Paper-Based Ion-Selective Potentiometric Sensors
Marta Novell,
†
Marc Parrilla,
†
Gastó n A. Crespo,
†,‡
F. Xavier Rius,
†
and Francisco J. Andrade
†,
*
†
Department of Analytical and Organic Chemistry, Universitat Rovira i Virgili, 43007 Tarragona, Spain
* S Supporting Information
ABSTRACT: A new approach to develop ultra low-cost, robust, rugged, and disposable potentiometric sensors is presented. A
suspension of carbon nanotubes in a water-surfactant mixture (carbon nanotubes ink) is applied on conventional filter papers to
turn them into conductive papers, which are then used as a substrate to build ion-selective electrodes. The electrodes are made by
drop casting a membrane on a small circular area of the conductive paper. In this way, the carbon nanotubes act as both electric
conductors and ion-to-electron transducers of the potentiometric signal. Electrodes for sensing K
+
, NH
4
+
, and pH were built and
tested using this approach, and the results were compared with classical solid-state ion selective electrodes using carbon
nanotubes as transducers and glassy carbon as a substrate. In all cases, the analytical performance (sensitivity, linear ranges, limits
of detection, selectivity, etc.) of these disposable paper electrodes was similar to that obtained for the more conventional type of
ion-selective-electrodes. This opens new avenues for very low-cost platforms for generation of chemical information.
H
aving access to robust, rugged, and low-cost chemical
sensors is becoming of paramount importance in a
growing number of situations. There are well established needs,
such as diagnostic tools for poor regions of the planet.
1
Additionally, the development of chemical sensing networks
2,3
and the increasing role of approaches such as point of care
4-6
and telemedicine
7,8
are pushing the demand for fast access to
bio(chemical) information. The term “vanguard analytical
approaches”
9
has been proposed to refer to these new platforms
that allow low-cost, rapid, on site chemical analysis.
In these new platforms, traditional performance parameters,
such as stability, detection limits, etc., must be balanced with
the need for speed, cost, and simplicity. Under these new
lenses, some techniques, such as potentiometry, are regaining
new value. Potentiometry has traditionally displayed an
unrivalled simplicity of operation and instrumentation.
10
For
this reason, it is still one of the workhorses in clinical
laboratories and almost the universal approach to measure pH.
Ion-selective electrodes have also become the standard
procedure for measuring several ions. Furthermore, the
development of solid contact ion-selective electrodes (SC-
ISE) during the last few decades has produced a “silent
revolution”
11
that has led to drastic improvements of the limits
of detection (LOD), increased range of applications, and
simplification of the sensor construction, operation, and
maintenance. Recent works have also shown the advantages
of miniaturization of the electrodes,
12
and the development of
the electrode arrays
13,14
that could be remotely operated. All in
all, potentiometric sensors are ideal “vanguard” tools for the
remote, out of the lab generation of chemical information.
Some limitations, such as the cost of the sensors, still remain
as a challenge when dealing with large scale applications.
Despite being among the most affordable instrumental
approaches, current potentiometric sensors are still too
expensive for large scale operations. Screen-printed electro-
des
15,16
have partially addressed this problem, but the need for
lower cost sensors still remains a challenge. The search for new
substrates to build electrodes as well as the use of mass
manufacturing techniques are crucial to further reduce the cost
of the sensors. For this reason, recent breakthroughs in areas
such as bendable electronics can be key to finding new
substrates and processes to fabricate rugged, robust, and
extremely low-cost potentiometric sensors.
Regarding the search of new substrates, paper has been
widely used to make simple, cost-effective analytical tools.
Paper dipsticks and lateral flow systems have been used for
decades for qualitative and semiquantitative analysis, and many
new applications on this area are still being developed.
17,18
Whitesides et al.
19,20
have recently expanded the analytical
usefulness of paper based devices exploiting the ability of
papers to produce pump-free capillary flow of liquids. Through
Received: November 9, 2011
Accepted: April 23, 2012
Published: April 23, 2012
Article
pubs.acs.org/ac
© 2012 American Chemical Society 4695 dx.doi.org/10.1021/ac202979j | Anal. Chem. 2012, 84, 4695-4702