title: Rapid and sensitive determination of diacetylpolyamines in human fingernail by ultraperformance liquid chromatography coupled with electrospray ionization tandem mass spectrometry.
abstract: A rapid and sensitive ultraperformance liquid chromatography coupled with electrospray ionization tandem mass spectrometry (UPLC-ESI-MS/MS) method has been developed and validated for quantitatively determining diacetylpolyamines in the human fingernail. N(1),N(8)-diacetylspermidine (DiAct-Spd), N(1),N(12)- diacetylspermine (DiAct-Spm) and 1,6-diaminohexane (DAH) the [internal standard (IS)] were extracted from human fingernail samples by MeOH: 5 M HCl solution, followed by 4-(N,N-dimethylaminosulfonyl)-7-fluoro- 2,1,3-benzoxadiazole (DBD-F) derivatization, and then separated on an ACQUITY BEH C18 column with a gradient elution of acetonitrile and water containing 0.1% formic acid. The derivatives of the diacetylpolyamines were fully separated within a short run time (3.0 min). The triple quadrupole mass spectrometric detection was performed in the multiple reactions monitoring (MRM) mode by the UPLC-ESI- MS/MS system in the positive ionization mode. MRM using the fragmentation transitions of m/z 455.20→ 100.07, 737.25 → 100.07 and 567.10 → 479.07 in the positive ESI mode was performed to quantify DiAct-Spd, DiAct-Spm and IS, respectively. The calibration curve is between 0.04 ng mL(-1) for DiAct-Spd and DiAct-Spm. The detection limits (signal to noise ratio of five) were 5-10 pg mL(-1). A good linearity was achieved from the calibration curves (r(2) >0.9999), and the intra-day and inter-day assay precisions were less than 7.06%. Furthermore, the recoveries (%) of the diacetylpolyamines spiked in the human fingernails were 79.18-97.11. The present method proved that the high sensitivity is characterized by the specificity and feasibility of the sample analysis. Consequently, the proposed method was used to analyze human fingernail samples from 15 lung- cancer patients and 22 healthy volunteers. Diacetylpolyamines were detected from the fingernails of the lung- cancer patients for the first time. The concentration of DiAct-Spd in the lung-cancer patient group tended to be higher than those in the healthy volunteers.
authors.affiliation: Labo ratory of Analytical and Bio-Analytical Chemistry, School of Pharmaceutical Sciences, University of Shizuoka, 52-1 Yada, Suruga-ku, Shizuoka 422-8526, Japan. Key Laboratory for Natural Resource of Changbai Mountain & Functional Molecules, Ministry of Education, College of Pharmacy, Yanbian University, Yanji 133002, Jilin Province, China. junzhe@u-shizuoka-ken.ac.jp.
authors.forename: Jun Zhe
authors.initials: JZ
authors.lastname: Min
authors.affiliation: Laboratory of Analytical and Bio-Analytical Chemistry, School of Pharmaceutical Sciences, University of Shizuoka, 52-1 Yada, Suruga-ku, Shizuoka 422-8526, Japan. ymorota@u-shizuoka-ken.ac.jp.
authors.forename: Yuka
authors.initials: Y
authors.lastname: Morota
authors.affiliation: Key Laboratory for Natural Resource of Changbai Mountain & Functional Molecules, Ministry of Education, College of Pharmacy, Yanbian University, Yanji 133002, Jilin Province, China. yzjiang@ybu.edu.cn.
authors.forename: Ying-Zi
authors.initials: YZ
authors.lastname: Jiang
authors.affiliation: Key Laboratory for Natural Resource of Changbai Mountain & Functional Molecules, Ministry of Education, College of Pharmacy, Yanbian University, Yanji 133002, Jilin Province, China. gli@ybu.edu.cn.
authors.forename: Gao
authors.initials: G
authors.lastname: Li
authors.affiliation: Key Laboratory for Natural Resource of Changbai Mountain & Functional Molecules, Ministry of Education, College of Pharmacy, Yanbian University, Yanji 133002, Jilin Province, China. kangdz@ybu.edu.cn.
authors.forename: Dongzhou
authors.initials: D
authors.lastname: Kang
authors.affiliation: Fengxian Branch of Shanghai Sixth People's Hospital, Shanghai 201400, China. yuhaifu78@163.com.
authors.forename: Hai-fu
authors.initials: HF
authors.lastname: Yu
authors.affiliation: Laboratory of Analytical and Bio-Analytical Chemistry, School of Pharmaceutical Sciences, University of Shizuoka, 52-1 Yada, Suruga-ku, Shizuoka 422-8526, Japan. kinoue@u-shizuoka-ken.ac.jp.
authors.forename: Koichi
authors.initials: K
authors.lastname: Inoue
authors.affiliation: Laboratory of Analytical and Bio-Analytical Chemistry, School of Pharmaceutical Sciences, University of Shizuoka, 52-1 Yada, Suruga- ku, Shizuoka 422-8526, Japan. todoroki@u-shizuoka-ken.ac.jp.
authors.forename: Kenichiro
authors.initials: K
authors.lastname: Todoroki
authors.affiliation: Laboratory of Analytical and Bio-Analytical Chemistry, School of Pharmaceutical Sciences, University of Shizuoka, 52-1 Yada, Suruga-ku, Shizuoka 422-8526, Japan. toyooka@u-shizuoka-ken.ac.jp.
authors.forename: Toshimasa
authors.initials: T
authors.lastname: Toyo'oka
mesh_terms: D000328:Adult; D000368:Aged; D000369:Aged, 80 and over; D002851:Chromatography, High Pressure Liquid / Q000379:methods*; D003959:Diamines; D005260:Female; D006801:Humans; D057230:Limit of Detection; D016014:Linear Models; D008175:Lung Neoplasms / Q000378:metabolism; D008297:Male; D000432:Methanol; D008875:Middle Aged; D009262:Nails / Q000737:chemistry*; D010080:Oxazoles; D015203:Reproducibility of Results; D021241:Spectrometry, Mass, Electrospray Ionization / Q000379:methods*; D013096:Spermine / Q000031:analogs & derivatives* / Q000032:analysis* / Q000737:chemistry / Q000302:isolation & purification; D013449:Sulfonamides; D053719:Tandem Mass Spectrometry / Q000379:methods
chemical_list: D003959:Diamines; D010080:Oxazoles; D013449:Sulfonamides; D013096:Spermine; C060548:4-(N,N-dimethylaminosulfonyl)-7-fluoro-2,1,3-benzoxadiazole; D000432:Methanol; C007297:1,6-diaminohexane