WO2011035633A1 - 使用掺杂剂的离子迁移谱仪的检测方法和系统 - Google Patents

使用掺杂剂的离子迁移谱仪的检测方法和系统 Download PDF

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Publication number
WO2011035633A1
WO2011035633A1 PCT/CN2010/074932 CN2010074932W WO2011035633A1 WO 2011035633 A1 WO2011035633 A1 WO 2011035633A1 CN 2010074932 W CN2010074932 W CN 2010074932W WO 2011035633 A1 WO2011035633 A1 WO 2011035633A1
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Prior art keywords
dopant
sample
gas
carrier
migration
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English (en)
French (fr)
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彭华
李徽
张仲夏
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Nuctech Co Ltd
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Nuctech Co Ltd
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Priority to PL10818327T priority Critical patent/PL2482065T3/pl
Priority to DE112010000007T priority patent/DE112010000007B4/de
Priority to EP10818327.8A priority patent/EP2482065B8/en
Priority to US12/994,293 priority patent/US8237110B2/en
Priority to BR112012003467-7A priority patent/BR112012003467B1/pt
Priority to GB1019221.9A priority patent/GB2485970B/en
Publication of WO2011035633A1 publication Critical patent/WO2011035633A1/zh
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
    • G01N27/622—Ion mobility spectrometry

Definitions

  • the present invention relates to ion mobility spectrometers (IMS) and detection methods and systems using dopants. Background technique
  • IMS Ion migration
  • the basic principle of the ion mobility spectrometer is: ionizing the sample vapor or the gasified solid particles to form ions, and then under the action of a weak electric field, the ions are directionally migrated in the migration tube, and the end of the migration tube.
  • the detector measures the migration time of the ions through the electric field, and then the mobility of the ions (ie, the migration speed of the ions under the unit electric field strength) can be calculated according to the migration time used by the ions.
  • the mobility of various substance ions is specific under certain conditions, and is related to the mass of the ion itself, the number of charges, and the spatial structure, the mobility and standard substance library corresponding to the different ions will be detected. By matching, you can determine the type of substance.
  • the migration tube is the core component of the ion mobility spectrometer.
  • the structure of the migration tube is shown in Figure 1. It includes several parts such as sample inlet, ionization zone, ion gate, migration zone and detector.
  • the foremost part of the migration tube is the sample inlet, and the sample to be tested enters the ionization zone by the carrier gas, and the carrier gas is generally purified air.
  • the electrons emitted by the ion source 63Ni in the ionization zone react with ⁇ or 0 2 in the air and a small amount of water molecules present in the air to form ( 0) nH+ , (H 2 0) nN0+ , ( 0) nNH 4 + , (H 2 0) n02-, ( 0) n (C0 2 ) m0 2 -, ( 0) nOH and other reactant cluster ions, when the analyte or sample molecule enters the compartment, it will react with the reactant The ionic reaction produces the corresponding product ions.
  • the product ions When the ion gate is smashed, the product ions enter the migration zone from the ionization zone, undergo directional migration under the action of the electric field, and finally impinge on the detector placed at the end of the migration zone, generating a weak current signal indicative of the intensity of the ion current, forming
  • the spectrum shows real-time information on ionic strength over time. Since the mobility of different product ions is different, the migration time required to reach the detector is also different. By spectral analysis and matching with the standard substance library, the type of the substance can be judged.
  • the ionization of the gas molecules to be tested in the ionization zone of the ion transport tube is a secondary ionization process: the concentration ratio of the carrier gas and the sample vapor is more likely to be ionized by the ion source than the sample vapor molecules. Therefore, the ionization process first proceeds to the air molecules to form reactant ions. Since the free path of the ionized carrier gas molecules is much smaller than the geometry of the reaction chamber, the ionized carrier gas molecules and the sample vapor molecules will collide frequently, thereby Charge or protons are transferred from the ionized carrier gas molecules to the sample molecules.
  • This charge or proton transfer reverses, V: is determined by the electron or proton affinity of the molecule participating in the reaction, and the charge is transferred from a molecule with low affinity or proton affinity to a molecule with high affinity.
  • the molecular composition and ionization mechanism of the reactants are usually changed by adding a dopant, thereby changing the chemical composition of the formed product to improve the detection sensitivity and selectivity of the instrument.
  • the doping reagent molecule must have lower electron affinity than the sample molecules (such as explosives) but higher than other components contained in the carrier gas, so it can be preferentially ionized to form a more stable group ion to avoid having carrier gas.
  • the lower affinity interferent is involved in the ionization reaction, and since the electron or mass affinity of the sample molecule is greater than the reagent molecule, these ions then react with the sample vapor molecule to form a sample molecular ion for detection.
  • the addition of the dopant can also shift the peak position of the corresponding product ion, so that the ion peak which is difficult to recognize due to the coincidence of the peak position is not separated when the doping reagent is not added, thereby realizing the presence of the interference. Identification of the components to be tested under conditions.
  • the commonly used dopants in the detection of explosives are halogenated compounds
  • the commonly used dopants in drug detection are niacinamide, acetone, ammonia water and the like.
  • the patents are disclosed, for example, in PCT patents WO2006129101 and WO2004102611, the apparatus described above employing at least two storage tanks to provide a plurality of different dopants, storage tanks and spectrometer ionization chambers. Connected, added to the side of the selective membrane facing the inlet, so that the sample gas is in contact with the dopant before ionization, and the circulation gas path in the migration tube is isolated from the doping gas path;
  • the described system includes a molecular sieve to which a dopant is added, and the first dopant can be continuously added.
  • the system further includes another storage tank containing different dopants, which is selectively added to the air through the gas supply.
  • the apparatus of the US Pat. No. 6,459,824 includes a plurality of tanks containing a plurality of doping reagents, selectively adding different doping reagents into the carrier gas stream according to changes in the detection signals, and reacting the samples to generate different mobility. Addition product.
  • a library of information can be created containing known reaction information of the analyte and different dopants. By comparing the observations of the sample with respect to a specific combination of the plurality of dopant reagents and the data in the information library, it can be determined whether the sample is in the sample. Does contain the substance to be tested.
  • the patent W02007082M1 is injected into the object to be tested through the atmospheric pressure ionization interface of the inlet of the instrument, and the additive is added to the mist gas.
  • US2002088936 combines a doping source with a dry cleaning device.
  • US5491337 In a closed vessel placed in front of the air inlet of the instrument sample, a low concentration of dopant is mixed with the carrier gas phase and introduced into the ionization chamber along with the sample gas.
  • EP 1672363 at The sample gas is mixed with the doping gas before entering the instrument, or the dopant is added to the migration gas to eliminate the interference problem when analyzing a large amount of inert gas test sample by ion mobility spectrometer.
  • Patents W020061231()7, EP0509171, US5283199, US5234838, US5032721, DR 19609582, ⁇ 2121 10, W02007085898, etc. describe different types of dopants that can be used for ion mobility spectrometry, and are suitable for various detection needs.
  • a dopant containing dipentanone is added to the circulation gas path; a small amount of sulfur dioxide dopant is added to the sample to be tested through a temperature-controllable permeation tube; acetone and carbon tetrachloride are added as a dopant to the carrier gas before the sample is injected.
  • a small amount of substituted phenol (such as methyl salicylate, 2-hydroxyacetophenone) dopant and amine (such as methylamine) dopant is added to the sample to be tested by using a temperature-controlled permeation tube; Dimethyl methylphosphonate (DMMP) monitors the ammonia content of the mixed gas; provides the use of amides as ionizing dopants, generates reactant ions and interacts with the analyte, and uses the peroxide peroxide Detection and so on.
  • DMMP Dimethyl methylphosphonate
  • FIG. 2 a schematic diagram of one configuration of an I MS mobility spectrometer detection system using dopants in the prior art.
  • the detection system includes an inlet 21, a transfer tube 20 having an ion source 10, and a pneumatic system in communication with the migration port.
  • a dopant gas source 41 is used to supply a gaseous dopant and is added to the system by a carrier gas or a migration gas; a sampling carrier for collecting a certain amount of sample and being introduced into the migration tube together with the sample to be collected In the inlet.
  • the pneumatic system includes a pump (not shown) and a filtering device 34, the outlets of which are respectively connected to the air inlets 31 and the ones at the opposite ends of the migration zone 3 ⁇ 4.
  • the ionization zone is in communication with the gas inlet 32 adjacent to the source to provide a clean gas stream, such as air, for use as a migrating gas stream and a sample carrier gas; the inlet is located adjacent to the ionization zone and the ion gate.
  • the gas outlets 33 are connected to each other, and are used for guiding the un-ionized migration gas and carrier gas molecules to the migration tube, and drying and purifying and recycling.
  • the manner in which the doping gas source 41 is disposed in the gas path that is, the manner in which the dopant is added, has various options, and the iU sets the doping gas source 41 to the carrier gas path or the intake air associated with the intake valve 31.
  • the migration of the port 32 is related to the generation of the dispersant vapor 3 ⁇ 4 migration gas or carrier gas mixed into the migration tube. It can also be used in combination with the doping gas source 41 and the dry cleaning device, and can also be used for injection and injection.
  • the device (not shown) is connected, usually the inlet and the ionization zone are separated by a selectively permeable membrane, and the miscellaneous addition port is arranged on the side of the selective permeable membrane facing the inlet, so that the sample gas is It is in contact with the doping agent before the ionization.
  • One of the objects of the present invention is to provide an ion mobility spectrometer (IMS) detection method using a dopant, which does not require the provision of the dopant gas source in the gas path system, thereby avoiding the prior art.
  • IMS ion mobility spectrometer
  • Another object of the present invention is to provide an ion mobility spectrometer (IMS) detection method using a dopant, wherein a suitable dose of a dopant is combined with a sampling carrier, and a sample is introduced into the instrument together with a sample by sampling and injection operations.
  • IMS ion mobility spectrometer
  • a further object of the present invention is to provide an ion mobility spectrometer (TMS) detection system using a dopant, wherein the overall structure of the apparatus is simplified and the apparatus is simplified because it is not necessary to provide a doping gas source in the gas path. Manufacturing costs of equipment.
  • TMS ion mobility spectrometer
  • an ion mobility spectrometer detecting method using a dopant
  • the ion mobility spectrometer comprising a migration tube having an inlet and a gas path system communicating therewith
  • the pneumatic system includes a pump and a filtering device and an air inlet and an air outlet disposed on the migration tube to provide a cleaning gas for use as a migration gas stream and a sample carrier gas
  • the detection method comprising: providing a sample carrier for collecting the sample; combining the dopant with the sample carrier; sampling the sample carrier with the dopant; and introducing the sample carrier after the sample is collected into the inlet of the ion mobility spectrometer for detection .
  • the method of combining a dopant with a sampling carrier comprises the steps of: forming a dopant into a solution; immersing the sampling carrier in the dopant solution; and removing the sample carrier and causing it to Dry storage in a closed environment.
  • the combining the dopant with the sampling carrier comprises the steps of: forming a dopant into a solution; and spotting the dopant solution into a sample collection zone of the sampling carrier.
  • the dopant comprises a halogenated hydrocarbon compound and niacinamide.
  • the halogenated hydrocarbon compound is trichloromethane
  • the solution prepared is a purity of one hundred parts.
  • the z[way system comprises: two inlet Us disposed on the migration tube for respectively providing a cleaning gas for migrating gas flow and sample carrier gas through the two gas inlets; and placing on the migration tube An air outlet for discharging the un-evaporated migration gas and carrier gas molecules out of the migration tube.
  • the present invention also provides a detection system using an ion mobility spectrometer (MS) incorporating a dopant, comprising: an ion mobility spectrometer comprising: a migration tube having an inlet, having an ion source; and communicating with the migration tube a pneumatic system comprising a pump and a filtering device and an air inlet and an air outlet disposed on the migration tube to provide a cleaning gas for use as a migration gas stream and a sample carrier gas; a sampling carrier for collecting The sample to be tested; a dopant that is combined with the sample carrier to be introduced into the inlet of the migration tube along with the sample carrier after the sample is taken.
  • MS ion mobility spectrometer
  • the detection method/detection system used in accordance with the present invention can achieve the following beneficial effects:
  • Figure 1 is a schematic view showing the basic structure of the migration pipe
  • FIG. 2 is a schematic view showing the structure of an ion mobility spectrometer in the prior art
  • Figure 3 is a schematic view showing the structure of an ion mobility spectrometer used in accordance with the present invention.
  • FIG. 4 is a schematic flowchart of a specific implementation manner of an IMS detection method according to the present invention
  • FIG. 5a-5cl are comparisons of detection spectrum effects obtained by a specific implementation manner of an IMS detection method according to the present invention
  • the ion mobility spectrometer (s) detecting method of the present invention includes a sampling device, a migration tube, and a gas path system connected thereto (described later with reference to FIG. 3).
  • the detection method of the present invention includes the following steps: providing a sample carrier S100 for collecting a sample; combining a dopant with a sample carrier S200; collecting a sample S300 with a sample carrier combined with a dopant; The sample carrier after the sample is collected is introduced into an inlet of the ion mobility spectrometer to perform ion mobility spectrometry detection S400.
  • a sample carrier is provided in step S1()0, and the sample carrier may be any suitable carrier known in the art, and the material may be knitwear, cotton cloth, Teflon, glass fiber or glass fiber. It requires no pollution source itself, without bleaching and dyeing; no fiber or cotton thread will fall off during operation, and the carrier material should be resistant to high temperature, with 3 ⁇ 4 good chemical inertness, good mechanical strength and deformation elasticity, easy to sample and Injection operation. The material can also be chemically treated to increase its adsorption capacity to the sample and to improve desorption efficiency.
  • the sampling carrier described above is combined with the detection of the dopant to be used in step S200, which can be achieved in a variety of ways.
  • the dopant is first made into a solution having a specific concentration including 100% concentration (pure liquid dopant); then the specific sampling provided in S100 is The descent is immersed in the dopant solution for a predetermined period of time; finally, the soaked sample carrier is taken out, dried in a closed container, and quickly sealed for use.
  • the above-described joining process can also be realized as shown in steps S220 and S240 on the right side of Fig. 6.
  • the dopant is still made into a specific concentration including 100% concentration (pure liquid dopant), sealed in a special reagent bottle; then the appropriate dose of the dopant solution is applied to the sampling carrier before the test. Sample collection area.
  • step S200 since the dose of the dopant will affect the separation effect of the substance ion peak in the finally obtained detection spectrum, in step S200, it is necessary to cause the sample carrier to bond a suitable amount of dopant.
  • concentration of the dopant solution prepared in S210, the material type of the sampling carrier provided in S'230, and S250 can be changed.
  • the soaking time of the crucible finally results in a sampling carrier incorporating an appropriate amount of dopant.
  • the sampling carrier and doping can be realized by changing the concentration of the dopant solution prepared in S210 and/or the amount of the dopant solution applied to the sample carrier sampling region. Moderate combination of agents.
  • step S300 the sample is collected using a sampling carrier incorporating an appropriate amount of dopant.
  • the sample carrier used already contains a dopant, which is different from the prior art carrier, the acquisition process is substantially the same as in the prior art. Thus, a detailed description of step S300 is omitted here.
  • step S400 the sample carrier of the collected sample is introduced into the inlet of the ion mobility spectrometer to be described below to obtain a detection spectrum.
  • the ion mobility detector comprises: an ion mobility spectrometer comprising: an inlet 210, a migration tube 200 having an ion source 100; and a gas path system in communication with the migration tube; a sampling carrier for collecting Detection a sample; a dopant, which is combined with a sample carrier to be introduced into the inlet of the migration tube together with the sample carrier after the sample is collected.
  • the gas path system of the present invention employs, but is not limited to, the same carrier gas path and migration gas path as those of the prior art.
  • the gas path system of the present invention comprises: a pump (not shown) and a filtering device 340 having outlets respectively directed to the end 310 disposed at the opposite end of the migration zone 4 and disposed in the ionization zone and ions
  • An air inlet 320 near the source is in communication to provide clean air for use as a migrating gas stream and a sample carrier gas; an inlet thereof communicates with an outlet port 330 disposed in the ionization zone adjacent to the ion gate for use in
  • the ionized migration gas and carrier gas molecules are led out to the migration tube, and are used after being dried and purified.
  • the difference from the prior art is: 1) no need to set the doping gas source in the pneumatic system; 2) the sampling carrier introduced into the inlet of the migration tube not only contains the sample carried by it, but also contains appropriate amount Dopant.
  • the structure and detection method/flow of the ion mobility spectrometer system of the present invention is schematically illustrated with reference to Fig. 4 and Fig. 3. Since the detection method/system of the present invention creatively uses a sampling carrier in combination with a dopant, the ion mobility spectrometry system is simplified in overall structure; and its control of the dose of the dopant can be more easily and accurate.
  • the ion mobility detector detection method/system of the present invention can be applied to different fields such as drug detection, explosive detection, and chemical warfare agent detection. Since different detection targets are used, different types are required.
  • the miscellaneous agents include halogenated hydrocarbon compounds such as trichloromethane, amide compounds such as niacinamide and the like.
  • the dopants used in the detection include liquid dopants such as dichloromethane, trichloromethane, and steroidal dopants such as hexachloroethane, niacinamide, and the like.
  • liquid dopants such as dichloromethane, trichloromethane, and steroidal dopants such as hexachloroethane, niacinamide, and the like.
  • the stock solution can be used as a dopant in liquid chloroform, it is more often the case that a solid solvent is used to dissolve the solid dopant.
  • even liquid dopants may be considered for miscellaneous doses. Use a lower concentration solution than the stock solution.
  • FIG. 5a - 5d there is shown a detection method according to the present invention, with black gold (RDX) as a sample example and chloroform as a dopant example, according to the above-mentioned corresponding flow in the right side of Figure 4
  • RDX black gold
  • the effect of the ion mobility spectrogram obtained before and after the combination of the agent and the sputum-like carrier is compared.
  • the abscissa is the migration time and the ordinate is the ion current intensity.
  • Figure 5a shows the detection spectrum when no sample carrier containing dopants and sample is introduced, in which case only the reactant ion peaks generated by the air molecules are present in the spectrum.
  • Figure 5b shows a detection spectrum obtained by applying a quantity of RDX sample to a sample carrier that is not bound to the dopant and is introduced into the inlet of the instrument. At this time, the spectrum of the RDX sample can be seen in addition to the reactant ion peak generated by the air molecules.
  • Figure 5c shows a test pattern obtained by introducing a sample carrier that has been combined with a dopant but no sample applied to the inlet of the instrument. At this time, the spectrum of the reactant ions generated by the air molecules having a substantially high height and the reactant ion peaks generated by the dopant molecules are shown in the spectrum.
  • Figure 5d shows the detection spectrum when the sample carrier has incorporated the dopant and contains the same amount of RDX sample as Figure 5b. At this time, the peak height of RDX in the spectrum is significantly increased due to the addition of the dopant, and the peak shape effect is improved.
  • the detection method of the present invention can provide a good separation map.
  • accurate detection can also be achieved by appropriately adjusting the amount of dopant incorporated in the sample carrier.
  • two kinds of dopants which are mutually soluble and do not react can be used as a "corresponding concentration" solution to soak the sample carrier, and can also be added to the sample carrier after being soaked in the corresponding solvent.
  • the dopant solution is used to achieve the combination to meet the need to use a variety of dopants in the detection. Therefore, although the combined process may be complicated, it is considered to simplify the overall structure of the detection system, and the dopant control. The accuracy and convenience are still of significant positive significance.
  • Those skilled in the art after obtaining the teachings of the above embodiments, can grasp the parameters of other bonding processes, including the composition of the solution, the time of soaking, and the like, from a limited experiment.
  • the "sampling carrier in combination with the dopant" of the present invention is not limited to the one-time combination with chloroform described in the examples, but includes separate from other dopants known in the prior art. Or multiple combinations of combinations; it is also not limited to bonding with dopants in the liquid state, but includes dopant bonding in any state.

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Description

使用掺杂剂的离子迁移谱仪的检测方法和系统
技术领域
本发明涉及使用掺杂剂的离子迁移谱仪（IMS)及检测方法和系统。 背景技术
离子迁移 （IMS ) 技术作为一种痕量探测技术起源于二十世纪六十年代， 早期的 专利 （US 3699333 和 4777363 ) 对这一技术进行了详尽的描述。 离子迀移谱仪的基 本原理是： 使被检测的样品蒸气或气化后的固体微粒离化形成离子， 然后在弱电场 的作用下， 离子在迁移管中进行定向迁移， 由迁移管终端的检测器测量出离子通过 电场所用的迁移时间， 进而根据离子所用的迁移时间可以计算出离子的迁移率（即单 位电场强度作用下离子的迁移速度）。 由于在一定的条件下， 各种物质离子的迁移率 具有特异性， 和离子本身的质量、 所带电荷数、 空间结构等因素相关， 因而将检测 得到的不同离子对应的迁移率与标准物质库进行匹配， 就可以判断出物质的种类。
迁移管是离子迁移谱仪的核心部件， 其棊本结构如图 1 所示， 包括样品入口、 离化区、 离子门、 迁移区和探测器等几个部分。
迁移管的最前部是样品入口， 被测样品在载气的带动下由此进入离化区， 载气 一般是净化过的空气。 离化区中的离子源 63Ni 发出的电子会和空气中的 ^或 02以 及空气中存在的少量水分子发生反应， 生成（ 0) nH+ ， (H20) nN0+ , ( 0) nNH4+， （H20) n02-， （ 0) n (C02) m02-， （ 0) nOH 等反应物团簇离子， 当 待测物或样品分子进入离化室后， 就会和反应物离子反应生成对应的产物离子。 当 离子门打幵时， 该产物离子由离化区进入迁移区， 在电场作用下发生定向迁移， 并 最终撞击到置于迁移区终端的探测器匕 产生表征离子流强度的微弱电流信号， 形 成的谱图显示离子强度随时间变化的实时信息。 由于不同产物离子的迁移率各不相 同， 到达探测器所需的迁移时间也不同， 通过谱图分析并与标准物质库进行匹配， 就可以判断出物质的种类。
在离子迁移管的离化区屮进行的待测样品气体分子的离化为二次离化过程： 载 气和样品蒸气的浓度比导致载气分子较于样品蒸气分子更易为离子源所离化， 因此 电离过程首先对空气分子进行， 生成反应物离子。 由于离化载气分子的自由程远远 小于反应室的几何尺寸， 离化了的载气分子和样品蒸气分子间将频繁碰撞， 从而使 电荷或质子从离化了的载气分子转移到样品分子上。 这种电荷或质子的转移反)、 V：由 参加反应的分子的电子或质子亲和力决定， 电荷会从电于或质子亲和力小的分子转 移到亲和力大的分子上面。 在离子迁移谱仪的实际使用中， 通常通过加入惨杂剂的 方式来改变反应物的分子组成和离化机理， 从而改变生成的产物离于的化学组成， 以提高仪器的检测灵敏度和选择性。 掺杂试剂分子必须具备低于样品分子（如爆炸物) 但高于载气中所含其它组分的电子亲和力， 因此可优先离化生成组成较为稳定的团 族离子，以避免载气中具有较低亲和力的干扰物参与离化反应， 同时由于样品分子的 电子或质了亲和力大于试剂分子， 这些离子继而再和样品蒸气分子反应生成可供检 测的样品分子离子。 掺杂剂的加入还可使生成的产物离子对应的谱图峰位发生移 动， 使原来没加入掺杂试剂时由于峰位重合而难以识别的离子峰分离开来， 从而实 现在千扰物存在状况下对待测组分的识别。 目前在爆炸物探测中常用的渗杂剂是卤 代化合物， 在毒品探测中常用的掺杂剂是烟酰胺、 丙酮、 氨水等。
在过去的 30多年里， 发达国家对 MS技术开展了大量的研究工作， 并在仪器结 构， 分离原理， 采样技术等诸多方面申请了许多专利 ( US4311669 , US4551624 , DE19502674 , W09306476等） 。 其中一些专利描述了化学掺杂剂的加入方式及相关应 用：
在化学掾杂剂的加入方式上， 涉及的专利如 PCT 专利 W02006129101 和 W02004102611 , 前者所述的仪器采用至少两个储罐以提供多种不同的摻杂剂， 储罐 和谱仪的离化室相连， 加入 ΓΊ设在选择透过性膜面朝进样口的一侧， 使样品气在离 化前即和掺杂剂相接触， 迁移管内循环气路与掺杂气路相隔离； 后者描述的系统包 括加入了摻杂剂的分子筛， 可连续加入第一种糁杂剂， 系统还包括另外的装有不同 掺杂剂的储罐， 通过幵关设 ¾向空气中选择性加入除第一种掺杂剂以外的其它不同 的掺杂剂。 此外， 美国专利 US6495824 涉及的装置包括多个装有多种掺杂试剂的储 罐， 根据检测信号的变化， 将不同掺杂试剂有选择地加入载气气流中， 和样品反应 生成具有不同迁移率的加和产物。 可建立一信息库， 包含待测物和不同掺杂剂的已 知反应信息， 通过将样品相对多种掺杂试剂特定组合的观测结果和信息库中的数据 相比较， 即可确定样品中是否确实含有待测物质。 专利 W02007082M1 是通过仪器入 口的常压离化界面注入待测物， 同吋将添加剂加入雾状气体中。 US2002088936 则将 掺杂气源和干燥清洁装置相结合。 US5491337 在置于仪器样品空气入口前的密闭容 器中， 将低浓度的掺杂剂和载气相混合， 和样品气一同引入离化室。 EP 1672363 在 样品气进入仪器前和掺杂气体相混合， 或将掺杂 体加入迁移气中， 来消除用离子 迁移谱仪分析大量惰性气体测试样品时的干扰问题。
专利 W020061231()7、 EP0509171 , US5283199、 US5234838、 US5032721、 DR 19609582, 圃 2121 10 、 W02007085898等则描述了可用于离子迁移谱分析的不同 种类的揍杂剂， 适用于各种检测需求。 如将包含二戊酮的掺杂剂加入循环气路； 通 过可控温渗透管将少量二氧化硫惨杂剂加入待测样品； 在样品注入前将丙酮和四氯 化碳作为糁杂剂加入载气中； 通过采用可控温渗透管的方式将少量取代酚类 （如水 杨酸甲酯， 2-羟基苯乙酮） 掺杂剂和胺类 （如甲胺） 掺杂剂加入待测样品； 利用甲 基膦酸二甲酯 （DMMP ) 对混合气体中氨气含量进行监测； 提供采用酰胺类物质作为 离化惨杂剂， 产生反应物离子并与待测物相互作用， 用丁过氧化物炸药的检测等。
参考图 2， 为现有技术屮使用掺杂剂的 I MS 迁移谱仪检测系统的一种结构的示 意图。
该检测系统包括进样口 21、 具有离子源 10的迁移管 20和与迁移筲相通的气路 系统。 掺杂剂气源 41 用于提供气态掺杂剂， 并由载气或迁移气加入到系统中； 采样 载体， 用于采集一定量的样品， 并与被采集的样品一起被导入到迁移管的进样口 中。 其中， 气路系统包括一泵 （未示出） 和过滤装置 34， 其出口分别与置于迁移区 ¾离化区相对的一端的进气口 31 和！!于离化区与离了源接近处的进气口 32 相连 通， 用以提供用作迁移气流和样品载气的清洁气流， 例如空气； 其入口与置于离化 区与离子门接近处的出气口 33相连通， 用于将未离化的迁移气和载气分子导出迁移 管， 经干燥净化后循环使用。 掺杂气源 41 在气路中的设置方式即糁杂剂的加入方式 有多种选择， 既 iU将掺杂气源 41设青在与进气门 31相关的载气气路或与进气口 32 相关的迁移 ί路上， 产生的惨杂剂蒸气 ¾迁移气或载气混合后进入迁移管， 也可使 掺杂气源 41 和十燥清洁装置相结合使用， 还可使其和进样装置 （未示出） 相连， 通 常进样口和离化区由一选择透过性膜相分隔， 惨杂加入口设在选择透过性膜面朝进 样口的一侧， 使样品气在离化前即和掺¾剂相接触。
在现有技术屮除需要由半透膜材料制备的盛装掺 ¾剂的气源外， 还需要控制气 源装置的温度， 以提供适宜浓度的掺杂剂量， 因而使检测系统的气路结构和装置设 计变得复杂。 而且， 由于通过单独气路连续不断的提供掺杂剂， 容易导致因掺杂剂 在系统内的累积造成掺杂剂量过高， 或因掺杂剂的消耗或结块而造成掺杂剂量过低 等难以迅速和准确地控制糁杂剂量的问题， 从而影响到仪器的检测灵敏度。 此外， 掺杂剂多有腐蚀件， 因此揍杂 源装置和气路及相关配件需要使用具有抗腐蚀的材 料， 也无疑也增加了检测系统的制造和保养费用。 发明内容
鉴于上述背景技术中提到的技术问题， 本发明的目的在于克服现有技术中的缺 陷和问题的至少一个方面。
本发明目的之一在于提供一种使用揍杂剂的离子迁移谱仪（IMS)检测方法， 其 屮， 不需要在气路系统中设置所述掺杂剂气源， 因此， 避免了现有技术中 ι 于掺杂 剂的加入和使用造成的气路系统设计复杂及对气路元件材料的抗腐蚀性要求较高的 缺陷。
本发明另 目的在于提供一种使用掺杂剂的离子迁移谱仪（IMS)检测方法， 其 中， 使适当剂量的掺杂剂与采样载体结合， 通过采样和进样操作， 和样品一同引入 到仪器中， 而起到和在系统中设置惨杂气源相似的掺杂剂加入效果， 同时避免了现 有技术中 于掺杂剂在系统中的累积造成的难以准确控制掺杂剂量的缺陷。
本发明再一目的在于提供一种使用掺杂剂的离子迁移谱仪（TMS)检测系统， 其 中， 由于不需耍在气路中设置掺杂气源， 因而简化了仪器的整体结构， 降低了设备 的制造成本。
根据本发明的 -个方面， 其提供一种使用掺杂剂的离子迁移谱仪（MS)检测方 法， 所述离子迁移谱仪包括具有进样口的迁移管和与其迮通的气路系统， 所述气路 系统包括泵和过滤装置以及置于所述迁移管上的进气口和出气口以提供用作迁移气 流和样品载气的淸洁气体， 所述检测方法包括： 提供用于釆集样品的采样载体； 将 惨杂剂与采样载体结合； 用结合有掺杂剂的采样载体采 样品； 以及将采集样品后 的采样载休导入到离子迁移谱仪的进样口， 以供检测。
优选地， 所述将掺杂剂与采样载体结合的方法包括下述步骤： 将掺杂剂制成溶 液； 将采样载体浸泡在所述掺杂剂溶液中； 以及取出釆样载体并使其在密闭环境中 千燥储存。
优选地， 所述将掺杂剂与采样载体结合包括下述步骤： 将掺杂剂制成溶液； 以 及将所述掺杂剂溶液点入采样载体的样品采集区。
优选地， 所述掺杂剂包括卤代烃类化合物和烟酰胺。
优选地， 所述卤代烃类化合物为三氯甲垸， 其制成的溶液为 Π分之百纯度。 优选地， 所述 z〔路系统包括： 置于迁移管上的两进 U， 用于通过所述两进气 口分別提供用作迁移气流和样品载气的清洁气体； 置于迁移管上的出气口， 用于将 未离化的迁移气和载气分子导出所述迁移管。
本发明还提供了一种使用掺¾剂的离子迁移谱仪（MS)的检测系统， 包括： 离子 迁移谱仪， 包括： 具有进样口、 具有离子源的迁移管； 和与迁移管相连通的气路系 统， 所述气路系统包括泵和过滤装置以及置于所述迁移管上的进气口和出气口以提 供用作迁移气流和样品载气的清洁气体； 采样载体， 用于采集被检测的样品； 掺杂 剂， 其与采样载体结合， 从而与采集样品后的采样载体一起被导入到迁移管的进样 口中。
根据本发明所釆用的检测方法 /检测系统可以达到如下有益效果：
整体结构简化， 掺杂剂的剂量 J得到精确控制。 附图说明
本发明的这些和 /或其他方面和优点从下面结合附图对优选实施例的描述中将变 得明显和容易理解， 其中：
图 1 出迁移管的基本结构的示意图；
图 2 示出现有技术中离子迁移谱仪的结构示意图；
图 3 示出根据本发明中使用的离子迁移谱仪的结构示意图；
图 4示出根据本发明 IMS检测方法的具体实施方式的示意性流程图； 图 5a-5cl为本发明的 IMS检测方法一具体实施方式得到的检测谱图效果对比； 具体实施方式
以下是根据特定的具体实例说明本发明的具体实施方式， 熟悉本领域的技术人 员可由以下实施例中所揭示的内容轻易地了解本发明的构造， 优点与功效。
参考图 4， 下面说明使用惨¾剂的离子迁移谱仪（IMS)检测方法的流程。
在本发明关于使用惨杂剂的离子迁移谱仪（ s)检测方法中， 所用的离子迁移谱 仪包括进样装置、 迁移管及与其相连通的气路系统 （后面参考图 3 进行说明） ， 参 考图 4, 本发明检测方法包括下述歩骤： 提供用于采集样品的釆样载体 S100; 将掺 杂剂与采样载体结合 S200; 用结合有掺杂剂的采样载体采集样品 S300; 以及将采集 样品后的采样载体导入到离子迁移谱仪的进样口， 以实施离子迁移谱检测 S400。 在步骤 S1()0中提供釆样载体， 所述采样载体可以是现有技术中已知的任意一种 适当的载体， 其材料可以是针织品、 棉布、 特氟纶、 玻璃丝或玻璃纤维等， 要求本 身无污染源， 未经漂染，上色； 不会有纤维或棉线在操作中脱落， 且载体材料应耐高 温， 具有 ¾好的化学惰性、 良好的机械强度和形变弹性， 易于进行取样及进样操 作。 也可对材料进行化学处理以提高其对样品的吸附能力及改进解吸效率。
在歩骤 S200中将上述采样载体与检测将要使用的掺杂剂结合， 所述结合可以通 过多种方式实现。 例如位于图 6中左侧的步骤 S210、 S230和 所示， 首先将掺 杂剂制成特定浓度包括 100%浓度 （纯液态掺杂剂） 在内的溶液； 然后将在 S100 中 提供的特定采样载休浸泡在该掺杂剂溶液中一段预定时间； 最后将浸泡好的采样载 体取出、 使其在密闭容器中干燥， 并迅速密封起来， 以备使用。
此外， 上述结合过程也可以如图 6中右侧的步骤 S220、 S240所示那样实现。 首 先仍将掺杂剂制成特定浓度包括 100%浓度 （纯液态掺杂剂） 在内的溶液， 密封在专 用的试剂瓶内； 然后在检测前将适当剂量的惨杂剂溶液施加在采样载体的样品采集 区。
如背景技术中所述， 由于惨杂剂的剂量将影响最终得到的检测谱图中物质离子 峰的分离效果， 因此， 在步骤 S200 中， 需要使采样载体结合适量的掺杂剂。 显然， 如果是由图 4中左侧的 S210、 S230和 S250步骤构成的结合， 可以通过改变 S210中 配制的掺杂剂溶液的浓度、 S'230中提供的采样载体的材料类 ¾、 以及 S250屮的浸泡 时间而最终得到结合有适量糁杂剂的采样载体。 而对于图 4 中右侧的实现方式， 可 以通过改变 S210 中配制的掺杂剂溶液的浓度及 /或施加在采样载体样品采集区上的 惨杂剂溶液的量， 来实现采样载体与掺杂剂的适度结合。
随后， 如步骤 S300所述， 用结合有适量惨杂剂的采样载体采集样品。 在这一过 程中， 虽然所用的釆样载体已含有掺杂剂， 这一点上与现有技术屮的釆样载体不 同， 但采集的过程与现有技术基本相同。 因而， 在此省略对步骤 S300的详细描述。
最后， 如步骤 S400所述， 将已采集样品的采样载体导入下面将要描述的离子迁 移谱仪的进样口， 以得到检测谱图。
下面， 参考图 3， 描述本发明的使用掺杂剂的离子迁移谱仪检测系统的一种结 构。
所述离子迁移 i普仪检测系统包括： 离子迁移谱仪， 包括： 进样口 210、 具有离 子源 100的迁移管 200; 和与迁移管相连通的气路系统； 采样载体， 用于采集被检测 的样品； 掾杂剂， 其与釆样载体结合， 从而与采集样品后的采样载体一起被导入到 迁移管的进样口中。
其中， 为了更好地与背景技术中所介绍的现有技术中对比， 本发明的气路系统 采用， 但不限于， 与现有技术的结构相同的载气气路和迁移气路。 具体地说， 本发 明的气路系统包括： 一泵 （未示出） 和过滤装置 340， 其出口分别与置于迁移区 4离 化区相对的一端的进 310和置于离化区与离子源接近处的进气口 320 相连通， 用以提供用作迁移气流和样品载气的清洁空气； 其入口与置于离化区与离子门接近 处的出气口 330 相连通， 用于将未离化的迁移气和载气分子导出迁移管， 经干燥净 化后循环使用。
而与现有技术不同的是： 1 ) 气路系统中不再需要设置掺杂气源； 2 ) 被导入到 迁移管的进样口内的采样载体， 不仅包含其携带的样品， 而且还含有适量的掺杂 剂。
由此， 参考图 4 和阁 3, 示意性地说明了本发明的离子迁移谱仪系统结构和检 测方法 /流程。 由于本发明检测方法 /系统创造性地使用了采样载体与惨杂剂相结合 这 . ·手段， 使得离子迁移谱系统在整体结构上简化； 同时其对于惨杂剂的剂量的控 制也可以更加容易和精确。
如背景技术部分所介绍那样， 本发明离子迁移 i普仪检测方法 /系统可以应用在毒 品检测、 爆炸物探测、 化学战剂检测等不同领域， 由于其针对的检测对象不同， 因 而需要使用不同种类的惨杂剂， 包括卤代烃类化合物如三氯甲垸、 酰胺类化合物如 烟酰胺等。
下面， 以黑索金 （RDX ) 为样品示例， 以三氯甲烷为掺杂剂示例， 说明在本发明 检测方法中如何将采样载体与掺杂剂相结合， 即， 如何具体实现图 4 中的步骤 S200。
或者， 按照图 4 中右侧的流程， 首先， 仍获得 100 %浓度的二氯甲垸； 然后使 用滴管将一定体积的三氯.甲垸原液滴到 ώ纤维材料制成的采样载体的样品采集区 内。
在上述示例中， 木领域技术人员应该理解， 由于检测中使用的惨杂剂包括液体 掺杂剂如二氯甲烷、 三氯 φ垸和冏体掺杂剂如六氯乙烷、 烟酰胺等， 丙此， 原液虽 然在以液态的三氯甲烷为摻杂剂中可以使用， 但更多的情况是使用适当溶剂溶解固 态的掺杂剂。 同时， 即使是液态的掺杂剂， 也可能出于惨杂剂量等方面的考虑， 使 用较低浓度的溶液而非原液。
参考图 5a - 5d， 示出根据本发明的检测方法， 以黑索金 （RDX ) 为样品示例， 以 三氯甲烷为掺杂剂示例， 按照前述对应图 4 中右侧流程所进行的惨杂剂与釆样载体 的结合前后而获得的离子迁移谱图效果对比。 在谱图中， 横坐标为迁移时间， 纵坐 标为离子电流强度。 通过将掺杂剂与采样载体结合前后对比， Hi观察到掺杂剂的加 入对 RDX检测灵敏度和选择性的改善效果。
图 5a示出在没有导入含有掺杂剂和样品的采样载体时的检测谱图， 此时， 谱图 中仅有空气分子生成的反应物离子峰。
图 5b示出将一定量的 RDX样品施加到未结合掺 ¾剂的采样载体上， 导入仪器的 进样口后得到的检测谱图。 此时， 谱图屮除了空气分子生成的反应物离子峰以外， 还可以看到 RDX样品峰。
图 5c示出将已结合了惨杂剂但未施加样品的采样载体导入仪器的进样口后得到 的检测普图。 此时， 谱图中显示出大体高度相当的空气分子生成的反应物离子峰和 掺杂剂分子生成的反应物离子峰。
图 5d示出采样载体已结合了摻杂剂并且包含与图 5b相同量 RDX样品时的检测 谱图。 此时， 由于掺杂剂的加入， 谱图中的 RDX 峰高显著增加， 且峰形效果改善明 显。
通过上述图 5a 5d， 可以看出在本发明的检测方法可以提供良好的分离图谱。 对于其他样品及相应的掺杂剂， ¾然通过适当地调整采样载体中所结合的掺杂剂的 量， 也可以实现精确的检测。 本领域技术人员可以想到的是， 可以使用互溶且不发 生反应的两种掺杂剂作为 "相应浓度" 的溶液来浸泡采样载体， 还可以向在相应溶 剂中浸泡后的釆样载体滴加掺杂剂溶液来实现结合， 以满足检测中需要使用多种掺 杂剂的情况， 此吋， 虽然结合的过程可能较为复杂， 但考虑到对于检测系统整体结 构上的简化， 以及掺杂剂控制上的精确性和便利性， 仍具有明显的积极意义。 而本 领域技术人员在得到上述实施方式的教导以后， 可以从有限的试验中掌握其他结合 过程的参数， 包括溶液的组成、 浸泡的时间等。
因而， 本发明所述的 "采样载体与惨杂剂相结合" 不限于实施例中所述的与三 氯甲烷的一次性结合， 而包括与现有技术中己知的其他掺杂剂的单独或组合的多次 结合； 其也不限于与液态下的掺杂剂结合， 而是包括 任何状态的掺杂剂结合。

Claims

权 利 要 求
1. 一种使用摻杂剂的离子迁移谱仪（IMS)检测方法， 所述离了迁移谱仪包括具 有进样口的迁移管和与迁移管连通的气路系统， 所述气路系统包括泵和过滤装置以 及置于所述迁移管上的进气口和出气口以提供用作迁移气流和样品载气的清洁气 体， 所述检测方法包括：
提供用于采集样品的采样载体；
将掺杂剂与采样载体结合；
用结合有掺杂剂的采样载体采集样品； 以及
将采集样品后的采样载体导入到离子迁移谱仪的进样口， 以实施离子迁移谱检
2. 根据权利要求 1 所述的检测方法， 其中， 所述将掺杂剂 ¾采样载体结合包 括下述步骤：
将掺杂剂制成溶液； 将采样载体浸泡在所述掺杂剂溶液中； 以及取出采样载体 并使其干燥。
3. 根据权利要求 I 所述的检测方法， 其中， 所述将掺杂剂与采样载体结合包 括下述步骤：
将糁杂剂制成溶液； 以及将所述掺杂剂溶液点入采样载体的样品采集区。
4. 根据权利耍求 2或 3所述的检测方法， 其中所述掺杂剂包括卤代化合物、 烟 酰胺、 丙酮或氨水。
5. 根据权利要求 4所述的检测方法， 其中所述卤代化合物为三氯甲垸， 其制成 的溶液为百分之百纯度。
6. 根据权利要求 4所述的检测方法， 其中所述气路系统包括：
置于迁移管上的两进气口， 用于通过所述两进气口分别提供用作迁移 z〔流和样 品载气的清沽气体； 置于迁移管上的出气口， 用于将未离化的载气分子和迁移气导 出所述迁移管。
7. 根据权利耍求 6所述的检测方法， 其中所述载气包括纯净的氮气或净化的空 气。
8. 一种使用掺杂剂的离子迁移谱仪 (IMS)的检测系统， 包括- 离子迁移谱仪， 包括： 离子源、 具有进样口的迁移管； 和与迁移管连通的气路 系统， 所述气路系统包括泵和过滤装靑.以及置于所述迁移管的进气口和出气 π以提 供用作迁移气流和样品载气的清洁空气；
采样载体， 用于采集被检测的样品；
掺杂剂， 其与采样载体结合， 从而与采集样品后的采样载体一起被导入到迀移 管的进样口中。
9. 根据权利要求 8所述的检测系统， 其中所述气路系统包括：
置于迁移管上的两进气口， 用于通过所述两进 〔口分别提供用作迁移气流和样 品载气的清洁 体； 置于迁移管上的出气口， 用于将未离化的载气分子和迁移气导 出所述迁移管。
10. 根据权利要求 9 所述的检测系统， 其中所述载气包括纯净的氮气或净化的 空气。
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CN102033100B (zh) 2013-03-13
EP2482065B8 (en) 2016-11-23
PL2482065T3 (pl) 2016-01-29
US20110297821A1 (en) 2011-12-08
EP2482065A1 (en) 2012-08-01
DE112010000007T5 (de) 2011-06-22
DE112010000007B4 (de) 2012-12-13
EP2482065A4 (en) 2013-05-01
BR112012003467B1 (pt) 2019-06-25
BR112012003467A2 (pt) 2016-03-01
EP2482065B1 (en) 2015-07-29
US8237110B2 (en) 2012-08-07
CN102033100A (zh) 2011-04-27

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