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Fiber-Optic Microsensor Array Based on Fluorescent Bulk Optode Microspheres for the Trace Analysis of Silver Ions

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Department of Chemistry and Biochemistry, Auburn University, Auburn, Alabama 36849
Cite this: Anal. Chem. 2005, 77, 15, 4706–4712
Publication Date (Web):July 7, 2005
Copyright © 2005 American Chemical Society

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    An optical microsensor array is described for the rapid analysis of silver ions at low parts per trillion levels. Because the ionophore o-xylylenebis(N,N-diisobutyldithiocarbamate) (Cu−I) was reevaluated and shown to exhibit excellent selectivity for silver ions, ion-selective electrode (ISE) membranes were optimized and found to exhibit the lowest reported detection limit so far (3 × 10-10 M). A corresponding Ag+-selective fluorescent optical microsensor array for the rapid sensing of trace level Ag+ was then developed. It was fabricated using plasticized PVC-based micrometer-scale fluorescent microspheres that were produced via a sonic particle casting device. They contained 156 mmol/kg Cu−I, 10 mmol/kg 9-(diethylamino)-5-[4-(15-butyl-1,13-dioxo-2,14-dioxanodecyl) phenylimino]benzo[a]phenoxazine (chromoionophore VII, ETH 5418), 2.3 mmol/kg 1,1‘ ‘-dioctadecyl-3,3,3‘,3‘-tetramethylindocarbocyanine perchlorate (internal reference dye), and 14 mmol/kg sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate and were deposited onto the etched distal end of a 3200-μm-diameter optical fiber bundle. The microarray was characterized by fluorescence spectroscopy in samples containing 10-12−10-8 M AgNO3 at pH 7.4, with selectivity characteristics comparable to the corresponding ISEs. The response time of the microsensor array was found to be less than 15 min for 10-9 M AgNO3, which is drastically shorter than earlier data on optode films (8 h) and corresponding ISEs (30 min). A detection limit of 4 × 10-11 M for Ag+ was observed, lower than any previously reported optode or silver-selective ISE. The microsensor array was applied for measurement of free silver levels in buffered pond water samples.

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     Present addresss:  Department of Chemistry, Purdue University, West Lafayette, IN 47907.


     Present address:  Adaptive Information Cluster, Dublin City University, Glasnevin, Dublin 9, Ireland.

     Present addresss:  Department of Chemistry, Renmin University of China, Beijing, P. R. China, 100872.


     To whom correspondence should be addressed. E-mail:  [email protected].

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