Clinical applications of LC-MS sex steroid assays: Evolution of methodologies in the 21st century

Current Opinion in Endocrinology, Diabetes and Obesity

Volumn 21, Issue 3, 2014, Pages 217-226

  Ketha, Hemamalini ^a   Kaur, Sukhbir ^b   Grebe, Stefan K ^a   Singh, Ravinder J ^a  

^a MAYO CLINIC   (United States)

^b BIRMINGHAM HEARTLANDS HOSPITAL   (United Kingdom)

Author keywords

dihydrotestosterone; estradiol; LC MS MS; testosterone

Indexed keywords

17 HYDROXYPREGNENOLONE; ANDROSTANOLONE; ANDROSTENEDIONE; ANDROSTERONE; DANAZOL; EPITESTOSTERONE; ESTRADIOL; ESTRONE; NORETHISTERONE; OXOSTEROID; PRASTERONE; SEX HORMONE; TESTOSTERONE;

AMENORRHEA; ASSAY; BREAST TUMOR; COLORIMETRY; HUMAN; HYPOGONADISM; IMMUNOASSAY; LIQUID CHROMATOGRAPHY; OVARY POLYCYSTIC DISEASE; OVARY TUMOR; PROSTATE TUMOR; PUBERTY DISORDERS; REVIEW; TANDEM MASS SPECTROMETRY; TESTIS TUMOR; FEMALE; MALE; MASS SPECTROMETRY; METABOLISM; RADIOIMMUNOASSAY; REPRODUCIBILITY; SENSITIVITY AND SPECIFICITY; TRENDS;

ANDROSTENEDIONE; CHROMATOGRAPHY, LIQUID; ESTRADIOL; FEMALE; GONADAL STEROID HORMONES; HUMANS; MALE; MASS SPECTROMETRY; RADIOIMMUNOASSAY; REPRODUCIBILITY OF RESULTS; SENSITIVITY AND SPECIFICITY; TESTOSTERONE;

EID: 84899992538     PISSN: 1752296X     EISSN: 17522978     Source Type: Journal    
DOI: 10.1097/MED.0000000000000068     Document Type: Review

References (55)

1. Hamilton JB. Androgenic activity per milligram of calorimetrically measured ketosteroids in urine; an index of the respective contributions from testicular and extra-testicular sources. J Clin Endocrinol Metab 1954; 14:452-471.
2. Gandy HM, Peterson RE. Measurement of testosterone and 17-ketosteroids in plasma by the double isotope dilution derivative technique. J Clin Endocrinol Metab 1968; 28:949-977.
3. Mayes D, Nugent CA. Determination of plasma testosterone by the use of competitive protein binding. J Clin Endocrinol Metab 1968; 28:1169-1176.
4. Abraham GE. Radioimmunoassay of steroids in biological fluids. J Steroid Biochem 1975; 6:261-270.
5. Vladutiu AO, Sulewski JM, Pudlak KA, Stull CG. Heterophilic antibodies interfering with radioimmunoassay. A false-positive pregnancy test. Jama 1982; 248:2489-2490.
6. Boscato LM, Stuart MC. Incidence and specificity of interference in two-site immunoassays. Clin Chem 1986; 32:1491-1495.
7. Tate J, Ward G. Interferences in immunoassay. Clin Biochem Rev 2004; 25:105-120.
8. Klee GG. Interferences in hormone immunoassays. Clin Lab Med 2004; 24:1-18.
9. Sacks SS. Are routine testosterone assays good enough? Clin Biochem Rev 2005; 26:43-45.
10. Kroll MH, Elin RJ. Interference with clinical laboratory analyses. Clin Chem 1994; 40:1996-2005.
11. Cole LA, Rinne KM, Shahabi S, Omrani A. False-positive hcg assay results leading to unnecessary surgery and chemotherapy and needless occurrences of diabetes and coma. Clin Chem 1999; 45:313-314.
12. Matsumoto AM, Bremner WJ. Serum testosterone assays: accuracy matters. J Clin Endocrinol Metab 2004; 89:520-524.
13. Herold DA, Fitzgerald RL. Immunoassays for testosterone in women: better than a guess? Clin Chem 2003; 49:1250-1251.
14. Wang C, Catlin DH, Demers LM, et al. Measurement of total serum testosterone in adult men: comparison of current laboratory methods versus liquid chromatography-tandem mass spectrometry. J Clin Endocrinol Metab 2004; 89:534-543.
15. Miller KK, Rosner W, Lee H, et al. Measurement of free testosterone in normal women and women with androgen deficiency: Comparison of methods. J Clin Endocrinol Metab 2004; 89:525-533.
16. Kushnir MM, Rockwood AL, Roberts WL, et al. Liquid chromatography tandem mass spectrometry for analysis of steroids in clinical laboratories. Clin Biochem 2011; 44:77-88.
17. Seger C. Usage and limitations of liquid chromatography-tandem mass spectrometry (LC-MS/MS) in clinical routine laboratories. Wien Med Wochenschr 2012; 162:499-504.
18. Grebe SK, Singh RJ. Lc-ms/ms in the clinical laboratory: where to from here? Clin Biochem Rev 2011; 32:5-31.
19. Netzel BC, Cradic KW, Bro ET, et al. Increasing liquid chromatographytandem mass spectrometry throughput by mass tagging: a samplemultiplexed high-throughput assay for 25-hydroxyvitamin d2 and d3. Clin Chem 2011; 57:431-440.
20. Koal T, Schmiederer D, Pham-Tuan H, et al. Standardized lc-ms/ms based steroid hormone profile-analysis. J Steroid Biochem Mol Biol 2012; 129: 129-138.
21. Rege J, Nakamura Y, Satoh F, et al. Liquid chromatography-tandem mass spectrometry analysis of human adrenal vein 19-carbon steroids before and after acth stimulation. J Clin Endocrinol Metab 2013; 98:1182-1188.
22. Guo T, Gu J, Soldin OP, et al. Rapid measurement of estrogens and their metabolites in human serum by liquid chromatography-tandem mass spectrometry without derivatization. Clin Biochem 2008; 41:736-741.
23. Broccardo CJ, Schauer KL, Kohrt WM, et al. Multiplexed analysis of steroid hormones in human serum using novel microflow tile technology and LC-MS/MS. J Chromatogr B Analyt Technol Biomed Life Sci 2013; 934:16-21.
24. Keelan JA, Mattes E, Tan H, et al. Androgen concentrations in umbilical cord blood and their association with maternal, fetal and obstetric factors. PLoS One 2012; 7:e42827.
25. Huhtaniemi IT, Tajar A, Lee DM, et al. Comparison of serum testosterone and estradiol measurements in 3174 european men using platform immunoassay and mass spectrometry; relevance for the diagnostics in aging men. Eur J Endocrinol 2012; 166:983-991.
26. Taieb J, Benattar C, Birr AS, Lindenbaum A. Limitations of steroid determination by direct immunoassay. Clin Chem 2002; 48:583-585.
27. Faupel-Badger JM, Fuhrman BJ, Xu X, et al. Comparison of liquid chromatography-tandem mass spectrometry, RIA, and ELISA methods for measurement of urinary estrogens. Cancer Epidemiol Biomarkers Prev 2010; 19:292-300.
28. Moal V, Mathieu E, Reynier P, et al. Low serum testosterone assayed by liquid chromatography-tandem mass spectrometry. Comparison with five immunoassay techniques. Clin Chim Acta 2007; 386:12-19.
29. Boudou P, Taieb J, Mathian B, et al. Comparison of progesterone concentration determination by 12 nonisotopic immunoassays and gas chromatography/mass spectrometry in 99 human serum samples. J Steroid Biochem Mol Biol 2001; 78:97-104.
30. Taieb J, Mathian B, Millot F, et al. Testosterone measured by 10 immunoassays and by isotope-dilution gas chromatography-mass spectrometry in sera from 116 men, women, and children. Clin Chem 2003; 49:1381-1395.
31. Sharp AM, Fraser IS, Caterson ID. Further studies on danazol interference in testosterone radioimmunoassays. Clin Chem 1983; 29:141-143.
32. Jeffery J, Mackenzie F, Beckett G, et al. Norethisterone interference in testosterone assays. Ann Clin Biochem 2013; 284-288.
33. Mean F, Pellaton M, Magrini G. Study on the binding of dihydrotestosterone, testosterone and oestradiol with sex hormone binding globulin. Clin Chim Acta 1977; 80:171-180.
34. Azziz R. Androgen excess disorders in women: polycystic ovary syndrome and other disorders. Humana Press Inc.; 2007; Edition. pp. 63-76.
35. Lee M. Basic skills in interpreting laboratory data. 4th ed. American Society of Health-System Pharmacists; 2009, 4th Edition. pp. 541-564.
36. Singh RJ. Validation of a high throughput method for serum/plasma testosterone using liquid chromatography tandem mass spectrometry (LC-MS/MS). Steroids 2008; 73:1339-1344.
37. Keevil B, Macdonald P, Macdowall W, et al. Salivary testosterone measurement by liquid chromatography tandem mass spectrometry in adult males and females. Ann Clin Biochem 2013. [Epub ahead of print]. doi: 10.1177/0004563213506412.
38. Danaceau JP, Scott Morrison M, Slawson MH. Quantitative confirmation of testosterone and epitestosterone in human urine by LC/Q-TOF mass spectrometry for doping control. J Mass Spectrom 2008; 43:993-1000.
39. Bui HN, Sluss PM, Blincko S, et al. Dynamics of serum testosterone during the menstrual cycle evaluated by daily measurements with an ID-LC-MS/MS method and a 2nd generation automated immunoassay. Steroids 2013; 78:96-101.
40. Bhasin S, Pencina M, Jasuja GK, et al. Reference ranges for testosterone in men generated using liquid chromatography tandem mass spectrometry in a community-based sample of healthy nonobese young men in the framingham heart study and applied to three geographically distinct cohorts. J Clin Endocrinol Metab 2011; 96:2430-2439.
41. Cummings SR, Duong T, Kenyon E, et al. Serum estradiol level and risk of breast cancer during treatment with raloxifene. J Am Med Assoc 2002; 287:216-220.
42. Amin S, Zhang Y, Sawin CT, et al. Association of hypogonadism and estradiol levels with bone mineral density in elderly men from the framingham study. Ann Intern Med 2000; 133:951-963.
43. Ettinger B, Pressman A, Sklarin P, et al. Associations between low levels of serum estradiol, bone density, and fractures among elderly women: the study of osteoporotic fractures. J Clin Endocrinol Metab 1998; 83:2239-2243.
44. Hogervorst E, Williams J, Combrinck M, David Smith A. Measuring serum oestradiol in women with alzheimer's disease: the importance of the sensitivity of the assay method. Eur J Endocrinol 2003; 148:67-72.
45. Yang DT, Owen WE, Ramsay CS, et al. Performance characteristics of eight estradiol immunoassays. Am J Clin Pathol 2004; 122:332-337.
46. Ankarberg-Lindgren C, Norjavaara E. A purification step prior to commercial sensitive immunoassay is necessary to achieve clinical usefulness when quantifying serum 17 beta-estradiol in prepubertal children. Eur J Endocrinol 2008; 158:117-124.
47. Handelsman DJNJ, Jimenez M, McLachlan R, Sartorius G. Performance of direct estradiol immunoassays with human male serum samples. Clin Chem 2014; 60:510-517. A study comparing five immunoassays for measurement of serum estradiol in 101 healthy asymptomatic men demonstrating a positive bias across the measurement range.
48. Anari MR, Bakhtiar R, Zhu B, et al. Derivatization of ethinylestradiol with dansyl chloride to enhance electrospray ionization: Application in trace analysis of ethinylestradiol in rhesus monkey plasma. Analytical Chem 2002; 74:4136-4144.
49. Nelson RE, Grebe SK, OKane DJ, Singh RJ. Liquid chromatography-tandem mass spectrometry assay for simultaneous measurement of estradiol and estrone in human plasma. Clin Chem 2004; 50:373-384.
50. Stanczyk FZ, Clarke NJ. Advantages and challenges of mass spectrometry assays for steroid hormones. J Steroid Biochem Mol Biol 2010; 121:491-495.
51. Hsing AW, Stanczyk FZ, Belanger A, et al. Reproducibility of serum sex steroid assays in men by ria and mass spectrometry. Cancer Epidemiol Biomarkers Prev 2007; 16:1004-1008.
52. Bystrom CE, Salameh W, Reitz R, Clarke NJ. Plasma renin activity by LC-MS/MS: development of a prototypical clinical assay reveals a subpopulation of human plasma samples with substantial peptidase activity. Clin Chem 2015; 56:1561-1569.
53. Cunningham GR, Toma SM. Clinical review: why is androgen replacement in males controversial? J Clin Endocrinol Metab 2011; 96:38-52.
54. Koutsari C, Ali AH, Nair KS, et al. Fatty acid metabolism in the elderly: effects of dehydroepiandrosterone and testosterone replacement in hormonally deficient men and women. J Clin Endocrinol Metab 2009; 94:3414-3423.
55. Handelsman DJ, Wartofsky L. Requirement for mass spectrometry sex steroid assays in the Journal of Clinical Endocrinology and Metabolism. 2013; 98:3971-3973.