives produces both syn- and anti-forms as well as hydroxylamine, and their ratios were evaluated and shown in presented work. An efficiency enchantment from two to up to five times was achieved with a novel derivatization reagent. Its applicability for qualitative analysis of steroids in urine was presented at real samples. Additionally, the reproducible fragmentation of the derivatizing agent in collision-induced dissociation offers opportunities for simplified non-targeted steroidomic screening. Furthermore, cyanoacetohydrazide increases ionization efficiency in positive mode, which can eliminate the need for redundant high-resolution instrument runs required for both positive and negative mode analyses.

References

Olesti E, Garcia A, Rahban R, Rossier M, Boccard J, Nef S . Steroid profile analysis by LC-HRMS in human seminal fluid. J Chromatogr B Analyt Technol Biomed Life Sci. 2019; 1136:121929. DOI: 10.1016/j.jchromb.2019.121929. View

Song Z, Gao H, Xie W, Sun Q, Liang K, Li Y . Quantitative MALDI-MS assay of steroid hormones in plasma based on hydroxylamine derivatization. Anal Biochem. 2020; 616:114089. DOI: 10.1016/j.ab.2020.114089. View

Ney L, Felmingham K, Bruno R, Matthews A, Nichols D . Chloroform-based liquid-liquid extraction and LC-MS/MS quantification of endocannabinoids, cortisol and progesterone in human hair. J Pharm Biomed Anal. 2021; 201:114103. DOI: 10.1016/j.jpba.2021.114103. View

Kalogera E, Pistos C, Provatopoulou X, Athanaselis S, Spiliopoulou C, Gounaris A . Androgen glucuronides analysis by liquid chromatography tandem-mass spectrometry: could it raise new perspectives in the diagnostic field of hormone-dependent malignancies?. J Chromatogr B Analyt Technol Biomed Life Sci. 2013; 940:24-34. DOI: 10.1016/j.jchromb.2013.09.022. View

Elmongy H, Masquelier M, Ericsson M . Development and validation of a UHPLC-HRMS method for the simultaneous determination of the endogenous anabolic androgenic steroids in human serum. J Chromatogr A. 2019; 1613:460686. DOI: 10.1016/j.chroma.2019.460686. View

Falk R, Xu X, Keefer L, Veenstra T, Ziegler R . A liquid chromatography-mass spectrometry method for the simultaneous measurement of 15 urinary estrogens and estrogen metabolites: assay reproducibility and interindividual variability. Cancer Epidemiol Biomarkers Prev. 2008; 17(12):3411-8. PMC: 4158914. DOI: 10.1158/1055-9965.EPI-08-0355. View

Temerdashev A, Nesterenko P, Dmitrieva E, Zhurkina K, Feng Y . GC-MS/MS Determination of Steroid Hormones in Urine Using Solid-Phase Derivatization as an Alternative to Conventional Methods. Molecules. 2022; 27(18). PMC: 9502991. DOI: 10.3390/molecules27185796. View

Girel S, Markin P, Tobolkina E, Boccard J, Moskaleva N, Rudaz S . Comprehensive plasma steroidomics reveals subtle alterations of systemic steroid profile in patients at different stages of prostate cancer disease. Sci Rep. 2024; 14(1):1577. PMC: 10796437. DOI: 10.1038/s41598-024-51859-1. View

Storbeck K, Schiffer L, Baranowski E, Chortis V, Prete A, Barnard L . Steroid Metabolome Analysis in Disorders of Adrenal Steroid Biosynthesis and Metabolism. Endocr Rev. 2019; 40(6):1605-1625. PMC: 6858476. DOI: 10.1210/er.2018-00262. View

10.

Keevil B . Novel liquid chromatography tandem mass spectrometry (LC-MS/MS) methods for measuring steroids. Best Pract Res Clin Endocrinol Metab. 2013; 27(5):663-74. DOI: 10.1016/j.beem.2013.05.015. View

11.

Weitzel K . Bond-dissociation energies of cations--pushing the limits to quantum state resolution. Mass Spectrom Rev. 2011; 30(2):221-35. DOI: 10.1002/mas.20276. View

12.

Faqehi A, Denham S, Naredo G, Cobice D, Khan S, Simpson J . Derivatization with 2-hydrazino-1-methylpyridine enhances sensitivity of analysis of 5α-dihydrotestosterone in human plasma by liquid chromatography tandem mass spectrometry. J Chromatogr A. 2021; 1640:461933. PMC: 7938423. DOI: 10.1016/j.chroma.2021.461933. View

13.

Emond J, Lacombe L, Caron P, Turcotte V, Simonyan D, Aprikian A . Urinary oestrogen steroidome as an indicator of the risk of localised prostate cancer progression. Br J Cancer. 2021; 125(1):78-84. PMC: 8257651. DOI: 10.1038/s41416-021-01376-z. View

14.

Labrie F, Belanger A, Belanger P, Berube R, Martel C, Cusan L . Androgen glucuronides, instead of testosterone, as the new markers of androgenic activity in women. J Steroid Biochem Mol Biol. 2006; 99(4-5):182-8. DOI: 10.1016/j.jsbmb.2006.02.004. View

15.

Devier M, Labadie P, Togola A, Budzinski H . Simple methodology coupling microwave-assisted extraction to SPE/GC/MS for the analysis of natural steroids in biological tissues: application to the monitoring of endogenous steroids in marine mussels Mytilus sp. Anal Chim Acta. 2009; 657(1):28-35. DOI: 10.1016/j.aca.2009.10.023. View

16.

Olesti E, Boccard J, Visconti G, Gonzalez-Ruiz V, Rudaz S . From a single steroid to the steroidome: Trends and analytical challenges. J Steroid Biochem Mol Biol. 2020; 206:105797. DOI: 10.1016/j.jsbmb.2020.105797. View

17.

Marta Z, Bobaly B, Fekete J, Magda B, Imre T, Meszaros K . Simultaneous determination of thirteen different steroid hormones using micro UHPLC-MS/MS with on-line SPE system. J Pharm Biomed Anal. 2017; 150:258-267. DOI: 10.1016/j.jpba.2017.12.014. View

18.

Matysik S, Liebisch G . Quantification of steroid hormones in human serum by liquid chromatography-high resolution tandem mass spectrometry. J Chromatogr A. 2017; 1526:112-118. DOI: 10.1016/j.chroma.2017.10.042. View

19.

Hansen M, Jacobsen N, Nielsen F, Bjorklund E, Styrishave B, Halling-Sorensen B . Determination of steroid hormones in blood by GC-MS/MS. Anal Bioanal Chem. 2011; 400(10):3409-17. DOI: 10.1007/s00216-011-5038-8. View

20.

Wells P, Mackenzie P, Chowdhury J, Guillemette C, Gregory P, Ishii Y . Glucuronidation and the UDP-glucuronosyltransferases in health and disease. Drug Metab Dispos. 2004; 32(3):281-90. DOI: 10.1124/dmd.32.3.281. View