Hair analysis of histamine after fluorescence labeling by column-switching reversed-phase liquid chromatography with electrospray ionization mass spectrometry and application to human hair.
Hair analysis of histamine after fluorescence labeling by column-switching reversed-phase liquid chromatography with electrospray ionization mass spectrometry and application to human hair.
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DOI：
10.1016/j.ab.2004.06.037
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发表时间：
2004-10
影响因子：
2.9
通讯作者：
T. Toyo′oka;A. Suzuki;T. Fukushima;Masaru Kato
中科院分区：
文献类型：
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作者：
T. Toyo′oka;A. Suzuki;T. Fukushima;Masaru Kato
建立了柱切换反相高效液相色谱-电喷雾质谱联用（HPLC-ESI-MS）法测定头发中组胺（HA）的方法。HA用过量的4-（N，N-二甲基氨基磺酰基）-7-氟-2，1，3-苯并恶二唑（DBD-F）在60 ℃下在0.1M NaOH（pH 9.3）和乙腈（CH 3CN）的混合物中标记30分钟。所得DBD-HA衍生物通过Mightysil RP-18 GP（100× 2 mm i.d.，3μm），含0.1%三氟乙酸的酸性移动的相。然后通过Wakopak Navi C30（150× 2 mm i.d.，5μm）与20 mM AcONH 4-CH 3CN（8：2）混合。对于使用质子化分子离子[M+H]+（m/z 337）作为前体离子通过MS-MS测量获得的产物离子（m/z 292），质谱仪在选择反应监测（SRM）模式下运行。通过绘制内标物（HA-d4）的峰面积比与HA进样量（1.66- 16.6 pmol，r2=0.999）的校准曲线，获得了良好的线性。在1.66和16.6 pmol进样时的变异系数分别为5.6和3.7%（n=6）。检出限为0.167pmol。推荐程序的有效性通过腹腔内给予HA后大鼠毛根中的测定来确定。将所建立的方法应用于黑曲霉大鼠和健康志愿者毛干中HA的测定。在大鼠和人体中，每1 mg毛干中的浓度变化范围分别为0.80-1.84pmol（平均值±SD=1.33±0.33，n=12）和0.94-72.3pmol（17.2±21.5，n=16）。用此方法测定了大鼠和人血浆中的HA。由于该方法提供了良好的精密度和痕量检测头发中的HA，分析技术似乎是适用于测定头发中的各种生物胺。
Sensitive determination of histamine (HA) in hair was carried out by column-switching reversed-phase high-performance liquid chromatography coupled with electrospray ionization mass spectrometry (HPLC–ESI–MS). HA was labeled with excess amounts of 4-(N,N-dimethylaminosulfonyl)-7-fluoro-2,1,3-benzoxadiazole (DBD-F) at 60°C for 30min in a mixture of 0.1M borax (pH 9.3) and acetonitrile (CH3CN). The resulting DBD–HA derivative was roughly separated by a Mightysil RP-18 GP (100×2mm i.d., 3μm) with an acidic mobile phase containing 0.1% trifluoroacetic acid. DBD–HA in the fraction flowing due to a position change in the six-port column-switching valve was then completely separated by a Wakopak Navi C30 (150×2mm i.d., 5μm) with 20mM AcONH4–CH3CN (8:2). The mass spectrometer was operated in the selected reaction monitoring (SRM) mode for the product ion (m/z 292) obtained from MS–MS measurement using the protonated molecular ion [M+H]+(m/z 337) as the precursor ion. Good linearity was achieved from the calibration curve obtained by plotting peak area ratios of the internal standard (HA–d4) against the injected amounts of HA (1.66–16.6pmol, r2=0.999). The coefficients of variation, at 1.66- and 16.6-pmol injections, were 5.6 and 3.7%, respectively (n=6). Furthermore, the detection limit was 0.167pmol. The efficiency of the recommended procedure was identified from the determination in the rat hair root after intraperitoneal administration of HA. The proposed method was applied to HA determination in the hair shaft of Dark Agouti rats and healthy volunteers. The variations in the concentrations in 1mg of hair shaft were 0.80–1.84pmol (mean±SD=1.33±0.33, n=12) in rats and 0.94–72.3pmol (17.2±21.5, n=16) in humans. The determination of HA in the plasma of rats and humans was also performed successfully by this method. Because the proposed method provides good precision and trace detection of HA in hair, the analytical technique seems to be applicable for the determination of various biogenic amines in hair.