Iwai Takahiro, Kakegawa Ken, Okumura Kensuke, Kanamori-Kataoka Mieko, Miyahara Hidekazu, Seto Yasuo, Okino Akitoshi
Department of Energy Sciences, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama, Kanagawa, 226-8502, Japan.
J Mass Spectrom. 2014 Jun;49(6):522-8. doi: 10.1002/jms.3368.
Plasma-based ambient desorption/ionization mass spectrometry (ADI-MS) has attracted considerable attention in many fields because of its capacity for direct sample analyses. In this study, a high-power pulsed microplasma jet (HPPMJ) was developed and investigated as a new plasma desorption/ionization source. In an HPPMJ, a microhollow cathode discharge is generated in a small hole (500 µm in diameter) using a pulsed high-power supply. This system can realize a maximum power density of 5 × 10(8) W/cm(3). The measured electron number density, excitation temperature and afterglow gas temperature of the HPPMJ were 3.7 × 10(15) cm(-3), 7000 K at maximum and less than 60 °C, respectively, which demonstrate that the HPPMJ is a high-energy, high-density plasma source that is comparable with an argon inductively coupled plasma while maintaining a low gas temperature. The HPPMJ causes no observable damage to the target because of its low gas temperature and electrode configuration; thus, we can apply it directly to human skin. To demonstrate the analytical capacity of ADI-MS using an HPPMJ, the plasma was applied to direct solid sample analysis of the active ingredients in pharmaceutical tablets. Caffeine, acetaminophen, ethenzamide, isopropylantipyrine and ibuprofen were successfully detected. Application to living tissue was also demonstrated, and isopropylantipyrine on a finger was successfully analyzed without damaging the skin. The limits of detection (LODs) for caffeine, isopropylantipyrine and ethenzamide were calculated, and LODs at the picogram level were achieved. These results indicate the applicability of the HPPMJ for high-sensitivity analysis of materials on a heat-sensitive surface.
基于等离子体的常压解吸/电离质谱(ADI-MS)因其能够直接进行样品分析而在许多领域引起了广泛关注。在本研究中,开发并研究了一种高功率脉冲微等离子体射流(HPPMJ)作为一种新的等离子体解吸/电离源。在HPPMJ中,使用脉冲高功率电源在一个小孔(直径500μm)中产生微空心阴极放电。该系统可实现最大功率密度为5×10⁸W/cm³。测量得到的HPPMJ的电子数密度、激发温度和余辉气体温度分别为3.7×10¹⁵cm⁻³、最高7000K和低于60°C,这表明HPPMJ是一种高能、高密度等离子体源,与氩电感耦合等离子体相当,同时保持较低的气体温度。由于其较低的气体温度和电极配置,HPPMJ对目标物不会造成明显损伤;因此,我们可以将其直接应用于人体皮肤。为了证明使用HPPMJ的ADI-MS的分析能力,将等离子体应用于药物片剂中活性成分的直接固体样品分析。成功检测到了咖啡因、对乙酰氨基酚、乙磺酰胺、异丙安替比林和布洛芬。还展示了其在活体组织上的应用,成功分析了手指上的异丙安替比林,且未损伤皮肤。计算了咖啡因、异丙安替比林和乙磺酰胺的检测限(LOD),并实现了皮克级的检测限。这些结果表明HPPMJ适用于对热敏表面上的材料进行高灵敏度分析。