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19 views4 pages

Vandervee

Uploaded by

AnkitMishra
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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SELECTIVE OPTODE MEMBRANES FOR HEAVY METAL

ION DETECTION.

Niels J. van der Veen, Richard J.M. Egberink, Johan F.J. Engbersen
and David N. Reinhoudt

Department of Supramolecular Chemistry and Technology, MESA Research


Institute, University of Twente, P.O. Box 217, 7500AE, Enschede, The Netherlands

O. Abstract

Optode membranes for Lead(II) based on an ion-exchange mechanism and neutral


ionophores show that the calix[4]arene ionophores developed for CHEMFETS can be used in
optical sensing schemes. To achieve pH independent sensor response, chromoionophores
have been developed based on these neutral ionophores, which show a optical response to the
complexation of metal ions.

Keywords: optode membrane, chromoionophores, heavy metal ions

1. Introduction

The monitoring of heavy metal concentrations in surface water, harbor sludge, ground
or waste water will be crucial in solving environmental problems related to these pollutants.
Ionophores selective for several heavy metal ions have been used in chemically modified field
effect transistors (CHEMFETs)[I], which involve the transduction of the supramolecular
recognition of the ions by the selector molecules into an electrical signal. In principle, these
ionophores can also be applied in optode membranes. The use of optical transduction has a
number of advantages, such as the absence of a reference electrode, the insensitivity to
electric or magnetic fields, the possible variation of transduction schemes and the possibility
of remote sensing using fiber optics.

A well studied optical transduction scheme was developed by Simon et al. It involves
the use of pH dyes by an ion exchange process, which changes the absorption spectrum of the
optode membrane. The method has been used to develop optode membranes for detection of
metal ions such as lead(II)[2] and silver(I).[3] The principle disadvantages of these optode
membranes is that the response is intrinsically pH dependent and that plasticized PVC is
used, which limits the durability because of leaching of the plasticizer. We therefore work on
the development of optode membranes based on polysiloxanes, which are intrinsically
elastomeric and therefore do not need plasticizers. The membrane processing with these
polymers is compatible with IC technology.[4] This would make it possible to
photochemically bind the optode membrane to a silica waveguide and so integrate membrane
and optics in a device. For pH independent optode membranes a different transduction
scheme should be employed. We present the synthetic strategy for preparation of selective
heavy metal ion chromoionophores which could be used in such a scheme.
107

A. Berg et al. (eds.), Sensor Technology in the Netherlands: State of the Art
© Springer Science+Business Media Dordrecht 1998
108

2. Application of calix[ 4]arene receptors in ion exchange optode membranes

The metal ion receptors developed for use in CHEMFETs can be used in ion exchange
optode membranes involving pH dyes. These liquid polymer membranes contain ionophores,
a pH dye and lipophilized anionic sites. When the membrane is exposed to an analyte
solution, the complexation of ions by the receptor causes an influx of positive charge into the
membrane. This triggers deprotonation of the pH dye, which is accompanied by a change in
absorption spectrum. The two equilibria involved, ion complexation-decomplexation by the
receptor and pH dye protonation-deprotonation, compete and result in a reversible color
response of the membrane. This mechanism is illustrated in figure 1.

Sofution
..
D

0
: Oeprotonate<! Dye

: Protonate<! Dye

: Metal Ion
E]
e;>

~
: lonophor&

: Anionic sile

: Comptex

Membrane

Substrate

Figure 1: Mechanism of response of an optode membrane containing a pH dye

In figure 2, the response of a DOS-plasticized PVC membrane containing a calix[4]arene


based Pb(m receptor is demonstrated. As the concentrations of Pb(II) get higher, the
absorption spectrum of the membrane shifts from the spectrum dominated by the protonated
pH dye to the spectrum dominated by the deprotonated dye. The response is reversible.

[Ionophore]: 61.1 mmoVkg


pH =4.64
0.7

pH Dye

0.25
400 500 600 700 800

Wavelength

Figure 2: Response of a Lead selective plasticized PVC optode membrane based on ion-
exchange.
109

3. Chromoionophores derived from selective heavy metal ion receptors

Optode membrane response should preferably be pH insensitive. This cannot be


achieved when the transduction involves pH dyes. An improved transduction scheme requires
chromoionophores which couple the recognition event directly to a color change. The
synthetic strategy for making selective chromoionophores is to couple chromophores to
known receptors. Therefore, chromoionophores 2 and 4 in figure 3 are currently being
synthesized as derivatives of the Pb(II) and eden) ionophores 1 and 3, respectively. Recent
results will be reported.

Figure 3: Chromoionophores for selective recognition of lead and cadmium ions

The molecule depicted in figure 4 is a compound en route to a chromoionophore


selective for Lead(n) ions. The dye functionalities are conjugated with the amide carbonyl
groups, which are responsible for the complexation of metal ions. These amide groups will
later be transformed to thio-amide groups to obtain selectivity for heavy metal ions. The
molecule has no acidic or basic sites, which should make its response to changes in pH small.
In figure 5 the response is shown of this chromoionophore to complexation of Sodium ions. It
can be seen that by coupling of chromophores to the metal complexing amide-moieties
transduction of the complexation in an optical signal is indeed possible. The spectral changes
upon complexation of the metal ion are clear.

Figure 4: Chromoionophore for optical transduction of selective recognition of metal ions.


110

O.S

Free Ligand Chromoionophore:

sat. NaCID.

0.0
2S0 300 400 500 SOD

Wavelength

Figure 5: Optical transduction of the complexation of Sodium ions by a chromoionophore.

4. Conclusions

It has been shown that calix[4]arene neutral ionophores can be used in optical
transduction schemes. Also, chromoionophores based on integration of a dye functionality
into the chemical structure of these ionophores respond to complexation of metal ions by
changing their spectral characteristics.
5. Acknowledgment
We thank the Technology Foundation (STW) and the Netherlands Organization for
Scientific Research (NWO) for financial support.

6. References

P.L.H.M. Cobben, RJ.M. Egberink, lG. Bomer, P. Bergveld, W. Verboom


and D.N. Reinhoudt, 1. Am. Chem. Soc. 114 (1992) 10573.
2 M. Lerchi, E. Bakker, B. Rusterholz and W. Simon,Anal. Chem. 64 (1992)
1534-1540.
3 M. Lerchi, F. Orsini, Z. Cimerman, E. Pretsch, D.A. Chowdhury and S. Kamata,
Anal. Chem. 68 (1996) 3210-3214.
4 RJ.W. Lugtenberg, M.M.G. Antonisse, RJ.M. Egberink, J.FJ. Engbersen,
D.N. Reinhoudt, 1. Chem. Soc., Perkin Trans. 2, (1996) 1937-1941.

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