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急速-蜗牛

铁虫 (小有名气)

[求助] 求助关于LC/APCI-MS 已有1人参与

1、请问在LC/APCI-MS中,中性分子在APCI离子源中是不是只被离子化,不发生裂解?离子被碎片化是在APCI中还是在质谱中被碎片化的(离子是在哪里被碎片化的?)?
2、APCI(大气压化学电离源)的负离子模式的工作基理是什么?是怎么由中性分子转变为负离子的?
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thecoldest

金虫 (正式写手)

https://en.wikipedia.org/wiki/At ... chemical_ionization

Ionization[edit]The analyte in solution is directly introduced into a pneumatic nebulizer via a direct inlet probe or through a connection to a standard high-performance liquid chromatography (HPLC) with an eluent flow rate between 0.2 and 2 mL/min. Once in the nebulizer, the analyte in solution is converted into a thin fog through the use of a high-speed nitrogen beam, and the droplets are then displaced by the gas flow through a heated quartz tube called a desolvation/vaporization chamber. [4]

The mobile phase and the sample in the gas flow are then vaporized by the heat transferred to the spray droplets in the desolvation chamber and leave the tube as a mixture of the compounds of interest and hot gas (120oC).[4] They are subsequently carried along a corona discharge electrode where ionization occurs.

The ionization can either be carried out in positive or negative ionization mode. In the positive mode, the relative proton affinities of the reactant ions and the gaseous analyte molecules allow either proton transfer or adduction of reactant gas ions to produce the ions of the molecular species. [4] In the negative mode, however, the ions are produced by either proton abstraction or adduct formation.

In most cases, the evaporated mobile phase acts as the ionization gas and reactant ions are formed because of the effect of the corona discharge on the nebulized solvent. Generally, the primary ions formed by the corona discharge are ions such as a positively charged nitrogen or oxygen radical which can then form secondary reactant gas ions though collision with vaporized solvent molecules.[5]

In a major distinction from chemical ionization, the electrons needed for the primary ionization are not produced by a heated filament, as a heated filament cannot be used under atmospheric pressure conditions. Instead, the ionization must occur using either corona discharges or β- particle emitters, which are both electron sources capable of handling the presence of corrosive or oxidizing gases.
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2楼2015-12-28 13:03:44
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thecoldest

金虫 (正式写手)

【答案】应助回帖

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感谢参与,应助指数 +1
急速-蜗牛: 金币+25, ★★★★★最佳答案 2015-12-29 20:43:43
1. 离子应该是在ACPI中和电离气体带正电的N 或 氧自由基反应的过程中碎片化的,发不发生裂解跟分子本身的稳定心有关。
2. 负离子反生成的原理应该是,中性分子中的H被电晕放电产生的氧自由基吸附H,或中性分子吸附气体中电离的负离子产生。

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3楼2015-12-28 13:24:06
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急速-蜗牛

铁虫 (小有名气)

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3楼: Originally posted by thecoldest at 2015-12-28 13:24:06
1. 离子应该是在ACPI中和电离气体带正电的N 或 氧自由基反应的过程中碎片化的,发不发生裂解跟分子本身的稳定心有关。
2. 负离子反生成的原理应该是,中性分子中的H被电晕放电产生的氧自由基吸附H,或中性分子吸附 ...

你好,能再请问一下么,我用的是天冬氨酸溶液,水是溶剂,氮气是载气,然后溶液在APCI中汽化。你能帮忙写出天冬氨酸在负离子模式下去质子过程的反应机理么?最好写出各个反应步骤的方程式(最好是有文献支持)谢谢了
4楼2015-12-29 20:49:39
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