Analytical and Bioanalytical Chemistry

, Volume 406, Issue 3, pp 727–734 | Cite as

Simultaneous high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS-MS) analysis of cyanide and thiocyanate from swine plasma

  • Raj K. Bhandari
  • Erica Manandhar
  • Robert P. Oda
  • Gary A. Rockwood
  • Brian A. Logue
Research Paper

Abstract

An analytical procedure for the simultaneous determination of cyanide and thiocyanate in swine plasma was developed and validated. Cyanide and thiocyanate were simultaneously analyzed by high-performance liquid chromatography tandem mass spectrometry in negative ionization mode after rapid and simple sample preparation. Isotopically labeled internal standards, Na13C15N and NaS13C15N, were mixed with swine plasma (spiked and nonspiked), proteins were precipitated with acetone, the samples were centrifuged, and the supernatant was removed and dried. The dried samples were reconstituted in 10 mM ammonium formate. Cyanide was reacted with naphthalene-2,3-dicarboxaldehyde and taurine to form N-substituted 1-cyano[f]benzoisoindole, while thiocyanate was chemically modified with monobromobimane to form an SCN-bimane product. The method produced dynamic ranges of 0.1–50 and 0.2–50 μM for cyanide and thiocyanate, respectively, with limits of detection of 10 nM for cyanide and 50 nM for thiocyanate. For quality control standards, the precision, as measured by percent relative standard deviation, was below 8 %, and the accuracy was within ±10 % of the nominal concentration. Following validation, the analytical procedure successfully detected cyanide and thiocyanate simultaneously from the plasma of cyanide-exposed swine.

Keywords

Bioanalysis Method validation Chemical warfare agent Monobromobimane Naphthalene-2,3-dicarboxaldehyde 

Notes

Acknowledgments

The research was supported by the CounterACT Program, National Institutes of Health Office of the Director, and the National Institute of Allergy and Infectious Diseases, Interagency agreement numbers Y1-OD-0690-01/A-120-B.P2010-01, Y1-OD-1561-01/A120-B.P2011-01, and AOD12060-001-00000/A120-B.P2012-01 and the US Army Medical Research Institute of Chemical Defense (USAMRICD) under the auspices of the US Army Research Office of Scientific Services program contract no. W911NF-11-D-0001 administered by Battelle (Delivery order 0079, contract no. TCN 11077). We thank the National Science Foundation Major Research Instrumentation Program (grant no. CHE-0922816) and the State of South Dakota for funding the purchase of the AB SCIEX QTRAP 5500 LC-MS-MS. The LC-MS-MS instrumentation was housed in the South Dakota State University Campus Mass Spectrometry Facility which was supported by the National Science Foundation/EPSCoR grant no. 0091948 and the State of South Dakota. The authors would also like to acknowledge Dr. George Perry, Animal and Range Science (South Dakota State University) for providing swine plasma. Furthermore, the authors are thankful to Dr. Vikhyat Bebarta, Susan M. Boudreau, RN, BSN, Maria G. Castaneda, MS, Toni E. Vargas, PA-C, MHS, and Patricia Dixon, MHS from the Clinical Research Division, Wilford Hall Medical Center (Lackland Air Force Base, San Antonio, TX) for providing potassium cyanide-exposed swine plasma. The opinions or assertions contained herein are the private views of the authors and are not to be construed as official or as reflecting the views of the Department of the Army, the National Institutes of Health, the Department of Defense, the National Science Foundation, or the State of South Dakota.

References

  1. 1.
    Conn EE (1978) Cyanogenesis, the production of cyanide, by plants. In: Keeler RF, Van Kampen KR, James LF (eds) Effects of poisons plants on livestock. Academic, San Diego, pp 301–310CrossRefGoogle Scholar
  2. 2.
    Baskin SI, Petrikovics I, Kurche JS, Nicholson JD, Logue BA, Maliner BJ, Rockwood GA (2004) Insights of cyanide toxicity and methods of treatment. In: Flora SJS, Romano JA Jr, Baskin SI, Shekhar K (eds) Pharmacological perspectives of toxic chemicals and their antidotes. Narosa Publishing House, New Delhi, pp 105–146, Ch. 9Google Scholar
  3. 3.
    Logue BA, Hinkens DM, Baskin SI, Rockwood GA (2010) The analysis of cyanide and its breakdown products in biological samples. Crit Rev Anal Chem 40(2):122–147CrossRefGoogle Scholar
  4. 4.
    Kaur P, Upadhyay S, Gupta VK (1987) Spectrophotometric determination of hydrogen cyanide in air and biological fluids. Analyst 112(12):1681–1683CrossRefGoogle Scholar
  5. 5.
    Naik RM, Kumar B, Asthana A (2010) Kinetic spectrophotometric method for trace determination of thiocyanate based on its inhibitory effect. Spectrochimica acta Part A, Molecular and Biomolecular Spectroscopy 75(3):1152–1158. doi: 10.1016/j.saa.2009.12.078 CrossRefGoogle Scholar
  6. 6.
    Hamza A, Bashammakh AS, Al-Sibaai AA, Al-Saidi HM, El-Shahawi MS (2010) Dual-wavelength beta-correction spectrophotometric determination of trace concentrations of cyanide ions based on the nucleophilic addition of cyanide to imine group of the new reagent 4-hydroxy-3-(2-oxoindolin-3-ylideneamino)-2-thioxo-2H-1,3-thiazin-6(3H)-one. Analytica chimica acta 657(1):69–74. doi: 10.1016/j.aca.2009.10.025 CrossRefGoogle Scholar
  7. 7.
    Youso SL, Rockwood GA, Lee JP, Logue BA (2010) Determination of cyanide exposure by gas chromatography–mass spectrometry analysis of cyanide-exposed plasma proteins. Analytica chimica acta 677(1):24–28. doi: 10.1016/j.aca.2010.01.028 CrossRefGoogle Scholar
  8. 8.
    Youso SL, Rockwood GA, Logue BA (2012) The analysis of protein-bound thiocyanate in plasma of smokers and non-smokers as a marker of cyanide exposure. Journal of analytical toxicology 36(4):265–269. doi: 10.1093/jat/bks017 CrossRefGoogle Scholar
  9. 9.
    Frison G, Zancanaro F, Favretto D, Ferrara SD (2006) An improved method for cyanide determination in blood using solid-phase microextraction and gas chromatography/mass spectrometry. Rapid communications in mass spectrometry : RCM 20(19):2932–2938. doi: 10.1002/rcm.2689 CrossRefGoogle Scholar
  10. 10.
    Sano A, Takimoto N, Takitani S (1992) High-performance liquid chromatographic determination of cyanide in human red blood cells by pre-column fluorescence derivatization. J Chromatogr 582(1–2):131–135CrossRefGoogle Scholar
  11. 11.
    Tracqui A, Raul JS, Geraut A, Berthelon L, Ludes B (2002) Determination of blood cyanide by HPLC-MS. J Anal Toxicol 26(3):144–148CrossRefGoogle Scholar
  12. 12.
    Chen SH, Yang ZY, Wu HL, Kou HS, Lin SJ (1996) Determination of thiocyanate anion by high-performance liquid chromatography with fluorimetric detection. J Anal Toxicol 20(1):38–42CrossRefGoogle Scholar
  13. 13.
    Bhandari RK, Oda RP, Youso SL, Petrikovics I, Bebarta VS, Rockwood GA, Logue BA (2012) Simultaneous determination of cyanide and thiocyanate in plasma by chemical ionization gas chromatography mass-spectrometry (CI-GC-MS). Anal Bioanalytic Chem 404(8):2287–2294. doi: 10.1007/s00216-012-6360-5 CrossRefGoogle Scholar
  14. 14.
    Imanari T, Tanabe S, Toida T (1982) Simultaneous determination of cyanide and thiocyanate by high performance liquid chromatography. Chem Pharm Bull 30(10):3800–3802CrossRefGoogle Scholar
  15. 15.
    Toida T, Togawa T, Tanabe S, Imanari T (1984) Determination of cyanide and thiocyanate in blood plasma and red cells by high-performance liquid chromatography with fluorometric detection. J Chromatogr 308:133–141CrossRefGoogle Scholar
  16. 16.
    Chinaka S, Takayama N, Michigami Y, Ueda K (1998) Simultaneous determination of cyanide and thiocyanate in blood by ion chromatography with fluorescence and ultraviolet detection. J Chromatogr B, Biomed Scie appl 713(2):353–359CrossRefGoogle Scholar
  17. 17.
    Paul BD, Smith ML (2006) Cyanide and thiocyanate in human saliva by gas chromatography–mass spectrometry. J Anal Toxicol 30(8):511–515CrossRefGoogle Scholar
  18. 18.
    König W (1904) Über eine neue, vom Pyridine derivierende Klasse vom Farbstoffen. Zeitschrift für Praktische Chemie 69(1):105–137CrossRefGoogle Scholar
  19. 19.
    Bark LS, Higson HG (1963) A review of the methods available for the detection and determination of small amounts of cyanide. Analyst 88:751–760CrossRefGoogle Scholar
  20. 20.
    Sano A, Takezawa M, Takitani S (1989) Spectrofluorimetric determination of cyanide in blood and urine with naphthalene-2,3-dialdehyde and taurine. Anal Chim Acta 225:351–358CrossRefGoogle Scholar
  21. 21.
    Kosower NS, Kosower EM (1987) Thiol labeling with bromobimanes. Methods Enzymol 143:76–84Google Scholar
  22. 22.
    Guan X, Hoffman B, Dwivedi C, Matthees DP (2003) A simultaneous liquid chromatography/mass spectrometric assay of glutathione, cysteine, homocysteine and their disulfides in biological samples. J Pharm Biomed Anal 31(2):251–261CrossRefGoogle Scholar
  23. 23.
    Foley JP, Dorsey JG (1984) A review of the exponentially modified Gaussian (EMG) function: evalutation and subsequent calculation of universal data. J Chromatogr Sci 22:40–46CrossRefGoogle Scholar
  24. 24.
    Garofolo F (2004) LC-MS instrument calibration. In: Chan CC, Lam H, Lee YC, Zhang X-M (eds) Analytical method validation and instrument performance verification. Wiley, Hoboken, NJ, pp 197–220CrossRefGoogle Scholar
  25. 25.
    Whitmire M, Ammerman J, de Lisio P, Killmer J, Kyle D, Mainstore E, Porter L, Zhang T (2011) LC-MS/MS bioanalysis method development, validation and sample analysis: points to consider when conducting nonclinical and clinical studies according with current regulatory guidances. J Anal Bioanal Techniques S4:001Google Scholar
  26. 26.
    Van Eeckhaut A, Lanckmans K, Sarre S, Smolders I, Michotte Y (2009) Validation of bioanalytical LC-MS/MS assays: evaluation of matrix effects. J Chromatogr B Anal Technol Biomed life Sci 877(23):2198–2207. doi: 10.1016/j.jchromb.2009.01.003 CrossRefGoogle Scholar
  27. 27.
    Smith MR, Lequerica JL, Hart MR (1985) Inhibition of methanogenesis and carbon metabolism in Methanosarcina sp. by cyanide. J Bacteriol 162(1):67–71Google Scholar
  28. 28.
    Boxer GE, Rickards JC (1952) Studies on the metabolism of the carbon of cyanide and thiocyanate. Arch Biochem Biophys 39(1):7–26CrossRefGoogle Scholar
  29. 29.
    Knowles CJ (1976) Microorganisms and cyanide. Bacteriol Rev 40(3):652–680Google Scholar
  30. 30.
    Seto Y (1995) Oxidative conversion of thiocyanate to cyanide by oxyhemoglobin during acid denaturation. Arch Biochem Biophys 321(1):245–254. doi: 10.1006/abbi.1995.1392 CrossRefGoogle Scholar
  31. 31.
    Seto Y (1996) Determination of physiological levels of blood cyanide without interference by thiocyanate. Jpn J Tox Env Health 42(4):319–325CrossRefGoogle Scholar
  32. 32.
    Lundquist P, Rosling H, Sorbo B (1985) Determination of cyanide in whole blood, erythrocytes, and plasma. Clin chemistry 31(4):591–595Google Scholar
  33. 33.
    Pollay M, Stevens A, Davis C Jr (1966) Determination of plasma-thiocyanate binding and the Donnan ratio under simulated physiological conditions. Ana Biochem 17(2):192–200CrossRefGoogle Scholar
  34. 34.
    Kage S, Nagata T, Kudo K (1996) Determination of cyanide and thiocyanate in blood by gas chromatography and gas chromatography–mass spectrometry. J Chromatography B, Biom Appli 675(1):27–32CrossRefGoogle Scholar
  35. 35.
    Dalferes ER Jr, Webber LS, Radhakrishnamurthy B, Berenson GS (1980) Continuous-flow (Autoanalyzer I) analysis for plasma thiocyanate as an index to tobacco smoking. Clin Chem 26(3):493–495Google Scholar
  36. 36.
    Connolly D, Barron L, Paull B (2002) Determination of urinary thiocyanate and nitrate using fast ion-interaction chromatography. J Chromatogr B, An Technol Biomed Sci 767(1):175–180CrossRefGoogle Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2013

Authors and Affiliations

  • Raj K. Bhandari
    • 1
  • Erica Manandhar
    • 1
  • Robert P. Oda
    • 1
  • Gary A. Rockwood
    • 2
  • Brian A. Logue
    • 1
  1. 1.Department of Chemistry and BiochemistrySouth Dakota State UniversityBrookingsUSA
  2. 2.Analytical Toxicology DivisionUS Army Medical Research Institute of Chemical DefenseAberdeen Proving GroundUSA

Personalised recommendations