敞开式离子化质谱技术研究进展

军事、公共安全和应急救援等对现场、实时、准确、快速检测技术提出了迫切需求。敞开式离子化质谱技术可以现场直接分析样品,具有简单、快速、无需样品前处理、可分析多种相态物质的特点。本文总结了基于激光、等离子体和电喷雾原理的敞开式离子化技术的研究进展,介绍了敞开式离子化质谱技术在化学战剂、生物和爆炸物检测领域的应用,并对敞开式离子化质谱技术面临的问题和未来研究方向进行了总结与展望。     

电感耦合等离子体离子源分析性能的影响因素探究

ICP(电感耦合等离子体)离子源是目前质谱分析中最常用的离子源之一,具有电离效率高、分析产物主要为单电荷离子等特点。因其优良的性能,现已广泛应用于不同行业中。为了继续提升ICP-MS(电感耦合等离子体质谱)的分析性能,拓宽应用领域,许多学者通过实验研究,建模仿真对ICP离子源进行了深入研究。本文对这些工作进行了阐述,介绍了不同的影响因素对等离子体特性的影响。如气体流速、功率大小、采样深度等,并对有无质谱采样接口时的等离子体的特性进行比较,为优化等离子体离子源提供思路。     

千瓦级微波等离子体质谱仪研究水体中锰元素

为了使微波等离子体电离源更好地用于分析水溶液中金属元素,本研究基于改进型千瓦级微波等离子体（KMP）电离源耦合线性离子阱质谱仪（LTQ MS）,在新型进样系统（Nafion H2SO4）下,研究水体中锰元素的质谱行为。锰元素的千瓦级微波等离子体质谱（KMP MS）特征谱图不同于传统的电感耦合等离子体（ICP MS）获得的特征信号,这可能有助于金属元素分析。使用KMP LTQ MS法分析水体中锰的络合物阴离子,证实锰的络合物阴离子是由流经KMP源中心管的水溶液在等离子体火焰中电离产生的,如NO3-。此外,解释了主要离子在多步碰撞诱导解离过程中特征碎片的形式,并在优化的条件下,使用锰的络合物阴离子二级质谱特征离子评估锰的检测限（LOD）为033 μg/L,线性动态范围涵盖至少2个数量级,在0~100 μg/L之间。因KMP源无Ar背景干扰,未来可将其与四极杆质谱结合,能够为水质检测提供新方法。     

实时直接分析质谱结合固相微萃取分析卷烟主流烟气粒相物

卷烟主流烟气(MSS)含有多种有害和致癌物质,威胁人们身体健康.本研究建立了一种固相微萃取(SPME)结合实时直接分析质谱法(DART-MS)检测直接耦合的、复杂卷烟主流烟气粒相物.优化后SPME时间20 min,DART离子源导轨移动速率0.2 mm/s,氦气温度350℃.通过SPME富集,可以提高复杂样品中多种物质...     

Self-triggered channel ion source

An ion source made from a continuous dynode electron multiplier of the straight channel type and an ion reflector device is described. Its principle of operation is based on a continuous self-sustained ion and electron cascade in the multiplier channel. Operating characteristics and the analysis of the ions produced are presented. The intensity of the total ion current delivered (10(-9) to 10(-8) A) is enhanced by at least six orders of magnitude relatively to previously described similar devices. This source, as illustrated, may be used in gaseous mass spectrometry.     

针-柱结构敞开式离子源和微型气泵集成系统的放电特性

设计了一种小型针-柱电晕放电结构,实现了敞开式离子源和微型气泵的系统集成。通过数码相机拍摄的针-柱放电图像和示波器记录的特里切尔放电波形,验证了该针-柱结构在没有外界气流、间隙仅2 mm的实验条件下实现了稳定的电晕放电。对针-柱结构电晕放电特性进行了研究,讨论了放电电压、镇流电阻、柱直径大小、针-柱间距等参数对针-柱电晕放电的影响,通过伏安特性曲线分析得出在放电电压为-3 800 V、镇流电阻为10 MΩ、柱直径为4 mm、间距为2 mm的实验条件下,产生的离子风气体流速最大（采用testo 405-V1风速仪测得最大气体流速为1.15 m/s）。该针-柱结构可采用微机电系统（MEMS）工艺加工实现,有望应用于质谱仪、离子迁移谱、高场非对称波形离子迁移谱等便携式分析仪器中,实现敞开式离子源和微型气泵的双重功能。     

高能量离子束诊断质谱仪的研制及性能表征

本研究开发了一台应用于高能量离子束诊断的直线式飞行时间质谱仪,实现了其与高能真空弧放电离子源的联用。该仪器加速电压30 kV,飞行腔有效飞行距离1.5 m,通过短脉冲离子门精确截取,ICCD高速相机优化聚焦,仪器分辨率优于90 FWHM,对放电过程中产生的等离子体可实现不同时间的离子成分分析。将该方法用于真空弧放电离子源放电过程中离子成分的检测,放电2 μs时,电离成分以气态离子C⁺、O⁺、C²⁺、O²⁺为主;放电6 μs后,除气体成分外,还可以检测到Fe⁺、Cu⁺及其同位素金属离子峰。该仪器能够给出离子源放电产生离子的种类、价态以及相对含量等信息,可实现整个放电过程产生离子成分信息的准确诊断。     

原位光电离质谱技术原理及应用

原位质谱技术具有原位、微量、实时、在线、无需样品预处理的特点.近年来,基于不同电离原理开发的原位离子化技术相继问世.原位光电离是一种基于大气压光电离的离子化技术,具有无电离极性歧视、电离碎片少以及抗基质效应强等优点.原位光电离通常需引入掺杂剂以增强离子化效率,待测物既可通过光致直接电离,亦可通过光电离诱导的离子分子反应...     

Low-vacuum cylindrical ion trap mass spectrometry

Low-vacuum mass spectrometry is desirable because it reduces the size, weight, cost, and power of the instrument by reducing the workload of the pumping system. To investigate low-vacuum mass spectrometry methods, a cylindrical ion trap (CIT) instrument was built. The platform used an electron impact source as the ionization source, a custom CIT as the mass analyzer, and an electron multiplier as the ion detector. The dimensions of the CIT were r₀?=?10?mm and z₀?=?8.98?mm. Aiming at low-vacuum conditions, its working parameters were optimized. By increasing the frequency of the radio frequency (RF) voltage, optimizing the electron impact source, using a higher voltage on the electron multiplier, and improving the current preamplifier, the mass spectrometry of methyl salicylate was successively performed at helium buffer gas pressures up to 2?Pa, which was dozens of times higher than the upper pressure limit of ion trap mass spectrometers. More importantly, this pressure can be obtained using a single pump, avoiding the use of a bulky turbo pump. In addition, we measured and analyzed the mass deviation of methyl salicylate with the changes in the background gas pressure and RF voltage frequency. The results experimentally verified the theory that the stability regions expand with increasing pressure for the first time. The methods we explored could be used to develop next generation hand-portable instruments and bring new applications to mass spectrometry.     

电过滤纸喷雾离子源的性能优化及应用研究

常压离子源是质谱技术在生命科学、环境保护、医药卫生、食品安全等领域的研究热点之一.随着质谱分析技术的应用范围越来越广,直接快速分析复杂体系的化合物组成和含量越发重要.本工作基于已研制的小型化离子阱质谱和电过滤纸喷雾离子源,对其分析性能和应用进行深入研究.以提高质谱信号强度和检测灵敏度为目标,对所用滤纸的孔径、离子源尖端...     

Multiplexed operation of a micromachined ultrasonic droplet ejector array

A dual-sample ultrasonic droplet ejector array is developed for use as a soft-ionization ion source for multiplexed mass spectrometry (MS). Such a multiplexed ion source aims to reduce MS analysis time for multiple analyte streams, as well as allow for the synchronized ejection of the sample(s) and an internal standard for quantitative results and mass calibration. Multiplexing is achieved at the device level by division of the fluid reservoir and separating the active electrodes of the piezoelectric transducer for isolated application of ultrasonic wave energy to each domain. The transducer is mechanically shaped to further reduce the acoustical crosstalk between the domains. Device design is performed using finite-element analysis simulations and supported by experimental characterization. Isolated ejection of approximately 5 microm diameter water droplets from individual domains in the micromachined droplet ejector array at around 1 MHz frequency is demonstrated by experiments. The proof-of-concept demonstration using a dual-sample device also shows potential for multiplexing with larger numbers of analytes.     

Characterization of plasma ion source utilizing anode spot with positively biased electrode for stable and high-current ion beam extraction

The operating conditions of a rf plasma ion source utilizing a positively biased electrode have been investigated to develop a stably operating, high-current ion source. Ion beam characteristics such as currents and energies are measured and compared with bias currents by varying the bias voltages on the electrode immersed in the ambient rf plasma. Current-voltage curves of the bias electrode and photographs confirm that a small and dense plasma, so-called anode spot, is formed near an extraction aperture and plays a key role to enhance the performance of the plasma ion source. The ion beam currents from the anode spot are observed to be maximized at the optimum bias voltage near the knee of the characteristic current-voltage curve of the anode spot. Increased potential barrier to obstruct beam extraction is the reason for the reduction of the ion beam current in spite of the increased bias current indicating the density of the anode spot. The optimum bias voltage is measured to be lower at higher operating pressure, which is favorable for stable operation without severe sputtering damage on the electrode. The ion beam current can be further enhanced by increasing the power for the ambient plasma without increasing the bias voltage. In the same manner, noble gases with higher atomic number as a feedstock gas are preferable for extracting higher beam current more stably. Therefore, performance of the plasma ion source with a positively biased electrode can be enhanced by controlling the operating conditions of the anode spot in various manners.     

Orthogonal acceleration time-of-flight mass spectrometry

The principles and applications of time-of-flight mass spectrometry involving instruments with independent (orthogonal) axes for ion generation and mass analysis are reviewed. This approach, generally referred to as orthogonal acceleration time-of-flight mass spectrometry, has proved particularly advantageous for the combination of continuous ionization sources with time-of-flight mass spectrometry. The history of the technique is briefly discussed along with the instrumental principles pertaining to all the stages of the instrumentation from ion source to detector. The applications of commercial and customized instruments are discussed for several ionization methods including electrospray, matrix assisted laser desorption/ionization, electron ionization, and plasma ionization.     

理论模拟和实验对照研究幅值扫描ac对离子阱质谱性能的影响

随着离子阱质谱分析技术的广泛应用,离子阱共振激发过程的理论模拟和实验验证对于深入研究离子阱质谱性能具有重要的意义.常见的线性离子阱所使用的共振激发弹出电压ac(alternating current)的设置有两种方式:一种是设定1个很小的恒定值(如1 V0-p),另一种是设定为1个幅值扫描范围.然而,鲜有人对比研究这两...     

Low-energy linear oxygen plasma source

A new version of a constricted plasma source is described, characterized by all metal-ceramic construction, a linear slit exit of 180 mm length, and cw operation (typically 50 kHz) at an average power of 1.5 kW. The plasma source is here operated with oxygen gas, producing streaming plasma that contains mainly positive molecular and atomic ions, and to a much lesser degree, negative ions. The maximum total ion current obtained was about 0.5 A. The fraction of atomic ions reached more than 10% of all ions when the flow rate was less then 10 SCCM O(2), corresponding to a chamber pressure of about 0.5 Pa for the selected pumping speed. The energy distribution functions of the different ion species were measured with a combined mass spectrometer and energy analyzer. The time-averaged distribution functions were broad and ranged from about 30 to 90 eV at 200 kHz and higher frequencies, while they were only several eV broad at 50 kHz and lower frequencies, with the maximum located at about 40 eV for the grounded anode case. This maximum was shifted down to about 7 eV when the anode was floating, indicating the important role of the plasma potential for the ion energy for a given substrate potential. The source could be scaled to greater length and may be useful for functionalization of surfaces and plasma-assisted deposition of compound films.     

Shunting arc plasma source for pure carbon ion beam

A plasma source is developed using a coaxial shunting arc plasma gun to extract a pure carbon ion beam. The pure carbon ion beam is a new type of deposition system for diamond and other carbon materials. Our plasma device generates pure carbon plasma from solid-state carbon material without using a hydrocarbon gas such as methane gas, and the plasma does not contain any hydrogen. The ion saturation current of the discharge measured by a double probe is about 0.2 mA∕mm(2) at the peak of the pulse.     

质谱仪离子导向装置的原理、应用和进展

离子导向装置（ion guide）是传输离子的重要手段。在质谱仪器中,离子导向装置是离子光学（ion optics）系统的重要组成部分,是联络处于低真空（或大气压）电离源和质量分析器的桥梁。离子导向装置不仅用于传输离子,还可降低离子的空间发散度和能量分散度,使离子最大限度到达质量分析器。本工作主要对一些常用的离子导向装置的原理、应用和进展进行了评述,并展望了未来的发展。     

Lithium ion sources for investigations of fast ion transport in magnetized plasmas

In order to study the interaction of ions of intermediate energies with plasma fluctuations, two plasma immersible lithium ion sources, based on solid-state thermionic emitters (Li aluminosilicate) were developed. Compared to discharge based ion sources, they are compact, have zero gas load, small energy dispersion, and can be operated at any angle with respect to an ambient magnetic field of up to 4.0 kG. Beam energies range from 400 eV to 2.0 keV with typical beam current densities in the 1 mAcm(2) range. Because of the low ion mass, beam velocities of 100-300 kms are in the range of Alfven speeds in typical helium plasmas in the large plasma device.     

敞开式小型线-筒电极负电晕放电离子源(英文)

针对目前商用质谱仪的离子源都为封闭式且工作在真空或者低气压环境中,应用范围十分受限这一问题,提出了一种新型的可在大气环境下工作的离子源.该离子源通过电晕放电产生离子,呈线-筒结构,由内电极和外筒电极组成,电极直径分别为0.16 mm和4 mm.外筒电极上开有对称的4个槽,用于通入样品和牵引离子.实验结果表明,在大气环境下,当载气为N2,内电极电压达到-3 800 V时,内电极和外筒电极之间发生电晕放电,可以很好地电离乙酸等负电性的化学物质.质谱图显示,大气中的N2和O2可能也参与电离,生成了NO-2 (m/z:46)、 NO-3 (m/z:62)和[M+NO-H]- (m/z: 89).结合COMSOL仿真软件,对该离子源的放电起始电压进行了理论分析,分析结果与实验结果相符.此外,该离子源接口简单,可广泛应用于敞开式质谱仪、离子迁移质谱仪(IMS)和高场非对称波形离子迁移质谱仪(FAIMS)中.     

Infrared multiphoton dissociation tandem charge detection-mass spectrometry of single megadalton electrosprayed ions

This work presents the implementation of tandem mass spectrometry for experiments on single electrosprayed ions from compounds of megadalton (MDa) molecular weight, using two charge detection devices. The first mass spectrometry stage (first charge detection device) combined with an ion gate allows both mass-to-charge ratio and charge selections of the megadalton ion of interest. The second stage is based on an electrostatic ion trap and consists of an image charge detection tube mounted between two ion mirrors. Single MDa ions can be stored for several dozen milliseconds. During the trapping time, single ions can be irradiated by a continuous wavelength CO(2) laser. We observe stepwise changes in the charge of a single trapped ion owing to multiphoton activation. Illustration of infrared multiphoton dissociation tandem mass spectrometry are given for single megadalton ions of poly(ethylene oxide)s and DNAs.