Anal. Chem. 1999, 71, 259-264
Molecular Design, Characterization, and
Application of Multiinformation Dyes (MIDs) for
Optical Chemical Sensings. 3. Application of MIDs
for λmax-Tunable Ion-Selective Optodes
Hideaki Hisamoto, Mihoko Tani, Sachiko Mori, Toshiki Yamada, Tomonori Ishigaki,
Hajime Tohma, and Koji Suzuki*
Department of Applied Chemistry, Keio University, 3-14-1, Hiyoshi, Kohoku-ku, Yokohama 223-8522, Japan
pH indicator dye plays an important role in detecting a signal
transduction process. Subsequently, many kinds of lipophilic pH
indicator dyes have been synthesized and utilized for ion-selective
optodes.14-19 In all cases, the detecting information is a simple
absorbance change relating to the pH indicator dye.
By utilizing “multiinformation dyes (MIDs)”, which have
plural spectral change characteristics such as an absorp-
tion maximum wavelength (λmax) shift based on a polarity
change and an absorbance change due to protonation,
novel λmax-tunable ion-selective optodes were proposed
and prepared by employing MIDs with membrane sol-
vents having different polarities. For controlling the
detecting λmax of the optode, the novel polar membrane
solvent [2-[[6-(2-nitrophenoxy)hexyl]oxy]methyl]isobutane-
1 ,3 -diol was designed and synthesized, which was used
together with a typical membrane solvent nitrophenyl
octyl ether. By mixing these two membrane solvents, the
λmax position of the optode detection wavelength can be
shifted and controlled and was successfully applied to a
Recently, we proposed a molecular design concept for the dyes
called “multiinformation dyes (MIDs)” for application to multidi-
mensional optical chemical sensing.20 Using MIDs of our devel-
oped merocyanine type, the simultaneous sensing of pH and water
content was demonstrated.21 The MIDs used in the present
investigation exhibit two kinds of spectral changes, which are a
λmax shift based on a polarity change and an absorbance change
based on protonation of the dye molecule. We think that employ-
ing MIDs rather than a simple lipophilic pH indicator dye can
lead to the development of a unique ion-selective optode.
Because the MID has plural spectral change properties, we
here report the design of a novel unique λmax-tunable ion-selective
optode as one of the applications of MIDs. Basically, the λmax
tuning was performed by varying the polarity of the membrane
solvent. In the present investigation, the binary membrane solvent
mixture of 2-nitrophenyl octyl ether (NPOE) and the newly
synthesized membrane solvent [2-[[6-(2-nitrophenoxy)hexyl]oxy]-
methyl]isobutane-1,3-diol (NPOE-OH) was used to continuously
λ
max-tunable Li+-selective optode based on a highly Li+-
selective ionophore TTD1 4 C4 . The λmax tuning technique
is useful for preparing an optode system using a low-cost
light source such as a light-emitting diode or a popular
laser.
Since the early stage in the development of ion-selective
optodes,1-3 the methodology has been widely recognized as a
useful ion-sensing tool and has grown as an active research area
in chemical sensors. Many kinds of ionic species have been
measured using the methodology of optodes, and these studies
have recently been compiled by Bakker et al.4 The direction of
the recent developments of novel ion-selective optodes has been
focused on sensing devices such as waveguide devices,5-7 fiber-
optic devices,8 sensing plate devices,9,10 flow analytical devices,11-13
and so on. In the development of ion-selective optodes, a lipophilic
(10) Hisamoto, H.; Sato, S.; Sato, K.; Siswanta, D.; Suzuki, K. Anal. Sci. 1 9 9 8 ,
14, 127.
(11) Hisamoto, H.; Watanabe, K.; Nakagawa, E.; Siswanta, D.; Shichi, Y.; Suzuki,
K. Anal. Chim. Acta 1 9 9 4 , 299, 179.
(12) Hisamoto, H.; Watanabe, K.; Oka, H.; Nakagawa, E.; Spichiger, U. E.; Suzuki,
K. Anal. Sci. 1 9 9 4 , 10, 615.
(13) Hisamoto, H.; Nakagawa, E.; Nagatsuka, K.; Abe, Y.; Sato, S.; Siswanta, D.;
Suzuki, K. Anal. Chem. 1 9 9 5 , 67, 1315.
(14) Bakker, E.; Lerchi, M.; Rosatzin, T.; Rusterholz, B.; Simon, W. Anal. Chim.
Acta 1 9 9 3 , 278, 211.
(15) Tan, S. S. S.; Hauser, P. C.; Wang, K.; Fluri, K.; Seiler, K.; Rusterholz, B.;
Suter, G.; Krttli, M.; Spichiger, U. E.; Simon, W. Anal. Chim. Acta 1 9 9 1 ,
255, 35.
(1) Suzuki, K.; Tohda, K.; Tanda, Y.; Ohzora, H.; Nishihama, S.; Inoue, H.; Shirai,
T. Anal. Chem. 1 9 8 9 , 61, 382.
(2) Suzuki, K.; Ohzora, H.; Tohda, K.; Miyazaki, K.; Watanabe, K.; Inoue, H.;
Shirai, T. Anal. Chim. Acta 1 9 9 0 , 237, 155.
(3) Morf, W. E.; Seiler, K.; Rusterholz, B.; Simon, W. Anal. Chem. 1 9 9 0 , 62,
738.
(16) He, H.; Li, H.; Mohr, G.; Kovacs, M.; Werner, T.; Wolfbeis, O. S. Anal.
Chem. 1 9 9 3 , 65, 123.
(4) Bakker, E.; Buhlmann, P.; Pretsch, E. Chem. Rev. 1 9 9 7 , 97, 3083.
(5) Hisamoto, H.; Kim, K.-H.; Manabe, Y.; Sasaki, K.; Minamitani, H.; Suzuki,
K. Anal. Chim. Acta 1 9 9 7 , 342, 31.
(17) Wang, E.; Zhu, L.; Ma, L.; Patel, H. Anal. Chim. Acta 1 9 9 7 , 357, 85.
(18) Lehmann, F.; Mohr, G. J.; Czerney, P.; Grummt, U. W. Dyes Pigments 19 95,
29, 85.
(6) Dohner, R. E.; Spichiger, U. E.; Simon, W. Chimia 1 9 9 2 , 46, 215.
(7) Freiner, D.; Kunz, R. E.; Citterio, D.; Spichiger, U. E.; Gale, M. T. Sens.
Actuators B 1 9 9 5 , 29, 277.
(8) Shortreed, M. R.; Bakker, E.; Kopelman, R. Anal. Chem. 1 9 9 6 , 68, 2656.
(9) Hisamoto, H.; Miyashita, N.; Watanabe, K.; Nakagawa, E.; Yamamoto, N.;
Suzuki, K. Sens. Actuators B 1 9 9 5 , 29, 378.
(19) Citterio, D.; Rasonyi, S.; Spichiger, U. E. Fresenius J. Anal. Chem., 1 9 9 6 ,
354, 836.
(20) Hisamoto, H.; Tohma, H.; Yamada, T.; Yamauchi, K.; Siswanta, D.; Yoshioka,
N.; Suzuki, K. Anal. Chim. Acta 1 9 9 8 , 373, 271.
(21) Hisamoto, H.; Manabe, Y.; Yanai, H.; Tohma, H.; Yamada, T.; Suzuki, K.
Anal. Chem. 1 9 9 8 , 70, 1255.
10.1021/ac980757x CCC: $18.00 © 1998 American Chemical Society
Published on Web 12/01/1998
Analytical Chemistry, Vol. 71, No. 1, January 1, 1999 259