Vacuum chemical ionization

Ion-molecule reactions occurring at atmospheric pressure are employed for analyte ion production in atmospheric pressure chemical ionization (APCI). Basically, APCI represents an atmospheric pressure variant of vacuum chemical ionization (Cl, Chap. 7). In APCI the reagent ion plasma is maintained by a corona discharge between the sharp tip of a needle and the spray chamber serving as the counter electrode. 

The ion guides are frequently used to transmit ions from an atmospheric-pressure inlet/source system (electrospray ionization, atmospheric-pressure chemical ionization) into the vacuum region of an m/z analyzer. 

Reversed-phase Cig chromatography column. Keystone Scientific Betasil, 100 x 2.0-mm i.d., 5-pm particle size, 100 A, Part No. 105-701-2-CPF TSQ 7000 LC/MS/MS system with electrospray ionization (ESI) or atmospheric pressure chemical ionization (APCI) interface and gradient high-performance liquid chromatography (HPLC) unit, or equivalent Vacuum manifold for use with SPE cartridges (Varian Vac Elut 10 or equivalent)... 

Resistance to physical shocks and vibration required careful attention to selection of rugged components and to securing electrical and vacuum systems, wiring, connectors, components, and boards. Chemical ionization (Cl) was used for the first time in a fieldable military detector because of the advent of rugged turbomolecular pumps capable of handling the gas load from the Cl reagent. 

Atmospheric Pressure Chemical Ionization. As its name reveals, APCI[16] is a Cl carried out at atmospheric pressure instead of under vacuum, as occurs for classical Cl. As for ESI, the sample must be in a solution that is continuously flowing into the APCI source (flow rate between 0.2 and 2 ml min ). The solution passes through a pneumatic nebulizer and is desolvated in a heated quartz tube or heating block, thus producing vaporization of solvent and analyte molecules (Figure 2.4). 

Volatile or volatilizable compounds may be introduced into the spectrometer via a pinhole aperture or molecular leak which allows a steady stream of sample molecules into the ionization area. Non-volatile or thermally labile samples are introduced directly by means of an electrically heated probe inserted through a vacuum lock. Numerous methods of sample ionization are available of which the most important are electron impact (El), chemical ionization (CY), field ionization (FI), field desorption (FD), fast atom bombardment (FAB), and radio-frequency spark discharge. 

The standard MAT 90 ion source is used for optimized FD/FI mode by means of the newly designed FD/FI probe. Conversion from electron impact (El), chemical ionization (Cl) or fast ion bombardment (FAB) to FD/FI operation does not require the exchange of the ion source. The FD/FI probe accommodates both the field emitter and the extraction electrodes, mounted at the probe tip. Both are introduced as a unit into the ion source through the ionization volume exchange lock without breaking vacuum. The fast and simple changeover illustrates the versatility of the Finnigan MAT 90 with no compromise on the performance. 

MS involves the separation of ions based on their mass-to-charge ratio (m/z). The concept was invented a century ago1 with a dramatic impact on analytical chemistry.2-3 The fundamental principle of MS requires vaporization of the molecules in the gas phase and in ionization. Early ionization methods such as electron impact (El) and chemical ionization (Cl)4-5 were limited to small organic molecules that were volatile and stable to heat and amenable to transfer into high vacuum. Introduction of the fast-atom-bombardment (FAB) method of ionization6... 

Note The lifetime of a filament is several weeks under proper operating conditions. However, harsh conditions such as aggressive analytes or reagent gases in chemical ionization, too high emission current, and in particular sudden breakdown of the high vacuum have devastating consequences. 

In atmospheric pressure chemical ionization (APCI) ion-molecule reactions occurring at atmospheric pressure are employed to generate the ions, i.e., it represents a high-pressure version of conventional chemical ionization (Cl, Chap. 7). The Cl plasma is maintained by a corona discharge between a needle and the spray chamber serving as the counter electrode. The ions are transferred into the mass analyzer by use of the same type of vacuum interface as employed in ESI. Therefore, ESI ion sources can easily be switched to APCI instead of an ESI sprayer, a unit comprising a heated pneumatic nebulizer and the spray chamber with the needle electrode are put in front of the orifice, while the atmospheric pressure-to-vacuum interface remains unchanged. [48,138]... 

LC/MS is the ultimate analytical technique, which combines the versatility of HPLC with the identification power of MS. The weak link in LC/MS has always been the interface which connects the liquid stream at atmospheric pressure to the high vacuum present inside the mass spectrometer. The development of several atmospheric pressure interfaces, electrospray and atmospheric pressure chemical ionization (APCI), has contributed to the tremendous success and popularity of LC/MS and LC/MS/MS in bioresearch, drug discovery, combinatorial analysis and pharmacokinetic assays. This topic is covered in more depth in a later chapter. 

In atmospheric pressure ionization sources (API) the ions are first formed at atmospheric pressure and then transferred into the vacuum. In addition, some API sources are capable of ionizing neutral molecules in solution or in the gas phase prior to ion transfer to the mass spectrometer. Because no liquid is introduced into the mass spectrometer these sources are particularly attractive for the coupling of liquid chromatography with mass spectrometry. Pneumatically assisted electrospray (ESI), atmospheric pressure chemical ionization (APCI) or atmospheric pressure photoionization (APPI) are the most widely used techniques. 

The device resembles a cylindrical differential mobility analyzer (DMA) in that a sample flow is introduced around the periphery of the annulus between two concentric cylinders, and charged particles migrate inward towards the inner cylinder in the presence of a radial electric field. Instead of being transmitted to an outlet flow, the sample is collected onto a Nichrome filament located on the inner cylinder. The primary benefit of this mode of size-resolved sampling, as opposed to aerodynamic separation into a vacuum, is that chemical ionization of the vapor molecules is feasible. Because there is no outlet aerosol flow, the collection efficiency is determined by desorption of the particles from the filament, chemical ionization of the vapor, separation in a mobility drift cell, and continuous measurement of the current produced when the ions impinge on a Faraday plate. 

A mass spectrometer adapted for chemical ionization can tolerate a solvent flow rate into the vacuum system of 5-10 yL/min. This suggested the use of a LC column operating at this low flow rate. A micropacked fused-silica column (1-3) is well suited for this application. 

In IC-MS systems, the core of the equipment is the interface. In fact, inside the interface evaporation of the liquid, ionization of neutral species to charged species and removal of a huge amount of mobile phase to keep the vacuum conditions required from the mass analyzer take place. Two main interfaces are used coupled to IC, namely electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI). In the ESI mode, ions are produced by evaporation of charged droplets obtained through spraying and an electrical field, whilst in the APCI mode the spray created by a pneumatic nebulizer is directed towards a heated region (400°C-550°C) in which desolvation and vaporization take place. The eluent vapors are ionized by the corona effect (the partial discharge... 

Ionization methods such as electrospray, ionspray, and atmospheric pressure chemical ionization, in which the analyte is sprayed at atmospheric pressure into an interface to the vacuum of the MS ion source, constitute the category of the atmospheric pressure ionization. 

API The atmospheric pressure ionization (API) source is the most common category of source for LC-MS analysis, in which ionization is performed outside of the high-vacuum region of the mass spectrometer. Electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI) sources are both examples of API sources. 

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