Electrospray
ionization (ESI) is one of the main techniques used
in mass spectrometry (MS) of nonvolatile compounds. ESI is a disordered
process, in which a large number of polydisperse droplets are projected
from a fluctuating Taylor cone and jet protruding ESI emitter. Here,
we disclose a system for sectioning electrospray plumes to discrete
packets with millisecond and submillisecond lifetime, which are introduced
to the MS orifice, one at a time. A high-speed camera was triggered
at 10,000 frames per second to capture consecutive images of the electrospray
packets transmitted to the mass spectrometer. We further correlated
the high-speed images of electrospray packets with MS signals of a
test analyte (acetaminophen). Following computational treatment of
the images, we determined the number of droplet observations (<300),
average diameter of droplets (∼10–20 μm), and
average volume of droplets (few tens of picoliters) in the individual
electrospray packets. The result shows that most micrometer droplets
(>10 μm) do not have any significant contribution to the
MS
signals. This finding is in agreement with the prior conjecture that
most of the MS signals are mainly attributed to nanodroplets. Based
on this finding, one can deduce that only a small number of the initial
microdroplets effectively carry analyte molecules that undergo ionization.
We discuss that, in future, one may propose a way to “recharge”
the emitted initial micrometer droplets to increase the efficiency
of conventional ESI setups.