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Chromatographic Determination of Denatonium Benzoate in Colognes

Year 2024, Volume: 12 Issue: 4, 1840 - 1848, 23.10.2024
https://doi.org/10.29130/dubited.1409022

Abstract

Denatonium benzoate, commercially known as Bitrex, is an ionic compound containing a quaternary ammonium cation (denatonium) and negatively charged benzoate. It is commonly used as a bittering agent in various alcohol-based products to deter ingestion. The national regulations regarding the production and domestic-foreign trade of ethyl alcohol and methanol states that ethyl alcohols for domestic use should contain 0.8 g denatonium benzoate per 100 L of absolute alcohol. This leads to the necessity of quantitative analysis of denatonium benzoate in alcoholic products. Cologne samples of different brands were analyzed using reversed-phase high performance liquid chromatography (RP-HPLC) coupled with UV/vis detector. Isocratic elution was performed on an ODS column with a mobile phase containing 75% MeOH:25% H2O. Since the proposed method does not require any pre-treatment step, the procedure is simple and rapid. The limit of quantitation was found to be 0.17 mg/L. The linearity of the method was tested in the range 0.26 – 15.75 mg/L with a limit of detection of 0.050 mg/L (signal-to-noise ratio of 3).

References

  • [1] P. Viñas, N. Campillo, M. Pastor-Belda, A. Oller, and M. Hernández-Córdoba, “Determination of phthalate esters in cleaning and personal care products by dispersive liquid–liquid microextraction and liquid chromatography–tandem mass spectrometry,” Journal of Chromatography A, vol. 1376, pp. 18–25, 2015.
  • [2] D. W. Lachenmeier, J. Rehm and, G. Gmel, “Surrogate alcohol: what do we know and where do we go?,” Alcoholism: Clinical and Experimental Research, vol. 31, no. 10, pp. 1613–1624, 2007.
  • [3] G. Velicelebi and, J. M. Sturtevant, “Thermodynamics of the denaturation of lysozyme in alcohol-water mixtures,” Biochemistry, vol. 18, no. 7, pp. 1180–1186, 1979.
  • [4] A. Bekatorou, “Alcohol: Properties and Determination,” Encyclopedia of Food and Health, pp. 88–96, 2016.
  • [5] J. R. Sibert and, N. Frude, “Bittering agents in the prevention of accidental poisoning: children's reactions to denatonium benzoate (Bitrex),” Emergency Medicine Journal, vol. 8, no. 1, pp. 1–7, 1991.
  • [6] E. Deloose, P. Janssen, M. Corsetti, J. Biesiekierski, I. Masuy, A. Rotondo and, J. Tack, “Intragastric infusion of denatonium benzoate attenuates interdigestive gastric motility and hunger scores in healthy female volunteers,” The American Journal of Clinical Nutrition, vol. 105, no. 3, pp. 580–588, 2017.
  • [7] J. A. García-Valenzuela and, M. R. Baez-Gaxiola, “Comments on the risks from exposure to denatonium benzoate (Bitrex®): denatured alcohol disinfection and pandemic times,” International Journal of Toxicology, vol. 40, no. 5, pp. 475–477, 2021.
  • [8] Etil alkol ve metanolün üretimi ile iç ve dış ticaretine ilişkin usul ve esaslar hakkında yönetmelik, T.C. Resmi Gazete, Sayı: 28100, 30 Ekim 2011.
  • [9] Z. Daunoravičius, I. Juknaitė, E. Naujalis and, A. Padarauskas, “Simple and rapid determination of denaturants in alcohol formulations by hydrophilic interaction chromatography,” Chromatographia, vol. 63, pp. 373–377, 2006.
  • [10] S. Liu, S. Chen, X. Li, Y. Yue, J. Li, P. N. Williams and, C. E. Chen, “Development and application of diffusive gradients in thin-films for in situ sampling of the bitterest chemical–denatonium benzoate in waters,” Journal of Hazardous Materials, vol. 418, pp. 126393, 2021.
  • [11] N. van Boxtel, K. Wolfs, M. Guillén Palacín, A. Van Schepdael and, E. Adams, “Comprehensive headspace gas chromatographic analysis of denaturants in denatured ethanol,” Journal of Separation Science, vol. 40, no. 20, pp. 4004–4011, 2017.
  • [12] G. Buszewicz, K. Bańka and, R. Mądro, “Determination of denatonium benzoate (Bitrex) in alcoholic products by LC-APCI-MS,” Problems of Forensic Sciences, vol. 63, pp. 270–274, 2005.
  • [13] B. Pranaitytė, Z. Daunoravicius and, A. Padarauskas, “Development and validation of a capillary electrophoresis method for the determination of denatonium benzoate in denaturated alcohol formulations,” Chromatographia, vol. 60, pp. 353–357, 2004.
  • [14] D. Zuba, C. Świegoda, Z. Byrska and, W. Lechowicz, “Assessment of the effectiveness of denatonium benzoate (Bitrex) removal from denatured spirit preparations using sodium hypochlorite,” Problems of Forensic Sciences, 63, pp. 288–298, 2005.
  • [15] R. Bąchor, A. Kluczyk, P. Stefanowicz and, Z. Szewczuk, “Facile synthesis of deuterium-labeled denatonium cation and its application in the quantitative analysis of Bitrex by liquid chromatography-mass spectrometry,” Analytical and Bioanalytical Chemistry, vol. 407, pp. 6557–6561, 2015.
  • [16] J. M. Herniman and, G. J. Langley, “Development of ultrahigh‐performance liquid chroma- tography/mass spectrometry and ultrahigh‐performance supercritical fluid chromatography/mass spect- rometry assays to determine the concentration of Bitrex™ and sodium saccharin in homemade facemask fit testing solutions,” Rapid Communications in Mass Spectrometry, vol. 34, no. 16, pp. e8848, 2020.

Kolonyalarda Denatonyum Benzoatın Kromatografik Tespiti

Year 2024, Volume: 12 Issue: 4, 1840 - 1848, 23.10.2024
https://doi.org/10.29130/dubited.1409022

Abstract

Ticari olarak Bitrex adıyla bilinen denatonyum benzoat, bir kuaterner amonyum katyonu (denatonyum) ve negatif yüklü benzoat içeren iyonik bir bileşiktir. Genellikle çeşitli alkol bazlı ürünlerde kazara yutmayı önlemek amacıyla kullanılır. Etil alkol ve metanol üretimi ve iç-dış ticaretine ilişkin ulusal düzenlemeler, evsel kullanım için etil alkollerin 100 L mutlak alkol başına 0,8 g denatonyum benzoat içermesi gerektiğini belirtmektedir. Bu durum, alkollü ürünlerdeki denatonyum benzoatın nicel analizinin gerekliliğini ortaya koymaktadır. Farklı markalara ait kolonya numuneleri UV/vis dedektörü ile ters-faz yüksek performanslı sıvı kromatografisi (RP-HPLC) kullanılarak analiz edilmiştir. %75 MeOH:%25 H2O içeren mobil faz ile ODS kolonda izokratik elüsyon gerçekleştirilmiştir. Önerilen yöntem herhangi bir ön işlem adımı gerektirmediğinden, işlem basit ve hızlıdır. Alt tayin sınırı 0,17 mg/L olarak bulunmuştur. Yöntemin doğrusallığı 0,26 – 15,75 mg/L aralığında test edilmiş ve gözlenebilme sınırı 0,050 mg/L olarak bulunmuştur (sinyal-gürültü oranı 3).

References

  • [1] P. Viñas, N. Campillo, M. Pastor-Belda, A. Oller, and M. Hernández-Córdoba, “Determination of phthalate esters in cleaning and personal care products by dispersive liquid–liquid microextraction and liquid chromatography–tandem mass spectrometry,” Journal of Chromatography A, vol. 1376, pp. 18–25, 2015.
  • [2] D. W. Lachenmeier, J. Rehm and, G. Gmel, “Surrogate alcohol: what do we know and where do we go?,” Alcoholism: Clinical and Experimental Research, vol. 31, no. 10, pp. 1613–1624, 2007.
  • [3] G. Velicelebi and, J. M. Sturtevant, “Thermodynamics of the denaturation of lysozyme in alcohol-water mixtures,” Biochemistry, vol. 18, no. 7, pp. 1180–1186, 1979.
  • [4] A. Bekatorou, “Alcohol: Properties and Determination,” Encyclopedia of Food and Health, pp. 88–96, 2016.
  • [5] J. R. Sibert and, N. Frude, “Bittering agents in the prevention of accidental poisoning: children's reactions to denatonium benzoate (Bitrex),” Emergency Medicine Journal, vol. 8, no. 1, pp. 1–7, 1991.
  • [6] E. Deloose, P. Janssen, M. Corsetti, J. Biesiekierski, I. Masuy, A. Rotondo and, J. Tack, “Intragastric infusion of denatonium benzoate attenuates interdigestive gastric motility and hunger scores in healthy female volunteers,” The American Journal of Clinical Nutrition, vol. 105, no. 3, pp. 580–588, 2017.
  • [7] J. A. García-Valenzuela and, M. R. Baez-Gaxiola, “Comments on the risks from exposure to denatonium benzoate (Bitrex®): denatured alcohol disinfection and pandemic times,” International Journal of Toxicology, vol. 40, no. 5, pp. 475–477, 2021.
  • [8] Etil alkol ve metanolün üretimi ile iç ve dış ticaretine ilişkin usul ve esaslar hakkında yönetmelik, T.C. Resmi Gazete, Sayı: 28100, 30 Ekim 2011.
  • [9] Z. Daunoravičius, I. Juknaitė, E. Naujalis and, A. Padarauskas, “Simple and rapid determination of denaturants in alcohol formulations by hydrophilic interaction chromatography,” Chromatographia, vol. 63, pp. 373–377, 2006.
  • [10] S. Liu, S. Chen, X. Li, Y. Yue, J. Li, P. N. Williams and, C. E. Chen, “Development and application of diffusive gradients in thin-films for in situ sampling of the bitterest chemical–denatonium benzoate in waters,” Journal of Hazardous Materials, vol. 418, pp. 126393, 2021.
  • [11] N. van Boxtel, K. Wolfs, M. Guillén Palacín, A. Van Schepdael and, E. Adams, “Comprehensive headspace gas chromatographic analysis of denaturants in denatured ethanol,” Journal of Separation Science, vol. 40, no. 20, pp. 4004–4011, 2017.
  • [12] G. Buszewicz, K. Bańka and, R. Mądro, “Determination of denatonium benzoate (Bitrex) in alcoholic products by LC-APCI-MS,” Problems of Forensic Sciences, vol. 63, pp. 270–274, 2005.
  • [13] B. Pranaitytė, Z. Daunoravicius and, A. Padarauskas, “Development and validation of a capillary electrophoresis method for the determination of denatonium benzoate in denaturated alcohol formulations,” Chromatographia, vol. 60, pp. 353–357, 2004.
  • [14] D. Zuba, C. Świegoda, Z. Byrska and, W. Lechowicz, “Assessment of the effectiveness of denatonium benzoate (Bitrex) removal from denatured spirit preparations using sodium hypochlorite,” Problems of Forensic Sciences, 63, pp. 288–298, 2005.
  • [15] R. Bąchor, A. Kluczyk, P. Stefanowicz and, Z. Szewczuk, “Facile synthesis of deuterium-labeled denatonium cation and its application in the quantitative analysis of Bitrex by liquid chromatography-mass spectrometry,” Analytical and Bioanalytical Chemistry, vol. 407, pp. 6557–6561, 2015.
  • [16] J. M. Herniman and, G. J. Langley, “Development of ultrahigh‐performance liquid chroma- tography/mass spectrometry and ultrahigh‐performance supercritical fluid chromatography/mass spect- rometry assays to determine the concentration of Bitrex™ and sodium saccharin in homemade facemask fit testing solutions,” Rapid Communications in Mass Spectrometry, vol. 34, no. 16, pp. e8848, 2020.
There are 16 citations in total.

Details

Primary Language English
Subjects Separation Science
Journal Section Articles
Authors

Emine Kübra İnal 0000-0001-8334-2791

Publication Date October 23, 2024
Submission Date December 23, 2023
Acceptance Date April 19, 2024
Published in Issue Year 2024 Volume: 12 Issue: 4

Cite

APA İnal, E. K. (2024). Chromatographic Determination of Denatonium Benzoate in Colognes. Duzce University Journal of Science and Technology, 12(4), 1840-1848. https://doi.org/10.29130/dubited.1409022
AMA İnal EK. Chromatographic Determination of Denatonium Benzoate in Colognes. DUBİTED. October 2024;12(4):1840-1848. doi:10.29130/dubited.1409022
Chicago İnal, Emine Kübra. “Chromatographic Determination of Denatonium Benzoate in Colognes”. Duzce University Journal of Science and Technology 12, no. 4 (October 2024): 1840-48. https://doi.org/10.29130/dubited.1409022.
EndNote İnal EK (October 1, 2024) Chromatographic Determination of Denatonium Benzoate in Colognes. Duzce University Journal of Science and Technology 12 4 1840–1848.
IEEE E. K. İnal, “Chromatographic Determination of Denatonium Benzoate in Colognes”, DUBİTED, vol. 12, no. 4, pp. 1840–1848, 2024, doi: 10.29130/dubited.1409022.
ISNAD İnal, Emine Kübra. “Chromatographic Determination of Denatonium Benzoate in Colognes”. Duzce University Journal of Science and Technology 12/4 (October 2024), 1840-1848. https://doi.org/10.29130/dubited.1409022.
JAMA İnal EK. Chromatographic Determination of Denatonium Benzoate in Colognes. DUBİTED. 2024;12:1840–1848.
MLA İnal, Emine Kübra. “Chromatographic Determination of Denatonium Benzoate in Colognes”. Duzce University Journal of Science and Technology, vol. 12, no. 4, 2024, pp. 1840-8, doi:10.29130/dubited.1409022.
Vancouver İnal EK. Chromatographic Determination of Denatonium Benzoate in Colognes. DUBİTED. 2024;12(4):1840-8.