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Atmospheric
Pressure Ionization (API)
is a soft ionization technique that provides
quasimolecular information. Two API methods are available
at our lab: Electrospray Ionization (ESI) and Atmospheric
Pressure Chemical Ionization.
Electrospray
ionization (ESI)
ESI is a technique used in mass spectrometry
to overcome the propensity of macromolecules to fragment.
In ESI, as illustrated below, a liquid is pushed through a
very small charged metal capillary by a carrier gas. The liquid
contains the substance which is to be studied, the analyte,
as well as a large amount of solvent, which is usually much
more volatile than the analyte. The charge contained in the
capillary transfers to the liquid which charges the analyte
molecule. As like charges repel, the liquid pushes itself
out of the capillary and forms a mist or an aerosol of small
droplets about 10um diameter, to increase the distance between
the similarly charged molecules. A neutral carrier gas is
sometimes used to evaporate the neutral solvent in the small
droplets, this in turn brings the charged analyte molecules
closer together. The proximity of the molecules becomes unstable,
however, and as the similarly charges molecules come closer
together, the droplets once again explode. This process repeats
itself until the analyte is free of solvent and is a lone
ion. The lone ion will then continue along to a mass analyzer.

Atmospheric
Pressure Chemical Ionization (APCI)
As the name implies, APCI is a technique which
creates ions at atmospheric pressure. A sample solution flows
through a heated tube where it is volatilized and sprayed
into a corona discharge with the aid of nitrogen nebulization
(see schematic illustration below). Ions are produced in the
discharge and extracted into the mass spectrometer. APCI i
s best suited to relatively polar, semi-volatile samples.
An APCI mass spectrum usually contains the quasi-molecular
ion, [M+H]+. This technique is used as an LCMS interface because
it can accomodate very high (1 ml/min) liquid flow rates.

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