Development of a Fully Integrated Analysis System
for Ions Based on Ion-Selective Optodes and
Centrifugal Microfluidics
R. Daniel Johnson, Ibrahim H. A. Badr,
²
Gary Barrett, Siyi Lai,
‡
Yumin Lu,
§
Marc J. Madou,
§
and
Leonidas G. Bachas*
Department of Chemistry, University of Kentucky, Lexington, Kentucky 40506-0055
A fully integrated, miniaturized analysis system for ions
based on a centrifugal microfluidics platform and ion-
selective optode membranes is described. The micro-
fluidic architecture is composed of channels, five solution
reservoirs, a measuring chamber, and a waste reservoir
manufactured onto a disk-shaped substrate of poly(methyl
methacrylate). Ion-selective optode membranes, com-
posed of plasticized poly(vinyl chloride) impregnated with
an ionophore, a proton chromoionophore, and a lipophilic
anionic additive, were cast, with a spin-on device, onto a
support layer and then immobilized on the disk. Fluid
propulsion is achieved by the centrifugal force that results
from spinning the disk, while a system of valves is built
onto the disk to control flow. These valves operate based
on fluid properties and fluid/ substrate interactions and
are controlled by the angular frequency of rotation. With
this system, we have been able to deliver calibrant
solutions, washing buffers, or “test” solutions to the
measuring chamber where the optode membrane is
located. An analysis system based on a potassium-selec-
tive optode has been characterized. Results indicate that
optodes immobilized on the platform demonstrate theo-
retical responses in an absorbance mode of measurement.
Samples of unknown concentration can be quantified to
within 3 % error by fitting the response function for a given
optode membrane using an acid (for measuring the signal
for a fully protonated chromoionophore), a base (for fully
deprotonated chromoionophore), and two standard solu-
tions. Further, the ability to measure ion concentrations
by employing one standard solution in conjunction with
acid and base and with two standards alone were studied
to delineate whether the current architecture could be
simplified. Finally, the efficacy of incorporating washing
steps into the calibration protocol was investigated.
Recent trends in analytical chemistry have been toward the
development of miniaturized measurement devices as embodied
in micro-total analysis systems ( μ-TAS) or microelectromechanical
systems (MEMS). Such systems usually consist of a microdimen-
sioned architecture of reservoirs and channels formed in a
substrate material (or “chip”) by a variety of microfabrication
techniques;
1,2
fluid manipulation through the architecture is
achieved by some type of microfluidic pumping mechanism. The
drive to produce these devices lay primarily in a number of
inherent advantages including low power and space requirements,
minimal reagent and sample consumption, shortened analysis
times, and disposability. The great challenge, then, in the develop-
ment of such analysis systems is to design a device that integrates
the capabilities for sample preparation, derivatization, calibration,
washing, or a number of other potentially useful steps.
3,4
To this
end, device prototyping and preparation,
5-9
the physical and
chemical characterization of fluid flow or substrate material,
3,10-16
and various methods of analyte detection “on-chip” have been
covered extensively in recent literature (refs 5 and 17-20 and
references therein).
* Corresponding author: (phone) (859) 257-6350; (fax) (859) 323-1069; (e-
mail) bachas@ pop.uky.edu.
†
On leave from the Department of Chemistry, Faculty of Science, Ain-Shams
University, Cairo, Egypt.
‡
Department of Chemical Engineering, The Ohio State University, Columbus,
OH 43210.
§
Department of Materials Science and Engineering, The Ohio State Univer-
sity, Columbus, OH 43210.
(1) Madou, M. Fundamentals of Microfabrication; CRC Press: Boca Raton, FL,
1997; pp 426-447.
(2) McCreedy, T. TrAC, Trends Anal. Chem. 2000 , 19, 396-401.
(3) Soper, S. A.; Ford, S. M.; Qi, S.; McCarley, R. L.; Kelly, K.; Murphy, M. C.
Anal. Chem. 2000 , 72, 643A-651A.
(4) Duffy, D. C.; Gillis, H. L.; Lin, J.; Sheppard, N. F., Jr.; Kellogg, G. J. Anal.
Chem. 1999 , 71, 4669-4678.
(5) Hilmi, A.; Luong, J. H. T. Anal. Chem. 2000 , 72, 4677-4682.
(6) Deng, T.; Wu, H.; Brittain, S. T.; Whitesides, G. M. Anal. Chem. 2000 , 72,
3176-3180.
(7) Duffy, D. C.; McDonald, J. C.; Schueller, O. J. A.; Whitesides, G. M. Anal.
Chem. 1998 , 70, 4974-4984.
(8) Ruano, J. M.; Benoit, V.; Aitchisin, J. S.; Cooper, J. M. Anal. Chem. 2000 ,
72, 1093-1097.
(9) Jingdong, J.; Locascio, L.; Gaitan, M.; Lee, C. S. Anal. Chem. 2000 , 72,
1930-1933.
(10) Handique, K.; Burke, D. T.; Mastrangelo, C. H.; Burns, M. A. Anal. Chem.
2000 , 72, 4100-4109.
(11) Culbertson, C. T.; Ramsey, R. S.; Ramsey, J. M. Anal. Chem. 2000 , 72,
2285-2291.
(12) Lapos, J. A.; Ewing, A. G. Anal. Chem. 2000 , 72, 4598-4602.
(13) Kamholz, A. E.; Weigl, B. H.; Finlayson, B. A.; Yager, P. Anal. Chem. 2000 ,
72, 5340-5347.
(14) Henry, A. C.; Tutt, T. J.; Galloway, M.; Davidson, Y. Y.; McWhorter, C. S.;
Soper, S. A.; McCarley, R. L. Anal. Chem. 2000 , 72, 5331-5337.
(15) Griffiths, S. K.; Nilson, R. H. Anal. Chem. 2000 , 72, 5473-5482.
(16) Barker, S. L. R.; Tarlov, M. J.; Canavan, H.; Hickman, J. J.; Locascio, L. E.
Anal. Chem. 2000 , 72, 4899-4903.
(17) Wallenborg, S. R.; Bailey, C. G. Anal. Chem. 2000 , 72, 1872-1878.
(18) Wang, J.; Polsky, R.; Tian, B.; Chatrathi, M. P. Anal. Chem. 2000 , 72, 5285-
5289.
(19) Tantra, R.; Manz, A. Anal. Chem. 2000 , 72, 2875-2878.
(20) Cunningham, D. D. Anal. Chim. Acta 2001 , 429,1-18.
Anal. Chem. 2001, 73, 3940-3946
3940 Analytical Chemistry, Vol. 73, No. 16, August 15, 2001 10.1021/ac0102819 CCC: $20.00 © 2001 American Chemical Society
Published on Web 07/13/2001