대한화장품학회지 (Journal of the Society of Cosmetic Scientists of Korea)

  • 제42권1호
  • /
  • Pages.65-73
  • /
  • 2016
  • /
  • 1226-2587(pISSN)
  • /
  • 2288-9507(eISSN)
대한화장품학회 (Society of Cosmetic Scientists of Korea)
권호 표지
DOI QR코드

DOI QR Code

간편한 DNPH 유도체화 HPLC 분석법을 이용한 화장품 중 포름알데하이드 분석

Determination of Formaldehyde in Cosmetics Using a Convenient DNPH Derivatization Procedure Followed by HPLC Analysis

  • 최종근 (청운대학교 화장품과학과)
  • Choi, Jongkeun (Department of Cosmetic Science, Chungwoon University)
  • 투고 : 2015.12.22
  • 심사 : 2016.03.15
  • 발행 : 2016.03.30
PDF 다운로드
⟨ 이전 논문 다음 논문 ⟩

초록

대한민국 식품의약품안전처(식약처)는 포름알데하이드 분석법으로 2,4-dinitrophenylhydrazine(DNPH) 유도체화-고성능액체크로마토그래프법(HPLC)을 고시하고 있다. 본 연구는 고시법의 복잡한 시료 전처리 과정을 개선하여 화장품 분석에 편리하게 사용할 수 있는 유도체화법을 개발하고자 수행되었다. 전처리법을 간단하게 하기 위하여 pH, 시간 및 온도 등 반응조건을 최적화하였다. 이 전처리법은 초산염 완충액(pH 5.0)을 사용한 검액의 pH 조정, 디클로로메탄을 사용한 액-액 분획 그리고 감압농축기를 사용한 증발건조와 같이 식약처 고시법의 복잡한 과정이 필요 없다. 유도체화 과정을 통하여 생성된 formaldehyde dinitrophenylhydrazone(formaldehyde-DNP)는 식약처의 시험방법을 약간 변형한 역상 HPLC법으로 분리하고 정량하였다. 2 ~ 40 ppm 농도 범위의 표준액들을 가지고 수행한 검량선 작성 결과, 본 시험법은 상관계수 값이 0.9999로 좋은 직선성을 보여주었다. 본 실험의 최소검출한계(LOD)와 최소정량한계(LOQ)는 각각 0.2 ppm과 0.5 ppm이었다. 또한 회수율 실험결과는 실험방법이 매우 정확하고 재현성이 높음을 보여주었다. 따라서 본 연구에서 제안된 시험법은 화장품 중 포름알데하이드를 신속하게 분석하는데 적용될 수 있을 것이다.

Korea Food and Drug Administration (KFDA) has officially announced 2,4-dinitrophenylhydrazine (DNPH) derivatization - high performance liquid chromatography (HPLC) methods for analysis of formaldehyde. This study was conducted to develop a convenient derivatization method for cosmetics by improving complex pre-treatment procedures included in KFDA method. To simplify pre-treatment procedures of KFDA method, reaction conditions including pH, time and temperature were optimized. This pre-treatment method does not require complicate pre-treatment steps of KFDA method such as pH adjustment of test solution with acetate buffer (pH 5.0), solvent-solvent partitioning with dichloromethane and concentrating procedure with vacuum evaporator. Formaldehyde-dinitrophenylhydrazone (formaldehyde-DNP) product produced by derivatization reaction was separated and quantified with a reversed-phase HPLC, which was slightly modified with KFDA method. The linearity test showed good results with 0.9999 of correlation coefficient ($r^2$) in the range of 2 ~ 40 ppm of standard solutions. In this method, limit of detection (LOD) and limit of quantitation (LOQ) values for formaldehyde were 0.2 ppm and 0.5 ppm, respectively. In addition, recovery test demonstrated that the method was also accurate and reproducible. Therefore, the proposed method can be applicable to rapid analysis of formaldehyde in cosmetics.

키워드

참고문헌

  1. S. H. Sim and Y. S. Kim, Characterization and assessment of indoor air quality in newly constructed apartments-volatile organic compounds and formaldehyde-, J. Env. Hlth., 32(4), 275 (2006).
  2. H. Choi, J. M. Choi, and W. J. Kim, Assessment of indoor volatile organic compounds (VOCs) and emission characteristics by humidity variation in new apartments, J. Korean Soc. Living Environ. Sys., 13(4), 283 (2006).
  3. A. C. De Groot and M. Veenstra, Formaldehyde releasers in cosmetics in the USA and in Europe, Contact Dermatitis, 62, 221 (2010). https://doi.org/10.1111/j.1600-0536.2009.01623.x
  4. W. D. Kerns, K. L. Pavkov, D. J. Donofrio, E. J. Gralla, and J. A. Swenberg, Carcinogenicity of formaldehyde in rats and mice after long-term inhalation exposure, Cancer Res., 43(9), 4382 (1983).
  5. R. A. Renne, K. M. Gideon, S. J. Harbo, L. M. Staska, and S. L. Grumbein, Upper respiratory tract lesions in inhalation toxicology, Toxicol. Pathol., 35(1), 163 (2007). https://doi.org/10.1080/01926230601052667
  6. B. W. Bailey and J. M. Rankin, New spectrophotometric method for determination of formaldehyde, Anal. Chem., 43(6), 782 (1972). https://doi.org/10.1021/ac60301a05
  7. P. Verma and V. K. Gupta, Spectrophotometric determination of formaldehyde in air, Talanta., 30(6), 443 (1983). https://doi.org/10.1016/0039-9140(83)80104-0
  8. Q. Li, P. Stitharathikhun, and S. Motomizu, Development of novel reagent for Hantzsch reaction for the determination of formaldehyde by spectrophotometry and fluorometry, Anal. Sci., 23(4), 413 (2007). https://doi.org/10.2116/analsci.23.413
  9. R. K. Beasley, C. E. Hoffman, M. L. Rueppel, and J. W. Worley, Sampling of formaldehyde in air with coated solid sorbent and determination by high performance liquid chromatography, Anal. Chem., 52(7), 1110 (1980). https://doi.org/10.1021/ac50057a026
  10. K. Kuwata, M. Uebori, H. Yamasaki, Y. Kuge, and Y. Kiso, Determination of aliphatic aldehydes in air by liquid chromatography, Anal. Chem., 55(12), 2013 (1983). https://doi.org/10.1021/ac00262a048
  11. C. Lv, J. Hou, W. Xie, and H. Cheng, Investigation on formaldehyde release from preservatives in cosmetics, Int. J. Cosmet. Sci., 37(5), 474 (2015). https://doi.org/10.1111/ics.12212
  12. G. Burini and R. Coli, Determination of formaldehyde in spirits by high-performance liquid chromatography with diode-array detection after derivatization, Anal. Chim. Acta, 511(1), 155 (2004). https://doi.org/10.1016/j.aca.2004.01.025
  13. R. T. Rivero and V. Topiwala, Quantitative determination of formaldehyde in cosmetics using combined headspace-solid-phase microextraction chromatography, J. Cosmet. Sci., 55(4), 343 (2004).
  14. B. Deng, Y. Liu, H. Yin, X. Ning, H. Lu, L. Ye, and Q. Xu, Determination of ultra-trace formaldehyde in air using ammonium sulfate as derivatization reagent and capillary electrophoresis coupled with on-line electrochemiluminescence detection, Talanta, 91, 128 (2012). https://doi.org/10.1016/j.talanta.2012.01.038
  15. L. Bolognesj and E. J. dos Santos, Determination of formaldehyde by flow injection analysis with spectrophotometric detection exploiting brilliant greensulphite reaction, Chemical Papers, 69(6), 791 (2015).
  16. C. Lv, J. Sun, and H. Cheng, Determination of formaldehyde residue in cosmetics by short-column high performance liquid chromatography with mass spectrometric confirmation, Anal. Methods, 7, 1630 (2015). https://doi.org/10.1039/C4AY02546F
  17. K. C. Lee, J. H. Park, and W. Lee, Determination of trace amounts of formaldehyde in water using high performance liquid chromatography and acetylacetone as a Derivative Reagent, J. Korean Soc. Environ. Eng., 37(2), 81 (2015). https://doi.org/10.4491/KSEE.2015.37.2.81
  18. T. Nash, The colorimetric estimation of formaldehyde by means of the Hantzsch reaction, Biochem. J., 55(3), 416 (1953). https://doi.org/10.1042/bj0550416
  19. J. Zhao, F. Liu, G. Wang, T. Cao, Z. Guo, and Y. Zhang, High performance liquid chromatography determination of formaldehyde in engine exhaust with unsymmetrical dimethylhydrazine as a new derivatization agent, Anal. Methods, 7, 309 (2015). https://doi.org/10.1039/C4AY02212B
  20. J. Zhao, G. Wang, T. Gao, and Z. Guo, Development of a novel derivate assay for formaldehyde determination by HPLC in beer samples, Food Anal. Methods, 2015, 183 (2015).
  21. M. K. L. Bicking, W. M. Cooke, F. K. Kawahara, and J. E. Longbottom, Effect of pH on the reaction of 2,4-dinitrophenylhydrazine with formaldehyde and acetaldehyde, J. Chromatogr., 455, 310 (1988). https://doi.org/10.1016/S0021-9673(01)82130-0
  22. X. Guan, E. Rubin, H. and Anni, An optimized method for the measurement of acetaldehyde by high-performance liquid chromatography, alcoholism, Clinical and Experimental Research, 36(3), 398 (2012). https://doi.org/10.1111/j.1530-0277.2011.01612.x
  23. A. Stafiej, K. Pyrzynska, A. Ranz, and E. Lankmayr, Screening and optimization of derivatization in heating block for the determination of aliphatic aldehydes by HPLC, J. Biochem. Biophys. Methods, 69(1-2), 15 (2006). https://doi.org/10.1016/j.jbbm.2006.02.009
  24. Y. L. Lin, P. Y. Wang, L. L. Hsieh, K. H. Ku, Y. T. Yeh, and C. H. Wu, Determination of linear aliphatic aldehydes in heavy metal containing waters by high-performance liquid chromatography using 2,4-dinitrophenylhydrazine derivatization, J. Chromatogr. A, 1216(36), 6377 (2009). https://doi.org/10.1016/j.chroma.2009.07.018
  25. A. Soman, Y. Qiu, and Q. Q. Chan Li, HPLC-UV method development and validation for the determination of low level formaldehyde in a drug substance, J. Chromatogr. Sci,. 46(6), 461 (2008). https://doi.org/10.1093/chromsci/46.6.461