WO2019129276A1 - 感应纳升电喷雾离子源及其工作方法 - Google Patents

感应纳升电喷雾离子源及其工作方法 Download PDF

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WO2019129276A1
WO2019129276A1 PCT/CN2018/125563 CN2018125563W WO2019129276A1 WO 2019129276 A1 WO2019129276 A1 WO 2019129276A1 CN 2018125563 W CN2018125563 W CN 2018125563W WO 2019129276 A1 WO2019129276 A1 WO 2019129276A1
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ion source
induction
electrospray ion
inner diameter
electrode
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PCT/CN2018/125563
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French (fr)
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赵鹏
闻路红
洪欢欢
章文天
毕磊
宁录胜
甘剑勤
陈安琪
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宁波华仪宁创智能科技有限公司
广州市华粤行仪器有限公司
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Publication of WO2019129276A1 publication Critical patent/WO2019129276A1/zh

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/02—Details
    • H01J49/10—Ion sources; Ion guns
    • H01J49/16—Ion sources; Ion guns using surface ionisation, e.g. field-, thermionic- or photo-emission
    • H01J49/165—Electrospray ionisation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/02—Details
    • H01J49/10—Ion sources; Ion guns

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  • the invention relates to an ion source, in particular to an induction nanoliter electrospray ion source and a method for its operation.
  • Cells are the basic unit of life activities. Real-time, in situ and dynamic detection of life activities at the single-cell and sub-cell level is a challenging problem for analytical chemistry in life sciences. Open mass spectrometry ion source technology has been widely used in single cell analysis due to its high sensitivity, ability to analyze ultra-small volume samples, good selectivity, and fast response.
  • Inductive nanoliter electrospray ion source technology enables sampling and high-efficiency analysis of single-cell metabolites and trace samples in an open environment.
  • the amount of sample can be reduced to pL level, with high sensitivity and accuracy, and can solve single cells. Or other biological samples that are difficult to detect below the nL level, providing scientific and efficient technical support for environmental testing, biological analysis, and the like.
  • the shortcomings of the above-mentioned induction nano-electrospray ion source technology are:
  • the spray rate of the sample is unstable, and the spray time of different samples cannot be adjusted, resulting in problems such as ionization efficiency, analysis sensitivity and low signal-to-noise ratio of different samples.
  • the present invention provides a high-sensitivity, high signal-to-noise ratio, reusable, induction nanoliter electrospray ion source, which realizes efficient single-cell metabolites and polar samples. analysis.
  • An induction nanoliter electrospray ion source comprises a showerhead and an electrode; and the induced nanoliter electrospray ion source further comprises:
  • a coating comprising a hydrophobic or hydrophilic material, the coating being disposed on an inner wall of the showerhead.
  • the working method comprises the following steps:
  • the distance between the electrode and the solution is 0.3-1 cm;
  • a voltage is applied to the electrode, and the sample in the head is ionized, ejected from inside the head, and enters the mass spectrometer inlet.
  • the present invention has the following beneficial effects:
  • the method is simple, the operation is convenient, and the nozzle can be reused.
  • FIG. 1 is a schematic structural view of an induction nanoliter electrospray ion source according to an embodiment of the present invention
  • Figure 2 is a mass spectrum of diphenylamine measured according to the prior art
  • Figure 3 is a mass spectrum of diphenylamine measured according to Example 2 of the present invention.
  • Figure 4 is a caffeine mass spectrum measured according to the prior art
  • Figure 5 is a mass spectrum of caffeine measured in accordance with Example 2 of the present invention.
  • the induction nano-liter electrospray ion source includes:
  • the nozzle 2 has two ends open, and the straight through section and the inner diameter shrinking section are sequentially distributed from the first opening to the second opening direction; the inner diameter is the largest at the first opening and the inner diameter is the smallest at the second opening;
  • the coating is made of a hydrophobic or hydrophilic material, depending on the sample to be tested, for example, the hydrophobic material is polyvinyl alcohol, and the hydrophilic material is coated with a hydroxyl group or an amino ion;
  • the coating is disposed on an inner wall of the showerhead, such as an inner diameter contraction section;
  • the hydrophobic or hydrophilic material is disposed on an inner wall of the showerhead by a PB-DS-PB method;
  • An electrode 3 that enters from the first opening and penetrates into the inner diameter contraction section; a central axis of the electrode is collinear with a central axis of the inner diameter contraction section;
  • a power source 1 that applies a high voltage DC voltage to the electrodes.
  • the working method comprises the following steps:
  • the distance between the electrode 3 and the solution 5 is 0.3-1 cm;
  • the coating adopts a matching hydrophobic material, such as a polyvinyl alcohol polymer; and the hydrophobic material is disposed in the inner diameter contraction section of the nozzle by the PB-DS-PB method.
  • the inner wall In order to be adapted to the detection of diphenylamine, the coating adopts a matching hydrophobic material, such as a polyvinyl alcohol polymer; and the hydrophobic material is disposed in the inner diameter contraction section of the nozzle by the PB-DS-PB method.
  • the sample is immersed in the sample solution for 10 to 15 seconds, and the sample solution can be introduced into the tip end of the nozzle, and the distance between the sample solution and the electrode is 0.3 to 1 cm.
  • the nozzle is located between the electrode and the mass spectrometry inlet, and the distance between the tip end of the nozzle and the inlet of the mass spectrometer may be 0.3 to 1.5 cm.
  • the high-voltage DC voltage is set to 1.0kV
  • the sheath gas flow rate is set to 0L/min
  • the mass spectrometric detection m/z range is set to 50-1000
  • the test sample is a diphenylamine standard sample (dissolved in methanol, concentration 50ppb), as shown in Figure 3.
  • the sensitivity of mass spectrometry detection is increased by 9 times, as shown in Figures 2 and 3.
  • the coating uses a matching hydrophilic material, such as an ion coating with a hydroxyl or amino group; the hydrophilic material is disposed in the PB-DS-PB method.
  • the inner diameter of the inner diameter of the nozzle is constricted.
  • the sample is immersed in the sample solution for 10 to 15 seconds, and the sample solution can be introduced into the tip end of the nozzle, and the distance between the sample solution and the electrode is 0.3 to 1 cm.
  • the distance between the tip end of the head and the inlet of the mass spectrometer may be 0.3 to 1.5 cm.
  • the high-voltage DC voltage is set to 2.0kV
  • the sheath gas flow rate is set to 0L/min
  • the mass spectrometry detection m/z range is set to 50-1000
  • the test sample is a caffeine standard sample (dissolved in methanol, concentration 50ppb), as shown in Figure 5.
  • the sensitivity of mass spectrometry detection was increased by 12 times, as shown in Figures 4 and 5.

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  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Plasma & Fusion (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Other Investigation Or Analysis Of Materials By Electrical Means (AREA)

Abstract

本发明提供了一种感应纳升电喷雾离子源及其工作方法，所述感应纳升电喷雾离子源包括喷头、电极；进一步包括：涂层，所述涂层采用疏水性或亲水性材料，所述涂层设置在所述喷头的内壁。本发明具有离子化效率高、灵敏度高、信噪比高等优点。

Description

感应纳升电喷雾离子源及其工作方法 技术领域
本发明涉及离子源，特别涉及感应纳升电喷雾离子源及其工作方法。
背景技术
细胞是生命活动的基本单元，在单细胞及亚细胞水平上对生命活动进行实时、原位、动态检测是生命科学对分析化学提出的一项挑战性的问题。敞开式质谱离子源技术因灵敏度高、能够分析超小体积样品、选择性好、响应速度快等特点在单细胞分析中获得了广泛应用。
感应纳升电喷雾离子源技术可以实现敞开式环境下单细胞代谢物和痕量样品的取样与高效分析，样品用量可降低至pL级别，且具有较高的灵敏度和准确性，能够解决单细胞或其它生物样品nL级别以下难以检测的问题，为环境检测、生物分析等提供科学、高效的技术支撑。上述感应纳升电喷雾离子源技术的不足在于：
样品喷雾流速不稳定，无法调节不同样品的喷雾时间，导致不同样品离子化效率、分析灵敏度与信噪比低等问题。
发明内容
为解决上述现有技术方案中的不足，本发明提供了一种灵敏度高、信噪比高、可重复利用的感应纳升电喷雾离子源，实现了单细胞代谢物和含量极性样品的高效分析。
本发明的目的是通过以下技术方案实现的：
一种感应纳升电喷雾离子源，所述感应纳升电喷雾离子源包括喷头、电极；所述感应纳升电喷雾离子源进一步包括：
涂层，所述涂层采用疏水性或亲水性材料，所述涂层设置在所述喷头的内壁。
本发明的目的还在于提供了上述感应纳升电喷雾离子源的工作方法，该发明目的是通过以下技术方案得以实现的：
根据上述的感应纳升电喷雾离子源的工作方法，所述工作方法包括以下步骤：
(A1)将上述喷头浸没于样品溶液中，所述样品溶液进入到喷头；
所述电极和溶液的距离为0.3-1cm；
(A2)在电极上施加电压，喷头内的样品被离子化，从所述喷头内部射出，并进入质谱仪进样口。
与现有技术相比，本发明具有的有益效果为：
1.能够提高样品的离子化效率，获得更高的灵敏度与信噪比；
2.能够针对不同样品键合不同化学性质的涂层，使感应纳升电喷雾离子源应用范围更广泛；
3.能够改变样品的喷雾流速，使喷雾时间可调，实现小体积极性样品和单细胞代谢物的高效分析；
4.能够保障样品形成持续、稳定、持久的电喷雾；
5.方法简单，操作方便，喷头可重复利用。
附图说明
参照附图，本发明的公开内容将变得更易理解。本领域技术人员容易理解的是：这些附图仅仅用于举例说明本发明的技术方案，而并非意在对本发明的保护范围构成限制。图中：
图1是根据本发明实施例的感应纳升电喷雾离子源的结构简图；
图2是根据现有技术测得的二苯胺质谱图；
图3是根据本发明实施例2测得的二苯胺质谱图；
图4是根据现有技术测得的咖啡因质谱图；
图5是根据本发明实施例2测得的咖啡因质谱图；。
具体实施方式
图1-5和以下说明描述了本发明的可选实施方式以教导本领域技术人员如何实施和再现本发明。为了教导本发明技术方案，已简化或省略了一些常规方面。本领域技术人员应该理解源自这些实施方式的变型或替换将在本发明的范围内。本领域技术人员应该理解下述特征能够以各种方式组合以形成本发明的多个变型。由此，本发明并不局限于下述可选实施方式，而仅由权利要求和它们的等同物限定。
实施例1：
图1示意性地给出了本发明实施例1的感应纳升电喷雾离子源的结构简图，如图1所示，所述感应纳升电喷雾离子源包括：
喷头2，所述喷头两端开口，从第一开口到第二开口方向上，直通段和内径收缩段依次分布；在第一开口处的内径最大，在第二开口处的内径最小；
涂层4，所述涂层采用疏水性或亲水性材料，具体根据待测样品决定，如，所述疏水性材料采用聚乙烯醇，所述亲水性材料采用羟基或氨基离子涂层；所述涂层设置在所述喷头的内壁，如内径收缩段；所述疏水性或亲水性材料通过PB-DS-PB方法设置在所述喷头的内壁；
电极3，所述电极从第一开口进入并深入到所述内径收缩段内；所述电极的中心轴线与内径收缩段的中心轴线共线；
电源1，所述电源为所述电极施加高压直流电压。
本发明实施例的根据上述的感应纳升电喷雾离子源的工作方法，所述工作方法包括以下步骤：
(A1)将上述喷头的第二开口端浸没于样品溶液中，如浸没时间为10-15s，所述样品溶液进入到喷头内；
所述电极3和溶液5的距离为0.3-1cm；
(A2)在电极上施加电压，喷头内的样品被离子化，从所述喷头内部射出，并进入质谱仪进样口；所述喷头1到所述质谱仪进样口5的距离为0.3-1.5cm。
实施例2：
根据本发明实施例1的感应纳升电喷雾离子源及其工作方法在二苯胺检测中的应用例。
在该应用例中，为了适应于二苯胺的检测，涂层采用相匹配的疏水性材料，如聚乙烯醇聚合物；疏水性材料通过PB-DS-PB方法设置在所述喷头的内径收缩段的内壁。
在离子源的工作方法中，也即检测二苯胺的过程中：
将上述喷头浸泡于样品溶液中10～15s，即可将样品溶液引入喷头的尖端部，样品溶液与电极之间的间距为0.3～1cm。喷头位于电极与质谱进样口之间，喷头的尖端部与所述质谱仪的进样口之间的距离可为0.3～1.5cm。高压直流电压设为1.0kV，鞘气流速设为0L/min，质谱检测m/z范围设为50～1000，检测样品为二苯胺标准样品(溶于甲醇，浓度50ppb)，如图3所示，质谱检测灵敏度提高了9倍，如图2、3所示。
实施例3：
根据本发明实施例1的感应纳升电喷雾离子源及其工作方法在咖啡因检测中的应用例。
在该应用例中，为了适应于咖啡因的检测，涂层采用相匹配的亲水性材料，如带羟基或氨基的离子涂层；亲水性材料通过PB-DS-PB方法设置在所述喷头的内径收缩段的内壁。
在离子源的工作方法中，也即检测咖啡因的过程中：
将上述喷头浸泡于样品溶液中10～15s，即可将样品溶液引入喷头的尖端部，样品溶液与电极之间的间距为0.3～1cm。喷头的尖端部与所述质谱仪的进样口之间的距离可为0.3～1.5cm。高压直流电压设为2.0kV，鞘气流速设为0L/min，质谱检测m/z范围设为50～1000，检测样品为咖啡因标准样品(溶于甲醇，浓度50ppb)，如图5所示，质谱检测灵敏度提高了12倍，如图4、5所示。

Claims (10)

  1. 一种感应纳升电喷雾离子源，所述感应纳升电喷雾离子源包括喷头、电极；其特征在于：所述感应纳升电喷雾离子源进一步包括：
    涂层，所述涂层采用疏水性或亲水性材料，所述涂层设置在所述喷头的内壁。
  2. 根据权利要求1所述的感应纳升电喷雾离子源，其特征在于：所述疏水性或亲水性材料通过PB-DS-PB方法设置在所述喷头的内壁。
  3. 根据权利要求1所述的感应纳升电喷雾离子源，其特征在于：
    所述喷头的两端开口，内部具有内径收缩段，沿着从第一开口到第二开口方向上，所述喷头的内径逐渐收缩，在第二开口处的内径最小；
    所述电极从第一开口进入并深入到所述内径收缩段内。
  4. 根据权利要求3所述的感应纳升电喷雾离子源，其特征在于：所述涂层设置在所述喷头的内径收缩段。
  5. 根据权利要求1所述的感应纳升电喷雾离子源，其特征在于：所述电极的中心轴线与内径收缩段的中心轴线共线。
  6. 根据权利要求1所述的感应纳升电喷雾离子源，其特征在于：所述疏水性材料采用聚乙烯醇。
  7. 根据权利要求1所述的感应纳升电喷雾离子源，其特征在于：所述亲水性材料采用羟基或氨基离子涂层。
  8. 根据权利要求1-7任一所述的感应纳升电喷雾离子源的工作方法，所述工作方法包括以下步骤：
    (A1)将上述喷头浸没于样品溶液中，所述样品溶液进入到喷头；
    所述电极和溶液的距离为0.3-1cm；
    (A2)在电极上施加电压，喷头内的样品被离子化，从所述喷头内部射出，并进入质谱仪进样口。
  9. 根据权利要求8所述的工作方法，其特征在于：所述喷头到所述质谱仪进样口的距离为0.3-1.5cm。
  10. 根据权利要求8所述的工作方法，其特征在于：喷头浸没于样品溶液中的时间为10-15s。
PCT/CN2018/125563 2017-12-31 2018-12-29 感应纳升电喷雾离子源及其工作方法 WO2019129276A1 (zh)

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