[en] A growing body of literature describes the potential effects of circadian disruption on human health. Indeed, psychiatric diseases, metabolic syndrome, and cancers may be linked to disturbance of the circadian rhythm. Currently, the best practice to assess circadian rhythm is the measurement of melatonin levels. Our goal was thus to develop and validate a highly sensitive LC-MS/MS method to follow salivary melatonin levels throughout the day and night. Our method reached a lower limit of the measuring interval (LLMI) of 0.8 pg/mL. To our knowledge, it is the most sensitive method allowing quantitation of melatonin in saliva. Saliva, obtained from passive drooling or salivette, was extracted by an efficient and quick liquid-liquid extraction with no further cleanup needed. The method was validated according to the European Medicines Agency (EMA) guidelines and provided excellent results regarding accuracy, precision, linearity, selectivity, and specificity. Comparison between radioimmunoassay and our method was performed and showed differences at low levels, most likely due to cross-reactivity with other indols. To assess daytime melatonin levels in humans, salivary melatonin levels of ten volunteers were monitored throughout the day and showed lower daytime levels than reported in previous studies.
Disciplines :
Médecine de laboratoire & technologie médicale
Auteur, co-auteur :
Demeuse, Justine ; Université de Liège - ULiège > Département de pharmacie > Chimie médicale
Calaprice, Chiara; Department of Clinical Chemistry, CHU Liège, 4000 Liège, Belgium
Huyghebaert, Loreen ; Centre Hospitalier Universitaire de Liège - CHU > > Service de chimie clinique
Rechchad, Marwa ; Centre Hospitalier Universitaire de Liège - CHU > > Service de chimie clinique
Peeters, Stéphanie ; Centre Hospitalier Universitaire de Liège - CHU > > Service de chimie clinique
Cavalier, Etienne ; Centre Hospitalier Universitaire de Liège - CHU > > Service de chimie clinique
Le Goff, Caroline ; Centre Hospitalier Universitaire de Liège - CHU > > Service de chimie clinique
Langue du document :
Anglais
Titre :
Development and Validation of an Ultrasensitive LC-MS/MS Method for the Quantification of Melatonin in Human Saliva.
Date de publication/diffusion :
02 mai 2023
Titre du périodique :
Journal of the American Society for Mass Spectrometry
Rajaratnam, S. M. W.; Arendt, J. Health in a 24-h Society 2001, 358, 999- 1005, 10.1016/S0140-6736(01)06108-6
Claustrat, B.; Leston, J. Melatonin: Physiological Effects in Humans. Neurochirurgie 2015, 61 ( 2-3), 77- 84, 10.1016/j.neuchi.2015.03.002
Hardeland, R. Melatonin and 5-Methoxytryptamine in Non-Metazoans. Reprod. Nutr. Dev. 1999, 39 ( 3), 399- 408, 10.1051/rnd:19990311
Van Tassel, D. L.; Roberts, N.; Lewy, A.; O’Neill, S. D. Melatonin in Plant Organs. J. Pineal Res. 2001, 31 ( 1), 8- 15, 10.1034/j.1600-079X.2001.310102.x
Pavlova, M. K.; Latreille, V. Sleep Disorders. Am. J. Med. 2019, 132 ( 3), 292- 299, 10.1016/j.amjmed.2018.09.021
Riemann, D.; Baglioni, C.; Bassetti, C.; Bjorvatn, B.; Dolenc Groselj, L.; Ellis, J. G.; Espie, C. A.; Garcia-Borreguero, D.; Gjerstad, M.; Gonçalves, M.; Hertenstein, E.; Jansson-Fröjmark, M.; Jennum, P. J.; Leger, D.; Nissen, C.; Parrino, L.; Paunio, T.; Pevernagie, D.; Verbraecken, J.; Weeß, H. G.; Wichniak, A.; Zavalko, I.; Arnardottir, E. S.; Deleanu, O. C.; Strazisar, B.; Zoetmulder, M.; Spiegelhalder, K. European Guideline for the Diagnosis and Treatment of Insomnia. J. Sleep Res. 2017, 26 ( 6), 675- 700, 10.1111/jsr.12594
Vorkapic, P.; Waldhauser, F.; Bruckner, R.; Biegelmayer, C.; Schmidbauer, M.; Pendl, G. Serum Melatonin Levels: A New Neurodiagnostic Tool in Pineal Region Tumor?. Neurosurgery 1987, 21 ( 6), 817- 824, 10.1227/00006123-198712000-00006
Van Faassen, M.; Bischoff, R.; Kema, I. P. Relationship between Plasma and Salivary Melatonin and Cortisol Investigated by LC-MS/MS. Clin. Chem. Lab. Med. 2017, 55 ( 9), 1340- 1348, 10.1515/cclm-2016-0817
Reid, K. J. Assessment of Circadian Rhythms. Neurol. Clin. 2019, 37 ( 3), 505- 526, 10.1016/j.ncl.2019.05.001
Nováková, M.; Paclt, I.; Ptáček, R.; Kuželová, H.; Hájek, I.; Sumová, A. Salivary Melatonin Rhythm as a Marker of the Circadian System in Healthy Children and Those with Attention-Deficit/Hyperactivity Disorder. Chronobiol. Int. 2011, 28 ( 7), 630- 637, 10.3109/07420528.2011.596983
Melo, M. C. A.; Abreu, R. L. C.; Linhares Neto, V. B.; de Bruin, P. F. C.; de Bruin, V. M. S. Chronotype and Circadian Rhythm in Bipolar Disorder: A Systematic Review. Sleep Med. Rev. 2017, 34, 46- 58, 10.1016/j.smrv.2016.06.007
Voultsios, A.; Kennaway, D. J.; Dawson, D. Salivary Melatonin as a Circadian Phase Marker: Validation and Comparison to Plasma Melatonin. J. Biol. Rhythms 1997, 12 ( 5), 457- 466, 10.1177/074873049701200507
Kennaway, D. J. Measuring Melatonin by Immunoassay. J. Pineal Res. 2020, 69 ( 1), 0- 2, 10.1111/jpi.12657
Rizzo, V.; Porta, C.; Moroni, M.; Scoglio, E.; Moratti, R. Determination of Free and Total (Free plus Protein-Bound) Melatonin in Plasma and Cerebrospinal Fluid by High-Performance Liquid Chromatography with Fluorescence Detection. J. Chromatogr. B Anal. Technol. Biomed. Life Sci. 2002, 774 ( 1), 17- 24, 10.1016/S1570-0232(02)00168-X
Hirano, J.; Hamase, K.; Fukuda, H.; Tomita, T.; Zaitsu, K. Novel Stable Fluorophore, 6-Methoxy-4-Quinolone, with Strong Fluorescence in Wide PH Range of Aqueous Media, and Its Application as a Fluorescent Labeling Reagent. J. Chromatogr. A 2004, 1059 ( 1-2), 225- 231, 10.1016/j.chroma.2004.10.020
Eriksson, K.; Östin, A.; Levin, J. O. Quantification of Melatonin in Human Saliva by Liquid Chromatography-Tandem Mass Spectrometry Using Stable Isotope Dilution. J. Chromatogr. B Anal. Technol. Biomed. Life Sci. 2003, 794 ( 1), 115- 123, 10.1016/S1570-0232(03)00425-2
Motoyama, A.; Kanda, T.; Namba, R. Direct Determination of Endogenous Melatonin in Human Saliva by Column-Switching Semi-Microcolumn Liquid Chromatography/Mass Spectrometry with on-Line Analyte Enrichment. Rapid Commun. Mass Spectrom. 2004, 18 ( 12), 1250- 1258, 10.1002/rcm.1473
Jensen, M. A.; Hansen, Å. M.; Abrahamsson, P.; Nørgaard, A. W. Development and Evaluation of a Liquid Chromatography Tandem Mass Spectrometry Method for Simultaneous Determination of Salivary Melatonin, Cortisol and Testosterone. J. Chromatogr. B Anal. Technol. Biomed. Life Sci. 2011, 879 ( 25), 2527- 2532, 10.1016/j.jchromb.2011.07.005
Dermanowski, M. M.; Hejduk, A.; Kuczyńska, J.; Wichniak, A.; Urbańska, A.; Mierzejewski, P. Assessment of Dim Light Melatonin Onset Based on Plasma and Saliva Samples. Chronobiol. Int. 2022, 39 ( 5), 626- 635, 10.1080/07420528.2021.2016796
Shin, S.; Oh, H.; Park, H. R.; Joo, E. Y.; Lee, S. Y. A Sensitive and Specific Liquid Chromatography-Tandem Mass Spectrometry Assay for Simultaneous Quantification of Salivary Melatonin and Cortisol: Development and Comparison with Immunoassays. Ann. Lab. Med. 2021, 41 ( 1), 108- 113, 10.3343/alm.2021.41.1.108
Flanagan, S. C.; Cobice, D.; Richardson, P.; Sittlington, J. J.; Saunders, K. J. Elevated Melatonin Levels Found in Young Myopic Adults Are Not Attributable to a Shift in Circadian Phase. Investig. Ophthalmol. Vis. Sci. 2020, 61 ( 8), 45, 10.1167/iovs.61.8.45
McBride, E. M.; Lawrence, R. J.; McGee, K.; Mach, P. M.; Demond, P. S.; Busch, M. W.; Ramsay, J. W.; Hussey, E. K.; Glaros, T.; Dhummakupt, E. S. Rapid Liquid Chromatography Tandem Mass Spectrometry Method for Targeted Quantitation of Human Performance Metabolites in Saliva. J. Chromatogr. A 2019, 1601, 205- 213, 10.1016/j.chroma.2019.04.071
Van Faassen, M.; Bischoff, R.; Kema, I. P. Relationship between Plasma and Salivary Melatonin and Cortisol Investigated by LC-MS/MS. Clin. Chem. Lab. Med. 2017, 55 ( 9), 1340- 1348, 10.1515/cclm-2016-0817
Simonin, G.; Bru, L.; Lelièvre, E.; Jeanniot, J. P.; Bromet, N.; Walther, B.; Boursier-Neyret, C. Determination of Melatonin in Biological Fluids in the Presence of the Melatonin Agonist S 20098: Comparison of Immunological Techniques and GC-MS Methods. J. Pharm. Biomed. Anal. 1999, 21 ( 3), 591- 601, 10.1016/S0731-7085(99)00150-8
Fourtillan, J. B.; Gobin, P.; Faye, B.; Girault, J. A Highly Sensitive Assay of Melatonin at the Femtogram Level in Human Plasma by Gas Chromatography/Negative Ion Chemical Ionization Mass Spectrometry. Biol. Mass Spectrom. 1994, 23 ( 8), 499- 509, 10.1002/bms.1200230807
Özer, E. T.; Güçer, S. Determination of Some Phthalate Acid Esters in Artificial Saliva by Gas Chromatography-Mass Spectrometry after Activated Carbon Enrichment. Talanta 2011, 84 ( 2), 362- 367, 10.1016/j.talanta.2011.01.003
Eugster, P. J.; Dunand, M.; Grund, B.; Ivanyuk, A.; Fogarasi Szabo, N.; Bardinet, C.; Abid, K.; Buclin, T.; Grouzmann, E.; Chtioui, H. Quantification of Serotonin and Eight of Its Metabolites in Plasma of Healthy Volunteers by Mass Spectrometry. Clin. Chim. Acta 2022, 535, 19- 26, 10.1016/j.cca.2022.08.012
Bonmati-Carrion, M. A.; Middleton, B.; Revell, V.; Skene, D. J.; Rol, M. A.; Madrid, J. A. Circadian Phase Asessment by Ambulatory Monitoring in Humans: Correlation with Dim Light Melatonin Onset. Chronobiol. Int. 2014, 31 ( 1), 37- 51, 10.3109/07420528.2013.820740
Kennaway, D. J. A Critical Review of Melatonin Assays: Past and Present. J. Pineal Res. 2019, 67 ( 1), e12572, 10.1111/jpi.12572
Kennaway, D. J. Measuring Morning Melatonin Levels with Plasma Melatonin ELISA Kits Is a Poor Choice on Two Levels. J. Pineal Res. 2022, 10.1111/jpi.12773
De Almeida, E. A.; Di Mascio, P.; Harumi, T.; Spence, D. W.; Moscovitch, A.; Hardeland, R.; Cardinali, D. P.; Brown, G. M.; Pandi-Perumal, S. R. Measurement of Melatonin in Body Fluids: Standards, Protocols and Procedures. Child’s Nerv. Syst. 2011, 27 ( 6), 879- 891, 10.1007/s00381-010-1278-8
