Horm Metab Res 2014; 46(09): 628-634
DOI: 10.1055/s-0034-1368717
Endocrine Research
© Georg Thieme Verlag KG Stuttgart · New York

Quantification of Thyroxine and 3,5,3′-Triiodo-Thyronine in Human and Animal Hearts by a Novel Liquid Chromatography-Tandem Mass Spectrometry Method

A. Saba
1   Department of Pathology, University of Pisa, Pisa, Italy
,
R. Donzelli
1   Department of Pathology, University of Pisa, Pisa, Italy
,
D. Colligiani
2   Department of Medicine, University of Pisa, Pisa, Italy
,
A. Raffaelli
3   National Research Council, Institute of Clinical Physiology, Pisa, Italy
,
M. Nannipieri
2   Department of Medicine, University of Pisa, Pisa, Italy
,
C. Kusmic
3   National Research Council, Institute of Clinical Physiology, Pisa, Italy
,
C. G. Dos Remedios
4   Muscle Research Unit, Bosch Institute, The University of Sydney, Sydney, Australia
,
W. S. Simonides
5   Laboratory for Physiology, Institute for Cardiovascular Research, VU ­University Medical Center, Amsterdam, The Netherlands
,
G. Iervasi
3   National Research Council, Institute of Clinical Physiology, Pisa, Italy
6   G. Monasterio Foundation, Pisa, Italy
,
R. Zucchi
1   Department of Pathology, University of Pisa, Pisa, Italy
› Author Affiliations
Further Information

Publication History

received 17 August 2013

accepted 27 January 2014

Publication Date:
03 March 2014 (online)

Abstract

Assaying tissue T3 and T4 would provide important information in experimental and clinical investigations. A novel method to determine tissue T3 and T4 by HPLC coupled to mass spectrometry is described. The major difference vs. previously described methods lies in the addition of a derivatization step, that is, to convert T3 and T4 into the corresponding butyl esters. The yield of esterification was ̴ 100% for T3 and 80% for T4. The assay was linear (r>0.99) in the range of 0.2–50 ng/ml, accuracy was in the order of 70–75%, and the minimum tissue amount needed was in the order of 50 mg, that is, about one order of magnitude lower than observed with the same equipment (AB Sciex API 4000 triple quadrupole mass spectrometer) if derivatization was omitted. The method allowed detection of T3 and T4 in human left ventricle biopsies yielding concentrations of 1.51±0.16 and 5.94±0.63 pmol/g, respectively. In rats treated with different dosages of exogenous T3 or T4, good correlations (r>0.90) between plasma and myocardial T3 and T4 concentrations were observed, although in specific subsets different plasma T4 concentrations were not associated with different tissue content in T4. We conclude that this method could provide a novel insight into the relationship between plasma and tissue thyroid hormone levels.

 
  • References

  • 1 Thienpont LM, Van Uytfanghe K, Beastall G, Faix JD, Ieiri JD, Miller WG, Nelson JC, Ronin C, Ross HA, Thijssen JH, Toussaint B. for the IFCC Working Group on Standardization of Thyroid Function Tests . Report of the IFCC working group for standardization of thyroid function tests; part 2: free thyroxine and free thriiodothyronine. Clin Chem 2010; 56: 912-920
  • 2 Morreale de Escobar G, Pastor R, Obregon MJ, Escobar del Rey F. Effects of maternal hypothyroidism on the weight and thyroid hormone content of rat embryonic tissues, before and after onset of fetal thyroid function. Endocrinology 1985; 117: 1890-1900
  • 3 Escobar-Morreale HF, Obregon MJ, Escobar del Rey F, Morreale de Escobar G. Replacement therapy for hypothyroidism with thyroxine alone does not ensure euthyroidism in all tissues, as studied in thyroidectomized rats. J Clin Invest 1995; 96: 2828-2838
  • 4 Pedraza PE, Obregon MJ, Escobar-Morreale HF, Escobar del Rey F, Morreale de Escobar G. Mechanisms of adaptation to iodine deficiency in rats: thyroid status is tissue specific. Its relevance for man. Endocrinology 2006; 147: 2098-2108
  • 5 Hamilton MA, Lynne WS. Thyroid hormone abnormalities in heart failure: possibilities for therapy. Thyroid 1996; 6: 527-529
  • 6 Ascheim DD, Hryniewicz K. Thyroid hormone metabolism in patients with congestive heart failure: the low triiodothyronine state. Thyroid 2002; 12: 511-515
  • 7 Pingitore A, Landi P, Taddei MC, Ripoli A, L’Abbate A, Iervasi G. Triiodothyronine levels for risk stratification of patients with chronic heart failure. Am J Med 2005; 118: 132-136
  • 8 Gerdes AM, Iervasi G. Thyroid replacement therapy and heart failure. Circulation 2010; 122: 385-393
  • 9 Soldin OP, Soldin SJ. Thyroid hormone testing by tandem mass spectrometry. Clin Biochem 2011; 44: 89-94
  • 10 Hoefig CS, Köhrle J. LC-MS/MS detection of thyroid hormone metabolites in tissue samples. Expert Rev Endocrinol Metab 2012; 7: 511-513
  • 11 Kunisue T, Fisher JW, Kannan K. Determination of six thyroid hormones in the brain and thyroid gland using isotope-dilution liquid chromatography/tandem mass spectrometry. Anal Chem 2011; 83: 417-424
  • 12 Ackermans MT, Kettelarij-Haas Y, Boelen A, Endert E. Determination of thyroid hormones and their metabolites in tissue using SPE UPLC-tandem MS. Biomed Chromatogr 2012; 26: 485-490
  • 13 Saba A, Chiellini G, Frascarelli S, Marchini M, Ghelardoni S, Raffaelli A, Tonacchera M, Vitti P, Scanlan TS, Zucchi R. Tissue distribution and cardiac metabolism of 3-iodothyronamine. Endocrinology 2010; 151: 5063-5073
  • 14 Henderson KK, Danzi S, Paul JT, Leya G, Klein I, Samarel AM. Physiological replacement of T3 improves left ventricular function in an animal model of myocardial infarction-induced congestive heart failure. Circ Heart Fail 2009; 2: 243-252
  • 15 Forini F, Lionetti V, Ardehali H, Pucci A, Cecchetti F, Ghanefar M, Nicolini G, Ichikawa Y, Nannipieri M, Recchia MA, Iervasi G. Early long-term L-T3 replacement rescues mitochondria and prevents ischemic cardiac remodelling in rats. J Cell Mol Med 2011; 15: 514-524
  • 16 World Medical Association, Inc . World medical association declaration of Helsinki. Cardiovasc Res 1997; 35: 2-3
  • 17 Hackenmueller SA, Marchini M, Saba A, Zucchi R, Scanlan TS. Biosynthesis of 3-iodothyronamine (T1AM) is dependent on the sodium-iodide symporter and thyroperoxidase but does not involve extrathyroidal metabolism of T4 . Endocrinology 2012; 53: 5659-5667
  • 18 Chace DH, Millington DS, Terada N, Kahler SG, Roe CR, Hofman LF. Rapid diagnosis of phenylketonuria by quantitative analysis for phenylalanine and tyrosine in neonatal blood spots by tandem mass spectrometry. Clin Chem 1993; 39: 66-71
  • 19 Liang HR, Foltz RL, Meng M, Bennett P. Ionization enhancement in atmospheric pressure chemical ionization and suppression in electrospray ionization between target drugs and stable-isotopelabeled internal standards in quantitative liquid chromatography/tandem mass spectrometry. Rapid Commun Mass Spectrom 2003; 17: 2815-2821
  • 20 Zanov KI, Yotova L, Klapa M. LC-MS quantitation of thyroid hormones, their metabolites, amino acids and neurotrasmitters in liver tissue. Biotechnol Biotec Eq 2009; 23: 818-822
  • 21 Liu Y, Redetzke RA, Said S, Pottala JV, Morreale de Escobar G, Gerdes AM. Serum thyroid hormone levels may not accurately reflect thyroid tissue levels and cardiac function in mild hypothyroidism. Am J Physiol Heart Circ Physiol 2008; 294: H2137-H2143