International Journal of Mass Spectrometry 299 (2011) 178–183
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International Journal of Mass Spectrometry
journal homepage: www.elsevier.com/locate/ijms
Characterization of a capillary spray cell for easy analysis of extracts of
biological samples
Christian Janfelt
∗
, Frants R. Lauritsen
Dept. of Pharmaceutics and Analytical Chemistry, University of Copenhagen, Universitetsparken 2, 2100 Copenhagen, Denmark
article info
Article history:
Received 17 September 2010
Received in revised form 22 October 2010
Accepted 24 October 2010
Available online 3 November 2010
Keywords:
Electrospray ionization
New instrumentation
Plant analysis
Biological extracts
Alkaloids
abstract
We present a very simple electrospray unit, a capillary spray cell, for easy analysis of small (10–50 L)
sample aliquots. The sample, e.g., an unfiltered extract, is injected to a small sample cell, made of alumina
and containing a short fused silica capillary mounted in its side. By the application of a 5 kV potential
between the sample cell and the entrance orifice of a mass spectrometer with an atmospheric pressure
interface, the sample is dragged out of the cell at a rate of a few L/min and an electrospray is generated
at the tip of the silica capillary. The capillary spray cell benefits from a high internal diameter (up to
250 m) and very easy and inexpensive replacement of the capillary, which makes the sprayer well
suited for analysis of unfiltered extracts. We demonstrate the direct analysis of extracts from plants and
insects. In quantitative measurements using internal standards, a relatively high sensitivity (low ng/mL)
is obtained together with good linearity (R
2
= 0.998) in the range of 10–1000 ng/mL. The capillary spray
cell is also suited for use with field portable mass spectrometers, since no syringe pump or nebulizer gas
is needed. Furthermore, the capillary spray cell is easily manufactured by most mechanical workshops.
© 2010 Elsevier B.V. All rights reserved.
1. Introduction
Since its breakthrough in the 1980s electrospray ionization mass
spectrometry [1] and later nanoelectrospray ionization mass spec-
trometry [2] have played increasingly bigger roles in today’s work
with mass spectrometry since they are particular well suited for
the polar compounds which are found in most biological samples
[3,4]. The majority of mass spectrometers today are sold with Elec-
trospray ion sources built to work in the hyphenation with an HPLC
system, thus accommodating liquid flows of up to 1 mL per minute.
These sources are typically fed with sample solution from either an
HPLC or a syringe pump, and gasses are used to various extents to
assist in the nebulisation of the sample solution and subsequent
desolvation of the analyte droplets [5]. At lower flow rates the neb-
uliser gas is not needed as the charged droplets can be formed by
the electrospray potential alone [6].
However, in most setups, even without nebuliser gas, a syringe
pump is still needed to provide the necessary transport of sample
solution to the spray. That changed with the introduction of the
static nanospray source where the sample, typically 2–10 L total
volume, is injected into a glass tube which has been pulled in one
end to obtain a tip with an orifice of 2–5 m and coated with a gold
film to enable electrical contact to the sample solution [2]. With
∗
Corresponding author. Tel.: +45 35 33 65 57; fax: +45 35 33 60 30.
E-mail address: cja@farma.ku.dk (C. Janfelt).
this setup a forced flow is not needed as the applied electric field is
able to generate a flow by itself, controlled by the diameter of the
capillary tip. The technique provides a stable signal for a long time
from just a few microlitres of sample, however with relatively high
expenses in consumables.
Very simple ways to generate an electrospray from a droplet of
sample solution have been demonstrated by Shiea et al., by deposi-
tion of a droplet on an object onto which high voltage is applied. This
object has been of various materials and shapes such as a copper
ring [7], a copper coil [8] or a gold coated optical fiber [9], pro-
viding simple ways to analyze tiny amounts of sample with low
costs of consumables and no use of nebuliser gas or sample deliv-
ery pumps. A variation of this is the so-called probe electrospray
by Hiraoka et al. [10] where a solid needle picks up a droplet of
sample in a motorized fashion and moves it to the proximity of
the MS inlet orifice. Ionization then occurs from the needle simi-
larly to the techniques describes above. This technique was later
implemented in a new ambient imaging technique where the nee-
dle systematically samples a whole area [11], similarly to other MS
imaging techniques such as, e.g., DESI imaging [12].
An alternative solution is the microfabricated electrospray emit-
ter presented by Sikanen et al. in 2008 which provides the options
of free flow as well as forced flow electrospray [13]. Operated in free
flow mode a sample amount of 20 L will give a very stable signal
for nearly 30 min. It was successfully applied for analysis of phar-
maceuticals, peptides and proteins. However, the construction of
these microfabricated emitters is quite complicated, as it requires
1387-3806/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.ijms.2010.10.032