Elliott Andrew G, Merenbloom Samuel I, Chakrabarty Satrajit, Williams Evan R
Department of Chemistry, University of California, Berkeley, California, 94720-1460.
Int J Mass Spectrom. 2017 Mar;414:45-55. doi: 10.1016/j.ijms.2017.01.007. Epub 2017 Jan 15.
A new charge detection mass spectrometer that combines array detection and electrostatic ion trapping to repeatedly measure the masses of single ions is described. This instrument has four detector tubes inside an electrostatic ion trap with conical electrodes (cone trap) to provide multiple measurements of an ion on each pass through the trap resulting in a signal gain over a conventional trap with a single detection tube. Simulations of a cone trap and a dual ion mirror trap design indicate that more passes through the trap per unit time are possible with the latter. However, the cone trap has the advantages that ions entering up to 2 mm off the central axis of the trap are still trapped, the trapping time is less sensitive to the background pressure, and only a narrow range of energies are trapped so it can be used for energy selection. The capability of this instrument to obtain information about the molecular weight distributions of heterogeneous high molecular weight samples is demonstrated with 8 MDa polyethylene glycol (PEG) and 50 and 100 nm amine modified polystyrene nanoparticle samples. The measured mass distribution of the PEG sample is centered at 8 MDa. The size distribution obtained from mass measurements of the 100 nm nanoparticle sample is similar to the size distribution obtained from transmission electron microscopy (TEM) images, but most of the smaller nanoparticles observed in TEM images of the 50 nm nanoparticles do not reach a sufficiently high charge to trigger the trap on a single pass and be detected by the mass spectrometer. With the maximum trapping time set to 100 ms, the charge uncertainty is as low as ±2 charges and the mass uncertainty is approximately 2% for PEG and polystyrene ions.
本文描述了一种新型电荷检测质谱仪,它结合了阵列检测和静电离子阱技术,可重复测量单个离子的质量。该仪器在带有锥形电极的静电离子阱(锥形阱)内有四个检测管,能在离子每次通过阱时对其进行多次测量,相较于传统的单检测管阱,可实现信号增益。对锥形阱和双离子镜阱设计的模拟表明,后者每单位时间可使离子通过阱的次数更多。然而,锥形阱具有以下优点:进入阱中心轴偏离达2毫米的离子仍能被捕获;捕获时间对背景压力不太敏感;仅捕获窄范围的能量,因此可用于能量选择。利用8兆道尔顿的聚乙二醇(PEG)以及50纳米和100纳米胺修饰的聚苯乙烯纳米颗粒样品,展示了该仪器获取非均相高分子量样品分子量分布信息的能力。PEG样品的测量质量分布集中在8兆道尔顿。从100纳米纳米颗粒样品的质量测量获得的尺寸分布与从透射电子显微镜(TEM)图像获得的尺寸分布相似,但在50纳米纳米颗粒的TEM图像中观察到的大多数较小纳米颗粒,单次通过时电荷未达到足够高的值以触发阱并被质谱仪检测到。将最大捕获时间设置为100毫秒时,对于PEG和聚苯乙烯离子,电荷不确定度低至±2个电荷,质量不确定度约为2%。