title: Determination of N-nitrosodiethanolamine, NDELA in cosmetic ingredients and products by mixed mode solid phase extraction and UPLC-tandem mass spectrometry with porous graphitic carbon column through systemic sample pre-cleanup procedure.
abstract: A rapid, sensitive, accurate and specific ultra-performance liquid chromatography coupled to tandem mass spectrometry (UPLC-MS/MS) method for the detection of N-nitrosodiethanolamine (NDELA), a highly toxic contaminant in cosmetic raw materials and products was developed and validated. Systematized sample preparation steps were developed according to product types. Various SPE cartridges and columns were examined to establish the condition of SPE and chromatographic separation for NDELA. Sample cleanup steps consisting of solvent and liquid-liquid extraction tailored to the various sample matrix types were established prior to mixed mode SPE (Bond Elut AccuCAT). Chromatographic separation was achieved within 7 min on a porous graphitic carbon (PGC) column using a gradient elution with the mobile phase of 1mM ammonium acetate containing 0.1% acetic acid and methanol. NDELA was monitored using an electrospray positive ionization mass spectrometry in the multiple reaction monitoring (MRM) mode (m/z 134.9>103.7(quantifier) and 73.7(qualifier ion)) with d8-NDELA (m/z 143.1>111.0) as internal standard. The standard curves were linear over the concentration range of 1-100 ng/mL with a correlation coefficient higher than 0.99. The limit of detection (LOD) and the limit of quantification (LOQ) was 10 and 20 μg/kg, respectively (0.5 and 1 ng/mL in standard solution). The intra- and inter-day precisions were estimated to be below 11.1% and accuracies were within the range of 90.8-115.8%. The validated method was successfully applied to the analysis of real samples including raw materials, skin care, make-up, shampoos and hair products.
authors.affiliation: AMOREPACIFIC CO/R&D Center, Gyeonggi-do 446-729, South Korea.
authors.forename: Kyung-Mi
authors.initials: KM
authors.lastname: Joo
authors.affiliation: AMOREPACIFIC CO/R&D Center, Gyeonggi-do 446-729, South Korea.
authors.forename: Mi-Sook
authors.initials: MS
authors.lastname: Shin
authors.affiliation: AMOREPACIFIC CO/R&D Center, Gyeonggi-do 446-729, South Korea.
authors.forename: Ji-hee
authors.initials: JH
authors.lastname: Jung
authors.affiliation: AMOREPACIFIC CO/R&D Center, Gyeonggi-do 446-729, South Korea.
authors.forename: Boo-Min
authors.initials: BM
authors.lastname: Kim
authors.affiliation: AMOREPACIFIC CO/R&D Center, Gyeonggi-do 446-729, South Korea.
authors.forename: John-Whan
authors.initials: JW
authors.lastname: Lee
authors.affiliation: School of Pharmacy, Sungkyunkwan University, Suwon 440-746, South Korea. Electronic address: hanjeong@skku.edu.
authors.forename: Hye-Jin
authors.initials: HJ
authors.lastname: Jeong
authors.affiliation: College of Pharmacy, Ewha Womans University, Seoul 120-750, South Korea. Electronic address: kmlim@ewha.ac.kr.
authors.forename: Kyung-Min
authors.initials: KM
authors.lastname: Lim
mesh_terms: D053000:Analytic Sample Preparation Methods; D002851:Chromatography, High Pressure Liquid / Q000295:instrumentation / Q000379:methods*; D003358:Cosmetics / Q000737:chemistry*; D004052:Diethylnitrosamine / Q000031:analogs & derivatives* / Q000032:analysis / Q000737:chemistry / Q000302:isolation & purification; D006108:Graphite / Q000737:chemistry*; D057230:Limit of Detection; D016014:Linear Models; D016062:Porosity; D015203:Reproducibility of Results; D052616:Solid Phase Extraction / Q000295:instrumentation / Q000379:methods*; D053719:Tandem Mass Spectrometry / Q000295:instrumentation / Q000379:methods*
chemical_list: D003358:Cosmetics; C014129:N-nitrosodiethanolamine; D004052:Diethylnitrosamine; D006108:Graphite
keywords: Cosmetics; Mixed mode solid phase extraction; N-nitrosodiethanolamine (NDELA); Porous graphitic carbon (PGC) column; UPLC–MS/MS